FIELD SAMPLING

BOOKS IN SOILS, PLANTS, AND THE

ENVIRONMENT
Editorial Board
Agricultural Engineering Robert M.Peart, University of Florida, Gainesville
Animal Science Harold Hafs, Rutgers University, New Brunswick, New Jersey
Crops Mohammad Pessarakli, University of Arizona, Tucson
Environment Kenneth G.Cassman, University of Nebraska, Lincoln
Irrigation and Hydrology Donald R.Nielsen, University of California, Davis
Microbiology Jan Dirk van Elsas, Research Institute for Plant Protection, Wageningen,
The Netherlands
Plants L.David Kuykendall, U.S. Department of Agriculture, Beltsville, Maryland
Kenneth B.Marcum, Arizona State University, Mesa, Arizona
Soils Jean-Marc Bollag, Pennsylvania State University, University Park, Pennsylvania
Tsuyoshi Miyazaki, University of Tokyo
Soil Biochemistry, Volume 1, edited by A.D.McLaren and G.H.Peterson
Soil Biochemistry, Volume 2, edited by A.D.McLaren and J.Skuji
Soil Biochemistry, Volume 3, edited by E.A.Paul and A.D.McLaren
Soil Biochemistry, Volume 4, edited by E.A.Paul and A.D.McLaren
Soil Biochemistry, Volume 5, edited by E.A.Paul and J.N.Ladd
Soil Biochemistry, Volume 6, edited by Jean-Marc Bollag and G.Stotzky
Soil Biochemistry, Volume 7, edited by G.Stotzky and Jean-Marc Bollag
Soil Biochemistry, Volume 8, edited by Jean-Marc Bollag and G.Stotzky
Soil Biochemistry, Volume 9, edited by G.Stotzky and Jean-Marc Bollag
Soil Biochemistry, Volume 10, edited by Jean-Marc Bollag and G.Stotzky

Organic Chemicals in the Soil Environment, Volumes 1 and 2, edited by C. A.I.Goring

and J.W.Hamaker
Humic Substances in the Environment, M.Schnitzer and S.U.Khan
Microbial Life in the Soil: An Introduction, T.Hattori
Principles of Soil Chemistry, Kim H.Tan
Soil Analysis: Instrumental Techniques and Related Procedures, edited by Keith A.Smith
Soil Reclamation Processes: Microbiological Analyses and Applications, edited by
Robert L.Late III and Donald A.Klein
Symbiotic Nitrogen Fixation Technology, edited by Gerald H.Elkan
Soil-Water Interactions: Mechanisms and Applications, Shingo Iwata and Toshio
Tabuchi with Benno P.Warkentin
Soil Analysis: Modern Instrumental Techniques, Second Edition, edited by Keith A.Smith
Soil Analysis: Physical Methods, edited by Keith A.Smith and Chris E. Mullins
Growth and Mineral Nutrition of Field Crops, N.K.Fageria, V.C.Baligar, and Charles
Allan Jones
Semiarid Lands and Deserts: Soil Resource and Reclamation, edited by J.
Plant Roots: The Hidden Half, edited by Yoav Waisel, Amram Eshel, and Uzi Kafkafi
Plant Biochemical Regulators, edited by Harold W.Gausman
Maximizing Crop Yields, N.K.Fageria
Transgenic Plants: Fundamentals and Applications, edited by Andrew Hiatt
Soil Microbial Ecology: Applications in Agricultural and Environmental Management,
edited by F.Blaine Metting, Jr.
Principles of Soil Chemistry: Second Edition, Kim H.Tan
Water Flow in Soils, edited by Tsuyoshi Miyazaki
Handbook of Plant and Crop Stress, edited by Mohammad Pessarakli

Genetic Improvement of Field Crops, edited by Gustavo A.Slafer

Agricultural Field Experiments: Design and Analysis, Roger G.Petersen
Environmental Soil Science, Kim H.Tan
Mechanisms of Plant Growth and Improved Productivity: Modern Approaches, edited by
Amarjit S.Basra
Selenium in the Environment, edited by W.T.Frankenberger, Jr., and Sally Benson
Plant-Environment Interactions, edited by Robert E.Wilkinson
Handbook of Plant and Crop Physiology, edited by Mohammad Pessarakli
Handbook of Phytoalexin Metabolism and Action, edited by M.Daniel and R.
P.Purkayastha
Soil-Water Interactions: Mechanisms and Applications, Second Edition, Revised and
Expanded, Shingo Iwata, Toshio Tabuchi, and Benno P. Warkentin
Stored-Grain Ecosystems, edited by Digvir S.Jayas, Noel D.G.White, and William
E.Muir
Agrochemicals from Natural Products, edited by C.R.A.Godfrey
Seed Development and Germination, edited by Jaime Kigel and Gad Galili
Nitrogen Fertilization in the Environment, edited by Peter Edward Bacon
Phytohormones in Soils: Microbial Production and Function, William T. Frankenberger,
Jr., and Muhammad Arshad
Handbook of Weed Management Systems, edited by Albert E.Smith
Soil Sampling, Preparation, and Analysis, Kim H.Tan
Soil Erosion, Conservation, and Rehabilitation, edited by Menachem Agassi
Plant Roots: The Hidden Half, Second Edition, Revised and Expanded, edited by Yoav
Waisel, Amram Eshel, and Uzi Kafkafi
Photoassimilate Distribution in Plants and Crops: Source-Sink Relationships, edited by
Eli Zamski and Arthur A.Schaffer

Mass Spectrometry of Soils, edited by Thomas W.Boutton and Shinichi Yamasaki

Handbook of Photosynthesis, edited by Mohammad Pessarakli
Chemical and Isotopic Groundwater Hydrology: The Applied Approach, Second Edition,
Revised and Expanded, Emanuel Mazor
Fauna in Soil Ecosystems: Recycling Processes, Nutrient Fluxes, and Agricultural
Production, edited by Gero Benckiser
Soil and Plant Analysis in Sustainable Agriculture and Environment, edited by Teresa
Hood and J.Benton Jones, Jr.
Seeds Handbook: Biology, Production, Processing, and Storage, B.B. Desai,
P.M.Kotecha, and D.K.Salunkhe
Modern Soil Microbiology, edited by J.D.van Elsas, J.T.Trevors, and E.M. H.Wellington
Growth and Mineral Nutrition of Field Crops: Second Edition, N.K.Fageria, V.C.Baligar,
and Charles Allan Jones
Fungal Pathogenesis in Plants and Crops: Molecular Biology and Host Defense
Mechanisms, P.Vidhyasekaran
Plant Pathogen Detection and Disease Diagnosis, P.Narayanasamy
Agricultural Systems Modeling and Simulation, edited by Robert M.Peart and R.Bruce
Curry
Agricultural Biotechnology, edited by Arie Altman
Plant-Microbe Interactions and Biological Control, edited by Greg J.Boland and L.David
Kuykendall
Handbook of Soil Conditioners: Substances That Enhance the Physical Properties of
Soil, edited by Arthur Wallace and Richard E.Terry
Environmental Chemistry of Selenium, edited by William T.Frankenberger, Jr., and
Richard A.Engberg
Principles of Soil Chemistry: Third Edition, Revised and Expanded, Kim H. Tan
Sulfur in the Environment, edited by Douglas G.Maynard

Soil-Machine Interactions: A Finite Element Perspective, edited by Jie Shen and Radhey
Lal Kushwaha
Mycotoxins in Agriculture and Food Safety, edited by Kaushal K.Sinha and Deepak
Bhatnagar
Plant Amino Acids: Biochemistry and Biotechnology, edited by Bijay K.Singh
Handbook of Functional Plant Ecology, edited by Francisco I.Pugnaire and Fernando
Valladares
Handbook of Plant and Crop Stress: Second Edition, Revised and Expanded, edited by
Mohammad Pessarakli
Plant Responses to Environmental Stresses: From Phytohormones to Genome
Reorganization, edited by H.R.Lerner
Handbook of Pest Management, edited by John R.Ruberson
Environmental Soil Science: Second Edition, Revised and Expanded, Kim H. Tan
Microbial Endophytes, edited by Charles W.Bacon and James F.White, Jr.
Plant-Environment Interactions: Second Edition, edited by Robert E.Wilkinson
Microbial Pest Control, Sushil K.Khetan
Soil and Environmental Analysis: Physical Methods, Second Edition, Revised and
Expanded, edited by Keith A.Smith and Chris E.Mullins
The Rhizosphere: Biochemistry and Organic Substances at the Soil-Plant Interface,
Roberto Pinton, Zeno Varanini, and Paolo Nannipieri
Woody Plants and Woody Plant Management: Ecology, Safety, and Environmental
Impact, Rodney W.Bovey
Metals in the Environment: Analysis by Biodiversity, M.N.V.Prasad
Plant Pathogen Detection and Disease Diagnosis: Second Edition, Revised and
Expanded, P.Narayanasamy
Handbook of Plant and Crop Physiology: Second Edition, Revised and Expanded, edited
by Mohammad Pessarakli

Environmental Chemistry of Arsenic, edited by William T.Frankenberger, Jr.

Enzymes in the Environment: Activity, Ecology, and Applications, edited by Richard
G.Burns and Richard P.Dick
Plant Roots: The Hidden Half, Third Edition, Revised and Expanded, edited by Yoav
Waisel, Amram Eshel, and Uzi Kafkafi
Handbook of Plant Growth: pH as the Master Variable, edited by Zdenko Rengel
Biological Control of Crop Diseases, edited by Samuel S.Gnanamanickam
Pesticides in Agriculture and the Environment, edited by Willis B.Wheeler
Mathematical Models of Crop Growth and Yield, Allen R.Overman and Richard
V.Scholtz III
Plant Biotechnology and Transgenic Plants, edited by Kirsi-Marja Oksman Caldentey
and Wolfgang H.Barz
Handbook of Postharvest Technology: Cereals, Fruits, Vegetables, Tea, and Spices,
edited by Amalendu Chakraverty, Arun S.Mujumdar, G.S. Vijaya Raghavan, and
Hosahalli S.Ramaswamy
Handbook of Soil Acidity, edited by Zdenko Rengel
Humic Matter in Soil and the Environment: Principles and Controversies, Kim H.Tan
Molecular Host Resistance to Pests, S.Sadasivam and B.Thayumanavan
Soil and Environmental Analysis: Modern Instrumental Techniques, Third Edition, edited
by Keith A.Smith and Malcolm S.Cresser
Chemical and Isotopic Groundwater Hydrology: Third Edition, Emanuel Mazor
Agricultural Systems Management: Optimizing Efficiency and Performance, Robert
M.Peart and W.David Shoup
Physiology and Biotechnology Integration for Plant Breeding, edited by Henry T.Nguyen
and Abraham Blum
Global Water Dynamics: Shallow and Deep Groundwater, Petroleum Hydrology,
Hydrothermal Fluids, and Landscaping, Emanuel Mazor

Principles of Soil Physics, Rattan Lal and Manoj K.Shukla

Seeds Handbook: Biology, Production, Processing, and Storage, Second Edition, Revised
and Expanded, Babasaheb B.Desai
Field Sampling: Principles and Practices in Environmental Analysis, Alfred R.Conklin,
Jr.
Sustainable Agriculture and the International Rice-Wheat System, edited by Rattan Lal,
Peter R.Hobbs, Norman Uphoff, and David O. Hansen
Additional Volumes in Preparation
Plant Toxicology: Fourth Edition, Revised and Expanded, edited by Bertold Hock and
Erich F.Elstner

FIELD SAMPLING
Principles and Practices in Environmental Analysis

ALFRED R.CONKLIN, JR.

Wilmington College
Wilmington, Ohio, U.S.A.
with
ROLF MEINHOLTZ
Environics USA
Port Orange, Florida, U.S.A.

MARCEL DEKKER, INC.

NEW YORK BASEL

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writing from the publisher.

To my wife, Petra

Preface
Field Sampling: Principles and Practices in Environmental Analysis is based on more
than 30 years of personal experience in environmental sampling and analysis. This work
involved walking fields, taking samples, putting them in appropriate containers, and
keeping a record in a project notebook. Samples were brought back to the laboratory
where I made the solutions and extractions necessary for the analyses and then carried
them out. This includes both simple analyses, such as pH and titrations, and complex
analyses involving gas chromatography, HPLC (high-precision liquid chromatography),
infrared spectroscopy, atomic absorption, and flame emission spectroscopy.
Rolf Meinholtz, who authored Chapter 10 and coauthored Chapter 11, has more than a
decade of experience analyzing environmental samples. This work has included sample
extraction and preparation, particularly for but not limited to volatile compounds, and he
has completed the actual analyses. He is familiar with and has carried out many U.S.
Environmental Protection Agency analytical procedures. He has also maintained and
repaired instrumentation used in these analyses.
The basic concept behind this book is to bring together in one place all the information
and tools important for successful sampling of the environment and to present it in a
manner useful in both commercial and academic settings. To accomplish this, a broad
range of topics are introduced. Because some sampling situations require additional
investigation of topics (e.g., ground penetrating radar, global positioning, etc.), references
have been provided that allow for this. In no case is this book intended to reflect, convey,
or impart knowledge, policy, or legal information about any particular type of sampling,
restrictions, or compliance codes relevant to any governmental, regulatory, or legal
organization or institution.
The tendency of many investigators is to go to a contaminated field and immediately
start taking samples; however, this approach is wasteful of natural resources. Making the
best sampling plan and using it saves time, limits human exposure to toxic situations, and
conserves chemicals and instrumentation. Even though it may initially seem to be timeconsuming and expensive, in the long run a good presampling and sampling plan saves
money. Proper application of modeling, statistics, and analytical methods also saves
manpower, limits exposure of workers, and saves money.
Analytical methods of analysis are accurate, precise, and very sensitive. It is possible
in some cases to be able to look at single atoms and molecules. However, soil, regolith,
and environmental samples in general show high variability. Soil, regolith, decomposed
rock, water, and air are constantly moving. Material is being added and lost on a minuteto-minute basis. A sample is a very small portion of this moving environment, and
because of this there is significant variability in all environmental samples.
In addition to the variability inherent in the material being sampled, there is variability
introduced by the acts of sampling, handling, and storage of samples before analysis. Of
these three the actual process of deciding what, where, and how to sample is the greatest

source of error. Because of this it is essential to have detailed knowledge of the material
being sampled. What are its characteristics, what should we expect it to contain, and what
kind of variability is inherent in the medium? Knowing the answers to these types of
questions will mean that we make better decisions in developing and executing a
sampling plan.
Many think of field sampling as simply going out to the field, getting some material,
and analyzing it. However, this is not an effective way to ascertain what is present. Today
there are tools, beyond just going to the field and sampling, that can greatly enhance the
sampling process. GPS (global positioning system) can be used to locate the
contaminated field and the limits of the contamination therein. In addition, it can be used
to identify sampling sites so that they can reliably be sampled at a later time. Some would
argue that flags or other markers can be left at sampling sites to facilitate repeated
sampling at the same place. Unfortunately, all too often such markers are lost, covered, or
moved without the investigators knowledge. Expensive GPS instruments are available
but so are simple, inexpensive systems, and often there is little difference in accuracy and
precision between expensive and inexpensive systems.
GIS (global information systems) can be used to locate pollution and its extent and to
tell the user whether the field is receiving additional contamination from adjacent areas. It
can also be used to follow the progress of remediation. This is accomplished by
producing maps with overlays of the contaminated field and surrounding areas. Because
GPS, GIS, and GPR (ground penetrating radar) provide additional information about an
affected field and its characteristics, they can be important tools in obtaining a better,
more representative sample for analysis. They also allow for mapping and provide
valuable data for modeling.
Digging is one way to find out what is below the surface; however, GPR can also be
used to find out what is below the surface. Using this technology can alleviate or lessen
the necessity for extensive sampling or movement of contaminated soil, sediment, or
regolith. It can also eliminate the possibility of dinging into gas and water pipes and data,
phone, and electric lines and possibly explosives.
Modeling programs can be used to predict where contamination is and where it is
likely to go in the environment, and thus to guide sampling. The data can then be used to
prevent the spread of contamination and contain the cost of cleanup or remediation.
Modeling programs, although useful, should always be checked against field evaluations
including laboratory analytical results.
Safety is extremely important when approaching an unknown field even if the field
appears open and without hazards. A safety plan needs to be prepared and implemented
before sampling begins.
In Chapter 10 some basic information about analytical methods is given. This may
seem out of place in a sampling book. However, what happens in the field and what
happens in the laboratory are interconnected. Ultimately, what happens in the field affects
both the precision and accuracy of analytical results in the laboratory. Laboratory results
can indicate that something has changed in the field and needs to be addressed. This is
well illustrated in Chapter 11, which discusses traps, mistakes, and errors encountered in
sampling. Taking samples from the wrong location, not taking the sample at the correct
depth, and handling or storing the sample incorrectly are a few examples.

This book includes all elements one needs to know about in order to take samples that
give a representative, accurate measurement of the conditions and concentrations of
components of concern in a field. Faithfully following the procedures outlined will
provide an excellent picture of a sampled area and its needs, if any, in terms of
remediation.
In the references at the end of each chapter are citations for Web sites. These are
extremely important because the information they contain tends to be more current than
is much hard copy information. Also, some information is available only on the
Internet. All the Web references have been checked several times; however, the Web is
much more fluid than printed work, which means that sites change as do their addresses.
If an address does not work, try accessing the parent site or home page. If an address has
epa in it, for example, it is an Environmental Protection Administration (EPA) site and
if the full address does not work, go to the EPA home page and look for the material from
that location. Most home pages have search engines that will help in locating the needed
information.
I wish to thank Rolf Meinholtz for contributing Chapter 10 and parts of Chapter 11 and
for offering many suggestions for other chapters. I also thank the following colleagues
who helped in reviewing this book: Mon Yee, Paul Thomas, Jennifer Krueger, Sally
Ullom, John Ryan, Pam Miltenberger, A.Warrick, Tom Hobbson, H.Bohn, F.Anliot,
M.Anderson, and D. Watts.
Remember that local rules apply. Each local area, township, county, state, and country
has its own rules for safety, sampling, and approved analytical procedures, as well as
individual interpretations and applications of analytical results to remediation of
environmental problems. For this reason the information presented is general, and some
parts may not be applicable in certain situations and places. Always find out about local
rules, interpretations, and applications.
Mention in this book of any program, organization, or company does not constitute an
endorsement or recommendation but is simply given as an example of the types of
support available to persons involved in field sampling.
Alfred R.Conklin, Jr.

Contents

Preface
1
2
3
4
5
6
7
8
9
10

Introduction to Field Sampling

Characteristics of the Environment
Presampling
Safety
Sampling
Statistics
Modeling
Sample Transport and Storage
What Is Present?
An Overview of Basic Principles of Analytical Methods
Rolf Meinholtz
11 Traps, Mistakes, and Errors
Alfred R.Conklin, Jr. , and Rolf Meinholtz
Appendix A: Abbreviations and Acronyms
Appendix B: Sources
Index

xii
1
23
51
82
107
143
172
200
219
246
277

292
295
297

1
Introduction to Field Sampling
Often there is a great desire to start sampling a field without knowing anything about it or
its surroundings and without a well-developed plan. Such an approach will not lead to
success in understanding the levels of the component or components of interest contained
therein. Successful sampling depends on a careful, thoughtful understanding of the
characteristics of the field, the components it contains, the surrounding fields or areas,
and its history. In addition, sample handling, transport, and the analytical methods to be
used will be essential components of a successful sampling plan.
Depending on where you are in the United States or elsewhere, a field may be a large
or small area. It may have an area of thousands of hectares or less than one. In urban
areas or in industrial settings a field may be referred to as a site, and the two terms may
be used interchangeably. In some cases the two may be put together and termed a field
site. The term site is often used in two different ways or sensesthat is, to refer to either
an area (field) or a precise location within a field. In the latter case it would normally be
the specific place from which the sample is taken.
In addition, the term field is used in a generic sense; that is, anytime someone leaves an
office, travels to a location, and takes a sample the person is said to be in the field and
field sampling. Anytime he or she is out of the office he or she is thus in the field. The
sample obtained might be air, water, soil, biological, or any other component of the
environment. Note that safety personnel have other definitions for the term field sample.
For the U.S. Occupational Safety and Health Administration (OSHA) a field sample may
be made for noise or for other safety concerns, such as guards on moving machine parts.
Although the emphasis here will be on field as a land area, the methods described apply
to field sampling in all respects. A sampling plan, a field sampling project notebook,
safety considerations, and so on, will all need to be taken into consideration in all field
sampling situations.
In this book we will use these terms in a specific way. Field will refer to any area to be
sampled, including fields, water, sediments under water, and air. Site will refer to a
specific location in the field from which a sample is to be taken. Figure 1.1 shows a
landscape that would contain many fields. It also shows subsurface features that would
affect sampling. A field sample may be obtained by physically sampling all or a portion
of this landscape.

Field sampling

FIGURE 1.1 A landscape including surface and subsurface features.

Sampling can include any method of obtaining information, such as remote sensing,
about the condition or components in the field. When discussing field sampling it is
important to make sure that all terms are used in an unconfusing way.

1.1. ASSESSING THE SAMPLING NEEDS

An eye-level examination from one position in a field may provide a biased assessment
of the sampling needed. It may also lead to unsafe and costly errors in developing the
sampling plan.
In addition to viewing the field, in starting a sampling project some premature work is
often done. Statistical tools may be applied to the assumed situation. Other times,
someone goes to the field without thinking and grabs a sample and has it analyzed. All
this activity may have the semblance of being intended to determine the level of a
component or components present in a field. Some useful information may be obtained.
To obtain accurate and useful information, however, a detailed, well thought out
sampling plan based on an understanding of the environment in general and the specific
characteristics of the field to be studied must first be developed.

Introduction to Field Sampling

An essential question to ask is what do we wish to accomplish by sampling this field.

In order to be able to answer this question we need to know about the environment so that
we know we are getting a sample that will give us the answers we need. We walk
outdoors, breathe the air, feel the rainfall, and feel our feet on the ground. It is easy to
take all this for granted and not consider the various characteristics of these and other
components of the environment and how they may affect a field sample.
To obtain the needed information the general and specific characteristics of the field
must be known. It is also important to know how the field is related to the rest of the
environment. For example, does water move into, on, through, or under the field? Is the
area being used (or has it been used in the past) mainly for manufacturing or agriculture?
Is the field low-lying and thus receiving inputs from surrounding areas, or is it high and
eroding? All possible and probable interactions of the field with the surrounding
environment must be taken into consideration.
The specific type or types of materials contained in the field must be known. Without
this information samples from a landfill might be mistaken for samples from a cornfield.
What is the source of the material? Is it the natural soil or has it been brought in as fill
from some other place? Imported material may unknowingly be contaminated and thus
add to the sampling problem.
More specifically, what are the characteristics of the medium (for instance, soil) to be
sampled? Is it a sandy soil that has little ability to retain water and chemicals, or is it clay,
which has high retentive capacity? Is there only one component, or are there several
components of interest present? What are the characteristics of the components? Are they
soluble or insoluble in water, toxic or carcinogenic, volatile or nonvolatile, flammable or
nonflammable? This information is added to the general information to obtain all the
information important to the sampling plan.
A visual evaluation of the present condition of the field, obtained by walking around its
perimeter, is important in assessing the situation. Is the field bare or planted, or does it
have weeds on it? What is its slope? Is there evidence of erosion? What are the
surrounding structures like and what is their relationship to the field? What is its
physiography? All these are noted and recorded while walking around the field.
As much information as possible about the background or history of the field is
obtained next. In how many different ways has it been used in the past? Do any of these
past uses impact the sampling plan? Are there likely to be pipes, tanks, or electrical or
communication cables buried in the field? All of this type of information needs to be
obtained and added to the other information before sampling is begun.
The understanding gained during the above activities provides information about how
extensive and intensive the sampling needs to be. If one or more of the contaminants is
volatile, soluble, or mobile the extent of the contamination will be greater than it would
be for an immobile contaminant. A contaminant soluble in water and carrying a negative
charge (anion) would be expected to move further and possibly contaminate water
supplies. This calls for a more extensive sampling plan. A low solubility contaminant
may remain in a restricted location for long periods of time and not constitute a hazard to
surrounding areas, thus calling for less extensive sampling. Putting this all together
allows for understanding the sampling requirements necessary for a successful
investigation [1].

Field sampling

Along with this information, careful consideration must be made of the safety
measures needed during sampling. The largest part of safety is to prevent contamination
of workers during the sampling procedure. For example, fields heavily contaminated with
petroleum may be flammable. In this case there can be a fire hazard caused by smoking
or sparks in the field, and this is a safety concern. It is also important, however, that
persons doing the sampling or other persons present not inadvertently remove
contamination from the field. In the above case samples taken off the field may be a fire
hazard if not stored and transported properly.
Considering what happens to the sample once it is taken, including during transport, is
also important. It is possible that the analyte (component or contaminant) of interest
easily undergoes rapid changes both in the field and in sample containers. This may
dictate the use of a rapid sampling and analysis procedure rather than slower, more
accurate, and more precise procedures. A commonly cited example is nitrogen
compounds. Under oxidizing conditions and moderate temperatures ammonia is rapidly
oxidized to nitrite and nitrate. Under anaerobic conditions nitrate can rapidly be reduced
to nitrogen gas. A two-week lag time between collection of a sample containing nitrate
and its analysis would mean that the analytical results would not represent the level of
nitrate in the field [2].

1.2. SOIL
Soil could be considered the loose material, derived from stone, on the Earths surface.
There are two distinct ways soil is used, however, for agriculture (growing crops and
raising animals) and for engineering (supporting structures). There are thus two distinct
ways of describing soil, and any persons involved in sampling must be familiar with both.
1.2.1. Soil Scientist Description
Normally a field will contain one or several soils. (See Figure 1.2.) It may also have rock
outcrops and water moving through it (or during a flood, over it). Soil will certainly have
water moving under it. If it is a fully developed soil, there will be several subsurface
horizons. (See Figure 1.3; also Figure 2.4 in Chapter 2). These horizontal layers will have
significantly different physical, chemical, and biological characteristics. They develop as
a result of the action of the soil-forming factors, time, topography, parent material, biota,
and climate, the effects of which extend 1.5 to 2 meters deep. This volume of active soil
development is called the solum.
In addition to the surface A horizon there may be several subsurface horizons, the most
common being B and C horizons. The A horizon is distinctive in that it contains more
organic matter and is darker than the underlying horizons. The B horizons are distinctive
in that they contain more clay than over- or underlying horizons and are usually divided
into several subdivisions, depending on changes in horizon characteristics. The C horizon
is the material from which the soil is forming and is considered the soil parent material.
Although the parent material has not been acted upon by the soil-forming factors it may
contain horizons that are a result of the original deposition or formation of this material.

Introduction to Field Sampling

FIGURE 1.2 A soil survey map of several soils showing different soil types
with differing slopes and erosion. The first two letters represent a
mapping unit (different soil), the following capital letter represents
the slope, and the last number represents the amount of erosion.

In the United States soils are classified as belonging to one of twelve soil orders, * which
are distinguished by the number and type of horizons they contain. Some orders, such as
Gelisols and Aridisols, are also distinguished by their location. Gelisols are frozen soils
that occur and develop in frigid regions and contain a permanent frozen layer. All soils in
arid or desert regions are called Aridisols. Other soils that have one very distinguishing
characteristic are the Andisols, which develop from glassy volcanic ash, and the
Vertisols, which develop cracks 30 cm wide and 1 meter deep when dry.
A complete list of the twelve soil orders is given in Table 1.1, along with an indication
of a characteristic important in the sampling of each.
* Other countries have

systems similar to the U.S. system, but often have more orders.

Field sampling

FIGURE 1.3 A simplified soil profile showing the development of several

horizons.

Introduction to Field Sampling

TABLE 1.1 The Twelve Soil Orders and Some Important Characteristics

Soil order

Characteristic

Entisol
Inceptisol
Andisol
Histosol
Gelisol
Aridisol
Vertisol
Alfisol
Mollisol
Ultisol
Spodosol
Oxisol

No horizon development
Minimal horizon development
Developing from volcanic ash
Organic soil
Frozen soil
Desert soils
Soils developing large cracks when dry
Horizon development under trees
Horizon development under grass
Horizon development under tropical and subtropical trees
Horizon development in sandy soil under coniferous trees
Most highly weathered

They are given generally in order from least to most developedthat is, from those
orders showing the least to the most horizon development [3].
1.2.2. Engineering Description
The engineering description of soils is very different from that of soil science given
above. For engineering purposes the carrying capacity, shrink-swell, and plasticity
characteristics of soil are more important than its chemical or biological characteristics.
The engineering classification gives more emphasis to larger components such as gravel
and its characteristics, and less to erosion and crop production characteristics. Engineers
describe soils using a two-letter designation that provides an indication of its
composition. Thus a soil composed of well-graded gravel would have the designation
WG, while a soil composed of clays with high plasticity would be designated as CH.
A soils plasticity and liquid limit play a large role in its engineering characteristics.
The plastic limit is the moisture level when the soil just becomes plastic; that is, it can be
molded into a shape and retain it. The liquid limit is the moisture level when the soil
becomes liquid, has a loose consistency, and will run.
A more detailed description of soil horizons, underlying materials, and engineering
characterizations will be presented in Chapter 2. The importance of these horizons and
ways of describing soils in developing a field sampling plan will also be discussed.

Field sampling

1.3. WATER AND AIR

Water and air are completely different from soil, although they make up a significant part
of the soil environment. They are more mobile, and contaminants diffuse and are mixed
with them more readily. Another difference is that the movement of water and air is
associated with currents, which are responsible for the mixing and movement of
components (either dissolved or suspended) in them. In the case of air these currents may
be called wind. Water and air carry soil and contaminants (both with and without
associated suspended particles) for long distances. Eventually materials carried by water
and air are deposited either on the soil surface or at the bottoms of bodies of water. The
potential and real movement and deposition of soil and other components carried by
water and air is extremely important in sampling.
One area in which soil, water, and air are similar is that all three have layers or
horizons that have different characteristics. In addition to currents and wind, the layers or
horizons from which samples are taken are thus important. However, because of the
differences among soil, water, and air, separate specialized sampling tools are used for
each. In many cases sample containers for these three will also be different.
In addition to their individual existences, air and water are also integral and active parts
of soil. Under idealized conditions a soil sample is half solid and half void space. Under
the same conditions soil is envisioned as having half the void space filled with water and
the other half filled with air. Figure 1.4 gives a graphical representation of this idealized
composition of soil. There is an inverse relationship between soil water and soil air; that
is, when it rains the void space is filled with water and there will be little or no air and
when the soil dries the space occupied by water is replaced by air. The result is that both
soil air and water content are highly variable.
Soil air itself is also highly variable. In general it contains the same constituents as
atmospheric air; however, these are in different concentrations in soil. Plant roots and soil
microorganisms respire, taking up oxygen and releasing carbon dioxide into soil air. The
soil atmosphere is thus higher in carbon dioxide and lower in oxygen than atmospheric
air. In addition, it is possible to find highly reduced gaseous species in soil air even when
the soil is aerobic. For instance, it is not unusual to find methane in the soil atmosphere
along with nitrogen, oxygen, carbon dioxide, and water vapor.
Soil water is variable in concentration, depending on the minerals and amount of water
present. In terms of ions the types present are determined by the mineral composition of
the soil and so are less variable in any one soil. Soil pH is also determined by the
minerals present and the amount of water available for leaching the soil profile. The more
water leaching through the soil, the more acidic it will be.

Introduction to Field Sampling

FIGURE 1.4 Composition of an idealized soil sample. Note that the organic
composition may be as little as 0.1% for some tropical soils and as
high as 30% or higher for histosols (organic soils).

1.4. PRESAMPLING
At the very beginning of any sampling project it is essential to have a project notebook.
This will be used to record all information about the project, including the sampling
location, the history of the location, and all of the activities in, on, and around it. All
entries in the book must be dated, sometimes with the specific time of the activity noted.
All samples taken must have on their container a designation, usually a combination of
letters and numbers, that directly points back to the pages in the project notebook in
which the samples are described.
The description in the project notebook must describe the sample precisely and in
depth, including its location and the depth and the date the sample was taken. The amount
of sample and any distinguishing characteristics (e.g., gravel, distinguishing color,
occurrence or lack of roots, sample taken during a rainy day) are examples of some other
important characteristics. Also, the sample container used and any other potentially
relevant data available are recorded. (The project notebook will be described in more
detail in Chapter 3.)
In addition to the project notebook another presampling activity as noted above is to
obtain as complete a history of the location as possible. This information is included in
the project notebook. This may seem superfluous at first, but can save a lot of time,
energy, and frustration during the sampling process. Uncovering some unforeseen
obstacle in the middle of sampling can disrupt the entire programto such an extent that
it may have to be started again from the beginning. (See the example in Section 11.7 in
Chapter 11.)

Field sampling

10

1.4.1. Maps
Several different maps and different types of maps (general area and detailed) are needed
for sampling. General area maps are used to determine if adjacent areas can affect or be
affected by sampling activities in the field. Detailed maps are used to record sampling
activities in the field. For this reason many simple copies of this map will be needed.
Whenever an activity is carried out in the field it should be noted on a map. Thus, there
should be a separate map for each activity and each days activities in the field.
An additional essential map is a soils map of the area. Such a map shows the soils and
their extent on an aerial photograph. They allow samplers to know which soils are being
sampled and to find uncontaminated reference soils to sample. Soils maps, an example of
which is shown in Figure 1.2, are included in a soil survey of the area and give invaluable
information about the areas characteristics.
In addition to maps, photographs of portions of the Earths surface are also available.
These may be simple pictures or specialized digitalized photographs, such as the digital
orthophoto quarter quadrangles (DOQQ). These digitalized photographs are corrected in
such a way that they faithfully represent the Earths surface. Because they are digitalized
they can be used with geographic information system (GIS) displays discussed below.

1.5. SAFETY
The safety of the personnel, the field, and the area surrounding the field must always be
of concern. Of these three, the safety of the personnel is of prime concern. In field
situations unforeseen discoveries are common. They may be simple and interesting or
they may be life-threatening. The first rule of field sampling is thus to never sample
alone. This is particularly important where the field is hundreds or thousands of hectares
in size and will involve being long distances from help, and applies whether the sampling
is done on foot, in a boat, on an airplane, or in an all-terrain vehicle. If you cannot walk
to safety you may also not be able to row, swim, fly, or drive to safety!
The second rule of sampling is to wear and have available safety equipment. This
means wearing appropriate clothing and eye protection at all times. Even under what
seem to be the safest conditions additional safety equipment must be readily available.
In addition to keeping the personnel who are doing the sampling safe, precautions must
be taken to make sure that unsafe conditions do not develop in other areas either inside or
outside the field being sampled [4]. The field office, associated laboratory, and sample
storage area are part of this concern. Also of concern is that samples do not spread
contamination during storage and transport. More detailed information about safe
sampling will be given in Chapter 4.

1.6. SAMPLING
The environment is four-dimensional. It has three physical dimensionslength, width,
and depth. The dimension of time also has a significant effect on the contaminant,

Introduction to Field Sampling

11

sampling, and analytical results. When taking samples it is important to take all four
dimensions into consideration. For instance, it is not sufficient to only take samples from
the surface even if there appears to be no way that the contaminant could have moved
through the surface and into the lower layers. To know what is happening to the part of
the environment being sampled, samples must be taken at various depths and over a
period of time.
1.6.1. Grab Samples
When starting to sample, the first thing people want to do is grab a sample and have it
analyzed. Indeed, there is a type of sample called a grab sample. The sample selected for
grabbing usually looks different from the bulk material, and thus is assumed to be
contaminated. Such a sample might just as well look different because it is
uncontaminated and thus it is not known what this sample represents or how it should be
handled.
There are two further problems with this type of activity. First is a safety issue. It is not
a good idea to go onto a contaminated area without the proper safety equipment. Second,
by the time more systematic sampling is carried out the location of this sample will be
lost, and so the place of this analytical data in connection to other data obtained will be
unknown. There will also be a time difference between this sample and subsequent
samples, further lessening its value. Any information gained will thus be of little or no
value. Grab samples are potentially dangerous and a waste of time and money.
1.6.2. Preliminary Transect Sampling
When all preliminary nonsampling work is completed, some organized preliminary
transect sampling can be initiated. A transect is a straight line passing through the
contaminated or other field of interest. Samples are taken at various sites along the
transect, both surface and subsurface, and include samples assumed to be outside the
contaminated area. A second transect may also be needed if the field contains several
different soil types or areas. This transect is chosen so that all soil types or areas are
sampled.
Preliminary sampling is important because it is the basis for the application of stastical
tools and the development of a realistic, honest, and detailed sampling plan. It is also the
basis for determining the handling of the samples from acquisition to final analysis.
Handling includes the type of sampler used, sample containers, sample labeling, storage,
and transportation. It also provides data needed to determine the type of analysis needed.
1.6.3. Systematic Sampling
On the basis of the historical background and transect sampling a detailed systematic
sampling plan can be developed and carried out. This sampling plan includes the areas to
be sampled and how sampling sites will be determined and designated. The total number
of surface and subsurface samples to be taken will also be part of the plan. Questions
such as whether the surface and subsurface will be sampled at each site or only one and

Field sampling

12

whether different soils will be sampled differently or only be noted with a unique label
will be answered. Over what length of time sampling is to continue and what criteria are
to be used in determining when sampling is terminated will also need to be determined.
All of these considerations, along with all other available information, are put together to
produce the final detailed sampling plan [5].

1.7. STATISTICS
Statistics and statistical analysis are essential tools in any sampling plan. First, statistical
analysis of preliminary sampling data can help determine the number of samples that
need to be taken to obtain an accurate picture of the amount and extent of contamination.
The same statistic is applied when remediation has been effected to be certain that the
field is indeed clean [6].
In any sampling some of the samples will give analytical results that the researcher
cannot accept as being valid. A nonbias estimation of the validity of these analytical
results needs to be made, however. There are statistical tools that can be applied to
determine if the analytical results of such a sample are indeed valid or can be discarded.
These tools should be applied to both sample analytical results that are too high and those
that are too low [7].
There are also statistical methods called geostatistics, which can be used to estimate
the extent of contamination. These tools allow one to map the concentration or level of
contaminants over an area. Geostatistical methods can be used in conjunction with global
positioning system (GPS) and GIS in developing an effective sampling plan [8].

1.8. MODELING
Sampling, statistics, GPS, and GIS (see below) are all ways of obtaining information
useful in making a model of a portion of the Earth. In this case a model that will lead to
the most effective sampling plan is produced. Here the word effective includes labor,
containment of the spread of contamination, safety, resources, and money.
Models can be physical models of the environment, simple mathematical models of
single components, or dynamic, complex models of environmental systems. In Chapter 2
some physical nonmathematical methods for modeling the environment will be
described. Although they are nonmathematical, they can lead to an improved and
increased under-standing of what happens in certain environmental conditions. Models
may not be exact, and many refinements may be suggested; however, they do provide
valuable and insightful information about the portion of the environment modeled. For
instance, a model of the way water moves through porous media of different textures and
pore sizes can be informative in many sampling situations [9, 10].
There are a number of computer software programs and complex mathematical
equations that are useful in modeling water movement through the environment. They
can also be used to estimate the fate of contaminants or pollutants. Many of these
programs are specifically aimed at predicting the movement of water through porous

Introduction to Field Sampling

13

media, including soil, rock, and fractured rock. Such models can be invaluable in
developing an effective sampling and remediation plan. Models are only as good as the
data used in them, however. Of particular concern are areas in which water moves
through layers of different media or rock that have significantly different hydraulic
conductivity (K) and effective porosities (theta; ). It is also good to keep in mind that the
contaminant may affect both K and theta by changing the viscosity of water, which in
turn changes the way it moves through the environment. Modeling is treated further in
Chapter 7.

1.9. SAMPLE HANDLING

Once the sample is obtained it will be analyzed. Some analytical data, such as pH, will be
obtained in the field, while other needed data will require sophisticated laboratory
analysis. This means that samples will need to be placed in suitable containers and
labeled. Labeling is critically important because a sample that arrives at the analytical
laboratory without a label is useless. This means the time and effort used in obtaining and
transporting the sample is lost. A more costly result is that the sample usually cannot be
replaced and thus the data it contained are lost; that is, by the time the problem is found
some time has elapsed and so a subsequent sample will not be the same as the previously
taken sample. Sometimes this may not be a problem, but in other cases significant
changes in the sampling area may have occurred. For instance, a heavy rainfall might
change the concentration or distribution of the contaminant.
Depending on the type of sample, the type of component, the analytical laboratory
specified, sample handling, storage, and transport procedures must be followed. Some
samples may be dried, some must be sealed in their original condition, and some must be
kept at a specific temperature between sampling and analysis. During these operations the
sample must be safely handled, stored, and transported in such a manner that the
constituent or contaminant of interest is not lost or its concentration changed. These
conditions must be not only followed, but also recorded and verified using chain of
custody forms.
Once samples are in the analytical laboratory they will be handled in an appropriate
manner for the contaminant of interest. It is important for the people in charge of and
actually doing the sampling to have some idea of what happens to samples in the
analytical laboratory, because what happens there can affect what happens both in the
field and during sampling (and vice versa) [11]. Specific examples of this type of
interaction will be presented in Chapter 11.

1.10. WHAT IS PRESENT?

In any sampling it is always good to know what is present or likely to be present in the
sample. This is important for three reasons. The components present or likely to be
present will determine what sampler and what sample container is used. They will also
determine what safety precautions need to be taken in both the field and the laboratory.

Field sampling

14

For the laboratory it is also good to know the likely concentration of the contaminants,
because some analytical procedures may be sensitive to components other than those of
primary interest present in the sample. This could mean over- or underestimation of the
level of contamination of interest, which would in turn affect the sampling and
remediation plan.
Part of this information will be obtained by a thorough investigation of the history of
the field. For instance, the types and concentration of components will be different if the
field is or has been used for agriculture, manufacturing, housing, or a municipal dump.
The length of time a field is used for a particular activity will often indicate the level of
contamination likely to be found.
The occurrence of either an inorganic and organic toxic component in a soil sample,
however, is not necessarily an indication of contamination. All soils naturally contain low
levels of compounds that are toxic in high concentration. For example, all soil contains
low levels of such things as lead and arsenic. The analysis of humic materials may result
in finding many simple organic compounds, including phenols, alcohols, acids, and
aromatic compounds. Thus in a high-sensitivity gas chromatographic/mass spectral
analysis of soil or water extracts a low level of a wide variety of organic compounds
should be expected to be found [12]. When evaluating the results of soil analysis it is
critical to look at the occurrence of toxic compounds, their concentrations, and the natural
occurrence of these same compounds in similar but uncontaminated soils.

1.11. ANALYTICAL METHODS

Samples will be analyzed in several different ways using three different methodologies.
Some samples (e.g., transect samples) will be analyzed for some components using rapid
methods designed to determine the extent, width, breadth, and depth of contamination.
These analyses may be done in the field as the samples are taken or at the field office
laboratory. Samples from detailed sampling will be analyzed for some characteristics in
the field or at the field office laboratory, but most analysis will be done at a commercial
laboratory.
Those samples sent to the commercial laboratory will be treated in a manner
appropriate for the contaminant or component that the organization submitting the sample
wishes to know about. This is important because samples to be analyzed for metals will
be treated differently from samples to be analyzed for organic contaminants, and the two
procedures are not compatible. A sample extracted for metals cannot subsequently be
used for the analysis of organic contaminants and vice versa.
It is advisable to use the same procedures, analytical methods, and analytical
laboratory for all samples. For example, it is not advisable to change the method of
determining soil pH in the middle of the sampling plan. For some extraction procedures
slight changes in the way the procedure is carried out can make a significant difference in
the analytical results. The results will be more consistent, and it will be easier to interpret
them if they are all carried out the same way and are sent to the same laboratory [13].

Introduction to Field Sampling

15

1.12. TRAPS
There are many traps into which the inexperienced or unknowledgeable person doing
sampling can stumble in the field. The scenario below is an example of what can happen.

Scenario
An agricultural field planted to sugarcane and having a 5% slope is sampled
by two people. No instructions are given to the persons doing the sampling.
The first persons samples are found to have phosphate levels equivalent to
200 kg per ha, and remediation is recommended to prevent contamination of
adjacent water supplies. The second persons samples have phosphate levels
equivalent to only 50 kg per ha, and no remediation is recommended.
From this scenario the question arises as to how such different results could be obtained
from the same field. The answer is both in the depth to which the soil was sampled and
the place from which the sample was taken. A sample of the top 4 cm of a soil in a
depressional area will usually show a high level of whatever you are looking for. On the
other hand, a sample of the top 30 cm of soil at the highest point in the field will show a
lower level of what you are looking for. The first step in solving this riddle is to make
sure that all samples are taken to the same depth. The second is to make sure that random
samples are taken from the whole field. A third point is to know the history of the site to
make sure that previous usage is not contributing to the differences in the results. The
fourth point is to know where phosphate fertilizer was applied and account for this during
sampling.
When thought about, this makes sense. Contaminants, fertilizer elements, pesticides,
and toxic substances will erode from the high places in the field and collect in the low
areas. In the middle between the two extremes the results will be closer to the average.
Samples taken from throughout the field are required in order to have a representative
indication of the level of phosphate, in this case, in the soil.

1.13. ESSENTIAL UNITS

A common unit used to express the concentration of components or contaminants in the
environment is parts per million (ppm). This is a base unit of measurement and can be
thought of as 1 part per 1,000,000 parts. Usually we use grams or kilograms, so 1 g in
1,000,000 g would be 1 ppm. It may also be expressed as g/L, which assumes that 1 ml
of water weights 1 g. It is then valid, because a liter is equal to 1,000,000 L.
Today you will also find units such as ppb and ppt (parts per billion and parts per
trillion) being used. (See Table 1.2.) The amount of a component or contaminant in the
field is easily calculated using these units

Field sampling

16

TABLE 1.2 Common Units Used to Express the Concentration of a Component in a

Field

Prefix
Micro
Nano
Pico
Fento
Atto

Value
1a

0.00000
0.000000001
0.000000000001
0.000000000000001
0.000000000000000001

Abbreviation
ppm
ppb
ppt
ppq
ppa

aEquals 1/1,000,000.

when used in conjunction with a medias bulk density. These units also allow for easy
conversion between the unit, the mass of material, often soil, and the amount of
component or contaminant present. Other units of importance include bulk density and
what is called a hectare furrow slice.
1.13.1. Bulk Density and Particle Density
In field sampling a sampler is inserted into the soil and a sample extracted. When using a
core or bucket sampler a volume of soil is obtained. To understand the relationship
between sample volume and the mass of soil it is essential to know the bulk density of the
soil. As noted above, soil is composed of both solids and void space filled with water and
air. Because of this the term bulk density is used rather than density.
The bulk density of a soil is the amount of soil per unit volume. The official units for
bulk density are Mg/m3. However, the older units of g/cc will commonly be encountered.
Both units are the same in that 1.24 Mg/ m3=1.24 g/cc (1 g/cm3). Most soils have bulk
densities between 1.00 and 1.70 Mg/m3. Lower or higher bulk densities indicate an
unusual situation, such as an organic soil or a compacted layer.
Knowing the bulk density the mass of soil taken can be calculated if its volume is
known. On the other hand, knowing the mass the volume can be calculated. The bulk
density will disclose the occurrence of compacted zones in soil, which can affect
sampling. Often it is also important to know how much of the sample is solid and how
much is void space. For this determination the particle density of the soil particles is
needed.
Soil scientists assume that the individual particles in soil have an average density of
2.65 Mg/m3. From this it is obvious that soil must contain a significant amount of void
volume. As noted above, a soil sample is assumed to be half solid and half void space.
The void space is assumed to contain water and soil air. The percentage of the soil
sample with this void space can be calculated by dividing the bulk density by the particle
density. More information about the calculation of void space is given in Chapter 2.
Other more specific examples of how bulk density is used in sampling will be given in
later chapters [14].

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17

1.13.2. Hectare Furrow Slice

Fields are measured in square units. In most of the world the units used are hectares (ha
104m2). In the United States and some other countries acres are used (one acre equals
0.405 ha). Because farmers often work the soil 15 to 30 cm deep we talk of a hectare
furrow slice (hafs). (A furrow is a cut, usually between 15 and 20 cm deep, made in the
soil by a plow.) If a soil has a bulk density between 1.3 Mg/m3 and 1.4 Mg/m3 and the
soil is worked to a depth of 15 cm, an hafs will weigh approximately 2,000,000 kg. This
same type of calculation done with acres gives a value of approximately 2,000,000 1b per
acre furrow slice (afs). All of these units will be used extensively in this book.

1.14. DEFINITIONS
Environmental work and field sampling will require knowledge of a number of
abbreviations and acronyms. These terms abound in environmental work and literature,
especially in field sampling and environmental cleanup. The U.S. Environmental
Protection Agency (USEPA) has a Web site called Terms of Environment devoted to
such terms. The section of abbreviations and acronyms beginning with A through D is 13
pages long, and thus the complete list will not be given here. Table 1.3, however, gives a
very few commonly encountered abbreviations and their explanation. There has been no
attempt to try to pick only the most commonly used abbreviations for inclusion in Table
1.3. This Web site is especially helpful when trying to understand environmental reports
[15].
Because many concepts, procedures, and terms are known by their acronyms and
abbreviations, many are included in the following chapters. Sometimes it is hard to find
information about these concepts, procedures, and terms if their acronyms are not known.
A list of acronyms and abbreviations used in this book are included in Appendix A.
Several of the abbreviations given in Table 1.3 are very commonly used. VOC, which
stands for volatile organic compound, is an excellent example of one of these. VOCs are
compounds having low boiling points, below 200C, or high vapor pressure. Common
solvents such as acetone,

TABLE 1.3 Environmental Abbreviations and Acronyms and Terms (ATT)

ATTs Explanation
BMP Best management practice(s)
CFC Chlorofluorocarbon
DO Dissolved oxygen
GEMS Global environmental monitoring system; global exposure modeling
system
MDL Minimum detection limit
O3
Ozone

Field sampling

18

PM10 Particulate matter 10 m or smaller

RCRA Resource Conservation and Recovery Act
TCP Transport control plan
TPH Total petroleum hydrocarbon
VOC Volatile organic compound

methylethylketone, diethyl ether, which is commonly just called ether, and hexanes are
examples of compounds that fall in this category. Total petroleum hydrocarbons (TPHs)
are any hydrocarbons from a petroleum source and commonly refer to fuels such as
gasoline, kerosene, and diesel fuel. Another common reference is to heavy metals, which
are any of the metallic elements from the lower part of the periodic chart [16].
A very important term that is not an abbreviation is hot. Normally we understand this
to mean that something is at a high temperature. In sampling we understand this to mean
that a sample has a high concentration of contaminant. Any sample with the word hot on
it thus should be handled especially carefully. Having hot on a label will also alert
laboratory personnel to the high concentrations. This can mean that the sample is handled
and analyzed in such a way as to obtain the best possible results.

1.15. OTHER WAYS OF SAMPLING AND REPRESENTING THE

ENVIRONMENT
There are many other ways of obtaining information about a field. Two of the most
important are ground-penetrating radar (GPR) and remote sensing. Ground-penetrating
radar might be considered remote sensing; however, it is not similar to most remote
sensing in that it involves moving a radar system over the soil surface. Remote sensing is
generally understood to involve taking or sensing the Earths surface from an airplane or
satellite, but radar used in weather prediction can be considered a common example of
remote sensing.
1.15.1. Ground-Penetrating Radar
Ground-penetrating radar is a relatively recent development. An instrument emitting
radar waves is moved along the Earths surface. Microwaves in the range of 80 to 1000
MHz (megahertz) are directed into the soil. Microwaves are reflected by buried objects
with differing dielectric or insulating properties, and the returning waves are detected by
a receiving antenna and displayed on a monitor. Such an instrument can locate
underground features and obstructions that can hinder or prevent sampling and/or
remediation. It can also prevent costly and embarrassing mistakes, such as cutting power
or communication lines. Likewise it can prevent the breaking of pipelines carrying water,
gas, fuel, or other materials. In the latter case it can prevent additional pollution,
contamination, or fire and explosion.
There are other methods of detecting buried objects. Any physical parameter that
varies with the composition of the soil will give a signal that can be detected and mapped.

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Resistivity (resistance per unit of area), electromagnetic induction, and magnetic

susceptibility are some of the properties that have been used to investigate subsurface
features in soil. These methods all have severe limitations that restrict their applicability
and usefulness.
In spite of limitations there are occasions in which GPR and these other methods are
extremely useful. Buried explosives and explosive devices are likely to be found in any
field traversed by an army. These methods can detect both metal and nonmetal explosive
devices buried in soil. Detection of these devices is a safety issue, but their occurrence
will also alert the persons sampling to other possible field contaminants [17].
1.15.2. Remote Sensing
Remote sensing is another way to obtain information about a field. A sensor placed in the
soil and connected to a radio so that sensor readings are sent back to a central location is
remote sensing. Sensors held over the surface of a field on arms attached to a truck would
also be remote sensing. Often this type of sensing is used to calibrate sensors for specific
use in airplanes and satellites. Normally remote sensing is understood to refer to using
either airplanes or satellites to obtain information about the condition of the Earths
surface and subsurface. The sensors may be cameras that obtain black and white or
colored pictures of the Earths surface, or they may record electromagnetic radiation in
other parts of the spectrum.
More advanced remote sensing involves the use of spectrometers or special films.
These are sensors that record the electromagnetic radiation reflected in a narrow range of
wavelengths from the Earths surface. Some sensors record wavelengths in the ultraviolet
part of the spectrum, some in part or all of the visible spectrum, and some in the infrared
region of the spectrum [18].

1.16. GLOBAL POSITIONING SYSTEM (GPS)

The GPS is useful in finding a position on the Earths surface. Signals from two or more
satellites are combined by a receiving unit to provide a person or vehicles location,
altitude, and speed. Airplanes and ships routinely use this type of information between
airports or at sea. It is also available on some automobiles, and there are also handheld
units that an individual can use. Receiving units, either on a vehicle or handheld, can be
used in sampling to identify sample sites. This capability can be extremely useful,
especially during first-time and subsequent sampling of the same field. It is common to
mark sampling spots using various types of physical markers. Unfortunately it is also
common for markers to be removed, lost, or destroyed between sampling times. The GPS
can guide samplers to the same sampling location even if the marker was forgotten or has
been moved or destroyed.
The GPS is also a surveying tool. It can make finding direction and elevation of points
far apart much easier and more accurate than can traditional surveying tools. It can make
surveying points separated by obstructions possible. The GPS can also be used to follow
the spread of pollution or a toxic compound. Not only can the direction of spread be

Field sampling

20

followed, but also its speed. This provides valuable information that can dramatically
decrease the deleterious impact of spills such as those that occur when an oil tanker runs
aground.
All activities that use GPSs are termed precision. The use of GPS in farming activities
would be termed precision farming or precision agriculture. Weather stations having a
GPS receiver would be called precision weather stations. Field sampling using GPS
would be called precision sampling [19].

1.17. GEOGRAPHICAL INFORMATION SYSTEMS (GIS)

Satellite and any other digital information can be combined on an image of the Earths
surface using a GIS. This is a computer program that allows any digital information about
the Earths surface to be superimposed on a picture of that part of its surface (e.g.,
temperature and rainfall). In a like manner pollution concentration in a certain location
can be mapped on a picture, aerial photograph, or satellite image of that location using a
GIS system.
Although aerial photographs and satellite images are of the Earths surface, it is also
possible, using GIS, to map any known information about subsurface features and thus
make a three-dimensional map of an area. Using GIS the location and movement of the
pollutant underground or in caves can be mapped using images of the Earths surface as a
reference.
Geographical information systems are systems that allow not only the mapping of the
Earths surface and subsurface, but also the relating of the data in these maps to other
data. It makes use of GPS, remote sensing, and other means of obtaining data about the
environment, including taking physical samples for analysis in the laboratory. All these
data can be related to a map of the area of concern and can then be used to analyze all the
data related to the area [20].

1.18. CONCLUSIONS
Before thinking about sampling a field or any part of the environment a firm grasp of
important characteristics of the environment relevant to sampling must be understood.
These characteristics must also be kept in mind while developing the sampling plan,
while carrying out the sampling, and during the transport and analysis of the samples.
The four most important considerations derive from the fact that the environment is fourdimensional. The area to be sampled has length, width, and depth, and changes with time.
Samples must be obtained from various places on the surface and from the subsurface
using a well-developed plan taking these into consideration. The characteristics of
samples and the constituents they contain will vary over time. It is not acceptable to take
samples from part of an area one month and then a month later sample another part of the
area and put the analytical results from these two sampling times together and assume or
assert that they represent one sampling.

Introduction to Field Sampling

21

QUESTIONS
1. What must one know about a field before developing a sampling plan?
2. Would the area to be sampled be expected to be larger with a mobile or immobile
contaminant or pollutant?
3. Describe the characteristics of an A horizon. What common component in the A
horizon might have the greatest effect on the analytical results?
4. Of the four dimensions of a soil, which is uncontrollable or is constantly changing in
one direction?
5. What information is usually available from soil maps and soil surveys?
6. Explain what the following abbreviations stand for:
(a) BMP
(b) CFC
(c) MDL
(d) VOC
(e) O3
7. Explain why ppm is such a handy unit when dealing with soil or solum material. If a
sample of soil is found to contain 10 ppm naphthalene, how much naphthalene in grams
is found in a hectare furrow slice of this soil?
8. What are the units used to express bulk density in soil media? What is an equivalent
older unit?
9. GPS and GIS go together. Explain how.
10. What three statistical tools are commonly used in dealing with environmental
sampling?
11. Knowing what is likely to be present in an environmental sample can be important
in three ways. Explain.

Field sampling

22

REFERENCES
1. Patterson GT. Site description. In: Carter MR, ed. Soil Sampling and Methods of
Analysis. Ann Arbor, MI: Lewis, 1993:13.
2. Brady NC, Weil RR. The Nature and Properties of Soils. 12th ed. Englewood Cliffs,
NJ: Prentice Hall, 1999:495511.
3. Soil Survey Staff. Soil Taxonomy: A Basic System of Soil Classification for Making
and Interpreting Soil Surveys. Soil Conservation Service, U.S. Department of
Agriculture. Agriculture Handbook no. 436. Washington, DC: U.S. Government
Printing Office, 1975:1371.
4. Petersen D. Human Error Reduction and Safety Management. 3rd ed. New York: Van
Nostrand Reinhold, 1996.
5. Crptin J, Johnson RL. Soil sampling for environmental assessment. In: Carter MR, ed.
Soil Sampling and Methods of Analysis. Ann Arbor, MI: Lewis, 1993:518.
6. Kempthorne O, Allmaras RR. Errors and variability of observations. In: Klute A, ed.
Methods of Soil Analysis: Part 1Physical and Mineralogical Methods. Madison, WI:
American Society of Agronomy and Soil Science Society of America, 1994:131.
7. Dixon WJ. Extraneous values. In: Klute A, ed. Methods of Soil Analysis: Part 1
Physical and Mineralogical Methods. Madison, WI: American Society of Agronomy
and Soil Science Society of America, 1994:8390.
8. Warrick AW, Myers DE, Nielsen DR. Geostatistical methods applied to soil science.
In: Klute A, ed. Methods of Soil Analysis: Part 1Physical and Mineralogical
Methods. Madison, WI: American Society of Agronomy and Soil Science Society of
America, 1994:5381.
9. Environmental Modeling with GIS. Goodchild MF, Parks BO, Steyaert LT, eds. New
York: Oxford University Press, 1993.
10. Conklin A. Soil Demonstrations for Geoscience, Environmental Science, Soil
Science, Environmental Chemistry, Soil Chemistry, Earth Science, Environmental
Engineering. Wilmington, OH: Petra Publishing, 2000:137140.
11. Bates TE. Soil handling and preparation. In: Carter MR, ed. Soil Sampling and
Methods of Analysis. Ann Arbor: Lewis, 1993:1924.
12. Bohn HL, McNeal BL, OConnor GA. Soil Chemistry. 2nd ed. New York: Wiley,
1979:272315.
13. Stevens JL, Green NJL, Bowater RJ, Jones KC. Interlaboratory comparison exercise
for the analysis of PCDD/Fs in samples of digested sewage sludge. Chemosphere
2001; 45:11391150.
14. Blake GR, Hartge KH. Bulk density. In: Klute A, ed. Methods of Soil Analysis: Part
1Physical and Mineralogical Methods. Madison, WI: American Society of
Agronomy and Soil Science Society of America, 1994:363375.
15. Abbreviations. USEPA. http://www.epa.gov/searchforCEPPO.
16. Hong J. Environmental Acronyms. Rockville, MD: Government Institutes, 1995.
17. Conyers LB, Goodman D. Ground-Penetrating Radar: An Introduction for
Archaeologists. New York: Rowman & Littlefield, 1997.
18. Remote Sensing Change Detection: Environmental Monitoring Methods and
Applications. Lunetta R, Elvidge C, eds. London: Taylor & Francis, 1999.
19. Letham L. GPS Made Easy. 3rd ed. Seattle: The Mountaineers, 2001.
20. Korte GB. The GIS Book. 5th ed. Albany, NY: OnWord Press, 2001.

2
Characteristics of the Environment
In order to successfully sample a portion of the environment one must understand the
characteristics and dynamics of the portion of the environment being sampled. It is also
critical that the relationship and interaction between the specific part of the environment
being sampled and the rest of the environment be understood. The term successful sample
refers to a sample that truthfully and accurately describes the characteristics of the part of
the environment sampled at that particular time. In addition to using the results of a
sample analysis to predict the future of a particular component or contaminant in an
environment, its relationship to all parts of that environment must be understood.
It might be assumed that the lithosphere is inert and impenetrable to water and
contaminants. Sandstones can contain large amounts of water, however, which can move
through it at significant rates. Even bedrock, such as limestone and shale, can contain
numerous cracks that allow ready movement of water and contaminates. It is important to
know not only where a component is at a given time, but also where that component may
move to in the future and how a particular environment may change a contaminant.
Another example is the atmosphere, which can affect sampling in three ways,
particularly in windy conditions. It can remove contaminants from a contaminated field,
thus changing their concentration. It may also deposit contaminants, including particulate
matter, such as contaminated silt and clay particles, on a field. To a lesser extent it can
also move sand-sized particles from one location to another. Thus, wind can
recontaminate an area or a field that has been remediated. Wind can carry contaminants
long distances, and so its effects can be widespread.
A third example is water, which may be seen as a nuisance when it rains or when a
river floods and covers a field that is to be sampled. Rain can leach contaminants deep
into a soil or through a soil and into the water table. If this happens, water from wells in
and around the field will need to be sampled and analyzed. Flooding can wash away
contaminants, spreading the hazard. It may also mix contaminants with more soil or
cover a contaminated area with clean soil that must be removed to effect remediation.
While the soil is saturated with water it becomes anaerobic and thus changes the chemical
and biological condition of the contaminants. For these reasons water is an extremely
important factor in sampling. If contaminants are being carried by water, sampling the
water itself will become an important sampling activity.
It might be assumed that soil is a homogeneous mixture with a well-defined movement
of air, water, and contaminants when water moves through it. Soil has horizons of
differing composition, however, which allow differential movement of water downward
through the soil. Some horizons may cause water to move horizontally rather than
vertically, thus causing contaminants to be found in unexpected places.

Field sampling

24

2.1. PARTS OF THE ENVIRONMENT

At first glance it seems obvious that there are several parts to the environment. There is
the atmosphere, which is the gaseous layer around the Earth. It extends from the Earths
surface to space, which is often accepted to be 80 km (50 miles) above the surface. The
hydrosphere includes all bodies of water covering the Earths surface. It is variable in
depth, depending on the underlying lithosphere. The lithosphere is the solid portion of the
Earth. It is not only the dry portion of the Earths surface, which sticks up above oceans,
lakes, streams, and rivers, but also the solid portion underlying bodies of water.
Layers of different characteristics are common in all parts of the environment. (See
Figure 2.1.) It is not immediately obvious that the atmosphere and hydrosphere are
composed of various fluid layers, but they are. On the other hand, examples of layers in
the lithosphere are easily observed. Roads that are cut through mountainsides expose
observable layers of both rock and soil.

FIGURE 2.1 Layering in the atmosphere, hydrosphere, and lithosphere. CD is

cold, light water, while WL is warm, dense water.

2.1.1. The Atmosphere

There are different ways of looking at the layers in the atmosphere. In the older

Characteristics of the environment

25

terminology the atmosphere has three layersthe troposphere, stratosphere, and

ionosphere. Newer terminology divides it into five layersthe troposphere, stratosphere,
mesosphere, thermosphere, and exosphere. This terminology stems from space
exploration and extends the atmosphere much further than 80 km out into space. If one
looks at the atmosphere from space when it is backlit by the sun, there is a reddish layer
near the Earths surface, a lighter layer above that, and a blue layer above that.
What could the atmosphere possible have to do with field sampling? There are really
three possible answers to this question. One has to do with the occurrence and movement
of sand, silt, clay, contaminants, and particulate matter in the troposphere. The second has
to do with the amount of sunlight, particularly ultraviolet light, reaching the Earths
surface, because some components in the soil may evaporate or vaporize into the
atmosphere or be chemically changed by light. The third is that since the atmosphere is
part of the environment it may need to be part of the field environment that is sampled [1,
2].
Air has a limited carrying capacity for most soil components. Sand cannot be picked up
by wind and moved long distances. Silt and clay can, however. Wind can carry
atmospheric contaminants long distances from their origin (e.g., the acidification of lakes
in the northeastern United States by sulfate released into the atmosphere in the Midwest).
During the dust bowl era in the United States some of the dust from the western United
States was eventually deposited in the eastern United States and Caribbean. Another
well-known example is ash from volcanoes. It can travel great distances around the Earth
if it is ejected high enough into the atmosphere. Wind can thus carry contaminants from
various sources, and these can be deposited in a field and should be of concern in any
field sampling [1, 3, 4].
Field samples exposed to sunlight for extended periods of time after being obtained
from the field can have dramatic changes in their composition. In addition, solar
radiation, rain, and wind can also affect the level of contaminant in surface soil through
evaporation or vaporization [5, 6]. Zimbabwe in south-central Africa is at an average
altitude of approximately 1.4 km. It has relatively low rainfall, usually occurring from
December through March. During the remainder of the year the sun intensity is quite high
and can affect the chemical form of contaminants found in air, water, or soil. Even during
the rainy season daytime radiation levels are frequently high. People in Zimbabwe
complain about the rapid decomposition of plastics, which is caused by the intense
sunlight. Intense solar radiation and its effects on samples are not limited to Africa and
Zimbabwe, but can be present anyplace.
The atmosphere will also have indirect effects on field sampling and the resulting
samples. These are caused by the composition of the atmosphere and can be both highly
variable and dramatic. The atmosphere is composed of nitrogen, oxygen, carbon dioxide,
argon, and water vapor plus other gases in low concentration. The nitrogen and argon
content of air is constant and inert. The water vapor, carbon dioxide, and oxygen content
varies however, and they are reactive. Changes in carbon dioxide will change the pH of
associated media, which will change the chemical form and reactivity of contaminants. In
the hydrosphere and lithosphere water vapor is less variable, while carbon dioxide and
oxygen concentrations are more variable.
On the Earths surface the composition of atmospheric air may seem unimportant.

Field sampling

26

When taking samples from various depths in water, soil, or sediment, however, the
gaseous composition of the material being sampled is important. Samples from
submerged or water-saturated zones will have reduced chemical species, which will
oxidize when exposed to atmospheric oxygen. This means that if the samples are exposed
to air the species identified during analysis will be different from the species actually
present in the environment sampled. Different species have different physical, chemical,
and biological properties, and thus knowing their exact form is important. Ammonia is a
reduced form of nitrogen and is basic. Nitrite is a partially oxidized form of nitrogen and
is toxic, and nitrate is fully oxidized nitrogen and is less toxic than nitrite. A sample from
a reducing environment can have ammonia in it. When this sample is exposed to air the
ammonia can be oxidized to nitrite and nitrate, which can subsequently be reduced to
nitrogen gas if the environment becomes reducing again [7].
2.1.1.1. The Soil Atmosphere
At first glance the soil atmosphere is much like the rest of the atmosphere, and it is, in
that it contains nitrogen, oxygen, argon, carbon dioxide, and water vapor. Two factors
make the soil air different from atmospheric air. First, soil air is constrained in soil pores
and because pores are torturous it moves slowly between soil and atmosphere. There are
three forces that move air from the soil to the atmosphere and vice versa. Two cause a
mass flow of air into and out of soil. The other force causing movement is diffusion.
When the soil warms the air in it expands and moves out of the pores. This happens
during sunny days in accordance with the gas law PV=nRT. Rearranging this becomes
V=nRT/P. This equation states that as the temperature increases the volume of gas
increases. (All other factors nR and P are constant.) During the day when the soil is
warmed air thus expands out of the soil and at night when the soil cools its gaseous
constituents decrease in volume and air moves back into the soil.
Rain fills soil pores with water and air is forced out. The little oxygen remaining in
water-saturated soils is quickly consumed by plant roots and microorganisms. At this
point the soil becomes anaerobic and reducing. When the water moves out of the soil
either by evaporation or percolation, air replaces it. The oxygen content increases and the
soil becomes aerobic.
Soil air is typically higher in carbon dioxide and lower in oxygen than atmospheric air.
Plant roots and soil microorganisms respire, taking in oxygen and giving off carbon
dioxide. Carbon dioxide builds up to levels that may be 10 times higher than in
atmospheric air. Carbon dioxide diffuses from high concentration in soil air to the lower
concentration in atmospheric air. Likewise, oxygen diffuses in the opposite direction [8].
The higher carbon dioxide content in soil air is not insignificant. In soils with pH less
than 7 carbon dioxide dissolves in soil water and produces carbonic acid. The acid
dissolves soil minerals; for example, calcium carbonate. In soils underlain by limestone
this leads to the development of a karst landscape (see Figure 2.2) [9]. In basic soils
carbon dioxide reacts with calcium, forming calcium carbonate or lime. Calcium
carbonate precipitates out of solution, forming compacted layers that inhibit the
movement of water in soils. Heavy metal contaminants may also be precipitated as
carbonates and thus change their availability during analysis.

Characteristics of the environment

27

Changes in the oxygen content of soil affect both the chemistry and biology therein.
Changes in the anaerobic/aerobic and oxidizing/reducing conditions of a soil sample
affect the oxidation states of the metal cations it contains, the oxidation state of nitrogen
compounds, and whether or not organic matter is decomposed by aerobic or anaerobic
mechanisms. It also affects the primary types of organisms living in the sample. These
organisms, particularly microorganisms, are responsible for many chemical changes in
the environment. For this reason changes in the organisms present in a sample can
dramatically affect the results of an analytical procedure.
The atmosphere can affect the field sampling in many ways and should always be kept
in mind. Samples that are oxidizing must be kept that way. Likewise, soils under
reducing conditions must be kept in a reducing environment [10].

FIGURE 2.2 An example of a karst landscape.

2.1.2. The Hydrosphere

The solution making up the hydrosphere comprises water containing small amounts of
dissolved gases and inorganic and organic ions and molecules. Water, with its familiar
chemical formula H2O, is of fundamental importance, both in the environment and in
environmental sampling. Water has unique chemical and physical characteristics and
chemical reactivity related to hydrogen bonding and attraction to both positive and
negative atoms or charges in other molecules. (See Figure 2.3.) It is often called the
universal solvent because even the most insoluble components are to a measurable extent
soluble in water [2, 11].
Layers of water occur in both oceans and lakes. In northern temperate regions lakes

Field sampling

28

freeze in the winter. During the freezing process the water and the subsequent ice is less
dense than the underlying warmer water. During the winter the lower layers gradually
cool and become more dense. In the spring the surface melts and the water warms,
becoming more dense than the underlying water. At this point the lake turns over, with
the upper layer sinking to the bottom and the bottom layer coming to the top.
Air is more soluble in cold water than in warm water. However, water that has been
trapped at the bottom of a lake under ice for an extended period of time becomes anoxic
(lacks oxygen). When a lake turns over in the spring, oxygen-rich surface water moves to
the bottom of the lake and there is a flurry of oxidative reactions. The composition of the
water and sediments in terms of oxidized and reduced species changes dramatically
during this time [12].
In temperate and tropical lakes layers with varying amounts of oxygen are also
possible, along with areas of differing temperature. These lakes can also turn over,
sometimes with catastrophic effects. Turnover can be due to

FIGURE 2.3 Water molecules hydrogen bonded to each other and attracted to
the oxygens in a soil particle.

incoming streams and rivers, springs, uneven heating caused by currents, and underlying
geothermal activity. For these reasons changes in the oxidative state can occur. For areas
in which there is a pronounced dry period during the year the bottom of a lake may
become anoxic. When the rains come oxygen-rich, water flows into the lake, changing its
oxidative status [13].
Even in situations in which turnover or incoming sources of oxygenated water are not
of concern, the solubilityeven though it is lowof air in water is important. As noted
above, air is less soluble in warm water than in cold water, and thus its concentration is
dependent on the temperature of the water being sampled. No matter what the
temperature is, however, the deeper the water the lower the oxygen content. Thus, at the
bottom of bodies of water there is very little (or no) oxygen, producing anaerobic or
reducing conditions. Not only are sediments anaerobic and reducing, but so is any portion
of the lithosphere saturated with water for a period of time. This condition routinely
occurs in soil and in any material covered by floodwaters. Sampling of any watersaturated soils and sediments must thus be done carefully to maintain their physical and

Characteristics of the environment

29

chemical integrity.
Soils at the bottom of bodies of water thus need special sampling considerations. They
will often need to be sampled, and represent a unique sampling environment. In addition
to being anaerobic, soil and sediment at the bottom of bodies of water are under pressure.
A field sample taken under these oxygen and pressure conditions must be kept oxygenfree and under pressure until analyzed. Such samples will frequently be easily dispersed
and this must be avoided as much as possible. The void spaces between soil particles are
completely filled with water, which is called interstitial water. In many cases the
interstitial water and the solid particles will need to be analyzed separately.
2.1.2.1. Solutes in Water
Sometimes people are surprised that a chemical analysis of water can result in finding the
presence of gasoline components, including ethers. The everyday observation is that
these compounds are not soluble in water. There are two answers to this puzzle. First, as
already noted, water is capable of dissolving small amounts of almost any material [11].
Second, analytical methods and instrumentation are extremely sensitive. Detection of
parts per million was once considered good. Today, however, detection of parts per
billion or trillion are routinely and easily made. In some cases it is even possible to look
at single molecules or atoms. The detection of a component in water is thus important,
but it only tells part of the story.
The occurrence of surfactants (soaps) in water will also dramatically increase the
apparent solubility of insoluble compounds. Soaps can come from man-made sources;
however, there are a large number of plants that produce soaplike compounds. Both
sources can lead to solubilization of insoluble compounds and thus increased levels of
these compounds in water.
Suspended, colloidal-sized particles are present in water and carry sorbed material.
This material can show up in analysis and be reported in such a way as to indicate that it
was in solution. In this way components may appear to be present in water in
concentrations above their solubility limit.
2.1.3. The Lithosphere
Geologists classify rocks as being sedimentary, igneous, or metamorphic, depending on
how they were formed. Sedimentary rock is the result of rock and rock components being
eroded, usually into a body of water. The material sediments and comes under enough
pressure to allow the particles to be cemented together. Common sedimentary rocks are
shale, sandstone, and limestone. Most often rock is considered hard; however, many
sedimentary rocks are quite soft. Some are soft enough to allow them to be broken by
hand. Another completely different type of sedimentary rock is coal. This is rock derived
from organic matter and is composed of carbon, and thus is very different from other
types of rock.
Igneous rock results from the cooling of magma (melted rock material) or lava. This
cooling can occur when magma reaches the Earths surface as lava or when it flows into
cracks in nearby rocks and cools. Common igneous rocks are granite, pumice, and basalt.

Field sampling

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Metamorphic rock is rock material that has undergone a change in appearance as a

result of melting caused by high temperatures and pressure. Sometimes this also causes a
change in the mineral composition of the rock. Both sedimentary and igneous rocks can
undergo this process. Common metamorphic rocks are slate, marble, and quartzite.
Water can often move through rock, even when it appears solid. Softer rocks will have
pores, and when near the surface, even the hardest rock in the Earths crust will have
cracks in it. In both cases pores and cracks allow the movement of water and
contaminants downward. There are many springs in the hills on the islands of the
Philippines. Rainwater enters the soil and the underlying fractured rock layers on the
upper slopes of the hills. This water moves downhill under the ground through the
fractured rocks until it finds an outlet. At this point a spring forms, the outflows of which
can be large enough to support large waterfalls year round. At other places wells can be
dug into these broken rock layers and a good, steady supply of water obtained.
About a fourth of the Earths surface is underlain by limestone. Two features of
limestone are caves and sinkholes. When rainwater enters limestone, soft or easily
dissolved portions dissolve, leaving caves, which are sometimes extensive. Such
landscapes are called karst, a good example of which is Mammoth Caves in the state of
Kentucky in the United States. Limestone caves are common throughout the world,
however. When the size of the dissolved area becomes very large the cavity cannot
support the roof and the cave collapses inwards. This produces a sinkhole that may or
may not have a hole connecting to the cave network (see Figure 2.2) [14].
Water can pass directly from the surface to the underground karst network, which may
extend for hundreds of miles, and will have an underground river associated with it.
Contamination entering such networks can travel long distances and contaminate large
areas. In addition, animals living in the caves, such as bats, can contribute to this
contamination. This is particularly dangerous because many water wells may tap into its
water system.

2.2. SOIL FORMATION

It is easy to assume that soil is simply decomposed rock lying above a consolidated rock
layer. Soil is much more than simply ground-up rock, however. Immediate evidence of
this is that ground rock would be gray, while soil is brown to black on the surface with
red hues in the subsoil. There are soils with very light colored surface horizons and little
color in the subsurface horizons, but even these soils are not gray.
When rock is exposed on the Earths surface it is subject to degradation. Rain falling
on the decomposing rock dissolves salts as it infiltrates. These salts are eluviated with
percolating water and moved lower in the regolith. With a moderate passage of time and
rainfall soil salts are lost and less soluble components remain, forming soil. Illuviated less
soluble materials result in the development of horizons. With sufficient time and rainfall
salts and other easily dissolved components are completely leached out of the solum.
Most of these salts eventually are deposited in the oceans.
Oceans are not the only reservoirs of salts. When the water falling on mountains is
caught in a basin without an outlet to the sea, a salt sea such as the Great Salt Lake in

Characteristics of the environment

31

Utah or the Dead Sea is formed. If rainfall is low and evaporation high then a salt flat is
formed where there is a crust of salt on the soil surface.
2.2.1. Horizonation
Soils contain horizons, which develop as a result of soil-forming factors. These factors
are time, topography, parent material, climate, and biota. The soil-forming factors cannot
be put in order of more to less important; all are interdependent and all interact to provide
the environment under which the soil is developing. During sampling activities, these
factors will be overlain, mixed, and complicated by the activities of plants, animals, and
man.
Soil does not develop directly from rock but rather from decomposed rock. The type of
soil developed and the time necessary for its development will thus be strongly
influenced by the parent material or decomposed rock from which it is developing. If the
material is rock ground up during movement by air, water, or ice, the soil will develop
faster than if it is developing from slowly decomposing rock.
It takes a long time for a fully developed soil to be formed (see Figure 2.4), perhaps as
long as 1000 years. Thus, time is a critical factor in soil formation. In order for time to
work the material must be remain in the same place. The tendency to remain or move will
depend on the topography of the area, so this is another important factor in soil
formation. Soil developing on a hillside will be subjected to more erosion than a soil on a
flat plane. A depressional area will have more water and will collect decomposed
materials from which its soil is forming. The soil formation will thus tend to be more
rapid under these conditions.
Climate is another critical factor during the development of a soil. Salts may be
completely leached from soil, while other materials are moved into lower horizons by
percolation water. For this reason rainfall is extremely important, and soil will tend to
develop faster where there is more rainfall. However, along with rainfall, the average
temperature also will be important. The rate of chemical and biological reactions in soil
increases twofold for each 10C increase in temperature. For this reason the climate
under which a soil develops has a strong influence on both its physical and chemical
characteristics.
Finally, both the vegetation adapted to the climate and the animals present have a
pronounced influence on soil development. Plant roots produce acids and increase the
carbon dioxide content in the soil atmosphere. Different soils develop under trees than
under grass vegetation because of their different growth and rooting habits. Animals also
play a role in soil-forming processes. Worms, termites, moles, groundhogs, and many
other animals move soil from lower horizons to the surface. In addition, they leave large
holes that water can flow into and through.

Field sampling

32

FIGURE 2.4 Designations applied to the layers of loose material over rock. On
the right are typical peds found in soil.

All soil-formingfactors, time, topography, climate, biota, and parent materialare

interrelated. The amount of rainfall and the average temperature affect the types and
abundance of plants growing and animals living in a locality. The amount of water
infiltrating the soil and leaching salts out depends both on the rainfalls intensity and
amount and on topography, which influences the likelihood of rain infiltrating or running
off the surface. All of these are inextricably intertwined with the length of time these
factors are at work and the parent material they are working on.
Once a soil has developed, it is characterized and named on the basis of its inherent
characteristics. An obvious characteristic is that it has horizons. As in Figure 2.4, the
major horizons are designated by a capital letter. The A horizon is the surface horizon
usually observable because it has higher organic matter than underlying layers and is thus
darker. Under the surface A horizon will occur several other master or major horizons.
The most common are the master horizons X, E, B, and C, and they occur in this order
from the surface downward. There will also be transition horizons between all the master

Characteristics of the environment

33

horizons.
In Figure 2.4 an O horizon is also given. This is an organic horizon, which may be
called an Oi, Oe, or Oa, depending on the organic matter decomposition state (Oi
represents incompletely, Oe intermediately, and Oa completely decomposed organic
material). These horizons are not common, but are important because they are very
different from mineral horizons and require different handling, extraction, and analysis.
Horizons designated by two capital letters or a slash between capital letters are
transition horizons, depending on the mixing of the two layers. This then indicates that
the transition horizons contain characteristics of both the overlying and underlying
materials.
In soils developed under tree vegetation an E horizon will be the next major horizon
below A. It is lighter in color than the horizons above or below and is coarser. In soils
developed under other types of vegetation the A horizon will transition to a B horizon.
There will typically be several of these horizons. They are higher in clay and redder than
overlying horizons.
The B horizons transition to a C horizon, which is the material from which the soil is
developing. It shows no evidence of the effects of the soil-forming factors and may be
very thin or thick. Soils developing on underlying rock may have thin, almost nonexistent
C horizons, while those developing from glacial till or other deposited materials may
have C horizons that are several meters thick. Rock underlying this horizon will often be
referred to as the R horizon.
It is common to find situations in which there are more or fewer horizons. A soil may
have an A horizon that is underlain by a C horizon. The A horizon may not be present,
and the topmost layer may be a B horizon. In cases of severe erosion the topmost horizon
may be a C. In river valleys and stream and river terraces there can be buried soils. There
may be A and B horizons underlain by another set of A and B horizons. All possible
variations of this basic situation can and do occur (e.g., A and B might be underlain by a
different B horizon).
Horizons with a capital letter followed by a small letter have distinctive characteristics.
In Figure 2.4 the small letter t in Bt indicates that the B horizon has a high amount of clay
in it. There are many other ways in which differences in horizons may be designated.
These will not be described here; however, if needed they can be found in basic soils or
soil taxonomy texts [15]. The local soil conservationist or soil scientist can interpret more
complex horizon designations if need be.
Different soils and different horizons may need different sampling. For this reason
knowledge of the soils and their characteristics will be needed in developing a field
sampling plan.

2.3. SOIL TYPES

On the basis of the characteristics of a soils profile it is described as belonging to one of
twelve soil orders. These range from the Entisols, which have a minimal A (or no)
horizon development to Oxisols, which have undergone intensive weathering. A
complete list of the twelve soil orders is given in Chapter 1, Table 1.1. Six of these

Field sampling

34

orders, described below, are of particular concern during field sampling.

2.3.1. Gelisol
The Gelisols are soils developing in parent material that is frozen most of the year. They
contain permafrost, which is a layer frozen for two or more years in a row within 100cm
of the surface. These soils are slow to develop and may show extreme mixing because of
freezing and thawing. Gelisols occur in the northern regions of Russia, Alaska, and
Canada. Because of the frozen layer and low temperatures contamination will not be
easily removed by natural processes.
2.3.2. Andisols
Andisols develop in volcanic ash and often contain 4050% cinders, which are larger
than 2 mm in diameter. They are young soils that are poorly developed and have high
infiltration and percolation rates. Because of their high porosity and lack of profile
development pollutants may pass rapidly through them.
2.3.3. Histosols
Histosols are organic soils in the upper 80 cm of the soil profile containing organic matter
that can either be fully or partially decomposed. They develop in depressional areas under
water-saturated and anaerobic conditions. Organic matter has a high affinity for many
soil contaminants, and thus must be treated and analyzed differently than mineral soils.
2.3.4. Vertisols
Vertisols contain large amounts of expanding clays, and because of these clays develop
cracks that are 30 cm wide and 1 m deep when dry. When wetted the cracks close.
During dry periods surface material falls into the cracks, thus producing an inverted soil.
Not only can soil and organic matter fall into these cracks, but also pollutants. This is
important to keep in mind when sampling. Remediation of these soils is difficult because
water moves through them extremely slowly and the cracks allow pollutants to penetrate
deeply into the soil.
2.3.5. Aridisols
Aridisols occur in arid climates, and because there is little rainfall these soils tend to have
high pHs, usually above 7.5, and are often affected by salts. This means that pollutants
will react differently in these soils when compared to acid soils. The salts will affect
remote sensing, particularly ground penetrating radar (GPR), and both the sampling and
analysis of samples from these soils.
2.3.6. Spodosols
Spodosols occur in acid, sandy soils and develop under conifer (cone-bearing trees

Characteristics of the environment

35

commonly called pine) forests. These soils have a subsurface horizon called a spodic
horizon in which aluminum oxides and organic matter have accumulated. Iron oxides
may or may not be included in this area. The occurrence of iron and aluminum oxides
and organic matter can affect analytical procedures applied to samples from this horizon.
This is thus an important horizon that requires special consideration during sampling and
analysis.
2.3.7. Other Soil Orders
Each of the other soil orders has its own unique characteristics, but these do not influence
sampling procedures as directly as the orders mentioned above. Their various unique
horizons, such as the Bt, however, require special attention. Persons carrying out the
sampling need to know what soil orders or soil types are present. Local soil scientists can
provide needed information about the local soils and their characteristics, which will
affect the sampling plan and analytical methods [16].

2.4. SOIL TEXTURE, STRUCTURE, AND BULK DENSITY

Knowledge of soil texture and density is essential in field sampling. Texture can be
described using either soil science or engineering descriptions. Density is described as the
mass per unit of dry soil, Mg/m3 or g/cc, and is universally the same.
2.4.1. Texture
The two different methods of describing soil texture depend on whether the soil is to be
used for agriculture or engineering. In agriculture it is used for growing plants, and in
engineering as a medium to support structures. Soil scientists are most interested in the
relative amounts of sand, silt, and clay, as well as the biological characteristics of soil.
Engineers are interested in the characteristics of larger stone and gravel, sand, and fine
particles. Each of these components is called a soil separate and is defined as having a
particular size. (See Table 2.1.) The soil in a field to be sampled may be described by
either of these approaches, so it is important to be familiar with both.
2.4.1.1. TextureSoil Scientist Definition
Soil scientists name soil textures using the percentage of sand, silt, and clay present. Sand
is between 2.00 and 0.02 mm in diameter, silt between 0.02 and 0.0002 mm in diameter,
and clay less than 0.002 mm in diameter. Using the percentages of sand, silt, and clay and
a textural triangle (see Figure 2.5), a

Field sampling

36

TABLE 2.1 Size Characteristics of Soil Separates Using Soil Science and Engineering
Definitions

Soil
component

Subdivision

Cobbles/gravel
Sand
Silt
Clay

Coarse
Medium
Small

Engineering
designation
75/4.75
4.752.00
2.000.425
0.4250.075
>0.075

Soil science
designationa

2.000.02
0.020.002
>0.002

aThis is the international definitionthe U.S. Department of

Agriculture definition is somewhat different.
Note: (All units are in mm.)
Source: Data from Refs. 15 and 18.

Characteristics of the environment

37

FIGURE 2.5 Textural triangle used by soil scientists to assign textural names
to soils of different textures.

textural name of a soil can be determined. A soil containing 10% sand, 15% clay, and
75% silt would have a silt loam texture. The term loam is used for textures for which the
sand, silt, and clay fractions contribute equally to the characteristics of the soil. The
percentage of clay is lower than silt or sand in loam because it has much higher activity
and so it takes less to have an equal effect. Table 2.1 gives the relationship between the
soil scientists and the engineers definition of soil particle size. If appropriate, a soils
textural name may be prefixed by an indication of larger components. Thus, there might
be a gravely silt loam. This would indicate that the soil has a large percentage of gravelsized material in it. For the soil scientist the particles larger than 2.00 mm in diameter are
not as important as the sand, silt, and clay.
In addition to the above names there are other common, nonscientific, less specific
terms in common usage, such as light, heavy, clayey, and sandy. Heavy soils are high in

Field sampling

38

clay and light soils high in sand. In regions of the world with a predominance of sandy
soils, however, a soil with 12% clay might be called clayey. In other areas a soil with
2030% clay might be called clayey. A similar sort of thing happens with sand. In areas
with clayey soils a significant sand content might be called sandy. These common local
usages need to be checked by referring to laboratory determinations of texture [17].
2.4.1.2. TextureEngineering Definition
Engineers classify soil textures using a different classification scheme. They approach the
texture of the loose material on the Earths surface from a broader perspective than does
the soil scientist, being concerned with a much larger range of sizes of separates. From an
engineering perspective the ability of a material to carry a load is most important. Also
from a load-carrying perspective, the uniformity of the material in terms of size is
important.
Engineers size soil components by noting the size of the sieve retaining the soil
component. The size can then be reported as the sieve number, which is sometimes
confusing because as the sieve number increases the size of the holes in the sieve
decreases. Table 2.2 gives a number of important sieve numbers and corresponding hole
sizes. Material not passing a #4 sieve is cobbles, which are larger than about 75 mm in
diameter. On the other hand, gravel is smaller, but is larger than 4.75 mm. Sand is
designated as coarse (smaller than 4.75, but larger than 2.00 mm), medium (smaller than
2.00 but larger than 0.425 mm), and fine (between 0.425 and

TABLE 2.2 Sieve Numbers and Hole Sizes

Hole size (mm)a

Sieve number
#4b
#10c
#40
#200

4.75
2.00
0.425
0.075

aActually, the average

diameter of the particles of gravel, sand, or

silt passing through it.
bThere are larger hole sieves that do not have the # designation.
cThis is the upper limit for sand in the soil science textural
designations.

0.075 mm in diameter). Material smaller than 0.075 mm is silt or clay. (See Table 2.2.)
Engineers use a combination of capital letters to indicate the texture of the material one
is working with. The letters and what they signify are given in Table 2.3. Combinations
of letters are used in pairs to indicate a particular type of material. For instance, GW
would be well-graded gravels with no fines (silt or clay). On the other hand, CL would be
clay with low or slight plasticity. Another possibility would be OH, which is organic
matter with high plasticity. In this way a wide variety of materials with varying size
components and plastic or organic matter contents can be described.

Characteristics of the environment

39

As can be seen in Table 2.3, plasticity is an important characteristic of soils from an

engineering perspective. A plasticity index (PI) can be calculated for any soil or similar
material. It is the difference between the plastic limit (PL) and the liquid limit (LL).
When water is added to an air dry soil, individual soil peds are moistened first. At a
certain water content the soil becomes plastic (PL), which means that it can be molded
into a shape and will retain it. If more water is added it becomes liquid and runs; this is
the LL. The difference between these two limits is the PI, which is simply calculated
using the formula below.
PI=LLPL

TABLE 2.3 Engineering Classification of Soils

Symbol
GW
GP
GM
GC
SW
SP
SM
SC
ML
CL
OL
MH
CH
OH
Pt

Meaning
Gravel (G) larger than #4 sievewell (W) sorted
Gravel poorly (P) sorted
Gravel containing silt (M)
Gravel containing clay (C)
Sand (S) smaller than #4 but larger than #200 sievewell sorted
Sand poorly sorted
Sand containing silt
Sand containing clay
Inorganic silts with low plasticity (L)
Inorganic clay with low plasticity
Organic matter with low plasticity
Inorganic silts of high plasticity (H)
Inorganic clay of high plasticity
Organic matter of high plasticity
High organic matter soils

Source: Taken from Ref. 18.

Soils with a high PI typically contain large amounts of clay. This gives an indication of
the water movement and the retention of contaminants spilled on soil.
There are several other terms or physical characteristics of soils and soillike media that
engineers use. One is the Attenburgh limits, which refer to the PL and LL of a particular
medium. There is also COLE, which is the coefficient of linear extensibility. As the name
implies, this is a measure of the amount of swelling and shrinking a material undergoes
between wetting and drying. It indicates the amount and type of clay in a soil. In working
with engineers one is likely to hear these terms used frequently.
Engineers will also talk of the A-line. This is a graph that relates the PI to the LL. Soils
with characteristics above the A-line and with a LL greater than 50 are inorganic clays of
high plasticity. In the same region but below the A-line are fine sands or silts and elastic

Field sampling

40

silts. Below the A-line and less than a 50 LL are inorganic silts and very fine sands with
low plasticity. In the same region but above the A-line are inorganic clays of low to
medium plasticity. (See Figure 2.6.)
When developing a sampling plan the soils in the area may be described by either soil
science or engineering terminology. It is important to be able to understand both types of
descriptions and use these to determine how sampling should be done. In most cases both
descriptions will be valuable. In situations in which gravel is prevalent the engineering

FIGURE 2.6 The A-line used by engineers to describe fine soil fractions. Data
taken from Ref. 14.

descriptions will be very useful in deciding on the type of sampler to be used [18].
2.4.2. Structure in Soil
Figure 2.4 shows the components in an idealized, well-developed soil profile. All of the
loose materialincluding water-saturated layersabove rock is called the regolith. The
material above the saturated zone is called the vadose zone. The material in which active
soil development is taking place is called the solum. The characteristics of these areas is
determined by both texture and structure.
The texture of soil is extremely important because it controls important characteristics
related to the movement of water and the sorption and retention of contaminants. Texture
is not, however, the only factor in movement in the soil. Soil particles, sand, silt, clay,
and organic matter do not act independently of each other, but are cemented together to
form secondary particles called peds, which are the soil structure. The cementing agents
are organic matter, clay, microbial gums, and various cations.
Different sizes and shapes of peds are found in different soil horizons. The different
kinds of peds and their typical location in a soil profile are given in Figure 2.4. Note that
platy structure or peds can be found in any horizon, but are commonly found between the

Characteristics of the environment

41

A and underlying B horizons. Good water-stable peds result in a soil having increased
percolation and aeration rates, making it easer to work with and easier to sample and
remediate [19].
The increased rates of percolation and aeration are a result of increased porosity in the
soil. Pores occur both within peds and within the lines of weakness between peds. Some
pores are large and drain readily, while other smaller pores retain water, which is used by
plants. Still smaller pores remain filled with water even under the driest soil conditions.
More information about pores and their effect on water movement is given in Chapter 7.
2.4.3. Bulk Density
Both soil texture and structure are related to a soils bulk density. Because bulk soil is
composed of both solid and void space or pores it has a variable density, which is
specifically called its bulk density. Bulk density is the dry mass of oven-dried soil
divided by its volume. Typically the density is obtained by inserting a ring of known
volume into the soil using an instrument that does not cause compaction of the sample
being taken. The ring is removed and the soil in it leveled. The ring and the soil are
placed in a oven at 105 for 24 hr.
The ring plus soil is weighed again, and the weight of the ring is subtracted from the
total to give the soil weight. (Equations 2A and 2B in Figure 2.7 are used for these
calculations.) At this point one need only divide the mass by the volume of the ring to
obtain the bulk density. (Equation 2C is used for this calculation.) Bulk density is usually
obtained as grams per cubic centimeter. Soil bulk density is most often reported as
Mg/m3, however.
Typically soil bulk densities range from 1 to ~1.7 Mg/m3. Sandy soils generally have
higher and silty and clayey soils lower bulk densities. This is variable, however,
depending on the structure and compaction of the sand, silt, and clay. Subsoils have
higher bulk densities than surface soils, partially because of lower organic matter content
and pressure from overlying soil. Examples of common bulk densities, their associated
void space, and associated soil types and conditions are given in Table 2.4.
The void volume in soil is determined using the average particle density of individual
soil particles. On the basis of a great many measurements, soil scientists take the particle
density of soil to be 2.65 Mg/m3. The amount of solids in a soil sample is calculated by
dividing this into the bulk density. Subtracting this from 1 gives the amount of void
space. Multiplying these by 100 gives the percentage of each. Equations for these
calculations are given in Figure 2.7, Equations 2D and 2E.
Knowing the bulk density of soil in a field we can make many useful and important
calculations. Calculations of the kilograms or tons of soil that must be removed or
remediated can be determined, as can the volume of soil. Such calculations will also
allow mass balance calculations, which allow accounting for all the contaminant present.
In field sampling

Field sampling

42

FIGURE 2.7 Equations for calculating a soils percentage of solids and void
space. In Equation 2A r is the radius of the sampling ring and h is the
height.

TABLE 2.4 Common Soil Bulk Densities

Bulk density
(Mg/m3)

Void
volume (%)

Soil type

Condition

1 or less

62

Indicates organic soil or soil with

high organic matter contact

Light in weight subject to

wind and water erosion

1.25

52

Common average bulk density for Good structure

agricultural soils

11.6

6239

Normal range for soils

Good to poor ped structure

1.5 and above

43

Usually clayey soils

Compacted limited water

movement through soil

1.7 and above

35

Usually clayey

Compacted

Source: Ref. 17.

situations one may find layers of soil with different bulk densities. The density of the
layers must be known if one wishes to obtain comparable samples (on a weight basis). To
obtain the same amount of soil solid and the contaminant it contains, it is essential to take
different volumes of soils, so that the mass of solid obtained is equivalent. This would
mean that the volume of sample would need to be different for the different layers. This
type of calculation is illustrated below.

Calculating Volume of Soil Needed for Equal Mass of Samples

A soil with a bulk density of 1.2 Mg/m3 is to be compared to a soil layer
with a bulk density of 1.5 Mg/m3. The sampler being used has a crosssectional area of 5 cm2. The sampler itself is 30 cm long. How many

Characteristics of the environment

43

centimeters of soil should be taken from each layer so that the same amount
of soil is obtained for analysis?
Answer: The first step is to remember that bulk density can also be
represented as g/cm3, thus for this soil the bulk densities for this unit are
1.2 and 1.5 g/cm3 (which is the same as g/cc.) The next step is to decide
how many grams of soil are needed in the sample. If each sample is to
contain
50 g the equation to make the required calculation is:
Bulk densityareadepth=50 g
rearranging the equation
Carrying out the calculation for the soil with a bulk density of 1.2g/cc the
depth of the sample taken would be 8.3 cm and the sample with bulk density
of 1.5 g/cc would be 6.6 cm.
The bulk density of soil horizons and underlying layers is important in determining the
volume of soil needed during the sampling process. In addition, knowing the bulk density
of the horizons can indicate the likely path of water and contamination through the soil
(see Figure 2.8) [19].

2.5. WATER MOVEMENT OVER AND THROUGH SOIL

Water is the great mover in the environment. Air and ice also move soil; however, air
cannot directly move particles larger than sand, while water and ice can. Although ice can
move large boulders, it is not a major component of most of the environment. Water and
ice move very large rocks and boulders, and in this process they are reduced to gravel,
sand, and silt, and clay may be released if present in the rock. Ground rock is deposited
on banks along rivers and streams and at the mouth of rivers and the end of glaciers.

FIGURE 2.8 Water moving downward and horizontally in soil containing

compacted layers.

Field sampling

44

Rivers and streams may bury materials, including contaminants. When a river confined in
a valley comes to an open plane its velocity will decrease and the material it is carrying
will be deposited. This gives rise to

FIGURE 2.9 A soil profile, knife at the bottom of the A horizon. The very dark
material at the bottom (below white line) is buried material.

Characteristics of the environment

45

what are called alluvial fans, which are similar to deltas except that they are deposited on
dry land. In addition to simply carrying material and depositing it, streams and rivers tend
to meander. Over a number of years a stream might move from one side of its valley to
the other, completely reworking the landscape in the process. Contaminated materials
may be buried in all three of these situations. Figure 2.9 shows a soil profile with buried
material.
In practical terms this means that contaminated material in the stream may be buried
anyplace in the floodplain (Figure 2.10). A field sampling plan must take this potential
burying of contamination into consideration. Also, all floodplains are subject to flooding,
and thus are not appropriate places to store hazardous materials or to set up field office
buildings, particularly those for storage of equipment and samples.
Also as seen in Figure 2.10, a contaminant on a hillside may be closer to the soil
surface at the top of the hill and deeper lower on the hill, because erosion will remove
soil from the top of the hill and deposit it at the bottom. Gravity can also move soil down
a slope and thus tends to bury contaminated areas. Soil moved under the influence of
gravity is said to be colluvial. Figure 2.11 shows a hillside where material has moved
under the influence of gravity.

FIGURE 2.10 Stream terraces and stream meandering across a stream valley.

Field sampling

46

FIGURE 2.11 Soil moving down a bank under the influence of gravity
(colluvial). Note the tree (A), which has moved with the soil.

In addition to moving over the surface of the soil, water percolates down through the soil
into the underlying loose material and rock. Salts, amendments, and spills will tend to
move down through the soil and underlying material with the water. Horizons in soil,
their texture, structure, and density, will be important in determining how the water and
material it is carrying moves. If at any place in the soil profile or in underlying material
there is a change, water will stop and move laterally along the boundary. (See Figure
2.8.)
In Figure 2.12 there is a sand layer overlain by a gravel layer (gravel does not pass a
#10 sieve), which in turn is overlain by a sand layer. Water moves into the upper sand
layer and fills this upper layer before it moves through the gravel layer. Sand has finer
pores or capillaries than the gravel. Water can move from large into smaller pores or
capillaries, but without an

Characteristics of the environment

47

FIGURE 2.12 Movement of water through a soil having layers of differing

texture and composition.

energy source it cannot move from small to large. Thus, the water will not move into the
gravel layer unless there is enough pressure exerted by water buildup to move it from the
small sand pores into the larger gravel pores.
Lateral movement along boundaries, as shown in Figure 2.8, will continue until one of
two things happens: the water encounters a change in the horizon that will allow deeper
movement or the water above the horizon accumulates to such an extent that it exerts
enough pressure to push the water lower. In Figure 2.8 water-carrying contaminants
encounter a compacted layer that prevents deeper movement. When a hole in the
compacted layer is encountered the water moves deeper. Note that it still continues to
move further along the compacted layer. Also, once through the compacted layer it
moves in both directions (left and right). Almost any change in the composition or

Field sampling

48

characteristics between layers in the soil or underlying material will cause water to move
laterally.
Another important factor in the movement of water in soil is plants. Soil having plants
growing on it will have higher infiltration rates than bare soil. Even coarse sandy or
gravely soils will have higher infiltration rates when plants are growing on them.

2.6. CONCLUSIONS
In field sampling it is important to keep all aspects of the environment in mind. The
atmosphere can have significant effects on sampling as a result of windblown
contaminants, photochemical reactions, and the exposure of anaerobic samples to
oxygen. In terms of the hydrosphere, water is the great mover in the environment and is
important in predicting where contaminants will be found. The lithosphere will either
affect or control the movement of water, particularly through the soil characteristics of
texture, structure, and bulk density, and the rock characteristics of porosity and cracks.
Thus, it is important to know the characteristics of soil and rock in order to know where
and how to sample. All three parts of the environment are intimately interconnected and
thus are important in field sampling. (The characteristics of the environment described in
this chapter will be necessary inputs for the environmental models described in Chapter
7.)

QUESTIONS
1. List the three major spheres of the Earth.
2. Name two surface and two subsurface horizons commonly found in soil. Give some
important characteristics of each horizon.
3. Using the textural triangle find the percentage of clay in a soil sample having 85%
sand and 3% silt. What should the textural name of such a soil be?
4. What would the engineering letter designation for the soil in question 3 probably be?
5. Two soil samplesARC32a and ARC32bare taken from a field while traversing
it. One has a bulk density of 0.95, and the other a bulk density of 1.25 Mg/m3. What is
the major constituent of these two samples?
6. From just the bulk densities can you tell what happened between the two samples?
7. A field sample is given an engineering designation of SM. What does this
correspond to in the textural triangle?
8. Give two examples of how one of the Earths spheres might affect another in a way

Characteristics of the environment

49

that would impact sampling activities.

9. Using diagrams and words describe the various layers of loose material on the
Earths surface.
10. In the diagram in question 9 where would the capillary fringe be located?
11. A soil bulk density sample is taken. The ring containing the soil has a diameter of 6
cm and a height of 3 cm. The soil plus ring weight is 114.9 g, and the ring weight is 15 g.
Determine the bulk density of this soil and its percentage solid portion and percentage
void space.
12. Describe the relationship between atmospheric air and soil air.
13. What is the effect of plants on the infiltration of water into soil?

REFERENCES
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stream chemistry of a northern forest ecosystem to atmospheric emission controls from
the 1970 and 1990 amendments of the Clean Air Act. Environ Sci Tech 2002;
36:47144720.
2. Martin W, Nunnally NR. Air and Water: An Introduction to the Atmosphere and
Hydrosphere. Dubuque, IA: Kendall/Hunt, 1999.
3. Pierzynski GM, Sims JT, Vance GF. Soils and Environmental Quality. 2nd ed. New
York: CRC, 2000:2226.
4. Schwab GO, Fangmeier DD, Elliot WJ. Soil and Water Management Systems. 4th ed.
New York: Wiley, 1996:144.
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during sample storage: Effects of daylight radiation and temperature. Environ Sci Tech
2001; 35:27172720.
6. Johnson CA, Leinz RW, Grimes DJ, Rye RO. Photochemical changes in cyanide
speciation in drainage from a precious metal ore heap. Environ Sci Tech 2002; 36:840
845.
7. Brady NC, Weil RR. The Nature and Properties of Soils. 12th ed. Upper Saddle River,
NJ: Prentice-Hall, 1999:485521.
8. Rendig VV, Taylor HM. Principles of Soil-Plant Interrelationship. New York:
McGraw-Hill, 1989:5357.
9. Hromnik CA. Karst, Kas er Karasattu: Whence the name? Cave and Karst Science.
London: British Cave Research Association, 2001; 28:7988.
10. Jury WA, Gardner WR, Gardner WH. Soil Physics. 5th ed. New York: Wiley,
1991:196.
11. Pierzynski GM, Sims JT, Vance GF. Soils and Environmental Quality. 2nd ed. New
York: CRC, 2000.
12. Strahler AN, Strahler AH. Introduction to Environmental Science. New York: Wiley,
1974:68.
13. Kling GW. Seasonal mixing and catastrophic degassing in tropical lakes Cameroon,

Field sampling

50

West Africa. Science 1987; 237:10221024.

14. Massei N, Lacroix M, Wang HQ, Mahler BJ, Dupont JP. Transport of suspended
soils from a karstic to an alluvial aquifer: The role of the karst/ alluvium interface. J
Hydrol 2002; 260:88101.
15. Soil Survey Staff. Soil Taxonomy: A Basic System of Soil Classification for Making
and Interpreting Soil Surveys. Soil Conservation Service, U.S. Department of
Agriculture. Agriculture handbook no. 436. Washington, DC: U.S. Government
Printing Office, 1975.
16. Buol SW, Hole FD, McCracken RJ. Soil Genesis and Classification. Ames, IA: Iowa
State University Press, 1980.
17. Foth HD. Fundamentals of Soil Science. 8th ed. New York: Wiley, 1990:2426.
18. Soils Manual for Design of Asphalt Pavement Structures, manual series no. 10 (MS10). College Park, MD: Asphalt Institute, 1969:6978.
19. Brady NC, Weil RR. The Nature and Properties of Soils. 12th ed. Upper Saddle
River, NJ: Prentice Hall, 1999:125149.

3
Presampling
Before a physical sample is actually taken the whole sampling procedure and all required
equipment must be in hand and ready to use. For large projects a field office, laboratory,
and storage area must be in place and functioning at the field. The sampler or samplers to
be used must be at the field, along with the project notebook, the sampling plan or
diagram, maps of the area, and suitable containers for samples. The sample storage and
transport containers must be present and ready to use, along with chain of custody and
other forms. Plans for shipment and analysis must have already been discussed and
planned with the commercial laboratory doing the analysis. (See Chapter 10 for a more
complete description of this process.)
A minimal field office will include not only a building with two main rooms (office
and laboratory) and a washroom; a sample storage area separate from any of these areas
must also be available. Both the office and laboratory will need to be equipped (chairs,
desks, computers, etc. for the office, and laboratory benches and standard laboratory
equipmente.g., balances, mixers, pH meters, and other meters or measuring devices
needed for the particular sampling situation). These will all need to be installed and
functioning before sampling begins.
Other tools to be used during the sampling will also need to be acquired. For instance,
if ground-penetrating radar (GPR) is to be used, the equipment and operators must be
contracted. Suitable GPS units, computer programs for statistical analysis, and
geographic information display (GIS) will also need to be purchased. Personnel will need
to be educated or trained in both the use of these tools and the interpretation of the data
produced. If inexperienced personnel will be sampling, they need some specific training
in proper sampling techniques. (See Chapter 11 for further discussion of personnel.)

3.1. FIELD OFFICE

A field office consisting of one or several buildings with electricity, phone service, and
running water will be set up at the field. This building is usually a trailer with one to three
rooms. One room will be for such things as the computer, phone, project notebook, and
chain of custody and other forms. Two phone lines are recommended because one will be
used for the modem in the computer. A second room will be set up as a small laboratory,
in which needed field analytical procedures can be carried out. This will be particularly
useful during transect sampling and for testing and analysis that needs to be
accomplished immediately. A bathroom for cleanup is essential, along with an outside
shower for situations in which sampling personnel become massively contaminated. It
will also be useful for washing off boots and equipment after sampling.
A separate building is needed for storing samples and another is needed for storing

Field sampling

52

equipment, including any needed chemicals. Note that chemical storage must be well
separated from sample storage to prevent cross-contamination. Any storage building
designated for chemicals needs to have ventilation and an explosion-proof fan for moving
air through and removing fumes.
In a rural or farming-type setting buildings may already be at the field and available for
use. Such buildings may already have electricity, water, and bathroom facilities and be
suitable for use as the office and field laboratory. However, it is preferable to have a
separate sample storage building. Farm buildings are used to store all manner of
chemicals, from fertilizers to pesticides to antibiotics to disinfecting chemicals. Fumes
from any of these sources can be absorbed by field samples, contaminating them and
causing complications in analytical procedures later. This could result in the analytical
results showing contamination that is not in the field but is actually in the storage
building. In a worst-case situation a recomendation may be made for a field to be
remediated for a contaminant that it does not contain.
The importance of a separate room that has never been used before for sample storage
cannot be overemphasized. Even if a room or building has been thoroughly cleaned and
has no smell or other evidence of contamination it can still be there. Colorless and
odorless contamination can be contained in cracks and dust in the walls, floor, and ceiling
and can be just as detrimental to samples as any other contamination.

3.2. FIELD OFFICE LABORATORY

Many field sampling situations will call for setting up a small laboratory at the field
office. This should not be a table in a corner of a busy area or where samples for
shipment to commercial analytical laboratories are stored. This is an area that needs to be
in its own room with running water, electricity, an explosion-proof exhaust fan, and
sufficient bench space to allow for setting up instruments and working with samples.
The laboratory will be provided with a minimal amount of common laboratory
equipment. Any work done in any laboratory will require purified water, which can either
be distilled in the laboratory or purchased. Another source is water that has gone though
several ion exchangers and reverse osmosis processes and is called deionized (DI) water.
Distillation equipment is usually bought, while DI/reverse osmosis equipment can be
rented. This water will be used for preparing solutions and for final cleaning of
glassware.
Soil samples will require drying and sieving. Drying is usually done by placing a thin
layer of the soil sample on a clean surface, such as a piece of plastic, and allowing it to
air dry. It will always be more convenient to dry the sample using an oven.
Unfortunately, drying a soil sample at even slightly elevated temperatures causes
irreversible changes, thus soil samples should never be mechanically dried before
analysis.
In most cases a #10 and #200 sieve will be sufficient for most sieving needs. It is good
to have a receiving can or pan to place under the sieve to catch sieved material. Typically
sieves are constructed of brass with soldered-in mesh. This means that sieved samples
can pick up metals such as copper, zinc, lead, and silver during sieving. Stainless steel

Presampling

53

and plastic sieves are also available for more demanding situations in which metal
contamination must be avoided. Metals will normally not be of concern for the samples
analyzed at the field laboratory. In cases in which samples are to be sent to a commercial
laboratory for further analysis, however, contact with metals will be of concern.
Other equipment needed will include a balance and dissolved oxygen and pH meters.
At minimum a top-loading electronic balance having a capacity of several kilograms and
a readability of at least 0.01 g will be needed. Balances with readability of 0.001 g are
readily available, but such sensitivity is not generally needed. A pH meter will be needed
in all field sampling situations, but a dissolved oxygen meter will only be required when
sampling water or water-saturated samples. Inexpensive portable and handheld pH meters
are readily available. The more versatile multifunctional pH meters are more useful and
usually more durable, however. These meters can measure pH and temperature and
accommodate ion selective electrodes (ISE). Ion selective electrodes are available for
measuring ammonia, a wide range of metal cations, and anions, including cyanide,
nitrate, nitrite, and many others. These types of electrodes and measurements can be very
useful, particularly during the transect sampling phase.
Using pH and other electrodes requires filling and standardizing solutions. Most of the
required solutions can be obtained premade, and this is recommended. In no case should
electrode filling solutions be made at the field laboratory. Standardizing solutions for pH
and ISE can be prepared at the field laboratory from premeasured packets of the required
solutes. These are dissolved in the prescribed amount of distilled or DI water, which
should be freshly prepared for this purpose to assure high quality.
An assortment of typical laboratory equipment will also be needed. A shaker for
shaking samples, an oven, and a rack for drying glassware will be useful in the
laboratory. Also, Erlenmeyer flasks, beakers, graduated cylinders, spatulas, weighing
paper, wash bottles, brushes, and laboratory cleaning detergents must be available. In
some cases, other project-specific equipment (e.g., flammable gas detectors for areas
contaminated with fuels) will be needed. Some forethought as to the equipment needed
will allow smooth operation of the field office laboratory. A summary of general
equipment and supplies needed for a field laboratory are given in Table 3.1.
Unless there is some important reason for doing otherwise, only minimal analysis
should be undertaken at the field laboratory. Instrumentation, conditions, and knowledge
are needed for proper operation of sophisticated instrumentation such as spectrometers
and gas chromatographs. Analysis requiring these instruments should be left to the
commercial analytical laboratory.
The operation of any laboratory entails the generation of waste. The waste may be in
the form of broken glassware, discarded excess sample material, chemicals used in
analysis, and innocuous materials, such as paper towels for drying hands. Broken
glassware is the source of cuts in the laboratory, and if not disposed of properly, may be
hazardous to persons handling trash. Special broken-glass containers are available and
should be used for all broken glass. Any samples containing hazardous material either
from samples or from analytical procedures should be disposed of properly. Other
material can be disposed of in local landfills.

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TABLE 3.1 Field Laboratory Equipment and Supplies

Equipment/supply

Comments

Room

Separated from other work areas and containing bench space, running
water, electricity, and explosion-proof exhaust fan

Purified water source

Distilled or deionized water

Bench space

For air drying samples

Sieves

#10 and #200; others may also be needed

Balance

Capacity kilograms, readability 0.01 g

pH meter

Capable of ISE measurement

Dissolved oxygen (DO)

meter

Portable meter preferable

ISE electrodes

For the contaminants expected

Standardizing solutions

For pH, DO, ISE

Shaker

Reciprocal to hold Erlenmeyer flask

Drying oven

Medium size for glassware

Other as needed

Beakers, flask, spatulas, graduated cylinders, weighing paper, bottles,

etc.

Waste disposal
containers

Must be capable of safe disposal of broken glass

More information about laboratory procedures and analytical methods as they relate to
field sampling are given in Chapter 10.

3.3. THE PROJECT NOTEBOOK

The project notebook (sometimes called a field notebook) is a book in which all
information about the project is placed. It is intended for use in the field and is the place
in which all notes, diagrams, sketches, maps, and information about the project are kept.
This is traditionally a bound book into which additional notes, maps, and other
information are inserted and fixed. The fixing should be done with either glue or tape, not
paper clips or staples.
The most important problem with the project book is neatness. It is good to have a
project book be as neat as possible. In too many instances, however, workers fail to put
important data in the project book because they are afraid that it will not be neat. They
would rather write notes on scraps of paper and then write a neat entry in the project
notebook. Sometimes people wish to write in pencil so that mistakes can be erased. It is
important both for completeness and legal reasons that none of the above be allowed.

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55

All data, observations, and any other pertinent information must be put directly and
permanently into the project notebook with a nonsmearing pen. Although neatness is
preferred, it is not unprofessional for smudges and crossed out (but not whited out)
entries to occur on some or even all pages. For both practical and legal purposes it is
better for the project notebook to be a little less neat but absolutely complete. In Figure
3.1 the entry on line 7 has a part marked out. Entries or even whole pages can be crossed
out, but pages are never taken out of the project notebook. Missing pages are an
indication that serious problems exist. The project notebook should thus be bound rather
than loose-leaf, which means that for large projects there may need to be several volumes
of the project notebook.

FIGURE 3.1 An example of a project notebook.

A standard way of handling entries is to first number all the pages. In Figure 3.1 the page
number is in the upper right-hand corner. Second, it is highly recommended that five to
ten pages at the beginning of the book be left blank. These pages will be used as a table
of contents. As work progresses, samples are taken, observations are made, and results
are obtained, these will be written up in the body of the book and noted in the table of
contents. The table of contents tells where these data are located so that when a report is

Field sampling

56

needed later the required information is easy to find. The table of contents is also handy
in connecting observations and data collected at different times and bringing them
together. Samples will be taken, and two weeks later the analytical results will be
returned. In the meantime entries have been made in the project book. Information about
how and when the samples were taken will need to be combined with the analytical
results in reports, so the ability to readily access the sampling data and the analytical
results is important.
The date on which entries are made in the project notebook must be placed at the top of
each page. In some cases it may also be necessary to note the times at which activities
were undertaken either at the top of the page or in the body of the write-up. In Figure 3.1
the date is at the top of the page on the left and follows a notation that the samples were
taken in the afternoon (i.e., p.m.).
When samples are taken, the numbers they are given should refer back to the project
book. Specifically, the sample numbers should refer back to the page number where a
description of the sampling process and the location of the sample are given. It is usually
a good idea to prefix the sample number with the initials of the person taking the
samples. In addition, people often like to have the sample number include a reference to
date and time. For instance, the sample number might be AC12A31a1 12102 pm. Here
12A is the field number, 31a the sample number in the project book, 112102 the date, and
pm the time of sampling. As can be seen, this can produce an unwieldy sample number if
carried too far.
In Figure 3.1 the samplers initials are at the top of the page and each sample entry
begins with his initials followed by the page number. The first entry has a small letter a
following the sample number. This tells the reader that it is the first sample noted on this
page. Also note that the sample number is repeated in the left-hand margin for easy
reference. Under each sample number various observations are made about the sample as
it is obtained. Such observations can add critical insight into the nature of the sample and
its components.
An example of a simple observation is the color of a soil sample, which can be
important in interpreting sampling and analytical results. A soil sample showing color
variations of reds, browns, grays, or blues indicates that the soil is under reducing
conditions during a significant period of time during the year. The ease or difficulty of
inserting the sampling tool is another observation that can indicate the occurrence of
compacted layers. Samples might also show a change in texture or the occurrence of a
gravel or sandy layer. As mentioned in Chapter 2, all of these are important to note
because they can indicate where additional sampling may be needed or where a
contaminant is likely to be found.
In a similar fashion observations about water and air samples must be made as they are
taken. These may include color, suspended matter, and odor, and may help in
identification of the nature and concentration of the contaminant or contaminants.
Observations will also provide either clues or evidence as to the source of the
contamination, which could be essential in preventing further contamination.

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57

3.3.1. Number Changes

Sometimes another sample number replaces the number given in the field when the
sample is processed for storage, shipping, or almost always, in the commercial
laboratory. Renumbering opens up the whole process to error and is not recommended. If,
however, it cannot be avoided it is strongly recommended that the original sample
number be kept on or with the sample even after a new number is given. In all these cases
a cross-reference list relating the two different numbers must be readily available and a
copy must be kept with the samples at all times.
Sample numbering and recording process mistakes will be made during the sampling.
Numbers will not be written legibly, or they will get erased or smeared and become
unreadable. To the extent possible every effort should be made to eliminate or limit these
types of errors. Using nonsmearing pens, using paper that can be written on when wet,
and putting the sample numbers on the sample containers in several places are all good
approaches to limiting these problems. It is far less expensive and less time consuming to
spend extra time on sample labeling than on taking another sample or assuming a
samples identity [1].
One way to help minimize sample labeling errors is bar coding. There are software
programs, computers, and printers that can print bar codes on various media, including
labels of different sizes. Not only will bar codes help prevent mistakes in labeling, they
will also speed up sample handling, especially in maintaining the chain of custody. If bar
codes are used, a bar code for the sample needs to be in the project notebook in which the
sample is described (see Chapter 8 for more information on bar coding) [2].
A GPS unit will often be used in sampling a field. This will give the location of a
sample site and may even record a sample number to be associated with that site. Even in
this case it is important to have a project notebook to record these and other data about
the sample when the sample is taken. At the time of sampling this will seem to be
unnecessary repetition, while a week later it will be found to be an essential, time-saving
step.

3.4. MAPS
Maps are the heart of the sampling process and are essential for any successful sampling
program. There are many types of maps available; for example, surface, topographic, and
three-dimensional. Especially valuable are aerial photographs of the specific area to be
sampled. If they are not available there are both firms and computer programs that can be
called upon to produce the needed maps, aerial photographs, or both. Before doing
anything at a contaminated field it is essential to have several maps of different scales of
the area. One map should show the contaminated field and the surrounding areas. Several
maps showing details of the field itself will also be needed.
I would not, however, recommend producing a large number of very detailed and
expensive maps. What is needed are many simple maps of the area suitable for recording
data on. Each time some activity takes place on the field it needs to be recorded not only
in the project notebook but also on a field map, so that the location is precisely known.

Field sampling

58

The place in which the activity takes place must be on the map, along with date and time
and the name of the person leading the activity. It can be separate from the project
notebook during the activity, but either the original or a copy must be permanently
attached to the project notebook in the appropriate location when the activity is
completed. Each map should have its own entry in the table of contents. Alternately, a
separate page listing just the location of maps can be in the table of contents. Data
recorded on a map can subsequently be entered into a computer either manually or by
scanning the information. Once in a digital form GIS can be used to display and follow
sampling and other field activity.
An example of a simple map of a field to be sampled is shown in Figure 3.2, and
includes a symbol showing which direction is north (which must always be present). The
map must also show some distinct characteristic that allows the reader to specifically
locate it. In Figure 3.2 the roads specifically locate the position of the fields of interest,
provided, of course, that we know the state in which these roads are located. Additional
locators such as longitude and latitude can be included on the map and are recommended.
These are useful especially when using GPS for locating the

FIGURE 3.2 Simple map of three fields (12a, 12b, and 12c) to be sampled.

fields and sample sites and can be entered from the GPS unit during sampling.
A cross-sectional map of soil depths and the depths of various layers (see Figure 3.3) is
also valuable to have. Such a map is helpful in developing

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59

FIGURE 3.3 Cross-sectional map of the profile of regolith in field 12a. Units
at the bottom of the map are meters.

both the transect and detailed sampling plan. It can help in determining where a
contaminant may have moved and thus where more samples need to be taken. Such a
map may be developed from data in the soil survey of the field, which is discussed below.
Another useful type of map is the topographical or topo map of the area. An example
of a topo map is given in Figure 3.4. The topo map has lines of equal altitude drawn on it.
They thus show slopes, escarpments, and other important features of a landscape. They
also show which direction water will flow in and where erosion is most likely. In many
cases topological characteristics will need to be taken into consideration when sampling.
For many areas the United States Geological Survey and other government entities
have digital orthophoto quarter quadrangles (DOQQ) photographs or maps of areas of
interest. These are digital photographs that are placed on the Universal Transverse
Mercator Projection (UTM) on the North American Datum (NAD-27). There is also a
NAD-83, and others, that can be used. Digital orthophoto quarter quadrangles have a
ground resolution of 1 meter and cover an area of 3.75 minutes latitude by 3.75 minutes
longitude. It is useful to note that both UTM and NAD-27 are used by GPS units, and
since they are digital, they are compatible with

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FIGURE 3.4 A contour map of fields 12a, 12b, and 12c showing contour lines
which give the elevation of different parts of the field.

FIGURE 3.5 An example of a portion of a DOQQ map from Clinton County,

Ohio, showing roads, buildings, and fields.

GIS systems An example of a portion of a DOQQ map is shown in Figure 3.5 [3, 4].
The DOQQ images produced have both the look of a photograph and the geometric
qualities of a map. They are a true representation of the Earths surface. Because of this

Presampling

61

both distances and areas can be determined directly from the DOQQ. Software for
manipulating these maps (e.g., MrSID GeoViewer) is availablesome of it freeon the
Internet [5].
Digital orthophoto quarter quadrangles are very useful in sampling, and are available at
a minimal cost. Unfortunately they are often hard to find, even on the Internet. One
relatively easy place to find information about DOQQs is the local GIS office. Many
county courthouses will have a GIS office, and personnel doing GIS for the county will
be very helpful in obtaining needed DOQQs. If no county GIS office is available, try the
state GIS office or officer.
When sampling, site positions can be determined using a GPS unit. These site
positions are saved and later loaded into a GIS system. A DOQQ is then also loaded into
the GIS system. The system is then used to generate a map that shows the true location of
sample sites in the field. This map and a GPS unit can be used to locate the sampling sites
at any time in the future. It is also possible to enter other sampling data, such as sample
depth, altitude, vegetation cover, and other information deemed necessary into the GIS
system. These data can also be displayed on the thematic map, and all the data can be
interrelated as needed or desired.
3.4.1. Soil Survey
The soil survey is another invaluable map to have before sampling a field begins. This is
a map of soils in an area, but it also contains additional information about the area it
represents. The soil survey is made up of aerial photographs of an area of the Earths
surface with the designations of the soils in the field indicated on it, as shown in Figure
1.2 in Chapter 1. Descriptions of the soils, their characteristics, and their suitability to
various uses are also given, as are characteristics of the landscape, such as slope,
buildings, waterways, and roads. This is an extremely useful type of map and source of
information and no field sampling project should be undertaken without having a soil
survey of the area available for ready reference. In situations in which the field sampling
is primarily of water or air a soil survey and associated maps are still useful.
Soil surveys have typically been carried out only in rural areas; that is, they have been
seen as tools for agriculture, particularly in erosion control. In areas of rapid urbanization
older soils maps may show the soils in an area because it was agricultural land when the
map was made. New soils maps attempt to include all land in the soil survey, thus both
the older and newer soils maps can be valuable in a field sampling project.
Field sampling will include sampling a similar uncontaminated field or soil. The soil
survey will be indispensable in finding uncontaminated soils, which are the same as those
in the field under investigation. Such comparison soil samples are essential to be certain
that the analytical results represent an unusual situation in the field of concern. It is often
important to know the base or natural level of a component so that it is not mistaken for a
contaminated level. See Chapter 9 for an introduction to the types of elements and
inorganic and organic compounds likely to be found in soil.

p2000c566g67001.png

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3.5. PRELIMINARY FIELD SURVEY

Before any sampling an initial survey of the field should be carried out. This means
looking at the field from all directions. The first step is to walk completely around the
field looking at it from all aspects and noting all the conditions in and around it. During
this process keep asking what is seen and what is going on. Another important question to
keep in mind is whether there are additional sources of contamination that might affect
the sampling, analytical results, or the cleanup plan.
Field characteristics that should be noted during this first survey are given in Table 3.2.
The topics in this list and others, such as the clay and clay type, bulk density, roots, pH,
electrical conductivity, and organic matter content, will be given in the local soil survey.
In spite of this it is a good idea to check these data by making observations in the field,
because significant changes may have occurred between the time the soil survey was
made and the sampling undertaken.
An example of such a situation occurred at a Superfund field. This field was 1 ha in
size. On the upslope side of the area was a railroad siding consisting of three sets of
tracks that carried heavy freight train traffic. On another side was an electrical power
substation. Of concern here would be heavy metals, grease, tar, and creosote from the
railroad. This was of particular concern because the tracks were upslope from the site.
The other concern would be polychlorinated biphenyl (PCB) contamination from the
electrical substation.
Although this is a relatively simple and obvious example it is not an unusual situation.
In this case routine sampling and analysis might not show additional needed cleanup and
remediation work. On the other hand, a routine analysis might have indicated additional
contamination requiring additional sampling and analysis, which could have been
minimized by recognizing the sources of additional and continuing contamination [6].
Another similar problem is that different, unrelated contaminants may interfere with each
other in analytical procedures. This could mean that the analytical laboratory might
obtain confusing results related to the additional sources of contamination from a rail line

TABLE 3.2 Types of Field Characteristics to Be Noted During Preliminary Survey

Characteristic
Slope
Climate
Wind direction
Vegetation
Erosion
Water
Contamination
aAn area

Types of observation
Steep, gentle, flat, depressionala
Arid, semihumid, humid
Note predominant direction
Luxurious, sparse, crops, grass, trees
Obvious evidence of erosion? Rills, gullies, etc.
Evidence of water movement into, over, or through area
Sources of contamination and continuing contamination

or field in which water from surrounding areas collects during a rain event. Often this
area does not have an outlet.

Presampling

63

or a power station. (See Chapters 10 and 11.) Knowing what is around the field and other
possible sources of contamination will make discovering and understanding these sources
of confusion much easier.
As with all activities related to field sampling notes about this initial survey must be
put in the project notebook. All observations about the field need to be entered with
particular reference as to where the items of note are located in the field, and as indicated
above these observations are to be included on the appropriate maps of the field and their
positions marked using GPS.

3.6. FIELD HISTORY

After surveying the field the second thing to be put in the project book is a field history.
The best field history is one that includes all available information about the field use or
uses before its latest use and the use that has necessitated the sampling or cleanup. The
sources of this information will be owner records, along with deeds of sale and
municipal, county, state, and governmental records and any available GIS thematic maps.
In some cases it may also be valuable to talk with people living in and around the field
about what has happened there. Do not assume that an isolated field on a back road in the
country is not contaminated. I have seen hidden fields 20 miles from a city being used
clandestinely as dumpsites. Also, isolated areas on a farm might be used to dispose of
agricultural chemicals.
As indicated above, it is also a good idea to know what the areas around the site were
being used for historically. These surrounding areas can be a source of additional
contamination, (e.g., low-lying areas can become contaminated as water washes
contaminants or eroding soil from surrounding or neighboring fields into the area).

Field History in Relationship to Phosphate Content

I often work on projects in developing countries. One project involved a
search for a source of phosphate, which might have been used as fertilizer. I
was supplied five soil samples from an area, composed of several fields,
which were suspected to contain a phosphate rock deposit. Analysis of the
samples gave mixed results. Some samples had undetectable amounts of
phosphate, and other samples had moderate to high levels of phosphate.
In this case a lot of money would have been saved if a detailed history of
the fields had been obtained. A map showing the location of previous
activities in the fields and the sampling sites before detailed sampling and
analysis was done would also have been useful. It turned out that the samples
were taken from fields that had at one time been a village and at another time
a burial site. Soil samples that came from cooking fire sites showed moderate
levels of phosphate. Samples containing chips of bone showed high levels of
phosphate. Soil not contaminated with ash or bone had undetectable levels of
phosphate.

Field sampling

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Often historical information about a site is not as complete as one might wish. It is not
unreasonable to talk with people who have worked on various projects that were carried
out at the field and with people living around the area. Sometimes some surprising
activities can come to light during this investigative phase.
The purpose of this phase of investigation is to understand the sampling needs, provide
proper safety for workers, and avoid unpleasant surprises. The potential depth and extent
of sampling will be indicated during this phase, as will the type of sampler or samplers
needed. The types of samplers used will depend on the composition of the field, the type
of component to be determined, and the depth of sampling. In a field requiring small
numbers of shallow samples a hand sampler capable of sampling 3 meters deep may be
sufficient. If more or deeper sampling is required, powered samplers or drills may be
needed [6].
Without knowing the history of the field it is hard to anticipate such safety needs as
what or how much protective and emergency equipment is needed. Will safety glasses
and work boots be sufficient or will more sophisticated coveralls, rubber gloves,
respirators, and so on be needed? There is also an economic aspect to knowing the history
of the field in that the amount of safety equipment needed will change, depending on the
level and the type of contamination. If there is no contamination and the sampling is for
other purposes, minimal safety protective and emergency equipment will be needed [7,
8].
Another aspect of obtaining the history of the field is to avoid unpleasant surprises.
One such surprise might be discovering underground tanks containing unknown waste.
Another might be discovering unsuspected contaminants that affect the sampling and
remediation plans. It is far less expensive to know about these beforehand than to have to
contend with them later.
One last piece of information to obtain is to identify all possible sources of
contamination or pollution. Sources may be point sources, so that the exact location of
the source of the contamination, such as a spill of fuel oil from a tank car, can be
pinpointed. The other is the nonpoint source. In this case the contaminant may be spread
out over a large area, such as an agricultural field of several hundred acres. This diffuse
material may wash off the soil surface and be concentrated in low areas or bodies of
water. It is much easier to find, identify, sample, and remediate point sources of
contamination than nonpoint sources, but it is essential to identify all possible sources as
early as possible.

Surprises in the Field

At one cleanup field that I was assured had been previously investigated, I
found an unpleasant surprise, which is the one thing I do not wish to find at a
field. I attempted to take a soil sample only to encounter a board 5 cm under
the surface. Five cm deeper I found a brick, and under that a large rock. I was
immediately concerned. What had been dumped in this area? If it was fill, the
question was, from where? Was the fill clean to begin with? Had this been a
dump at one time? It turned out that relatively clean fill had been used. This is

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65

one example of surprises that can be unearthed if an adequate history of the

field is not obtained.
As part of the history of the field find out about the soils present and their characteristics.
This information can be obtained from soil surveys. If the soil is not the same as
indicated in the soil survey, it is either fill or disturbed by various activities on the field.
Knowing the soilparticularly its texturewill help determine the type of sampler
needed. This information will also be required to determine how deep sampling must be
done or is likely to be needed. The soil survey will also indicate if water is likely to be
encountered during sampling [9]. Information in the soil survey will also be needed in
any modeling of the field.

3.7. SAMPLING TOOLS

During the presampling stage decisions about sampling tools and their sources need to be
made. Solid materials, particularly soils, will require different samplers, depending on
their characteristics. Water and air will each require different samplers, although in many
cases no sampling tool will be needed.
On the basis of the characteristics of the soils present or likely to be present as
indicated by the soil survey, what type of sampler is likely to be most useful? In part this
will be determined not only by the texture of the soil but also the moisture levels likely to
be encountered. Dry, sandy soils will require a different type of sampler than wet, clayey
soils. Likewise, a stony or rocky soil will require yet another type of sampler. Another
important consideration is the depth to which sampling is to occur. The sampler must be
able to sample to the maximum depths needed to account for all the contaminant likely to
be present. (See below and Chapter 5 for more detailed information about samplers.)
Contaminant type, whether inorganic or organic, will affect the choice of sampler. For
inorganic components the metal used in the sampler will be important. If, for instance,
zinc is the component of interest the sampler must not have zinc in it. Many different
types of metals are used in the construction of samplers, so it is important to be sure that
the composition of the sampler is compatible with the sample being taken. If the
component is organic, there are two other considerations. The first is that the sampler (or
sampler liner, if used) is not adding organic material to the sample. The second occurs
when the sample contains volatile organic compounds (VOCs). In this case the sampler
should, as much as possible, minimize the loss of the organic components during the
sampling process [9].
3.7.1. Soil Samplers
There are three different basic types of soil sampler headssimple auger, bucket auger,
and core. The three different types are shown in Figure 3.6. (See also Figures 5.5 and 5.6
in Chapter 5.) A simple auger looks like an old-fashioned wood drill bit. It can be used in
moist and wet fine-textured and rocky soils but does not work well with sandy soils,

Field sampling

66

particularly when they are dry. Auger samplers will penetrate rocky soils and allow
sampling of finer fractions, but will not remove larger stones. With extension handles and
proper soil conditions it can be used to sample up to 6 meters deep. If many deep samples
are to be taken, however, using this sampler will require a lot of work and be very timeconsuming.
The bucket-type auger is effective for sandy, muddy, and rocky soils. Hand-operated
samplers of this type can sample up to 6 meters deep, but need extension handles and the
proper soil conditions, along with a lot of effort and time for sampling. Rocks will
sometimes cause problems if they get caught in the blades of the sampler. In such a case
they prevent further sampling, and their removal can interfere with the sampling process
and obtaining an adequate sample. Larger rocks can prevent this sampler from
penetrating the soil and thus prevent a sample from being obtained.
There are a number of types of core samplers, which consist of a hollow tube inserted
into the soil. When the tube is withdrawn it contains a core of soil. This core is removed,
and all or part of it is taken as the sample. Simple versions of this type of sampler are
inserted by hand and work well with fine-textured soils without too much moisture.
Under such conditions it can be used to sample 1 meter or more in depth. Under
favorable conditions this is the quickest and easiest type of sampler to use. This sampler
is not productive when used with very dry, sandy soils, however. A

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67

FIGURE 3.6 Soil samplers. From left to rightauger, bucket auger, and coretype samplers.

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68

variation on this sampler is a special type in which the soil core is contained in a sleeve or
liner that fits inside the sampler and can be removed with the sample inside. This type of
sampler is particularly good for samples in which contamination or loss of a constituent is
of concern. More sophisticated core samplers remove cores under even more controlled
conditions (e.g., some will even remove a continuous core over the depth of drilling).
Such cores can be important in reducing contamination and maintaining the physical and
chemical integrity of the sample.
All three types of samplers can be power-driven, which allows deeper sampling.
Powered samplers are frequently mounted on vehicles of various types (e.g., on a pickup
truck or a special four-wheel-drive vehicle) and can sample several meters deep. (An
example of this setup is shown in Chapter 5.) For very deep sampling a drill similar to or
the same as the ones used to drill wells may be needed. Deciding on the type of sampler
needed and obtaining the use of the proper sampler is essential in the presampling stage.
Often knowing the depth at which a sample is obtained will be important. For this
situation a core sampler is best. Although this type of sampler will compress the sample it
is still possible to determine the depth from which the sample came. With auger-type
samplers soil from the sides of the hole will invariably be scraped off and included in the
sample. For this reason these types of samplers are not preferred for situations in which
the depth of the sample is important or in which a clear distinction between contaminated
and uncontaminated sample is difficult to determine.
Samplers should be chosen for the type of soil or other material that is to be sampled
and should be easy to use. Many samplers are easy to understand and use, while others
are not, and sampling personnel must be taught how to use them (e.g., well-drilling rigs
will require experienced drill rig crews to operate them). Studies have shown no
difference, however, in analytical results that can be traced back to the type of sampler
used (common soil samplers are shown in Figure 3.6) [6].
3.7.2. Powder and Granular Material Samplers
There is another type of sampler designed for dry powders and granular material. This
instrument looks like a soil core sampler except that it has a solid point on the end and
three compartments along the shaft. There is a sleeve on the outside so that it can be
rotated to cover the compartments. The sleeve is rotated to cover the compartments and
the sampler is inserted into the material to be sampled. Once inserted to the desired depth
the sleeve is rotated so that the powder or granular material can flow into the
compartments. The sleeve is once again rotated to cover the compartments and the
sampler is withdrawn. This type of sampler is most often used to obtain samples in grain
bins.
Using this type of sampler three samples are obtained at the same time, and usually
several additional places in a grain truck or bin are sampled. Only dry powder and
granular material can be sampled effectively using this sampler. Granules larger than a
typical corn seed or moist, fine, wet, and very coarse materials are not effectively
sampled. It could be used to sample coarse, dry sands under the proper conditions,
however. A typical use of this type of sampler would be to obtain corn seed samples to
check for foreign seeds or other contamination and moisture levels.

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69

3.7.3. Water Sampling

Several types of water sampling are common. Surface waters and wells are sampled by
simply filling a sampling bottle or with water pumped out of a well. Sampling bottles can
simply be dipped into surface waters to obtain a sample. For pumped water it is common
to clean the outlet, sometimes even to try to sterilize it, and allow some water to run for a
period of time before taking the sample. Obtaining water from various depths is usually
done with a sampler that is similar to the powder sampler described above. It will have a
valve that works such that when it is at the required depth the valve is opened and a
sample taken. The valve is then closed and the sample retrieved.
3.7.4. Sediment Samplers
The bottom of bodies of water is saturated with water. Taking a sample of this material
requires a sampler that can retrieve both the solid and the water. The sampler bottom is
open when it enters the sediment and is then closed to retrieve the sample. An even more
complicated and specialized sampler is required when the sample pressure must be
maintained [10].
3.7.5. Air Sampling
Air can be sampled using an evacuated sampling container. When the container is opened
the surrounding air moves into the container. Other methods include pumping air into a
container by various means. Pumping air always carries the risk of the pump
contaminating the air sample. On the other hand, negative pressure can be used to move
air into a container without contamination. Figure 3.7 shows a number of sample
containers, including an air sample container, that can be evacuated.

3.8. OTHER SOIL SAMPLING CONSIDERATIONS

At this point the number of samples and the number of grids from which they should be
obtained is not known. Only after the transect sampling has been done and the analytical
results reviewed can this decision be made. There are some things that can be decided
upon at this point, however.

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FIGURE 3.7 Sample containers. Front (from left to right)paper, plastic, and
cloth bags. Back (from left to right)glass bottle and glass gas
sample bottle.

When initially surveying the area and obtaining information (i.e., history) about a field,
its pedology * and previous use, crop production, manufacturing, storage, and so forth
should be gathered. The accuracy and precision of sampling is best when both of these
factors are considered together in developing a sampling plan rather than when one is
used alone.
The number of samples or cores taken, the size of the sampling pattern, and the depth
of sampling are all important in obtaining accurate results. Three to six mixed cores give
four to five times better analytical results than analyzing the cores individually. Smaller
sampling grids give significantly better agreement between samples than do larger grids.
This of course has practical limitations, particularly if the contaminated area or fields to
be sampled are large. Also, if the problem is not agreement between samples but finding
threshold values, this issue may be moot. Also, when sampling with depth recognizing
the importance of horizonation is critical.
* Pedology is

types.

the scientific study of soils, including horizon formation, texture, and structure soil

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71

3.9. SAFETY
At this time information is collected that is based on the initial survey and history and
needed for safety in the field during sampling. Safety procedures, safety training,
emergency numbers, and development of a chemical hygiene plan all need to be
completed. Sources of safety clothing and equipment need to be located and appropriate
orders placed for needed equipment. Arrangements also need to be made for the safe
storage and transport of samples and equipment.
Sampling is not a casual activity. This is true even if there is no expectation of
encountering dangerous chemicals. Long pants, long-sleeved shirts (with stomach
covered), socks, boots, and hats are always required. Apparel covering less of the body is
not acceptable during sampling. The two most important pieces of safety equipment for
sampling are safety glasses or goggles and gas mask. Sufficient numbers of safety
goggles must be available at all times. All persons present during sampling must wear
safety goggles whether or not they are actually doing any sampling. Gas masks should be
kept nearby at all times in case they are needed. If significant contamination is present,
other appropriate apparel (e.g., coveralls, gloves, boots) also needs to be available.
If the contamination is dangerous, toxic, or corrosive, additional safety precautions,
such as fully protective clothing (including coveralls, boots, full face shields, respirators,
and gloves that are not only chemical-but also abrasion-resistant) must be used. Detailed
arrangements need to be made for decontamination of workers and others visiting the
field. Arrangements can thus be made at the field office for changing out of coveralls,
boots, or boot covers when leaving. The field office should have a wash area for hands
and face, including an eye wash station and an emergency shower in which workers
massively covered with contamination can be washed. This is essential because such
contamination must not be taken off the field and certainly not into a hospital!
All workers need to be constantly reminded to wash when leaving a contaminated
field. This means both hands and face. (This assumes that these are the only two body
surfaces exposed during sampling.) This also means that washing is required even if
protective face shields and gloves have been worn, because hands pick up food, and
contaminants on the hands can enter the body via the mouth [11].

3.10. SAMPLE CONTAINERS

Arrangements for obtaining a stock of the proper sample containers need to be made at
this juncture. Sample containers can be constructed from glass, cloth, paper, and plastic
in many different forms. Just as the sampler composition needs to be considered in
sampling, so does the sample container. Sample containers must be compatible with the
sample and not decompose, add to, or subtract from the sample components of interest.
Many companies sell specially cleaned and treated sample containers. In some cases
these are vials, which may come with a bar code containing a lot number and serial
number already on them. Usually these are glass bottles or vials with screw tops,
including a liner. The liner can be a simple rubber material or it may be a rubber backed

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72

by Teflon.
Bottles and vials with lined crimp-on caps are also common. Crimped tops require a
crimping tool and a separate top and liner. A sample is placed in the container. A liner is
added and then crimped in place. Such tops are not easily removed, so tampering is not
possible and accidental loosening and spillage is prevented. Special crimped top removal
tools are also readily available.
Both bottles and vials may have caps, either crimped or screw-on, with a hole in the
center so that samples can be taken directly from the bottle using a syringe. Direct
removal of a sample from the bottle without opening it prevents unintentional
contamination. When applicable, these can be timesaving, as the bottles can be purchased
to fit an automatic sampler.
Glass bottles have several drawbacks. First, they can be broken (although most small
vials are quite robust). Second, if clear bottles are used sunlight can affect the sample
contents, sometimes even changing the concentration of the component of interest. If
samples are always protected from direct sunlight this is not a problem. If protection
cannot be provided, however, brown bottles are preferred.
Other sample containers are made of cloth, paper, and plastic. All three of these can be
quite porous. Cloth is the most porous of the containers and does not make good storage
containers unless drying of the sample is particularly advantageous. Paper bags with or
without plastic or plastic-coated liners are commonly used for soil samples. These bags
are quite handy for many types of samples. Depending on their construction, drying of
the sample may or may not take place.
Of the three common sample container materials, plastic is the least porous to water,
but it can be very porous to organic vapors. In addition, plastics can react to or even be
dissolved by organic compounds. Specialty plastic containers are available. The
specifications of these containers must be investigated before their use, however. As with
glass, clear plastics will allow light to interact with the sample if precautions are not
taken to store them is a dark place. Most plastics can be punctured easily, and so must be
handled carefully. Figure 3.7 shows some common types of sample containers. A
summation of sample containers and their characteristics is given in Table 3.3.

TABLE 3.3 Characteristics of Sample Containers

Material

Characteristics

Good points

Deficiencies

Cloth

Strong, unaffected by water Easy to handle Contents dry, soil can sift out of
and mark, strong bag

Paper

Inexpensive, adversely
Easy to handle,
affected by water, may react and write on
with contaminants

Soil will dry even in closed bag;

no sifting; writing can smear

Plastic bags

Inexpensive, hard to write

on, marking rubs off

Porous to very porous for volatile

organics and gases, subject to
puncture, may react with
contaminant

Easy to handle,
moisture
retained

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73

Plastic-lined
cloth and
paper

Similar to plastic except

stronger and less subject to
puncture

See plastic
above

See plastic above

Special
plastic

Specially treated plastic

bags with Mylar or
aluminum lining

Easy to handle

Not impervious to all organics

(check manufacturers
specifications)

Rigid plastic Shatter-proof; make sure

container is chemically
cleana

Easy to handle,
nonwetting

Reactive with sample

components; contamination of
sample

Glass

Easily cleaned;
can be dried in
oven

Subject to breakage

Unreactive

aPlastics

are often manufactured using oils to release them from such things as molds. Note that in
some cases a certain type of container may be specified for a specific type of contaminant;
otherwise, a container compatible with the contaminants expected in the sample is used.

In many cases the analytical laboratory chosen to do the analytical work will have
specific bottles and other containers, along with the closures that it specifies for the type
of sample being obtained and the analysis required. The laboratory will supply the
bottles, along with directions for sample addition, amount, sealing, and returning to the
laboratory.

3.11. TRANSPORTATION AND STORAGE

Arrangements for the transportation and storage of samples also needs to be decided on
during this phase of the work. In many situations the analytical laboratory will have
procedures that it requires for sample transportation and storage. These must be followed
if the analytical results are to be meaningful. Note that different laboratories may have
different procedures. The analytical results are produced assuming the procedures for
storage and transport have been rigorously followed, however. Not following these
procedures can adversely affect or even invalidate the analytical results altogether.
Once in their container, in the field the samples should be placed in a box for transport
to the field office. A paper or wooden box is sufficient, although a polystyrene cooler
may also be used effectively and is probably preferable, as it is both sturdy and insulated.
The samples can be packed with paper, packing peanuts, or bubble wrap, or if cooling is
required ice can be used as a packing material for protection, insulation, and temperature
control. When full, the box is transported to the field office for storage. A separate
storage roomor, preferably, buildingis needed for the samples. This will prevent
contamination of the work space with material from the samples and prevent
contamination of the samples from the work space. At this point the samples are ready to
be either analyzed at the field office (sample characteristics such as pH are analyzed in
the field as soon after sampling as possible) or shipped to the analytical laboratory.

Field sampling

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Many restrictions apply to shipping dangerous or toxic compounds. All applicable

safety precautions, signage, and other shipping restrictions must be followed when
shipping samples to an analytical laboratory.

3.12. CHAIN OF CUSTODY

From obtaining a sample through the final analytical procedure applied to it, a chain of
custody must be kept. This is a trail or list of where the sample has been, who has
handled it and how, the length of time it was stored, and its transportation route. This
information must be meticulously recorded and maintained because it provides proof of
the authenticity of the sample. It also helps in preventing contamination of the sample, or
if analysis indicates that something untoward has happened between sampling and
analysis the chain of custody, can shed light on where and when this might have
happened. Chain of custody forms may be available from the commercial laboratory that
is to analyze the samples. More information about the chain of custody will be given in
Chapters 8 and 10.

3.13. ANALYTICAL LABORATORY AND PROCEDURES

Samples will be analyzed at two locations for one or many components. Analysis that
must be carried out immediately will be performed in the field or at the field office
laboratory discussed above. Samples needing more detailed or sophisticated analysis will
be sent to a commercial laboratory. At the commercial laboratory samples will be treated
appropriately for the analysis of the component of interest.
An analytical laboratory needs to be decided upon and at the same time the types of
components the laboratory will be asked to analyze for need to be decided. The
commercial laboratory will have a project manager assigned to the project. This person
will help in making decisions about various aspects of sampling, sample handling,
shipping, and the analytical methods needed to obtain the desired information. Often the
analytical laboratory will have special kits with appropriate sample containers and
shipping boxes, which may vary, depending on the type of analysis to be done. They may
also specify the conditions such as temperature needed during storage and transport.
These details are further discussed in Chapters 8 and 10.
The question then becomes what components in the sample are important. The first
most important division is between organic and inorganic. Samples to be analyzed for
inorganic components are obtained and handled differently from samples intended for the
analysis of organic components. As noted above the metal composition of the sampler
will be important in obtaining samples to be analyzed for inorganic components,
particularly metals. Samples to be analyzed for organic components must be handled in
such a way as to minimize the loss of organic compounds.
If the laboratory does not have sample shipping kits, discuss with them how the
samples should be handled. Along with this goes deciding on a numbering system for
samples and setting up the chain of custody, which must be decided upon and well

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described and established. All of this is also related back to the project notebook and the
question of the use of bar codes.

3.14. STATISTICS
All sampling and analysis will have variation, which is normal and expected. If variation
does not occur it is reasonable to suspect that the data are in error. Because of this
variation it will be essential to analyze the analytical results using statistics. These tools
will be used to be determine if samples taken at different places and times have different
amounts of a particular component or not. In many cases it will be important to know if
the results are within acceptable limits or not. Statistical analysis will also be important to
determine if an analytical result is an outlier or in error. Statistical analysis of analytical
results thus will be essential.
What statistical tools will be needed? The first calculation to be made is the mean and
standard deviation of the samples. Subsequently a t-test will be needed to determine if
two samples are different or the same or if the sample is within acceptable limits. This
may be between two samples from the same or similar places in the field or samples
obtained at different times. In all probability some more advanced geostatistical tools will
be needed to graphically represent the level of components of interest. These
representations will be used to understand what is happening in the field. They will also
be needed to explain the sampling needs to others, including the public.
Because there are many statistical tools and packages, some evaluation of the various
packages may be needed. For the statistical tools and programs to be most effective
personnel must know how to use them before sampling begins. Often the more powerful
programs will require more learning before they can be used effectively, and thus it may
be more useful to use a statistical program that the operator knows how to use rather than
to try to learn a new program. Another thing to remember is that the tools chosen must be
compatible with the computer system to be used.
In all cases it is essential to have a statistician check the statistical analysis for errors
and to make sure the correct tools have been used.

3.15. OTHER TOOLS TO CONSIDER

The use to be made of other sampling tools needs to be decided upon. How much use will
be made of GPS? What type of receiver will be needed? Is GPR called for? How much or
how will remote sensing and GIS be used? If these tools are to be used, what computer
software will be needed and what computer system will be used to collect and store the
data?
A word of caution would be that some of these applications use large amounts of
computer storage space. When deciding on a computer, both RAM and hard disk storage
should be maximized, thus RAM of 512 MB and an 80-GB hard drive are the minimum
recommended. Removable storage for presentations and backup must also be provided.
Either a CD or DVD recorder will be best suited to this task. Because CDs are

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inexpensive (less than

apiece), CD-R (not CD-RW) CDs are recommended. These are
record-only, so they make a permanent record of the work done and presentations made.
3.15.1. GPS
The use of GPS for locating sampling sites in the field is highly recommended, and in
many situations will be essential. Sample sites can readily be located even if other
markers are lost or destroyed. A GPS receiver can be set up to locate preselected sample
sites in a field, and will not only tell the person sampling when he or she is at the correct
location but how to get from that site to the next. In this way relatively unskilled
personnel can be used in sampling. The movement of water and other components of
interest can be followed by noting their change in position. The rate of movement can
also be obtained from the data, either directly, allowing the receiving instrument to do the
calculation, or indirectly, by noting the change of distance and the time. More discussion
about this use will be given in Chapter 11.
Decisions as to the type of receiving units needed are made at this point. Such
questions as the sophistication needed and whether a handheld or vehicle-mounted unit
are to be used must be answered. The equipment, including any software needed, should
be bought, and operators or persons doing the sampling should be trained in their use
[12].
Knowing the position of an airplane or boat far from landing or shore, or a sampling
site in fields that are hundreds or thousands of hectares in size to a precision of 15
meters is sufficient. When sampling a field of 1 ha, however, knowing a sampling site to
15 meters is not good enough. There are two ways to improve the accuracy. The first is
to use position averaging. A receiver capable of position averaging takes many readings
while stationary and averages them. In this way the position to 3 meters can be
obtained. This may be sufficient for many sampling situations. Two other ways to obtain
more precise positions are to use either a wide area augmentation system (WAAS) or a
differential GPS (DGPS)-capable receiver.
The WAAS methodology uses ground stations to correct signals received from
satellites, and a corrected signal is then broadcast by satellites. When a receiver capable
of accessing the WAAS system uses this information the variability in the accuracy of a
site position is less than 3 meters. The Federal Aviation Administration (FAA) and the
Department of Transportation (DOT) are developing this system, which is available
without charge to any GPS unit capable of receiving the signal and making use of it. The
WAAS is limited to North America and to areas that do not have obstructions that
interfere with the signal.
The second way is to use DGPS. It is similar to WAAS in that it uses corrected signals.
A receiver capable of DGPS is necessary. The use of DPGS can increase the accuracy to
2 cm. Obtaining DGPS accuracy using civilian GPS receivers however, requires that a
DGPS site be within range. The DGPS site is an accurately known location that
broadcasts position correction information to GPS units. This information can be used in
real time or after the fact to find the exact location. Real time would be preferable when
the exact place in the field needs to be sampled several times. Postprocessing, finding the
location after taking the sample, and returning to the field office, can also be done and is

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less expensive. If taking a sample from close to a previously sampled site is sufficient,
postsampling DGPS is sufficient. With this capability sampling sites can be determined
with exceptional accuracy.
Global positioning systems and equipment are constantly being upgraded and
improved, thus when deciding on a GPS receiving unit to use, all the latest advancements
in this technology should be investigated, along with best estimates of where the
technology will be in the foreseeable future.
3.15.2. Ground-Penetrating Radar
Ground-penetrating radar is called for when the field history indicates that something
might be buried in the field or when the field has been traversed by armed forces. The
field history is particularly important in determining if something dangerous, such as
explosives, might be buried in the area. Ground-penetrating radar is also indicated if there
is a likelihood that there are buried tanks, cables, pipelines, or drainage tiles. A hole 1
meter in diameter and 1 meter deep was found in a field in which a drainage tile had
broken and soil had been washed in. (Such a situation is called a blowout, even though
soil has been eroded into the tile.) This type of field condition can be hard to see until one
is nearly in it. It is thus extremely dangerous for personnel and equipment. Groundpenetrating radar can show where such blowouts are developing. It can also tell where
drainage tiles are so that they can be avoided during sampling.
Ground-penetrating radar could also be used if the area is suspected of being an
abandoned village or city [13]. In this case it would help determine areas under which
tunnels and caves are located, and thus needs special attention when sampling. Tunnels
and caves can collapse during sampling and trap and even kill personnel, and they thus
represent a hazard to sampling personnel and equipment.
3.15.3. Remote Sensing
Remote sensing in the sense of pictures taken from airplanes or satellites can be valuable
in locating underground features. These are often visible as differences in either the type
or the growth of vegetation. Such pictures can help to determine the sampling pattern that
will be the most useful in a particular field. It can also be useful in showing the
differences in the field before and after the sampling and remediation activities [14].
There is a great wealth of remote sensing information available from the U.S.
government. Much of this comes from NASAs Earth Observing System (EOS). There is
also an Earth Resources Observation Systems (EROS) data center, which specializes in
land processes. Other areas of the environment are covered by other organizations. All
these organizations and their data are brought together in the Distributed Active Archive
Center (DAAC). Much of this information is free or available at a nominal cost [1417].
3.15.4. GIS
Will a GIS system be used and how will it be used? It is a powerful system that can be
very helpful in relating data from different sources. Water movement through soil

Field sampling

78

combined with topography, soil type, and contaminant concentration can be combined on
one map of the field. This combined picture produces an informative map of the area
[18]. The most common computer software used for GIS is called Arc View. There is
other software that will do the same things, and all should be investigated before deciding
on a system to use. Note that even if you do not intend to start your own GIS you may
need some or all of the software to view and work with GIS produced by local, state, and
national governments.

3.16. MODELING
Data collected during sampling, or obtained by analysis of samples or from other sources
will be useful in building a model of the field and how it will react in the future. We can
think of this as a model of the field before sampling is started. It can also be a dynamic
model that will allow calculation of the expected future characteristics of the field. These
models can be very effective in explaining what is happening, in deciding where to
sample, what to analyze a sample for, and what type of follow-up sampling will be
needed.
Modeling requires a model. This can be a simple physical model or a complex
computer simulation. A physical model can provide information about many aspects of
the field but will have limited predictive capability. A complex computer simulation can
be used to predict the course of the work and will also allow changes in the inputs to
explore various situations that may occur in the future. It will also allow changes in the
model as more data become available.
Modeling is another component of the sampling plan that needs to be explored at this
time.

3.17. PERMITTING
In many instances it will be necessary to have permits for a sampling and remediation
plan. These will generally not be needed when sampling farm fields for such things as
plant nutrients. Sampling for toxic or dangerous materials or other situations may require
permits, however. Permits can be of many different kinds; earth disturbance, erosion and
sedimentation control, water obstruction and encroachment, and various permits
associated with landfills are a few examples of activities that may require a permit.
Permitting is a state activity, thus different states require different permits. One state may
require a permit for an activity while another does not. It is best to go to the state or local
Environmental Protection Agency office and check to see what may be needed in this
regard.

3.18. RESOURCES
Commercial and governmental sources of the equipment, supplies, computer software,

Presampling

79

and so on, mentioned in this chapter are given in Appendix B. Many times the place to
start the search for companies is at their Web site.

3.19. CONCLUSIONS
Once all the above information is obtained and all the decisions are made it is still not
time to start sampling. The needed equipment must be purchased and brought to the field
office. A laboratory and storage area must be prepared. Sample handling and
transportation procedures need to be written down, and a chain of custody protocol
developed and appropriate procedures for its implementation decided upon. With the
above information a detailed safety plan for sampling the field can be prepared. No
sampling can begin until all the safety precautions and equipment have been obtained and
everyone knows how to use them.
At this point a preliminary sampling plan can be put together. It should include plans
for transact sampling and detailed sampling. (See Chapter 5.) It is good to keep in mind
that during most transect sampling too few samples are taken. For this reason one should
err on the side of too many samples during transect or preliminary sampling.

QUESTIONS
1. Describe the characteristics of a project notebook.
2. What types of information can be obtained by walking around the outside of a field
in relationship to the sampling to be done?
3. Make a list of the types of information that one should obtain about a field when
preparing a summary of its history.
4. What two soil characteristics may have a pronounced effect on the type of sampler
used in sampling a field?
5. What three basic types of samplers are there? Explain where each might be used
most effectively.
6. What two pieces of safety equipment are most important to have in the field and at
the sampling site?
7. What kinds of statistical tests of data will be needed in analyzing sampling and
analytical results?
8. Explain why GPS is essential in obtaining accurate and repeatable sampling results.
9. Explain the following abbreviations. (Do not hesitate to use other chapters in your

Field sampling

80

explanation.)
(a) GPS
(b) GPR
(c) GIS
(d) EROS
(e) Remote sensing
10. Describe the characteristics of a field office, laboratory, and storage area. Why is it
a good idea to have the sample storage area separate from other rooms?
11. What advantages do DOQQs have over other types of photographs or maps?

REFERENCES
1. Kanare HM. Writing the Laboratory Notebook. Washington, DC: American Chemical
Society, 1985.
2. Palmer RC. The Bar Code Book: Reading, Printing, and Specification of Bar Code
Symbols. 2nd ed. Peterborough, NH: Helmers, 1991.
3. National Mapping InformationDigital Orthophoto Program. United States
Geological Survey. http://www.usgs.gov/. Look for DOQQ.
4. Ramos B, Miller S, Korfmacher K. Implementation of a geographic information
system in the chemistry laboratory: An exercise in integrating environmental analysis
and assessment. J Chem Ed 2003; 80(1):5053.
5. MrSID GeoViewer. Lizardtech software. http://www.lizardtech.com/download/.
6. Wagner G, Desaules A, Huntau H, Theocharopoulos, S, Quevauviller P.
Harmonisation and quality assurance in pre-analytical steps of soil contamination
studiesConclusions and recommendations of the CEEM soil project. Sci Total
Environ 2001; 264:103117.
7. The Use of Historical Data in Natural Hazard Assessments. Glade T, Albini P, Francs
F, eds. Boston: Kluwer Academic, 2001.
8. Huang CC, OConnell M. Recent land-use and soil erosion history within a small
catchment in Connemara, Western Ireland: Evidence for lake sediments and
documentary sources. CANTENA 2000; 41:293335.
9. Sastre J, Vidal M, Rauret G, Sauras T. A soil sampling strategy for mapping trace
element concentrations in a test area. Sci Total Environ 2001; 264:141152.
10. Fisher MM, Brenner M, Reddy KR. A simple, inexpensive piston corer for collecting
undisturbed sediment/water interface profiles. J Paleolim 1992; 7:157161.
11. Reynolds EM, Randle Q. Pocket Guide to Safety Essentials. Washington, DC:
National Safety Council, 2002.
12. Letham L. GPS Made Easy. 12th ed. Seattle: Mountaineers, 2001.
13. Conyers LB, Goodman D. Ground-Penetrating Radar: An Introduction for
Archaeologists. New York: Rowman & Littlefield, 1997.
14. Lunetta RS, Elvidge CD. Remote Sensing Change Detection: Environmental
Monitoring Methods and Applications. Chelsea: Ann Arbor Press, 1998.
15. Earth Observing System. NASAGoddard Space Flight Center.
http://eos.gsfc.nasa.gov/.
16. Earth Resource Observation Systems (EROS) Data Center. USGS.

Presampling

81

http://edcwww.cr.usgs.gov/.
17. GSFC Earth Sciences (GES) Distributed Active Archive Center. NASA,
http://xtreme.gsfc.nasa.gov/.
18. Korte GB. The GIS Book. 5th ed. Albany, NY: OnWord Press, 2001.

4
Safety

Field sampling is not a leisure time activity.

Safety must be practiced at all times.
Safety equipment must be used.
Clothing must be appropriate to the hazard.

A safe working environment is not an accident; it requires thought and work. Safety is
good from human, business, and economic perspectives. To realize these benefits a
number of things need to be done. First, safety information and physical resources are
identified or found. The types of fields to be sampled must be identified, along with the
type and concentration of the contaminants they contain. Once this is known, personnel
protection can be planned. Additionally, off-field and environmental protection must be
considered. When this is all brought together, a safety plan including the use of a
chemical hygiene plan (CHP), material safety data sheets (MSDS), and other resources
such as the Merck Index can be incorporated.
Safety can be, and often is, viewed as an unwanted expense. In reality it always results
in enormous savings. One key worker not doing his or her job for half a day can cause
serious delays in completing a sampling exercise. Often an accident happening to only
one worker will involve other workers as they help care for or evacuate the injured
person. In this case the work output of several persons is adversely affected. Add to this
the cost of transportation and medical treatment, and the expense can be quite a burden.
Even if everything is covered by insurance, repeated use of the coverage will result in
the increasing cost of insurance. From all ways of assessing accidents they are always
costly. This is a cost that need not be borne if personnel observe proper safety procedures
and precautions while on the job.
With all this said, Who actually suffers when an accident occurs? The answer is
always the injured worker. The company suffers because of the lost work time, the need
to replace the worker, the increase in insurance costs. But, truly, in the end the only one
who really suffers is the injured worker. They suffer due to the injury itself, the recovery
time, the possible loss of a limb, the loss of wages, the suffering the family has to endure,
and the possible loss of the job. For this reason workers need to always use the proper
personal protective equipment (PPE) because they are the most important reason to
protect themselves from possible injury [S.Ullom, Ullon Safety Resources, Inc.,
personal communication. (See Appendix B.)]

Safety

83

4.1. AREAS OF SAFETY CONCERN

There are five areas of safety to consider in sampling a contaminated field. The first
consideration is the safety of the personnel doing the sampling. What kinds of hazards
will personnel likely be exposed to? Will the fields contain fumes from gases, liquids, or
solids? Will they encounter flammable, toxic, or corrosive liquids? Will dangerous solids
be present? Answering these questions will allow for the development of good safety
measures. The second part of this is to ask, Do the personnel have the training and
expertise to be in the field and work with the components there, including sampling
equipment, without contaminating themselves and others?
A second essential component in answering the above questions is to consider the level
of contamination likely to be encountered. Areas containing high levels of contamination
are more dangerous than less contaminated areas. These areas require more exacting
safety precautions, and equipment and safety must be more carefully thought out. In no
case, however, no matter how safe or how uncontaminated a field seems, should safety be
taken for granted.
The United States Occupational Safety and Health Administration (OSHA) standard 29
CRF 1910.132 contains a requirement for a prework personal protection equipment (PPE)
assessment. This consists of filling out a personal protective hazard assessment
worksheet, such as that shown in Table 4.1. This sheet needs to be filled out and signed
by the person doing the sampling to make sure that he or she fully understands the safety
requirements. Note that not all hazards and not all PPE will be needed with

TABLE 4.1 An Example of a Hazard and Personal Protection Worksheet

Hazard and PPE* Assessment Work Sheet

Field Location:
Date, Name and Signature of Individual Completing Assessment
Anticipated Hazards Associated with Sampling. Check all that apply.
[] Chemical

[] Compression

[] Respiration

[] Impact

[] Atmospheric

[] Splash

[] Penetration

[] Noise

[] Light(optical)

[] Electrical

[] Engulfment

[] Laceration

[] Heat/Cold

[] Radiation

[] Bloodborne

All PPE* required for safe sampling

Head
Eye
Ear
Respiratory

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84

Hand
Clothing
Chemical Protective Clothing
Foot
Electrical
Other
Comments
* Personal Protective Equipment

all sampling environments. A thorough assessment of hazard and protection needs for
each field must be done, however.
The third consideration is the field itself and the people, animals, and plants around it.
Is there a possibility that sampling will cause any movement of contamination off the
field? This might be as solids tracked out by wheeled vehicles or as dust brought into the
air by various sampling activities.
The fourth is to make sure that contamination cannot move off the site during
nonworking hours. The field must be protected from water and wind erosion. Also, are
underground areas and water supplies safe from contamination? Will sampling activities
allow contamination to move into uncontaminated areas? The fifth is the safety of the
personnel transporting and analyzing the samples obtained. If samples are in appropriate
containers contamination of people and their surroundings during transportation should
not occur. Laboratory personnel must be apprised of the expected contaminants in the
samples, however, so that appropriate safety precautions can be taken.

4.2. SAFETY RESOURCES

Information about safety in general and in sampling situations can be found in various
locations. Often topics relating to safety in environmental work are referred to as
environmental health and safety (either as EHS or EH&S) [1]. These are key words when
investigating specific safety concerns. The National Safety Council Web site has many
publications that can be helpful in any situation [2]. OSHA is another good source of
safety information, along with information about chemical hygiene plans [3]. The U.S.
Environmental Protection Agency (USEPA) also has information about safety,
particularly in terms of environmental contamination [4]. Safety information in
relationship to the dangers of a particular chemical can be found in material safety data
sheets, better known as MSDS sheets [5]. Additional safety information, including use
and toxicity information about chemicals, can be found in the Merck Index [6].
There are consultants and consulting organizations that can help with developing safe
working conditions. In addition they can help in making sure that all government
organization safety rules are followed. This can include ten 30-hr safety courses, which

Safety

85

are also known as outreach training programs and the 40-hr (HAZWOPER) courses
associated with safety and safe sampling issues. Examples of the types of topics covered
in these courses are given in Table 4.2. In addition to these programs most states

TABLE 4.2 Examples of Topics Covered in the 10-, 30-, and 40-Hour Courses

10-hr course

30-hr course

40-hr course

Walking and working

surfaces

Walking and working surfaces Principles of safety

Means of egress

Means of egress

Planning and organization

Fire protection Material

handling

Fire protection Hazardous

materials

Preparation for field work Chemical

hazards toxicology

Electrical, lockout/tagout Personal protective equipment Monitoring instrumentation, confined

space
Machine guarding

Confined spaces

Trenching and excavation

Confined space

Materials handling

Medical surveillance

Bloodborne pathogens

Electrical machine guarding

lockout/ tagout

Personal protective equipment, levels

of protection

Hazardous materials

Welding, cutting, brazing

Fire protection

Personal protective
equipment

Pathogens

Decontamination procedures

Record keeping

Hazard communication

Drums/containers sampling and

packaging

Hazard communication

Record keeping Safety and

health

Site emergencies

Note: The 40-hr course will only be found designated as Hazwoper. These are general topics
covered and are not intended to represent any actual course content.
Source: Ref. 2.

have free safety consultation programs, a list of which can be found at www.OSHA.gov.
While these are excellent sources of information, nothing can replace careful thought
and thorough preparation when working in hazardous situations. For example, spilling a
quantity of liquefied gas, even nitrogen, can quickly fill a room or enclosed space with
that gas and thus cause suffocation. If the gas is flammable an explosive situation can
also quickly develop. For this reason knowing only the toxicity or the flammability of a
gas is not enough. The question becomes what will happen if a spill occurs and what
needs to be done to protect people if this happens.
Another example would be spilling liquids. A volatile liquid spill can cause the same
hazards as described above; that is, the fumes may be flammable and can thus cause an
explosion if a source of ignition is present. On the other hand, spilling an acid may cause

Field sampling

86

damage to the surface on which it is spilled, produce no fumes, and cause no other harm.
Some acids and bases, however, such as hydrochloric, nitric, and acetic acids and
ammonium hydroxide can release fumes that can be overpowering. If acid is spilled on a
reactive metal, hydrogen gas can be released and cause a dangerous or even an explosive
situation to develop.

4.3. BASIC SAFETY

At the very start of a project all personnel need to be instructed in basic safety procedures
and practices. This may mean a basic Red Cross first aid course or in-house instruction,
including cardiopulmonary resuscitation (CPR) instruction. First aid supplies should
provide gloves and CPR shields to protect first aid givers from bloodborne pathogens.
Basically all personnel need to know first aid because it is not possible to know
beforehand who will be the person needing help [7]. General safety rules for all situations
are given in Table 4.3 [8].
Along with this table should go emergency phone numbers. These must include life
squad, fire department, hospital, hazmat, sheriff, police, state EPA, and other appropriate
entities. Communications must be set up to facilitate contacting the appropriate
organization without delay. Every person involved in field sampling must have easy
access to such communication.

4.4. SIGNAGE
Safety signs relating to safety concerns in and around the field and field office,
laboratory, and storage areas must be installed. It is not sufficient to simply have signs
placed in appropriate areas; workers also need to know

TABLE 4.3 General Safety Rules

Know basic first aid.
Do not sample alone.
Assess and select the proper PPE.
Know what types of materials are being sampled.
Have safety equipment, including fire extinguishers, and first aid nearby.
Know where help is and how to get you to it and it to you.
Store samples appropriately and away from food.

how to read the signs. In Figure 4.1 the sign illustrated at the top left is an example of a
hazard warning label. This indicates the general type of hazard present.
The label on the top right is an example of a hazardous material identification system

Safety

87

label (HMIS). This label not only provides the types of hazards involved but also the
severity of the hazard. The numbers can range from 0 to 4, indicating an increasing level
of hazard in each of the four small diamonds. The specific type of hazard is indicated by
both the position and the color of the interior diamond: the upper left diamond is blue and
is an indicator of the health hazard [3]; the upper right is red and is fire hazard [2]; the
lower right is yellow and indicates the reactivity; and the lower white

FIGURE 4.1 Examples of safety signs. Upper left: hazard warning label; upper
right: hazardous material system label (see also Figure 4.2), and
bottom: shipping label. Next page: explanation of label.

Explanation of Hazardous Material System Label (cont.)

Diamond

Hazard danger designations

1None

Health hazard hazard Blue (#3)

2Mild
3Extreme
4Deadly

Field sampling

88

4. Flash point below 23C (73F)

3. Flash point below 38C (100F)
Fire hazardRed (#2)

2. Flash point below 93C (200F)

1. Flash point above 93C (200F)
0. Does not burn
4. May detonate
3. Shock and heat may detonate

ReactivityYellow (#1)

2. Violent chemical change

1. Unstable when heated
0. Stable
OxidizerOXY
AcidACID

Specific hazard

AlkaliALK
CorrosiveCRO
Water reactiveW

diamond contains special hazard information as needed. Also given is specific

information contained in each diamond. Figure 4.2 shows another HMIS and its
associated safety labeling.
The bottom sign on p. 97 is an example of a shipping label. These are typically seen on
the sides of trucks and the outsides of shipping boxes. In this case the label tells the
handler that the material in the container is an oxidizer. If field samples have some
particular component that would be of concern if the package were dropped or if spilling
the contents would cause a hazardous situation, there should be a label on the box alerting
people handling the box.
Weather emergency plans and signs also need to be taken into consideration. Signs
giving information about weather emergency signals, emergency exits, and routes to safe
locations need to be in place. All workers must be aware of these signs and their
meaning. The location of safe areas must be easy to determine and get to.
There are many other types of safety signs. Some of these are used to show the location
of safety equipment, including safety showers, eyewash stations, safety equipment, and
danger zones. It is advisable to make liberal use of safety signs [2].

Safety

89

FIGURE 4.2 Another hazardous material identification system. Shades of gray

indicate background colors.

Key for Personal Protective Equipment

A. Safety glasses
B. Safety glasses, gloves

G. Safety glasses, gloves, vapor respirator

H. Splash goggles, gloves, chemical apron, vapor
respirator
C. Safety glasses, gloves, chemical apron I. Safety glasses, gloves, dust and vapor respirator
D. Face shield, gloves, dust respirator
J. Splash goggles, gloves, chemical apron, dust
and vapor respirator
E. Safety glasses, gloves, dust respirator K. Air line, hood or mask, gloves, full chemical
suit, boots
F. Safety glasses, gloves, chemical apron, X. Ask supervisor
dust respirator
Additional information
Route of entryentry of chemical into bodyingestion, inhalation, absorption
Health hazardeffects of overexposureacutely toxic, corrosive, or irritant
Physical hazardcharacteristics which make chemical hazardousexplosive, oxidizer
flammable
Target organsorgans affected by overexposurecentral nervous system, liver, kidneys

4.5. PERSONNEL EXPOSURE

4.5.1. Gases
Both compressed and liquefied gases are commonly found in the field. Compressed
gases, such as nitrogen, oxygen, acetylene, propane, and helium, are common in a variety
of agricultural and manufacturing facilities. If the top of one of these tanks is broken off,

Field sampling

90

the tank turns into a missile capable of penetrating cement block walls. For this reason
protective caps are placed on the tank during storage and transport. The tanks are secured
to some substantial cart or building structure when in use. Some gases, such as acetylene,
can ignite when escaping from a metal orifice and thus are of particular concern.
Acetylene and propane escaping from a tank can produce a flammable and potentially
explosive situation. Oxygen supports combustion, which means that both escaping
oxygen or oxygen-rich environments will support oxidation and burning where otherwise
it might not occur. Even inert gases such as nitrogen and helium can produce dangerous
situations. When released in large volumes these gases can replace all the oxygen in an
enclosed area, causing suffixation. Compressed gas tanks encountered during field
sampling must be treated with extreme caution.
Some gases, including those discussed above, are commonly liquefied under pressure
and are stored and transported in this form. Some are kept in insulated containers, while
others are in simple pressure tanks. These liquefied gases pose some of the same risks as
compressed gases in cylinders, and although they are not commonly under as much
pressure as compressed gas, dangerous leaks can develop in the tanks and cause serious
safety risks. A different hazard occurs when these liquids are spilled. One mole of liquid
nitrogen, 14 g, will occupy a volume of 22.4 liters when it warms up and becomes a gas.
The liquid can rapidly change to a gas, replacing oxygen and suffocating any people and
animals present.
In some cases liquefied gases are a fire hazard, and some are toxic or otherwise
hazardous. Flammable gases are colorless and must build up to a certain level before they
can burn or more likely explode. Liquid propane will be converted to a gas when pressure
is released and it will produce an explosive mixture with air. Unfortunately once these
gases start burning, the fire is hard to put out. Liquid ammonia will become a cloud of
ammonia gas, which is choking and toxic and will overcome a person trapped in the
cloud. All visible gasesthat is, gases that have colorare toxic; however, the reverse is
not true. Many colorless gases can be toxic, however.
Fumes originating from a monitoring well can also be dangerous. They may be toxic or
flammable, and so appropriate precautions must be taken at all times when opening a
monitoring well.
4.5.2. Liquids
Liquids can either be pure organic liquids, mixtures of organic liquids, inorganic liquids,
and solutions of organic and inorganic compounds in water. These liquids may be volatile
or nonvolatile, and can release strong fumes and/or be caustic. Volatile liquids can fill an
area with fumes that can burn. In this case the fire will be fed from the pool of liquid, and
so covering the pool with an appropriate flame extinguisher can stop the fire.
Fumes originating from a volatile liquid are heaver than air and can fill and travel
through low areas. If they contact a source of ignition, the flame can travel back to the
source of the fumes and cause a large fire or explosion. When confined in a small space
they can cause the suffocation of persons entering these spaces.
Many liquids present hazards of other types. Acids and bases frequently come as
solutions of gases in water. Most common are the mineral acidshydrochloric, nitric,

Safety

91

and sulfuricand the base ammonium hydroxide. When concentrated solutions of these
are opened hydrogen chloride, nitrogen oxides, sulfur oxides, and ammonia gas are
released. Because of this spills of these concentrated acids and bases must be treated with
extreme caution. In addition to the fumes they contain, these acids and bases can react to
release both toxic and flammable fumes. Diluted strong acids and bases often do not have
a strong smell but must still be treated with caution, although they are not as dangerous.
There are many other caustic and/or volatile and flammable liquids and solutions that
can be dangerous and thus must be handled with caution. Organic amines are bases and
have a strong smell of fish. All toxic organic amines must be treated as if they can be
absorbed through the skin, because many of them can. It cannot be guaranteed that
amines will not penetrate rubber or synthetic gloves. (More information about gloves is
given below.) For this and general safety precaution reasons amines should always be
treated with the utmost caution.
Some inorganic and organic liquids and solutions are unusually dangerous. Some, such
as solutions containing hydrides, will spontaneously ignite on exposure to air. Some
organic solvents, such as diethyl ether (often called ether), will ignite if it is dropped on a
hot hotplate. (No spark is necessary.) Under anaerobic conditions methyl mercury may be
produced, which can pass through protective gloves and cause death. There are many
other examples that people doing field sampling need to be aware of. This is why a
history of the field is so important.
4.5.3. Solids
Often solids are easier to deal with because they can simply be picked up, put in
appropriate containers, and then safely handled. There are numerous solid chemicals,
however, that produce dangerous situations. Phosphorus spontaneously ignites and burns
when exposed to air, and the fire is very hard to extinguish. Alkali metals such as sodium
react with water, releasing hydrogen. The reaction is so vigorous that sparks are
produced, setting the hydrogen on fire. Metal hydrides, which can come as solids as well
as the solutions mentioned above, release hydrogen when they become wet and can
produce explosions.
4.5.4. Unknown Materials
Extreme caution in handling any kind of unknown material is always prudent. When
sampling a field it is also always essential to follow all safety precautions because it is
not possible to tell when a sampler, handheld or machine-driven, might encounter and
break open a container of hazardous chemicals. This can happen in an area that
apparently has never had any waste dumped on it and is far from any population center. It
can also happen so quickly that fumes can overcome persons in the area.
Dangers associated with all of the above potential contaminants are compiled in Table
4.4.

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92

TABLE 4.4 Sources of Personnel Contamination

Gases

Permanent gasesmay be toxic, flammable,

explosive, or all three.
Compressed gas Gas can escape, sometimes with autoignition,
slowly or explosively from compressed gas
containers. Gases may be toxic, explosive,
flammable, or all three.
Organic liquids May be toxic or produce flammable gas or
explosive situations. All three can be produced at
the same time, especially when the liquid is heated.
Hot metal can cause ignition. Some organic
compounds can be absorbed through the skin.
Inorganic
The most common inorganic liquid is mercury,
liquids
which is toxic. It and its compounds may be
absorbed through the skin. Mercury fumes are also
toxic.
Inorganic
Containers of concentrated solutions may release
liquids and
gas when opened. Contact of solutions with other
solutions
chemicals may release toxic, explosive, or
flammable gases or all three. Contact with skin can
cause burns.
Organic and
Can sublimate, releasing flammable, toxic,
inorganic solids explosive gases. May be absorbed through the skin.
Unknown
Unless otherwise known, all unknown materials
gases, liquids, encountered are considered to fall into one of the
and solids
above categories and may be a mixture of two or
more of them.

4.6. PERSONNEL PROTECTION

Sampling a field involves entering it with personnel and equipment, and both need to be
protected from contamination while the sampling is being done. Once sampling is
completed personnel and equipment exiting the site need to be decontaminated [9]. This
means washing, and thus an appropriate area needs to be constructed for cleaning both
personnel and contaminated clothing and safety equipment. Washwater and other
contaminated materials need to be cleaned or disposed of in an appropriate manner to
prevent the spread of contamination outside the field. This is especially true for shoes or
shoe coverings.
Appropriate safety equipment must be available at both the field office and in the field.
Table 4.5 provides a list of common safety equipment that should be available. In
addition to these items there may be specialized safety equipment needed for unique
sampling situations. Careful thought about the sampling situation and the types of

Safety

93

materials to be handled will be needed to provide a safe working environment and to

have all potentially needed safety materials readily at hand.

TABLE 4.5 Standard Safety Equipment

Item

Description

First aid kit

Bandages (including liquid bandages), gauze pads, burn ointment, rubber gloves,
antiseptic, tape, and items to prevent exposure to bloodborne pathogens

Eyewash

An eyewash station to provide 15-min flushing and portable eyewash bottles

Eye
protection

Safety glasses and goggles

Ear
protection

Noise-suppressing ear plugsa minimum noise reduction provided by the ear

protector must be able to reduce noise to the ear to 85 decibels

Breathing

Gas mask with assorted cartridges

Head
protection

Hard hat

Gloves

Both work and rubber or chemical-resistant gloves

Water

Enough water to allow for emergence washing of exposed body areas

Personal
monitors

Air monitors for exposure to fumes

Oxygen

Compressed tank of oxygen

4.6.1. Do Not Sample Alone

Do not sample alone. No matter how safe a field looks, if you are not familiar with it it is
unsafe to sample alone. In addition to soft areas and unseen holes in the field there is the
danger of stumbling onto an area containing noxious fumes. Sampling or monitoring
wells can also often contain unpleasant surprises when uncovered. There is also the
possibility of encountering animals, such as poisonous snakes, which can be quite
dangerous. Sampling in pairs can be faster than sampling alone, and thus this does not
represent a large additional expense.
When additional samples are later taken from the same site at the same sampling
locations sampling alone may be acceptable. An open field with an unobstructed view of
the surroundings and no indication that the field was heavily contaminated might be such
a field. Even under these conditions, however, it is a good idea to have ready
communications available.
4.6.2. Goggles
Almost all surfaces of the body need to be covered during field sampling, and this is
particularly true of the eyes. Goggles that protect all around are preferred over visitor-

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type glasses (See Figure 4.3.) Protective eyewear is especially needed in areas that are
heavily contaminated or are suspected of being heavily contaminated. They are also
needed when working with drilling or powered sampling equipment.
Workers have many reasons and excuses as to why they should not have to wear safety
glasses or goggles. Often the complaint of workers is that they cannot see through them.
After wearing them for a couple of hours, however, they often forget to take them off
when they leave the work

FIGURE 4.3 Safety goggles (left) and visitor-type safety glasses (right).

area. Another argument is that the person will not spill anything and so there is no reason
to wear eye protection. In this case the counterargument is that they cannot say the same
thing about the people with whom they are working.

Goggles in the Laboratory

During the past 30+ years I have taught students laboratory skills and safety.
In that time I have never had a student lose his or her eyesight. For the whole
30+ years students constantly complain about safety goggles. The most
common complaint is that they cannot see with them on. After several
laboratory sessions, however, students often forget they are wearing goggles
and forget to take them off when exiting the laboratory!
Reminding workers and students to wear goggles is a constant chore. Even
after 3 years of reminders I will walk into a laboratory and find students not
wearing their goggles. I never allow anyone to work or even be in the
laboratory without goggles.
Workers have two valid complaints about wearing goggles. One is that in hot weather
they fog up. The second is that they leave marks on their faces. Fogging is a problem in
hot, humid conditions. Antifogging goggles are available, and workers can leave the
work area and remove the goggles and allow them to air out if need be. If marks are left
on the face then the straps are not adjusted correctly. Goggles need only be tight enough
to prevent liquids and solids from getting into the eyes; they generally do not need to be
tight enough to leave marks.

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Protective glasses or goggles must have shatterproof lenses. They must protect the eyes
not only from the front but also from the sides, bottom, and top. It is surprising how often
liquids and solids can splash and bounce around in such a way that they enter the area of
the eyes from the side, top, or bottom. Workers should be encouraged to maintain their
goggles, which means keeping them clean and sanitary at all times. Dirty lenses do
obstruct vision, and dirty sides may induce irritation and dermatitis. Cleanliness is a must
for the productive use of safety goggles.
4.6.3. Face Masks and Respirators
Whether in enclosed areas or open fields, very dusty situations call for the use of simple
filtering dust masks. These are made of paper and cover the nose and mouth. Dust masks
are designed to simply filter dust particles out of the breathing air; they must not be used
in situations in which gases or fumes are present because they will not protect personnel
from these dangers.
In some situations the nose and respiration system must be protected from toxic,
overpowering, or otherwise hazardous gases. In these cases a respirator, which can come
in two forms, is required. One covers just the nose and mouth and is called a half mask
respirator. (See Figure 4.4.) The other covers both eyes, the nose, and the mouth and is
called a full face mask. Both types come with a variety of filters suitable for different
situations. There are filters for organic vapors, acid vapors, ammonia and amines, dust,
and various combinations of these. In all cases it is essential that they be adjusted to fit
properly. They must also be checked for leaks before they can be effective in protecting
the wearer.
In agricultural sampling respirators should always be readily available. Anhydrous
ammonia, which is a gas at standard temperature and pressure

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FIGURE 4.4 Half mask respirator: Aabsorbing cartridge/filter; and Bbody

of respirator.

(STP),* is used as a fertilizer. It is stored, transported, and applied in a liquid form from
pressurized tanks. A leak from any pressurized tank is a potentially lethal situation, and
anhydrous ammonia is no exception. Ammonia fumes are choking. They cause eyes to
water, and can quickly overcome workers. A complete face-covering gas mask designed
for ammonia must be available when handing ammonia and must be worn when
contending with ammonia leaks
Gaseous ammonia reacts with water in air and soil to form ammonium hydroxide,
which is a strong base. Highly concentrated ammonium solutions continuously give off
ammonia gas. Because of these character-istics it is possible to find pockets of ammoniasaturated water in soil after a spill. Disturbing these pockets can release enough ammonia
gas to overcome a person sampling the field. Many other situations that may release
noxious gases can be encountered in field sampling, and this makes having a respirator
readily available essential for safety in field sampling.
* Standard temperature and pressure is 0C (32F) and 101 kPa (1 atmosphere).

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4.6.4. Gloves
There are two general types of gloves, those designed to protect from heat and abrasion
and those designed to protect from chemicals. When handling chemicals or
environmental samples chemical protective gloves are used. These are either the familiar
surgeons rubber gloves or a synthetic rubber glove often reputed to be more resistant to
chemicals. These gloves are not abrasion-resistant, and care needs to be taken to prevent
tears and holes, which render them totally ineffective. A second type of rubber glove is
the household type. This glove is more abrasion-resistant and often bulkier, making it
hard to handle equipment. It is not intended to be used to protect the wearer from
chemicals.
There are several important things to remember about chemically protective gloves.
Some chemicals are known to penetrate both the gloves and the skin, and enter the
bloodstream. For instance, it is known that amines and methyl mercury will penetrate
rubber gloves, penetrate the skin, and enter the bloodstream. No type of rubber or
synthetic glove can claim to give 100% protection from all chemicals. Indeed, it is
difficult if not impossible to determine which chemicals can pass through a glove and
onto or into the skin. Using gloves with a sense of impunity is dangerous, and hands
should always be washed thoroughly after handling chemicals or contaminated samples,
regardless of the type of gloves used [10].
4.6.5. Other Protective Clothing
In all sampling situations one must wear clothing that covers the body. As the severity of
the pollution increases, however, the protectiveness of the clothing must increase. Long
pants, a work shirt, and socks and boots are sufficient for agricultural field sampling for
plant nutrients. For a highly contaminated industrial site a moon suit with selfcontained breathing filters or tank of air is a must. The material of the suit must be
resistant to the types of chemicals, acids, bases, solvents, and volatile organic carbons
(VOCs) likely to be encountered in the contaminated field [11].
4.6.6. Decontamination
In agricultural situations, including soil sampling, clothing can be cleaned by normal
means. In fields contaminated with herbicides, pesticides, and other hazardous chemicals,
however, arrangements must be made for decontaminating persons, clothing, and
equipment at the field location. It is not responsible to allow workers to wear or carry
contaminated soil, water, clothing, or tools out of the field [9].
4.6.7. Bleeding
In many societies bleeding is considered bad and must be stopped immediately. In any
situation in which chemical or biological entry into the wound is likely, bleeding is good
because it washes out the affected area. In this case we are talking about a few milliters of
blood, not liters. The wound must also be thoroughly washed with soap and water,

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however. This is similar to the prudent use comments below. Once washed a protective
covering can be applied.
A first aid kit is an essential piece of safety equipment. While safety kits contain a
large variety of high-quality bandages and other medical supplies, I would highly
recommend making sure that they contain at least one liquid bandage kit. This is a
Superglue-type material that is spread on a wound. It holds the sides of the cut together,
seals the wound, and sterilizes itall without pain. This type of bandage can keep cuts
stabilized and in good condition until proper medical help can be arranged.
4.6.8. No Food or Drink
No food or drink should ever be allowed in the field to be sampled, in storage areas, or in
the laboratory. This is to make sure that no one ingests an injurious component. It is all
too easy to lay a sandwich on a contaminated counter and then pick it up and eat it or to
drink out of a container thinking it contains water only to find that it contains or
previously contained arsenic solutions. Do not allow even unopened food or drinks in any
of these areas. Also, do not allow empty food containers to be brought into these areas.
Seeing a food container in an area is tacit approval for eating in that area.
In addition to preventing contamination of food with the sample, contamination of the
sample with food is prevented. Food contamination of field samples can cause a lot of
confusion in the laboratory and in the interpretation of laboratory analytical results.
4.6.9. Toxic Fumes
Toxic fumes can be encountered in any situation. Most often, however, of primary
concern is a person being caught in a confined space and overcome by fumes. This could
happen in the bottom of a soil pit as well as a closed room. Even if the top is open, any
confined space is of concern. It is also possible to become exposed to toxic fumes when
opening a well casing or by hitting a pocket of gas trapped in soil. All wells should be
suspect in terms of containing toxic gases.
The first thing to do if a person is exposed to any fumes is to remove the person to
fresh air. This means outside the building or enclosure and away from the source of the
fumes. If the person continues to show signs of exposure, he or she should be taken to a
hospital.
4.6.10. Prudent Use
All chemicals (and some things not thought of as being chemicals, such as water) can be
dangerous if used inappropriately. A person can die from drinking too much water. Also,
many people drown each year. Observing prudent use and proper safety precautionsnot
swimming alone, for instanceshould always be followed.

Prudent Use of Chemicals in the Laboratory

At the beginning of a laboratory exercise I was telling my students that the

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chemicals we would be using that day were not particularly toxic or

dangerous. A student spoke up and said that if she drank a beaker of one of
the chemicals she would die. I answered that that was true but that my
comments were intended to be understood in relationship to using the
chemicals in the manner and amounts appropriate to the laboratory exercise
they were to be doing and that in any case drinking in the laboratory is
prohibited!

4.7. MONITORING
Monitoring will be an important component in any field sampling plan. Monitoring will
be of both the environment and the personnel doing the sampling. Methods of monitoring
will be different for each situation.
4.7.1. Environmental Monitoring
Environmental monitoring will involve monitoring both air and water. The air in and
around the field will need to monitored for dust and escaping gases. In many cases these
monitors will not need to be elaborate and may be electronic gas and particle detectors
incorporated into a field weather station. In addition to air sampling water sampling may
also be needed. This will entail installing one or several monitoring wells and sampling
the water frequently. It may also involve sampling surface runoff water if there is
significant rainfall in the area or the area is irrigated.
4.7.2. Personnel Monitoring
Personnel may need sampling devices on their person to measure their exposure to
contaminated materials. This may be as simple as making sure that persons working in a
field do not get contaminated materials on their skin. It may also mean making sure they
are not exposed to harmful vapors or gases.
If exposure does occur the affected part of the body is washed thoroughly with soap
and water. Thoroughly means that water is allowed to wash over the affected area for at
least 5 min. If massive exposure occurs all clothes must be removed from the person
without regard for modestyand the person washed in a shower. The clothes then need
to be disposed of properly or washed thoroughly.
Portable gas sensors are readily available and vary from a simple chemical test to
sophisticated electronic sensors. Indicating badges or tubes filled with indicating
materials are easy to use. Some indicators require air to be pulled or pushed through
them, while others are passive. There are also several types of electronic gas sensors
available. If gas sensors are deemed necessary, then gas mask or respirators, either half or
full face, must also be readily available at all times. Gas masks and respirators come with
a variety of filters designed for various types of gases or vapors, thus the type of filter
chosen must match the types of vapors likely to be encountered.

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4.8. SAFETY AT DIFFERENT FIELD TYPES

There are four types of fields that may need to be sampled. One is the agricultural field,
in which soil or feed is sampled, to determine the level of plant or animal nutrients or
various agricultural chemicals present. The second type is the abandoned industrial or
waste field. Such fields are likely to contain a mix of dangerous or toxic chemicals. The
third is an active industrial field in which a spill or accident has occurred or is occurring.
The fourth situation is where there has been a spill or contamination of water. In all the
situations described below a CHP is essential. Such a plan (see below) involves
developing procedures for the safe handling of chemicals and chemical emergencies [3,
12, 13].
4.8.1. The Agricultural Field
An important safety precaution in sampling agricultural sites is to remember that they are
usually remote from both medical facilities and rescue services. Treatment for any type of
injuryphysical (e.g., falling down and breaking a leg) or chemical (e.g., being
enveloped in a cloud of anhydrous ammonia) thus may be hours away. If you are only 30
min from the nearest rescue squad, it will take them 30 min to get to you and another 30
min to get you to the hospital!
Agricultural sites are often fields being sampled primarily for plant nutrients. Although
such fields are relatively safe (for exceptions see below), there are still some safety
precautions that must be taken. The first is that you should not sample alone. Even on a
farm on which all the surface of the land can be seen it is not safe to sample alone,
particularly if it is the first time sampling the field.
It is usually easy to determine what types of chemicals one is likely to encounter on a
farm. Indeed, the farmer should have MSDS sheets on the fertilizers, insecticides,
herbicides, and so on that he or she possesses and uses. In this situation a limited number
of MSDS sheets is needed. Two words of caution are needed here. There are a
tremendous number of old barns situated on agricultural lands. Many of these were
originally associated with houses that are no longer present. These old barns can contain
all manner of dangerous materials. Unless instructed to sample in and around an isolated
barn, stay away from them. (Also, see the section below about industrial-type situations
on farms.)
Proper clothing, which is capable of protecting the wearer from stickers and brush,
must be worn even if the weather is hot. Good-quality socks and sturdy boots are also
required. Other than that, sunscreen and insect repellent can be used as required by
location and conditions. It is often handy to have a jacket or vest with numerous large
pockets for carrying samples.
In some cases an agricultural sampling situation may involve a farm with animals
(horses, pigs, cattle, goats, sheep) as part of the farming operation. Although farm
animals are domesticated they are not safe to be around, especially if one is not familiar
with handling them. All of these animals are capable of killing, maiming, and in the case
of pigs eating humans. Sampling should never be attempted in fields containing animals

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without the farmers permission and preferably with the farmer present. These same
precautions can be extended to areas in which the person doing the sampling is not
familiar with the animals likely to be present. In this case (e.g., remote wilderness areas,
game preserve parks in Africa), a knowledgeable guide should accompany the sampler at
all times.
Agriculture fields can quickly and seamlessly develop into industrial-type sites. An
unusually high level of nitrogen in a soil sample may be traced back to a leaking tank of
liquid fertilizer. At this point a field sample needed to access plant nutrient levels has led
to an industrial-scale problem of sampling around a large tank of potentially dangerous
chemicals to find the leak.
4.8.2. Abandoned Industrial or Waste Field
As noted above, this might be an abandoned industrial field or a field in which chemical
or other wastes have been discarded, or it may be an active manufacturing plant. Such
fields have similar safety concerns. One of the most important is that large quantities of
concentrated toxic chemicals are likely to be present. These may be above ground and
easy to see. It is equally likely that they are in below-ground storage tanks, however. The
condition of the tanks will probably be unknown and they may or may not be leaking.
Samples from deep in the soil and from monitoring wells thus may be needed.
Toxic chemicals can have a wide range of dangers associated with them, depending on
their characteristics. It thus is not good enough to say that a field contains toxic
chemicals; one must know what type of chemicals are involved. For this reason it is
prudent to consult reference information about the types of chemicals likely to be present.
Such information can be found in MSDS sheets and the Merck Index described below [6].
The situation here is very different from that described above for agriculture because the
full range of possible compounds will not be known.
In this case a large number of chemicals may be involved. For that reason a large
number of MSDS sheets need to be readily available. Also in this situation there are
likely to be surprises; chemicals, tanks, barrels, and so on not previously reported as
being present may be found. From a safety standpoint it is important to be prepared for
any eventuality.
4.8.3. Active Industrial or Manufacturing Field
Sampling in and around active industrial or manufacturing sites should be similar to
agricultural sites in that you should be able to obtain an accurate list of the chemicals
present. The difference is that there will be large concentrations of highly dangerous
chemicals. The proper safety clothing for such a site should be known and must be
strictly adhered to.
4.8.4. Contaminated Water
Safety precautions discussed above are generally applicable to contaminated water. If
sampling water involves using a boat on a lake, river, or other body of water, however, all

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water safety precautions, such as life preservers, must also be followed.

4.9. CONTAMINATION TYPES AND CONCENTRATIONS

Two other aspects of safety are the contaminant concentration and type. We are all
exposed to radiation and arsenic every day but we do not feel it and there are not any ill
effects from them as long as they are at natural or background levels. There are some
toxic chemicals that are an essential part of the diet. Selenium is toxic and yet it is
essential for good health. Boron is an essential nutrient for plants and yet if levels are
even a little too high it is toxic to them. (See also Chapter 9.)
When concentrations above natural or background levels are likely to be encountered
in the field safety precautions are extremely important. On a site heavily contaminated
with VOCs it is critically important to eliminate all sources of ignition, such as matches
and cigarettes. In fields contaminated with heavy metals or selenium, inhalation of dust is
of concern. Fields contaminated with radioactive waste require special protective clothing
and radiation monitoring badges. In addition to knowing the type of toxic material likely
to be encountered it is thus also important to know its likely concentration.
Many types of contamination are designated toxic, but that does not mean that they are
all toxic in the same way. Gases are toxic by inhalation; liquids by inhaling fumes,
drinking, or getting on skin; and solids by contact, eating, or reaction to form toxic
substances. Because of these differences the way they are treated and the precautions
taken need to be appropriate to the material being handled. It is thus important to consult
MSDS sheets dealing with the particular toxic material present or being handled.

4.10. OFF-FIELD PROTECTION

Sample containers need to be clean on the outside before they exit a contaminated site. If
glass containers are used they should be sealed in a plastic bag and wrapped in protective
material, such as bubble wrap. No portion of the sample should escape during storage or
transportation to the analytical laboratory. Also, as noted above, the proper signage needs
to be affixed to containers of samples so that in the case of a spill persons handling the
samples will know how to respond appropriately.

4.11. THE CHEMICAL HYGIENE PLAN

The CHP will be a document that outlines appropriate safety procedures for the field
being sampled. It explains how to handle various types of chemicals and what to do in
case of spills and accidental exposure to dangerous materials. All personnel need to know
where the CHP is and how to use it. Some topics commonly covered in a CHP are given
in Table 4.6. Details of the development of a CHP can be found on the Internet, along
with a sample plan. There are also various publications describing CHP plans [3, 12, 13].

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TABLE 4.6 Typical Contents in a Chemical Hygiene Plan

Recognizing hazards
Handling laboratory chemicals
Control measure implementation
Protective equipment for personnel
Training
Laboratory operations approval
Handling extremely dangerous materials
Spill response
Reporting accidents
Medical assessment
Record keeping
Appendices

4.12. ENVIRONMENTAL PROTECTION

Environmental protection can be thought of as protecting the people, animals, plants, and
general area around the field to be sampled. This must include taking measures to prevent
contaminated material from exiting the field (e.g., caution must be exercised to make sure
that contaminated dust brought into the air by sampling does not exit the site). Likewise,
sampling procedures must not lead to situations in which contaminated material can be
eroded off the field by water and thus contaminate surrounding areas.
In addition, samples to be taken off the site for further analysis must be packaged
appropriately (i.e., in such a way that material cannot leak out during handling and
transport). (Also see clean up upon exiting above.) This is important for the safety of the
people handling the samples, but also for the integrity and validity of the samples.

4.13. MSDS SHEETS

Material safety data sheets are designed for industrial situations in which large amounts
of highly concentrated material are present at one time and in one place. As can be seen
in Table 4.7, the information provided is complete and thorough. Not all the information
may be applicable to all sampling

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TABLE 4.7 MSDS Sheet Contents

Section

Topics covered

Chemical product and company identification

Composition and information on ingredients

Emergency overview

First aid measures

Fire-fighting measures

Accidental release measures

Handling and storage

Exposure controls, personal protection

Physical and chemical properties

10

Stability and reactivity

11

Toxicological information

12

Ecological information

13

Disposal considerations

14

Transport information

15

Regulatory information

16

Additional information

situations. An MSDS sheet discusses the fact that zinc may explode or ignite on contact
with water. This is not applicable to zinc ions in soil that are at very low concentration,
however. Material safety data sheets must be interpreted in relationship concentrations
and form of material present and to the activity undertaken [5].

4.14. MERCK INDEX

The Merck Index is a particularly valuable resource because it provides information about
the chemical properties, uses, and toxicity of a chemical. For instance, arsenic is toxic,
but it is also commonly used in many items we come in contact with everyday.
Additional important information is the LD50 of chemicals. The LD50 is that amount
(dose) of a chemical or element that when administered to 100 animals will cause fifty of
them to die. Also given is the method of administering the dosage. It may be orally, as in
drinking, inhalation, as in breathing, dermal adsorption, or by injection. This gives an
indication of the part or parts of the body that must be protected.
Dosage gives one, and only one, indication of how dangerous a compound is. Dose is
given in kilogram, gram, or milligram (kg, g, mg) of compound or element administered

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per kg of animal body weight to obtain the LD50. If a compound has an LD50 of 1 kg per
kg of body weight it is probably not, but not certainly, as dangerous as a compound that
has an LD50 of 1 g per kg of body weight. This compound in turn is probably not as
dangerous as a compound that has an LD50 of 1 mg per kg of body weight. The word
probably is used because some chemicals may have long-term or other detrimental effects
not assessed by the LD50.
The method of administering the dose is also of importance. Inhalation is perhaps one
of the most dangerous and insidious ways materials enter the body. Gases, which are
often undetectable, can be breathed and toxic symptoms or death result. Ingestion and
injection both require that the person actively intake the material. This can but should not
happen, but accidents occur. As noted above one way to prevent this is to make sure that
people do not eat or drink where chemicals are being used or stored or are in the process
of being transported. This includes samples, which must not be stored near food or in
food containers [6].

4.15. CONCLUSIONS
Safety is extremely important in field sampling. Development of safety procedures and a
chemical hygiene plan are needed. Personnel protection, including safety glasses, proper
clothing and gloves, and other safety equipment must be available to all. Safety training
is a must, as is continued emphasis on safety. Safety training should be a continuing part
of the safety plan. With proper safety preparation and execution a minimum of safety
problems will occur, and this will result in savings of time and money.

QUESTIONS
1. List and describe two major types of field sampling.
2. List and describe the general safety rules to be followed at all times.
3. A person is found dead next to a container that apparently contained liquid nitrogen.
Explain how this could have happened considering the fact that nitrogen is not toxic.
(Hint: A mole of any gas occupies a volume of 22.4 liters.)
4. Explain why, giving some examples, it is important that at least two people be
present during sampling.
5. Fumes overcome a person. What is the first aid step to be taken?
6. What in general are the chief differences between sampling an agricultural field and
an industrial field?
7. Why is it that gloves do not always protect?

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8. Using a chemical supply catalog look up personal gas monitoring devices and
describe two that function on different principles.
9. Describe STP.
10. Describe in detail the contents of a CHP.
11. Explain tools used in off-field monitoring.
12. A compound is listed in the Merck Index as having an LD of 10 g/kg. What does
50
LD50 mean?
13. What do the following stand for?
(a) MSDS
(b) VOC
14. Give some examples of data important to sampling that are given in an MSDS
sheet.

REFERENCES
1. Environmental, Health and Safety. http://www.osha.com.
2. National Safety Council Online Resource/Library. http://www.nsc.org/library.htm.
3. National Research Council Recommendations Concerning Chemical Hygiene in
Laboratories (Non-Mandatory)-1910.1450. http://www.osha.gov.
4. Environmental Management. http://www.epa.gov.
5. The Physical and Theoretical Chemistry Laboratory. Oxford University. Chemical and
Other Safety Information. http://physchem.ox.ac.uk/MSDS.
6. The Merck Index: An Encyclopedia of Chemicals, Drugs, and Biologicals. 13th ed.
ONeil MJ, Smith A, Heckelman PE, Obenchain JR Jr, Gallipeau JAR, DArecca MA,
eds. Whitehouse Station, NJ: Merck and Co. 2002.
7. First Aid and CPR. National Safety Council. 3rd ed. Boston: Jones and Bartlett, 1996.
8. Reynolds EM, Randle O. Pocket Guide to Safety Essentials. Washington, DC:
National Safety Council, 2002.
9. Henry TV. Decontamination for Hazardous Materials Emergencies. Albany, NY:
Delmar, 1998.
10. Forsberg K, Mansdorf SZ. Quick Selection Guide to Chemical Protective Clothing.
3rd ed. New York: Wiley, 1997.
11. Martin WF, Gochfeld M. Protecting Personnel at Hazardous Waste Sites. Burlington,
MA: Butterworth-Heinemann, 2000.
12. Developing a Chemical Hygiene Plan. JA, Young WK, Kingsley GH, Wahl eds.
Washington, DC: American Chemical Society, 1990.
13. Works R, Morrison J. Chemical Hygiene Plan for Chemistry Laboratories.
Department of Chemistry Laboratory Safety. Illinois State University Office of
Environmental Health and Safety. http://www.che.ilstu.edu/ChemSafety/CHP.htm.
1995.

5
Sampling
When sampling, local rules apply.
No single, simple set of guidelines is applicable to all sampling
situations.
General sampling principles will need to be adapted for each field
and sampling situation.

When sampling, it is important to first keep general sampling basics in mind. The most
important of these is that the environment changes over distance and time. The second is
that information about a field may be obtained either without (noninvasive) or with
(invasive) sampling; in either situation, it is essential to know beforehand from where the
samples are to be taken. This information is essential because it is used when relating the
sample to the whole environment. It is also critical if we wish or need to sample this same
field again at a later date or to remediate it. All data must be readily available, and thus it
is essential to have a place to put field data, such as a map of the area, a project notebook,
a computer, or all three.
Data about a field can be obtained by both noninvasive and invasive sampling.
Noninvasive sampling is carried out using ground-penetrating radar (GPR), remote
sensing, or other noninvasive technologies. Invasive sampling is accomplished using
hand- or machine-driven samplers that extract a portion of the medium about which we
wish to obtain information. The sample thus obtained is subjected to laboratory analysis.
Both methods are valuable and sometimes essential in field sampling. Both have
limitations, and the best sampling results are obtained when all ways of investigating the
medium of concern are used. In all cases knowing the location of sampling activities is
essential. Determining the location is best done using a global positioning system (GPS).
Because of its importance, GPS will be discussed before examining either noninvasive or
invasive sampling.
In many cases noninvasive sampling is done before invasive or physical samples are
taken, mainly because these methods show surface and subsurface features affecting the
invasive sampling pattern. In some cases these methods are necessary for the safety of
sampling personnel and buried utilities. They will thus be used to develop the invasive
sampling plan. Because they will be used first they will be discussed before discussing
actual invasive sampling.
Data obtained by all sampling methods can be combined in a geographical information
system (GIS). Combining data allows them to be both stored and displayed on maps of
the area of interest (e.g., thematic maps). As many or as few data as needed can be
displayed at one time. Additionally, a GIS system can relate data obtained from sampling

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to data obtained from other sources, such as aerial maps and soil surveys.

5.1. GENERAL SAMPLING CONSIDERATIONS

Analytical and instrumental methods of analysis are very precise and accurate, but the
results of analyses of environmental samples are not. This means that the variability
comes either from the sampling procedures or during sample handling and storage prior
to analysis. Sampling is the most important source of variability, and both the sampling
and handling process must be carried out with great attention to detail.
Sampling is the act of isolating a portion of a larger entity, analyzing it, and using the
analytical results to describe the characteristics of the whole entity. In statistical terms the
sample is an individual, which is a member of a family of similar individuals. Analysis
shows that even environmental samples taken from sites close together may not be
individuals or members of a family. When samples are taken at progressively increasing
distances from a specific location they change in one of several ways. Characteristics can
change gradually until a very different individual is identified, or they may change in a
repetitive manner over long distances.
On the other hand, samples may show gradual or repetitive changes and all of a sudden
show a dramatic change in a completely different direction. For example, a soil at the top
of a hill might be well developed, with distinct A, E, and B horizons. As expected, the B
horizon is high in clay, but there is good internal drainage. The hillside profile might
have similar horizons except that they would be thinner and less well developed. At the
bottom of the hill next to a stream the soil has a thick, dark, high organic matter A
horizon underlain by a sandy B horizon with a small amount of clay in it. There is thus a
gradual change down the hill and an abrupt change at the bottom.
It is essential that such changes in the environment be kept in mind both when
designing a sampling plan and during noninvasive and invasive sampling. If unexpected
changes occur, they are recorded in the project notebook and accounted for in the
sampling procedures, sample analysis, and the interpretation of sample analysis.
In sampling, air and water variability is not as great as with soil. The atmosphere is
particularly uniform, but the hydrosphere is more variable in that the salt content of water
varies with location. It is important to remember, however, that there are layers and
definite direction in movement in both of these spheres. Downwind or downstream from
a source of contamination it is dramatically diluted, and thus changes in location, either
horizontally or vertically, may lead to sampling different layers, and this may result in
differing and perhaps confusing analytical results. These sources of possible variation and
error must be kept in mind when designing sampling plans for air and water as well as
soil [1].
In the United States sampling of hazardous fields and sites falls under the purview of
the United Stated Environmental Protection Agency (USEPA). This organization has a
publication, Test Methods for Evaluating Solid Waste Physical/Chemical Methods
(USEPA SW-846 3rd ed., November 1990). In addition, Standard Methods for the
Examination of Water and Wastewater, published by the American Public Health
Association, American Water Works Association, and Water Environment Federation

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(APHA, AWWA, WEF; 20th ed., 1998 and 1991 supplement) can also be consulted.
Numerous methods for sampling and assessment are available from the American Society
for Testing Materials (ASTM). (See Appendix B.) For health and safety issues related to
sampling, the Occupational Health and Safety Administration (OSHA), particularly
OSHA-29 CFR 1910.120, should be examined. Also in the United States, each state has
its own environmental protection agency (EPA), which will have state-specific
regulations for such things as sampling [24]. Most countries will have similar
organizations, and these must be consulted.

5.2. GLOBAL POSITIONING SYSTEM

It is highly recommended that GPS be used in locating sample sites. As discussed in
Chapter 3, the first step in sampling is to set up the coordinates for the field. This means
first deciding which coordinate system to use and finding the coordinates at the corners
and edges of the field. These are then put on the maps of the fields, which are then used
for all other sampling activities. Maps such as those shown in Figures 5.1 to 5.3 should
include these coordinate references at each corner as shown, because these locate the
field unequivocally.
A GPS works using satellites in orbit around the Earth. These satellites transmit signals
that are received by GPS units on the Earth. Using a minimum of two signals, a GPS unit
can show where it is located on the Earths surface. (It is highly recommended, however,
that a unit accessing twelve or more satellites be used.) This system can also give the

FIGURE 5.1 Transect sampling. The curved line encloses the suspected
contaminated area. Note that the samples along the transect lines are
taken randomly.

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FIGURE 5.2 Transect sampling when two or more distinct soil types are
present. Note that both surface and subsurface (dots) samples in all
three soil types are taken.

altitude, and if it is moving, the direction and speed of movement. The GPS location
given is a map location, and so this system is directly linked to maps of the Earths
surface. The maps must have the same units of geographical reference as displayed by the
GPS unit for both to be used together. Such units can also show the direction one needs to
go to get to an identified place on a map or on the Earths surface.
5.2.1. Coordinates and Time
Global positioning systems depend first on a datum, second on such coordinates as
longitude and latitude, and third on time. There are different data for different parts of the
world, but in North America, the 1927 North American datum is used (commonly
referred to as NAD-27). (There is also an NAD-83.) In addition to the usual longitude
and latitude used on maps and globes, a coordinate system called the universal transverse
mercator (UTM) is also in use and must be available in the GPS unit. Before starting to
use a handheld GPS unit, make sure that it is reading the correct datum and is giving
locations in the appropriate format for the maps being used.
Time is kept using atomic clocks in satellites, and, in turn, time is used for determining
the position of the GPS receiving unit (i.e., GPS time). Using this very precise time
satellites can be kept synchronized and GPS units convert GPS time to the universal time
coordinate (UTC), which is the same as Greenwich mean time (GMT). From this point,
the local time can

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FIGURE 5.3 Sampling grid placed on an aerial photograph showing sample

locations and numbers.

be obtained. A detailed description and discussion of the whole field of navigation, data,
UTM, and UTC will not be covered here; however, an excellent resource covering these
topics is given in Ref. [2].
Global positioning system instruments range from inexpensive handheld units with
limited capacities to stationary units with multiple capabilities. The two most common
are handheld units and mobile units intended to be carried on a vehicle. Antennas are an
important consideration in choosing either type of GPS unit. Several designs are
available, and the one chosen should be suitable to the terrain in which it is to be most
often used. Also, because basic GPS is not as accurate as one might like, it is essential to
have a unit that is capable of differential GPS (DGPS) or of using the wide area
augmentation system (WAAS). A discussion of these methods is given in Chapter 2.
Global positioning system units are powered by a number of different sources, the
most common of which are batteries, including adapters for using the battery of a vehicle.
The batteries in handheld units can be either rechargeable or of the dry-cell type. Dry-cell
batteries can last up to 20 hr and many units have battery-saving features. One set of
batteries can thus last for a day or two of sampling. If sampling will take longer,
rechargeable batteries are preferred. If the person sampling is riding a vehicle with a 12V battery, a battery connector is preferred.

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5.2.2. Sources of Error

Global positioning system units are capable of operation in overcast and other less than
ideal weather conditions. There are, however, some situations in which errors can occur.
These might cause only a slight error in location or they may cause errors of 1 or more
km. For instance, using the wrong datum leads to a wrong position being shown by the
GPS unit. Also, in coordinating the position shown on a GPS unit with a map be certain
that the coordinate system being used in both cases is the same.
Reflected multipath errors occur when the signal from one satellite is received both
directly and indirectly after it has bounced off an obstruction. Such errors occur where
there are large mountains or buildings near the field in which the GPS is being used. If
both the direct and reflected signals are used, the calculated position will be wrong. Some
GPS units can automatically correct for multipath signals, but others cannot. Two
precautions thus need to be taken. First, observe the surroundings for features that might
reflect a signal, and second, determine if the GPS receiving unit being used can correct
for multipath signals.
In actual use, handheld GPS units can be of great value. For instance, inexperienced
personnel can sample large fields two ways. First, the handheld unit can be
preprogrammed with waypoints. When the person doing the sampling reaches the
preselected site, the unit will beep or otherwise notify him or her. The sample can be
taken and the unit will indicate how to get to the next waypoint. A second way is to
provide the person with a map of the area showing the location of the sites to be sampled.
Even if the sites are not precisely located, the exact location can be identified if the
longitude and latitude indicated on the GPS unit are recorded at the time of sampling. At
a later time the same position can be found easily if the site location is clearly recorded.
If data are needed from between sampled sites, they can be either physically sampled
or the concentration of the desired constituent estimated using techniques such as kriging,
which is discussed further in Chapter 6.
5.2.3. Limitations in Field Sampling
Global positioning systems are extremely useful in field sampling, and no field sampling
should be undertaken without them. Sample sites should not be located at distances
shorter that the accuracy of the GPS unit, however; that is, a GPS should not be used to
locate sample sites 3 meters apart if its accuracy is 10 meters. If this is done, two sites
that are 4 meters apart may have the same longitude and latitude even though they are
obviously not at the same location. If such longitude and latitude data are taken,
erroneous data will be obtained, and when used these data will produce inaccurate and
confusing results, particularly if used in modeling.
Availability and use of a top-quality GPS unit does not make all other navigational and
site location tools obsolete. Maps, compasses, altimeters, pedometers, watches, and
project notebooks are all still essential and will find many uses [5]; for example, a
handheld GPS unit may not have a builtin compass. Figure 5.4 shows a handheld GPS
unit and watch with compass and altimeter. The GPS unit will show the direction in
which you are going once moving, but will not show the direction in which you should

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start moving to go to the next waypoint. A simple compass therefore can be a handy
addition when field sampling. Many watches, such as the one shown in Figure 5.4, have
various types of compasses built in, so these can be used in the field in place of a separate
compass. A word of caution, however; calibrate the compass before starting to use it in
the field.

FIGURE 5.4 Handheld GPS unit (top) and watch with compass and altimeter.

5.3. GROUND-PENETRATING RADAR

Before disturbing the soil surface, and especially before taking samples deep in the soil
profile, a GPR map of the field can be taken. This is particularly important if the field is
likely to contain utilities, gas, water, electric, or communication lines or if it has been
used by armies, in which case it is likely to contain explosives.
Because of its common use in weather forecasting and in both civilian and military
flying, radar is familiar to almost everyone. What is generally unknown is that it can also
be used to investigate underground features without disturbing the soil surface. Radar
works by sending out microwaves which, when reflected from an object (e.g., airplane),
are received by the radar antenna and displayed on a monitor. The direction the
microwaves came from and the distance of the object from the antenna can be calculated.
Both sets of information.are typically displayed on the monitor.
Ground-penetrating radar is similar to any other radar except that the microwaves are
directed into the soil and the reflected waves are analyzed. Radar waves penetrating the
soil are refracted at interfaces between layers or objects with different relative dielectric
permitivity (RDP). This means that the greater the difference in the RDPs the more

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radiation is refracted and the stronger the signal received. The largest difference is
between air and water. (See Table 5.1.) There is also an appreciable difference between
soil and both air and water. Originally, GPR was used in areas in which the soil tends to
be dry. Today it is used in both wet and dry conditions [6].
The RDP can be calculated using the equation
where k is RDP, C the
speed of light, and V the velocity of radar in the material being investigated. The exact
RDP cannot be accurately calculated when dealing with mixed materials, such as soil and
regolith. Under these field conditions

TABLE 5.1 Relative Dielectric Permitivity (RDP) of Some Common Environmental

Components

Medium

RDP

Air

Water

80

Dry silt

330

Wet silt

1040

Soil

12

Source: Data from Ref. [6].

it is either necessary or highly desirable to determine k by measurement. Burying a metal

bar at a known depth in the soil or regolith and passing the GPR instrument across the
area in which the rod is buried can easily accomplish this. The locally applicable k is thus
determined, and then used to calibrate the instrument for the medium where the survey is
to be made. At this point the depth to which the GPR survey will be useful can be
calculated, keeping in mind the limitations noted below. The equation used to find this
depth is

where A=approximate long dimension radius of footprint. The footprint is the buried
surface area illuminated by the radar signal. In the equation, =center frequency
wavelength or radar energy, D=depth from ground surface to the reflection surface, and
k=average RDP of the material being surveyed. Under the best conditions, the depth of
penetration of radar in soil is 40 meters (approximately 130 ft). Normally, however,
usable penetration is limited to 1 to 5 m (3 to 16 ft). Within this depth, the occurrence of
pipes, power lines, buried objects, caves, differing layers of soil and regolith, and the
depth to the water table can be observed.
Making a survey is done by passing a GPR instrument over an area in a grid pattern

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similar to the grid shown in Figure 5.3. In this case, however, the grid lines are typically
1 meter apart in both directions. The data obtained are displayed using computer
programs. In this way a three-dimensional picture of subsurface features can be
visualized. Computer programs can also be used to filter the raw radar data to give a
clearer picture of subsurface structures.
Table 5.1 gives the RDP for a number of common environmental components, but does
not give a figure for saltwater, which is an electrical conductor and thus does not have
any appreciable RDP. Ground-penetrating radar thus cannot be used in saltwater or in
salty soil conditions. In this case salts will include all the common fertilizer elements and
soil amendments, such as lime or calcium carbonate. Also, highly conductive clays are
not amenable to GPR methods. While GPR is useful in dry soils, it thus cannot be used
on many dry-region soils because of their high salt content. Note that this can also
include natural deposits of calcium carbonate, which are quite common in arid and
semiarid soils.
A number of other common environmental conditions interfere with GPR. The
radiation used in radar has a magnetic component, as does all electromagnetic radiation.
Thus soils or other media that are magnetic or high in iron or other magnetic materials
such as magnetite cannot be investigated using this method. Other common soil and
regolith components such as cobbles will also cause anonymities in the GPR signal.
Some subsurface features may be hard or impossible to detect by GPR. If the angle of
incidence refracts the waves away from the receiver the object will not be seen. Also, in
some instances the speed of the instrument over the surface may affect the clarity of the
readings [6].

5.4. REMOTE SENSING

The term remote sensing can be applied whenever data obtained from the environment
are transmitted from that location back to some central receiving station, processing
center, or office. This definition might include the case in which photographs are taken
from an airplane and the film physically delivered to the processing center. The most
common interpretation of remote sensing, however, is data about the Earth gathered by
satellites and transmitted back to Earth [7].
In all likelihood, remote sensing of the field being investigated has already been done,
thus one should look at various archives of remote sensed locations to determine if the
location of interest is there. These data archives can be accessed on the Web through the
Distributed Active Archive Centers (DAAC) and the Earth Observatory System (EOS)
data gateway (both of these are National Aeronautics and Space Administration, NASA,
sites) [5, 6]. Both these sites are extremely complicated and hard to navigate. It will take
some time to find the information you are interested in; however, if the desired data are
available, obtaining a copy of the images is relatively simple.
One potential problem with available data is that the images may not include the
portion of the spectrum that is most important to the sampling program. If the needed
data are not available, a request can be made to have an image taken of the area. It is
relatively simple and not very expensive to have satellite pictures taken of specific areas

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of the Earths surface. The resolution, which depends on the portion of the spectrum
needed, is typically between 30 and 60 meters. When ordering an image, both the
location of the area of interest and the portions of the spectrum to be recorded must be
specified [79].

5.5. GEOGRAPHICAL INFORMATION SYSTEMS

When developing a sampling plan and collecting historical data about a field a question
to ask is if there is a GIS for the field and the surrounding areas. A GIS may contain
important information about cadastral questions, such as easements and rights-of-way;
the natural environment, such as hydrology, topography, vegetation, watersheds, and
wetlands; and utilities, such as water lines. This information can be invaluable in
developing and carrying out a sampling plan. It can save time and money, especially if it
avoids breaking a power line or similar underground facility.
Any system that makes a map or representation of the Earths surface can be a GIS.
Today, however, it is generally understood that GIS refers to maps and other data stored
digitally on media that can be read and analyzed by computer. Such systems allow the
addition of any digital information to the map. This additional information can then be
displayed in a variety of different ways to help researchers understand phenomena
occurring on or below the Earths surface. Such maps are said to be thematic.
In making thematic maps GIS makes use of elements from other mapping tools. The
most important of these is CADD and AM/FM. CADD is computer-aided design and
drafting, the map-drawing capabilities of which are included in GIS, but it does not have
data correlation capabilities. For instance, when looking at a hazardous waste field, GIS
can be used to determine how much of it is in a flood-prone area, while CADD cannot.
AM/FM is automated mapping/facilities management, which is used extensively for
mapping networks and network element characteristics. Again, data analysis is better
carried out using GIS. Any information about a field that is in either of these two formats
can be easily imported into a GIS system.
The thematic maps produced using GIS work a little like having the base map and
making transparent overlays for it. Each overlay would contain data of interest. Although
the data could thus be visually observed they could not be analyzed in relation to the base
map or to other layers; the GIS system allows for this. In addition, GIS systems allow for
the addition and removal of one or more layers as needed.
For sampling, the most important feature of GIS is the ability to display sampling sites
and their characteristics on a map of the field being sampled. This allows the sampling
sites to be coordinated with other features of the environment, such as water flow. This is
important because water movement may indicate other areas that need to be sampled or
watched.
Information displayed on a map can be entered manually into a computer system, in
the form of tables, for example. Alternately, it can be obtained directly from any digital
source of information. For instance, data obtained by remote sensing from aircraft or
satellites. A familiar example of this use is the display of weather. The daily weather
report incorporates this type of technology. Population densities, lightning strikes, and

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ocean temperatures are other common examples of uses of GIS. Recently, mapping
Pacific Ocean temperatures using remote sensing has been used to predict the occurrence
of La Nia or El Nio. Whenever data are entered into a GIS system from any source,
their accuracy must be checked. This is especially important if they are entered manually.
Today, satellites are the most important source of information for GIS. Satellites can
access various portions of the electromagnetic spectrum, allowing analysis and evaluation
of conditions on the Earths surface. (For more information on satellite sensing, see the
previous section on remote sensing.) Having satellites use sensors to observe the Earths
surface and having these data digitalized allows for easy insertion into GIS systems.
Satellite sensors are very versatile, and different satellites have sensors for different
portions of the electromagnetic spectrum. A well-know satellite used for remote sensing
is the Landsat TM (Thematic Mapper) satellite. It has a broad range of sensors, which
among other things can detect both different vegetation types and changes in them. These
changes can be related to changes in a plants environment, including environmental
degradation. Airplanes equipped with sensors still play a role in remote sensing, and data
retrieved in this way can also be inserted into GIS systems.
In most cases, a sampling plan will not require the entity doing the sampling to
implement a GIS system. Desktop computers with GIS display and manipulation
software can be inexpensively obtained, however. The needed GIS data, including maps,
can thus be obtained from various sources and combined to obtain the information,
relationships, and analysis needed [10]. One important source is local GIS offices. It is
very common for even small cities, municipalities, and counties to have GIS systems, and
both the mapping and tax offices know who keeps these systems and where they are kept,
and there may even be a separate GIS office, which is often small and not easy to find. If
such an office exists, however, it is worthwhile finding because GIS personnel can be a
valuable resource in obtaining GIS data and in developing and executing a sampling plan.

5.6. SAMPLERS
There are many different types and constructions of samplers designed for each type of
media to be sampled. One of the most important considerations in deciding on the type
and construction of a sampler is the material that it is made of and whether or not it is
compatible with the type of material and contaminant being sampled. Figure 5.5 shows a
typical simple hand sampler, while Figure 5.6 shows a sampler mounted on a truck.
Additional

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FIGURE 5.5 A simple hand core sampler for sampling up to 30 cm deep.

FIGURE 5.6 Truck equipped with power sampler. Samples range from 2.5 to
7.5 cm in diameter and up to 2.5 meters deep.

examples of samplers and information about them are given in Figure 3.6 in Chapter 3.
5.6.1. Sampler Composition
Samplers can and are made of a great many different types of materials, from plastics to
metals and alloys. The choice of sampler construction material will be determined by the

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type of contaminant in the sample and its reactivity with sampler materials. For sampling
involving organic contaminants many different materials will be acceptable as long as
they do not react with the sample. When sampling is for metal contaminant the metal
composition of the sampler is of primary concern. In some situations a number of
different samplers of different composition will be required.
There is a great variety of plastics with different contaminant compatibilities. One
widely used plastic is Teflon and Teflon-coated samplers. This plastic is resistant to
almost all chemicals and has a nonstick surface. As with all plastics, however, it is not
good for situations in which the sampler must cut through abrasive material. Also, if the
sampler is Teflon-coated, it is imperative that care be taken to assure that there are no
holes or worn spots in the Teflon, which might lead to contamination or crosscontamination of sample.
All plastic and plastic-coated samplers are best suited to air and water rather than soil
sampling. Soil is abrasive and can rapidly wear away plastic coatings, which can also
develop gouges and cracks, exposing the underlying material to the sample. Also, cracks
can become filled with sample material and thus cross-contaminate samples.
In addition to plastic, samplers are also made of various metals, including brass, iron,
steel, and stainless steel alloys. Metal samplers are common and robust; however, they
can result in metal contamination of samples. This is particularly a problem when the
contamination of interest is a metal ion, metal, or heavy metal. This can be even more of
a problem when the material being sampled is very acid. Keep these considerations in
mind when choosing a sampler and sampler material.
5.6.2. Sampler Types
There are a large number of samplers designed for different soil types and depths of
sampling. Perhaps the simplest is a metal tube or core type 46 to 50 cm (18 to 20 in.)
long, usually with a section cut out of one side of the tube. (See Figure 5.5.) A piece of
tubing is fixed on the top, making a T, and the mouth at the bottom is shaped to make it
easy to insert into soil. The sampler is inserted, usually using hand or foot pressure, into
soil at the correct site and then withdrawn with the soil sample. The side opening is used
for removing the sample. This sampler is a most useful in fine-textured, moist soils.
When the soil and moisture conditions are favorable, it is only limited in how deep it can
sample by how deeply it can be pushed into the soil using hand or foot pressure.
For deeper sampling a larger, more robust sampler of the same basic design can be
inserted into soil using a manual or powered hammer. For even greater depths, a similar
core-type sampler can be attached to the back of a pickup truck equipped with a hydraulic
or mechanical system for insertion into soil. (See Figure 5.6.) The hydraulic press inserts
a length of pipe into the soil; when removed, the core is pushed out, again using the
hydraulic or mechanical system. In this way, cores of various depths can be easily
obtained. This sampler can be used to quickly and easily sample large areas. (See
Appendix B for sources of samplers.)
Another type of sampler is a rod about 46 to 50 cm long on the end of which is
attached an auger, which is like a wood drill bit. (These are shown in Chapter 3, Figure
3.6.) These samplers are most commonly used and useful for obtaining samples in soil

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containing gravel or other large stone fragments, in which they can be used to depths of
15 to 20 cm (6 to 8 in.). Auger-type samplers can have the same variations as the core
samplers mentioned above.
Another type of auger sampler is one with an integral bucket. These samplers are
screwed into the soil and a sample is collected in the bucket (Chapter 3, Figure 3.6). The
sampler may be fixed to a T-type handle with a definite length of pipe between the handle
and the auger. Some people keep a series of samplers of different lengths for different
jobs. In situations in which there is a constant need for samplers with different lengths the
lengths are threaded in such a way that additional pipe can be added or removed to make
the sampler longer or shorter.
For very deep sampling in complex situations it is imperative that a standard welldrilling outfit be used [11, 12].
No matter which type of sampler is being used, it is important to keep samples
separated and identified. Samples should not be allowed to become cross-contaminated
during the sampling procedure. The sampler therefore needs to be cleaned after the
collection of each sample.
Generally speaking there is no correlation between the precision or accuracy of
analytical results and the type of sampler use. Because of this, soil scientists familiar with
the area in which the field is located can give excellent guidance as to the best type of
sampler to use for the local soils and regolith [1].

5.7. SAMPLE AMOUNT

The amount of sample taken will be determined by two factors. How much sample is
needed for analysis, and what type of component is the sample to be analyzed for?
Because of these considerations the absolute size of the sample cannot be given. The
amount of sample needed in the field laboratory and the commercial laboratory are added
to obtain the total amount of sample needed. This may change, however, depending on
the sample container requirements, because some samples must fill the container
completely and this determines the amount of sample taken. In those cases in which
multiple analyses are called for, more sample is also needed.
In sampling, several cores will be combined to make a sample to be analyzed. For
instance, three or four cores might be taken from each grid in Figure 5.7. These would be
placed in the same bag as a single sample for analysis. Figure 5.8 shows three cores and a
core still in the sampler. If the cores are not about the same size, the larger core sample
characteristics will dominate the sample and analytical results. This can lead to dilution
or concentration of the component of interest. In either case the resulting analytical data
will not give a true picture of the area being sampled. It is

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FIGURE 5.7 Grids for sampling. Both surface and subsurface samples can be
taken randomly or systematically from each grid over time.

FIGURE 5.8 Soil cores with one core still in sampler.

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thus necessary to used the same sampler and take the same amount of sample each time.
This is true for both surface and subsurface samples.
Note that samples for volatile organic compounds (VOCs) analysis are handled very
differently. Samples must be taken, handled, and contained in such as way as to minimize
the loss of sample components. Some procedures call for the sample container to be filled
to the top, leaving as little headspace as possible. The container is then sealed with a top
that is proven to prevent leakage of VOCs. Other procedures will require more or less
sample, depending on the sampling, container, and analytical methods used. The
analytical laboratory can provide specifics as to sample handling, the amount of sample,
and the container needed for the specific VOCs being sampled and analytical methods to
be used.
When the sample arrives at the analytical laboratory it will be ground, sieved, and
mixed. A subsample of this mixture is usually on the order of 1 to 10 g, although larger
samples may be used in some cases. The size of the sample taken from the field thus does
not need to be large. As noted above, however, all samples should be of about the same
size so that observed changes are not due to changes in sample amount, but to the
inherent characteristics of the sample [12, 13]. Sample size can be a trap, and this will be
discussed in further in Chapter 11, along with other traps.

5.8. SAMPLE CONTAINER

Almost every conceivable type and composition of container has been used to contain
contaminated air, water, and soil. Glass bottles or containers are most frequently used for
air and water samples, however, while paper and plastic bags are used for soil samples.
Before deciding on a container material, however, it is essential to know the history of
the field and have a clear idea of the types of contaminants it contains or is suspected to
contain. It is also important to know as far as possible the species of the contaminant that
is of primary interest. For example, when sampling soil for VOCs, bags are not suitable
containers. In this case a glass container will be provided by the analytical laboratory,
along with use and filling instructions. A more complete list of typical containers and
their characteristics is given in Chapter 3 in Table 3.3 and Figure 3.7 [1113].

5.9. DUPLICATE, SPLIT, AND COMPOSITE SAMPLES

Duplicate samples are taken from the same location and are used to check the accuracy
and precision of analytical methods. In the case of water and air, duplicate samples may
serve this purpose very well. In soil or regolith sampling, duplicate samples are two cores
taken adjacent to each other. These two cores may not be identical, and indeed may be
significantly different from each other. Duplicate soil samples can be different by as
much as 510%. If the occurrence of this variation does not cause a problem, duplicate
samples may be useful. If duplicate soil samples give exactly the same analytical results,
the validity of the sampling and analysis is in question.
A single sample split into two subsamples placed in two different containers would

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represent split samples. Splitting air and water samples, which can be done in the field or
in the laboratory, can be an effective tool for comparing analytical results. Soil and
regolith samples must be ground, sieved, and mixed thoroughly before splitting. Thus,
splitting of these samples can only be done in the laboratory. Even with this type of
sample, significant variation between subsamples can sometimes be found.
Composite samples are obtained by taking two or more samples and combining them
to make one sample. For instance, three equally spaced, 20-cm-deep core surface samples
might be taken from grid 3 in Figure 5.7 and combined to make a composite sample for
this grid. Another approach among the many variations of this concept would be to take
more cores or take them randomly. The cores obtained are ground together and mixed
before subsamples are taken for analysis.
The above grid may be smaller than 1 ha or as large as 5 or more ha. The idea is that
this composite sample will provide an average value for the amount of contaminant or
constituent in the area represented by these multiple samples. Such a sample will allow
the same level of remediation to be applied to the whole area sampled as long as the
contamination is fairly evenly distributed in the area in which the compounded samples
are taken. This is also sometimes referred to as composting or composted samples,
especially if the sample is left for some period of time before analysis [13].
When samples from some depth in a field are to be taken, the same procedures are used
as described above. In this case, 15 in Figure 5.9 represents a volume of soil
corresponding to the area of grid 15 and depth of , and likewise for volume 15.
Because contaminants must leach down into the soil and because obtaining samples at
some depth is significantly more difficult than taking surface samples, usually fewer
samples at various depths will be taken and analyzed. In this case, the goal is to
determine the depth of leaching of the contaminant, so that the volume of soil to be
remediated is known. The models discussed in Chapter 7 are often valuable in deciding
on the frequency and depth of sampling in these cases.
In cases in which there is a buried tank or a leaking pipe contamination will originate
at some depth in the soil. In these and similar cases deep sampling will be mandatory, and
a large number of such samples will be required from various depths, depending on the
leaching of the contaminant.

5.10. SAMPLING STRATEGIES

There are several different strategies or ways in which people obtain samples from a
field. Actual determination of specific sites will be presented in Section 5.13.
5.10.1. Transect Sampling
A first step in sampling is to obtain information about the extent of contamination. To do
this, make one or several three-dimensional sampling transects of the field to be sampled.
In Figure 5.1, two transects are sampled across a field that is assumed to be uniform (i.e.,
one soil type). In this case, surface samples are taken at regular intervals across the
contaminated area. Also, samples from regular depths are taken at several sites along the

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transect(s). In this process it is essential to make sure that two types of controls are also
taken. The first is to make sure that the first and last samples are taken from outside the
area that is assumed to be contaminated. Also, samples from various depths must include
a sample obtained from below the contaminated material.
In Figure 5.2 transects are taken in an area containing three soil types. Note that the
transect lines are chosen in order to obtain samples from each soil type; the figure also
illustrates taking both surface and subsurface samples at regular intervals. Also, some
transect samples are taken outside the suspected contaminated areas. These samples are
essential to establish the boundaries of the contaminated areas.
Normally it is important to take into consideration what soil type is being sampled, and
this is true for the transect samples. In this case, however, it is only important to label
samples so that the soil type from which the sample is taken can be determined later. This
information is useful for the development of the detailed sampling plan. At this point, the
most important information to gather is the level and extent of the contamination
throughout the contaminated area. An advantage of transect sampling without regard to
soil type is that if analytical results are consistent for the different soil types the detailed
sampling plan and the final analytical work is simplified, which in turn saves resources,
including money.
During transect sampling, however, unusual soil characteristics should be noted; that
is, any indication that the soil types are different from those mapped or that the soil
characteristics have not been noted elsewhere. If the soil is mapped as a silt loam and an
area with sandy texture is encountered in the transect sampling, this is important. A sandy
soil will have absorptive, retentive, and extraction properties that are very different from
silt loam. Layers that are unusually hard or compacted must also be noted, because they
will affect contaminant movement, analytical results, and applicable remediation
procedures.
The transect sampling results can also be used to identify zones of contamination (i.e.,
some areas contaminated at uniform but relatively lower levels of contaminants than
surrounding areas). When determining the number of samples needed, these areas can be
treated separately from other areas (see Chapter 6), since they may, for example, require
less sampling. This leads to increased efficiency and less cost to the project.
The analytical method chosen for analyzing the transect samples should be simple,
rapid, and inexpensive. Accuracy and precision should be of secondary concern. Use of
an entirely different analytical procedure for the detailed sampling and analysis is
appropriate. Also, note that if the two different analytical methods give similar results,
confidence in the validity of the whole sampling and analysis process is greatly increased.

Preliminary Nitrate Sampling

I worked with some researchers concerned with nitrate contamination in well
water. They had ten wells they were sampling and wished to know which
wells were in need of monitoring. At the time I was using a nitrate ion
selective electrode (ISE) for some other work and was asked if I could
analyze their samples. Some of our colleagues scoffed at the idea, saying that

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the nitrate ISE was not sensitive or accurate enough for this work.
In analyzing the ten well water samples, the distinction between
contaminated and uncontaminated wells was obvious. The uncontaminated
wells gave no response. There were three wells that gave a response of 1000
ppm nitrate (NO3), however. This analysis allowed us to identify the
contaminated wells and to predict which other wells should be looked at using
more sensitive methods. It is important to point out that the sensitivity of the
ISE that I was using was 10 ppm NO3, and that the allowable level of nitrate
in drinking water in some places is 10 ppm and in other places higher.
The ISE is an example of a rapid analytical method that is suitable to transect samples.
Although it can be used in the field without elaborate sample preparation, the field office
laboratory is a better place to make the analysis.
The ISE is similar in appearance and operation to a pH electrode. Indeed, the more
sophisticated pH meters are able to accommodate many different ISEs. The use of an ISE
is as quick and easy as determining pH using a pH meter. Typically the time for doing an
ISE analysis is less than 1 min. Portable pH meters, which can do both pH and ISE
analysis, are readily available [14, 15].
Transect sample results can be combined with detailed sampling data to confirm the
detailed sampling data and to make statistical calculations as to the number of samples
needed. These analytical results will also provide information that can be used to
determine if a sample is extraneous or is indeed part of the population being sampled.
More information on this can be found in Chapter 6.
During transect sampling variations in soils and soil types in the sampling area are
noted but ignored. (See Figure 5.2.) However, when the detailed sampling plan is
designed, the soil and soil types present must be taken into consideration. This means that
the whole sampling plan may be designed without regard to soil types. The soil types are
recognized when samples are taken and analyzed, however. In this case the batch number
and the number on each individual sample must be unique, so that they can be identified
later if needed as being from one soil type [11].
When the transect samples have been taken and analyzed, a detailed sampling plan can
be developed. This plan will take into consideration observations and analysis made
during transect sampling and the statistical analysis of the analytical results. (Statistical
analysis will be described in Chapter 6.)
5.10.2. Detailed Sampling
Detailed sampling can be of four types. The first is sampling to determine the levels of
plant nutrients in a field. The second is sampling to determine the extent of contamination
so that the contaminated material can be removed for remediation. In this case, the field
will only be sampled once, and subsequent sampling in this location is not expected to
occur, although monitoring may be called for. In this case, it is important to identify all
the contaminated material and assure that it is safely removed. This is coupled to the third
type, which involves sampling the material once it is in its new location. This will entail

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random sampling not related to the position of the material in the environment but to the
amount of disturbance the material is subject to during the cleaning process.
The fourth detailed sampling situation occurs with bio- or phyto-remediation. In this
case the field will need to be sampled several times to ascertain if remediation is
progressing as planned and if additional steps need to be taken, and to certify that
remediation has been completed. In this case, sampling sites will initially be randomly
assigned or sited. Subsequent sampling will take place at or near these originally
designated sampling sites, however. Final sampling before designating the area as clean
should involve a few additional random sites to assure cleanliness.
There are several possible approaches to the detailed sampling plan. One is to make it a
totally random three-dimensional sampling. A potential problem with this approach is
that picking random sites to sample may have sampling occurring in many areas in which
you are certain there is little or no contamination. Another possibility is that you may
obtain less information about a particular field when multiple samplings are called for.
Another approach is to produce an imaginary three-dimensional grid of an area, each
grid of which will be sampled. Such a grid has been superimposed on the maps shown in
Figures 5.3 and 5.7. Note that in each case the position and limits of each field have been
unequivocally located with the longitude and latitude of the four corners of the field.
Another approach would be only to sample within randomly selected grids in the
girded area. Subsequent samples can again be taken randomly within the given grid.
Another possibility would be to take individual grid elements and apply them randomly
to the field. For instance, grid element 15 (see Figure 5.9) would be applied (with
their own individual designations) to random areas in the field to designate places in
which sampling is to occur [4]. It is important to remember that the grid is threedimensional and that every sampling event must include samples from all three
dimensions. (See Figure 5.9.) The fourth dimension will be determined by sampling at
different times.
It is often the case that the soil and underlying regolith is composed of several layers of
differing composition. These layers have different densities and may be at different
depths across the contaminated site. Such layers may need to be sampled specifically, and
the samples taken will need to contain the same amount of contaminated material. This
will necessitate sampling at different depths at different points across the contaminated
field. It will also necessitate taking a larger sample in some cases (low bulk density), or
smaller samples in other areas and at other depths (high bulk density strata; see Chapter
2) [11].

5.11. TOPOGRAPHY
A totally random sampling plan has the advantage of removing bias from the sampling.
In many situations, however, the topography of the landscape (see Chapter 2), including
that of the bottoms of bodies of water, affects the level, depth, location, and concentration
of the component of interest. For this reason, it is important that topography be taken into
consideration when the sampling plan and sampling sites are chosen. A sloping field

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FIGURE 5.9 Numbering across the top for surface samples. Greek letters
designate subsurface samples.

should be sampled differently from a flat field. A river bottom sampling plan should be
different from sampling a plateau above a river.
In the case of a sloping field, the top, middle, and bottom of the field should be
designated as separate sampling areas. If grids are used, a horizontal grid line should
occur at the top and bottom of the slope, with additional grid lines in the middle as
needed. A field with little slope can be sampled without regard to slope. However, such
fields commonly contain depressional areas that collect water from surrounding fields.
These areas are thus typically higher in organic matter and should be sampled separately.
Other unusual areas may be encountered, and these should be sampled separately, or at
least the unusual characteristics should be noted in the project notebook.
Sampling must occur on both sides of rivers, as well as the bottom. This is especially
true if contamination of the surface or subsurface is of concern. Even though it will not
look like this can happen, over time all streams and rivers gradually work their way back
and forth across the river valley and can thus both move and bury contaminants [16].

5.12. OTHER SAMPLING STRATEGIES FOR DIFFERENT FIELD

SITUATIONS
5.12.1. The Grab Sample
In taking a grab sample, the question is what is being grabbed. Too often the grab sample
is obtained in the excitement of first visiting a contaminated site. It is often taken without
regard to its position in the contaminated area, the depth of sampling, the sampling tool,
the labeling, or the type of container, and with no specific idea about the conditions of
transport or analysis. For these and for safety reasons, grab samples are not advisable.
In addition, the grab sample is particularly inappropriate where contamination may

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occur in an episodic fashion. The most common example is the episodic contamination of
water by agricultural chemicals, which occurs most frequently just before and after
planting. If a water sample is taken before or after the planting no unusual amount of
contamination may be found. It was not present yet or may later have been diluted to a
natural or undetectable level. Either sampling at regular intervals or some method of
taking a continuous sample, such as time-weighted average sampling based on solidphase extraction, thus may be appropriate.
A specific example would be the contamination of groundwater by nitrate from
agricultural fertilizer. The time to look for this is when fertilizer application is high and
plant use is low. Grabbing a sample at some other time will not illuminate the problem
[17, 18].
5.12.2. Agricultural Sampling
Farmland represents the largest area sampled and analyzed per year. Typically, only
surface samples 0 to 15 or 0 to 30 cm deep are obtained, and few if any deep samples are
taken. The typical soil analysis includes pH, cation exchange capacity, organic matter
content, and the amounts of calcium, magnesium, phosphorus, potassium, micronutrients,
and sometimes nitrogen. Such analyses are inexpensive and rapidly done.
There are three types of agricultural fields, each requiring different sampling strategies
(e.g., those planted to row crops, to grass, and to fields used for pasture). The most
commonly sampled are fields with row crops (i.e., any field containing crops planted in
discernible rows). Figure 5.10 shows a field planted to a row crop (corn) being sampled.
In this type of field, fertilizers and other agricultural chemicals may be broadcast, or
sprayed in such a way that the materials is spread evenly over

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FIGURE 5.10 Sampling a field containing a row crop (corn).

the surface. If uniform application has been made, then random sampling is appropriate.
In the case of row crops, however, it is common for some fertilizers and chemicals to
be placed in bands close to or in the row. When sampling this type of field, it is important
to know how the materials were applied so that samples are not taken from areas likely to
have high local concentrations of this material. This is particularly true if the analysis is
for the applied material or one of its components. It is also important because the applied
material may interfere or affect the analysis for other analytes.
A second type of field is one in which the fertilizers and chemicals are only added to
the surface in a uniform manner. This would include both hay fields and grassed areas,
such as golf courses, that are not pastured. A typical hay field is shown in Figure 5.11.
Here random sampling is appropriate.
In the case of fields used for pasture, sampling is a little more complex. Here
completely random sampling is not appropriate. Any place in which

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FIGURE 5.11 An example of a hay field to which additions would be made

uniformly.

animals congregate, such as around watering tanks or gates, will usually have high
amounts of manure, and thus is not representative of the field as a whole. Also, when a
sampling site is chosen it should not be covered by or be very near a pile of manure, as
this will again constitute an area with unusual characteristics. Even if the manure is
scraped off the top of the sample, organic matter and chemicals will have leached out of
the manure and into the soil. The amount leached will depend on how long the manure
has been in place and how much rain has fallen in the meantime. Both of these are
unknowns and cannot be corrected for. A pasture field with animals grazing is shown in
Figure 5.12.
The largest amounts of chemicals added to the environment each year are agricultural
chemicals. In this group, lime (CaCO3), which is usually spread evenly on the surface of
fields, is used in the highest quantity in areas with acid soils. In all areas, nitrogen
fertilizer is used in the greatest amount (second to lime on acid soils). Nitrogen is both
uniformly spread on the surface of soil and as a band near the seed in row crops. There
are also large amounts of pesticidesprimarily insecticides and herbicidesused, while
lesser amounts of fungicides and other agents to control nematodes, mites,

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FIGURE 5.12 A pasture field with cows.

and so on are applied. In some cases, organic additions are applied, often in the form of
animal manures, and these add not only plant nutrients, but also organic matter,
microorganisms, and antibiotics given to farm animals. Table 5.2 gives estimates of the
amounts of some amendments commonly added to agricultural fields.
5.12.3. Geological Sampling
Rock frequently has horizons that are horizontal, much like those in soil. Because of
upthrusting of rock layers and intrusion of lava or a different rock layer into an already
existing rock, however, there may also be layers that are not horizontal, and their slopes
vary from 0 to 90. An intrusion of one rock into another is shown in Figure 5.13. Thus,
it is possible to need to sample a layer that is vertical. In this case, a vertical sample may
extend for considerable depth and the same material is sampled through the length of the
sampler. It may be equally important in this case to sample adjacent rock vertically as
well; however, the horizons in the adjacent rock may be horizontal and thus require an
entirely different sampling procedure. A rock having horizontal layers is shown in Figure
5.14.
With steeply sloping layers, it is necessary to change sampling depth across the
sampled area. It will be essential to have some identifying characteristic that will show
the persons sampling that they are in the correct layer. A detailed record of the sampling
depth across such an area is essential.

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5.12.4. Environmental Sampling

Environmental sampling encompasses a wide range of activities that include not only air,
water, and soil sampling, but also such features as noise

TABLE 5.2 Typical Agricultural Additions to Soil in Order of Decreasing Amounts

Fertilizer/pesticide

Chemical composition

Amounts added/haa

Nitrogen

NH4+, NO3

100300 kg

Phosphorus

101 00 kg

Potassium

H2PO4
K+

Herbicides

Various

80900 g

Insecticides

Various

2002000 g

10100 kg

aAmounts do

not represent any specific value but are intended to give a general idea of the
amounts used. Specific information about amounts of herbicides and insecticides used can be
found in Crop Protection Reference, New York: Chemical and Pharmaceutical Press, 2003.

FIGURE 5.13 A rock intrusion is evident in the middle of the picture.

pollution. Although different samplers are used (see below), the three-dimensional grid

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sampling concepts are applicable to all sampling, as are using GPS and GIS. In a detailed
analysis of air, water, and soil, inorganic and organic gases, liquids, and solids, will be
determined. These analyses frequently require a sophisticated laboratory and
instrumentation that is expensive and time-consuming to operate, even when the
contaminant is known [19].
Often environmental sampling benefits from time-weighted average sampling.
Typically, placing an absorbent or cation or anion exchange polymer in contact with the
media, soil, water, or air to be sampled accomplishes this type of sampling. The polymer
is left in contact with the media for some time. It is then removed and the adsorbed
material extracted from it and analyzed. The absorbent can be extracted with a solvent, or
it may be heated to drive off the absorbed material. In the case of cation or anion
exchange resins, the extracting solution must contain a cation or anion that will replace
all cations or anions on the exchange resin.
The assumption is that the material adsorbed on the media is irreversibly attracted to
the absorbent under the conditions in the field. It is also assumed that the absorbent does
not become saturated during the

FIGURE 5.14 Rock showing various layers or horizons.

sampling time. If both these conditions are met, the amount of material on the sorbent
divided by the time it is in contact with the media will give the average concentration of
the contaminant in the media.
A word of caution is that there is another condition affecting the effectiveness of this
method; there must be continuous, intimate contact between the media and the sorbent

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during the entire sampling period. If the sorbent is placed in a river and the river level
alternately is above and below the sorbent, a representative sample for the time of
sampling will not be obtained. This same question would arise if the sorbent is alternately
in one layer and then in another layer of the media. Unless the time spent in each layer is
known, the average amount of contaminant in the layers would not be accurately known.
A similar argument can be made where the sorbent is in a medium that is moving. An
air-sampling sorbent that is alternately upwind and downwind from the contamination
source will produce an analytical result that is difficult or impossible to interpret. The
same thing would occur if the sorbent is placed in water having different currents or if the
water is moving over it in different directions at different times.
In soil there is always some question about the contact between the adsorbent and soil.
Coarse-textured and sandy soils have less contact than silty soils, while clay soils would
have the most contact between the soil and the adsorbent. The question of contact thus
must be adequately answered for both the absorbent being used or proposed for use and
the soil it will be used in.
This type of sampling can be very effective where there is an episodic nature to the
type of contamination being studied (i.e., contamination occurs at one time or over a
limited time during the year). It is also important in cases in which the time of the
occurrence of the contamination is not known. Placing absorbents in the media at various
times and removing and analyzing them after a certain time interval allows for
determination of the time of contamination [17, 18].
5.12.5. Underwater Samples
Often sampling stops at or above the water table. Sometimes it is necessary to sample the
soil or sediment at the bottom of a body of water, however. In this case, two additional
complications often occur. First, the material is loose and tends to disperse while the
sample is being taken. Second, the physical and chemical environment is very different at
the bottom of a body of water from the environment into which it is to be placed,
particularly in the analytical laboratory. These samples come from a high-pressure,
anaerobic, reducing environment and are put into a relatively low-pressure, aerobic, and
oxidizing environment. Because of these differences significant changes in components
of interest can occur if precautions are not taken in obtaining and handling the sample
(e.g., a sample containing large amounts of iron in an anaerobic, reducing environment is
black; exposed to air, the sample becomes yellow, then red, and the iron precipitates).
A special sampler is needed when sampling the bottom of streams, rivers, ponds, and
lakes. The sampler must retain the soil and its associated water and prevent
contamination by overlying water. As with other sampling, a grid pattern can be used
along with random sampling. The type of sampler needed can be constructed or obtained
from commercial sources (see Appendix B) [20].
5.12.6. Other Sampling
To a large extent, sampling water and air is similar to what has been described for soil.
Transect sampling should be carried out, including areas known not to be contaminated.

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This sampling must be three-dimensional (i.e., surface and subsurface water samples are
taken). Atmospheric samples should be taken at various altitudes. The sampling should
be as random as possible, but with attention to the different zones occurring in the area.
Differing zones are produced by strong currents of a river or in currents induced in a
lake by a river, and they do not give a true picture of the state of the whole river or lake.
Similarly, atmospheric samples taken at one altitude downwind from a pollution source
do not give an adequate picture of the pollution. The same can be said for samples taken
only upwind or away from entering water sources.
Here again sample size and uniformity of size are important, particularly if
comparisons are to be made between samples. The same can be said for samples in which
some regulatory criteria in terms of pollutant concentration are to be met [2123].
5.12.7. Monitoring Wells
Where is the water in the field going? Not only is it necessary to sample the soil or the
regolith, it is also essential to know where either rainwater or surface water goes when it
enters from adjoining areas and exits a contaminated site. It is assumed that incoming
water cannot be contaminated, but this must be verified. Incoming water is compared to
both the water in the contaminated site and the water exiting the contaminated site in
order to be sure of what is happening to the contaminant. Even if it seems that all the
water in the area stays in place or just flows over the top of the soil it is still essential to
keep track of it and its condition in and around the contaminated site.
To keep track of water and its condition, contamination, and movement, it is essential
that wells be installed at the contaminated site. The most logical location is downstream
from the contamination. It is essential to also have wells on all sides and upstream,
however. These wells need to be sampled frequently throughout the sampling and
remediation in the area. Keep in mind that well monitoring is recommended and
sometimes required, even if the material at the site is to be removed for remediation or
cleaning at some other site. Also, such monitoring wells are monitored for a period of
time after the site has been certified as being clean [24].
5.12.8. The Number of Samples Needed
Methods for estimating the total number of samples needed to obtain a representative
sample are presented in Chapter 6.

5.13. SAMPLE HANDLING

Sample locations can be chosen before actually going to the field. When in the field it is
sometimes tempting to move the sampling site if it is in the middle of a tuft of grass, on
top of a rock, or under a layer of plant residues. As much as possible, the site should not
be changed. Take the sample near to the plant or under the rock, or take plant residue, if
at all possible. Rocks or plant material occurring in the sample when it is removed from
the soil should be left with the sample rather than being picked out. To maintain sample

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integrity and for the safety of the sampler it is best not to touch the sample with bare
hands. In all cases, samples should be moved directly from the sampler to the sample
container. They should not be handled and should not be removed, placed someplace, and
then moved again into the container [12, 13].
Cleanliness is also important. During sampling gloves will often be worn, and these
must be changed between sampling events, particularly if the samples are heavily
contaminated. Also, the sampling instrument needs to be cleaned between sampling
events. This may involve washing or simply wiping the sampler.

5.14. SAMPLING USING GPS

Both the transect and detailed sampling sites are recorded using maps produced during
the presampling phase. These can be recorded using either UTM or latitude and
longitude. Using the UTM system or longitude and latitude, the notation for the position
of the sites will take the form given in Table 5.3.
It is highly recommended that sampling sites always be given one of these two locator
designations. During each sampling exercise a reference table giving the sample numbers
and the corresponding locator positions will be produced. Note that the designations are
given as examples and are not meant as actual positions on the Earths surface. The
project notebook designations are similar to those given in the notebook example in
Chapter 3. However, they are not intended to represent the same samples.
If digital orthophoto quarter quadrangle (DOQQ) maps are being used, the position of
the samples can be either manually entered into a computer or downloaded from the GPS
unit. Then, using ArcView or similar GIS software, a map showing the location of the
sampling sites can be produced by the computer. Such a map is shown in Figure 5.3, and
can be produced using a GPS unit and a DOQQ map. Note that the map has a grid on it
and sampling is done on the basis of this grid. It might also be noted that the samples are
taken from random spots in the grids.

TABLE 5.3 Examples of Sample Sites Locations Using Universal Transverse Mercator
(UTM) and Latitude and Longitude Designations

UTM designations
Field notebook designation

Easting

Northing

AC12a122602

485400m.E. 3704300m.N.

AC12b122602

485500m.E. 3708310m.N.

Latitude longitude designations

Latitude

Longitude

AC23a010603

N 47 19.56

E 101 42.84

AC23b010603

N 47 19.57

E 101 42.83

Figure 5.3 is intended as an example of how sampling might be done, but it does not
represent an actual sampling situation. Examples of different ways of designating the

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samples are also shown. In the lower right-hand corner, the sampling site is designated by
two sets of three numbers. These are the last three digits of the longitude and latitude
positions. The whole position is N39 26.456 and W83 48.157. Only the three last digits
need be shown, however, because the first four digits do not change throughout the field.
This designation lacks the initials of the person doing the sampling and does not give the
location in the project notebook in which a description of the sampling site is located.
The next sampling site is labeled by the samplers initials and the page in the project
notebook on which the samples are described. This is sufficient if the project notebook
page also gives the position in the field using longitude and latitude. The initials of the
person doing the sampling and six numbers representing the latitude and longitude
location of the sampling site identify the next sample. In the last case, the operators
initials, the page number in the project notebook (13b), and the longitudes and latitude
position are given.
In this last case the full project notebook designation plus the longitude and latitude
may be too big to fit on the map, and an abbreviated form may be called for. For
example, sample designation AC13b579190 might be simplified to AC13b579 or simply
13b. This may seem awkward, but is both invaluable as work continues and time-saving.
In all of the above situations, a second set of samples taken from a similar
uncontaminated soil in a similar location is needed as a comparison and control. It is
important in taking this sample that it comes from a field that has not been (and is not
now) contaminated by any process, especially in relationship to contamination occurring
at the field of concern. Again, both surface and subsurface samples are needed for
comparison.

5.15. DETERMINING SAMPLES SITES

Random places to be sampled can be obtained by throwing darts at a map of a field and
seeing where they land. In the case of field sampling, we could, for instance, take the
field shown in Figure 5.2, enlarge it, and throw darts at it. Each place a dart lands would
be a place at which a sample would be taken. Note that if this were done no distinction
would be made between different soil types. Another way would be to assign a number to
all possible sample locations in a field and randomly pick and sample these locations.
Because there are an infinite number of possible locations, this is not a practical
approach. Neither of these procedures is typically used in field sampling.
Another approach would be to pick a spot at the edge of a field as a starting point for
sampling. For example, point A in Figure 5.1 is chosen as the starting point. Two
randomly picked numbers are used to represent paces west and north. (Random number
generation will be covered in Chapter 6.) The respective paces are taken and a sample
obtained. This is then repeated to obtain a second sample. If only positive random
numbers are possible, then sampling would proceed north and west across the field,
leaving many portions of the field unsampled. If, on the other hand, both negative and
positive numbers are used, a more random sampling covering more of the field would
occur.
Although the above cases are statistically valid, they are not generally useful or

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practical in a typical field-sampling situation. First, it is not possible to analyze a very

large number of samples for each and every area of interest. Second, the size of the area
to be treated may be controlled by other than pure sampling or statistical considerations.
For instance, when soil plant nutrient levels are determined as a basis for the commercial
application of agriculture chemicals, the size of the area sampled is determined by
equipment size, capacity, and economics.
For contaminated fields, we are generally interested in differentiating between
contaminated and uncontaminated areas. It is important to know when the level of
contaminant is at or below some specified target level. When three samples from an area
have analytical results showing that the contaminant is below the target level at the 95%
confidence level, then the desired information has been obtained and further sampling
may not be needed. (Confidence levels will be discussed in Chapter 6.)
For these reasons, a more systematic sampling scheme is often used. An imaginary grid
can be set up to cover the field. At this point each grid can be randomly sampled, or a
selected number of grids can be sampled on a random basis. Even fewer random samples
can be obtained by specifying positions within each grid area in which samples are to be
taken. In this case, these positions can be repeatedly sampled to determine the changes in
contaminant or component concentration over time.
In the case of agriculture, grids large enough to be treated individually are usually
sampled. Here the desire is to have an estimate of the amount of fertilizer to be added to
reach a certain yield goal, but not to cause environmental harm. Also, if an adjacent grid
requires more or less fertilizer that adjustment can be made as needed. In this type of
sampling, the average amount of available plant nutrient present in each grid is important
for making fertilizer application. It should be kept in mind that very precise and accurate
applications rate cannot be obtained, and because of this it is not necessary to be able to
distinguish very small differences.
When contaminated areas are sampled the desired sampling outcomes are different.
Where in situ bioremediation is to be carried out repeated sampling of the area will be
necessary. Here we wish to make sure that the contamination is not spreading and to
know when the contaminant has fallen below a specified level in a specific area. In other
cases, the soil in the field sample is to be removed and remediated in another location. In
this case, sampling will only be done once, and so consideration of repeated sampling is
not in question [15].

5.16. QUALITY CONTROL

There is always a great deal of concern regarding quality control and quality assurance.
Does the analysis and reporting of the results accurately and faithfully represent the
situation in the field or in the environment? Often samples are spiked; a precisely known
quantity of contaminant is added to a control sample. Spiking should be done in the field
after the sample is in its container. If this precisely known quantity has changed during
transportation, storage, or handling, the results of analysis of samples are suspect.
A problem arises when the contaminant of concern is either highly toxic or volatile. It
is undesirable to increase the amount of toxic material in a sample, both from the

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standpoint of the safety of the personnel adding the contaminant and the person doing the
analysis. In such cases, a surrogate may be added to the sample. This is a compound that
is not toxic (or is very much less toxic), but has the same or similar physical, chemical,
and biological properties as the component of interest. The surrogate allows one to
determine if there is any change in the sample between sampling and analyses without
undue danger [25].
Liquid or solid contaminants or surrogate compounds added to soil or regolith
materials do not cover them uniformly. Only analysis of the whole sample will give an
accurate picture of the fate of the contaminant or surrogate. A subsample may give an
erroneous result because of nonuniform distribution, which can occur even if the sample
is ground, sieved, and mixed exhaustively.

5.17. LABELING
Labeling seems like a simple part of any sampling activity. Incomplete, unreadable, and
missing labels cause error, however, as well as a great deal of wasted time and money.
5.17.1. Labeling a Sample
Labels must include reference to the field position from which the sample was taken and
to the page in the project notebook on which sampling is described. Numbering of the
designated sampling areas, as indicated in Figure 5.9, is done sequentially. The sample
areas below the surface are indicated by Greek letters. In this instance, one would know
that sample 15 is the second sampling area below surface area 15. This gives an
unequivocal designation and location to this sample. The question might be asked as to
why Greek letters are used when the Roman alphabet will do. What most researchers find
is that they have use for the alphabet in designating other aspects of the sample. We
therefore save our alphabet for these uses and use the Greek alphabet for designating
subsurface sampling areas. A sample number must be unique, but allow for easy lookup
when needed.
The project notebook page on which the sampling is described is on the label, which
must also show the date and time sampling was performed as well as who took the
sample. Additionally, where it is to be stored and shipped must be shown, as well as the
shipping route.
There are other considerations in deciding on how to label a sample. First, during
handling, will the samples be subject to wetness, even if only from workers hands? The
answer is always yes. This means that any numbering or other designation that can be
removed with water will be removed, or at least smeared until it is no longer
recognizable. The first step is thus to use only tested permanent markers (e.g., a test
sample number is applied to the sample container when it is dry, and then it is wiped with
water, soap and water, etc.).
Another strategy is to put the sample label in several places on the sample container.
Thus a copy of the label can be put on the bottom of the sample container, since people
will not be rubbing against the bottom as much as the sides. The drawback is of course is

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that the bottom may be more moist that the top, and this may lead to smearing. The
bottom may also rub by sliding during transport. If the sample container is one that is
folded over and sealed by holding the folded area in place with ears, then the top that is
folded over is a good spot for a copy of the label. Other good labeling places will exist on
other types of sample containers.
This is not to indicate that the label should not be placed in some prominent location. It
should. It must occur prominently on the side on the container and must contain all the
information indicated above and information as to the organization requiring the
sampling or paying for the analysis. Other pertinent data, such as phone numbers and email addresses, should be included as necessary. This label is for convenience and
efficiency in processing samples. Sample numbers in other places are for safety and need
only be the sample number. Serious consideration should be given to including bar
coding on the label. (See Chapter 3.) Bar codes can be placed on all samples and a
duplicate placed in the project notebook and the chain of custody document. (See Chapter
8.) Not only does this simplify keeping track of samples, it will also decrease the chance
of error in reading and reporting sample labels [26, 27].

5.18. CONCLUSIONS
Sampling starts when all the preliminary data have been gathered and the equipment has
been assembled. A map of the area to be sampled is prepared, giving its position on the
Earths surface. Once this is done, the next step, assuming ground-penetrating radar
(GPR) and remote sensing are not to be used or have already been used, is to do a
transect sampling, including contaminated and uncontaminated areas. With these data a
detailed sampling plan involving gridding and labeling the areas to be sampled is
completed. The sampling plan may be random or may include a combination of random
and nonrandom components. As the samples are taken they are placed in suitable
containers for transport and analysis and given appropriate labels relating them to the
field notebook and position on the Earths surface. Additional tools such as monitoring
wells and GIS may also be used to obtain a more complete picture of the sampled field.

QUESTIONS
1. Describe the differences between a grab sample, transect sampling, and detailed
sampling.
2. What are two coordinate systems used in GPS?
3. Describe all the information that a label should contain and where it should be on the
sample container. In answering this question do not limit yourself to this chapter alone.
4. What is the accuracy of GPS and remote sensing?

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141

5. What is unusual about samples that are taken deep in water or soil that is saturated
with water? What precautions need to be taken with these samples?
6. There are three common types of samplers. Name the sampler types and describe the
situations to which they are best suited.
7. Explain how and why Greek letters might be used in labeling a sample.
8. The spectral range for satellite imagery is over what range of the electromagnetic
spectrum?
9. Explain which sample container would be used for a soil sample containing a heavy
metal contaminant and one containing a volatile organic carbon (VOC) contaminant.
Explain the bases of your choices.
10. Explain grid sampling.

REFERENCES
1. Wagner G, Desaules A, Muntau H, Theocharopoulos S, Quevauviller P.
Harmonization and quality assurance in pre-analytical steps of soil contamination
studiesConclusions and recommendations of the CEEM soil project. Sci Total
Environ. 2001; 264:103117.
2. Crptin J, Johnson RL. Soil sampling for environmental assessment. In: Carter MR, ed.
Soil Sampling and Methods of Analysis. Ann Arbor; MI: Lewis, 1993:518.
3. Patterson GT, Site description. In: Carter MR, ed. Soil Sampling and Methods of
Analysis. Ann Arbor; MI: Lewis, 1993:13.
4. Petersen RG, Calvin LD. Sampling. In: Klute A, ed. Methods of Soil Analysis. Part
1Physical and Mineralogical Methods. 2nd ed. Madison, WI: American Society of
Agronomy and Soil Science Society of America, 1994:3351.
5. Letham L. GPS Made Easy. Seattle: Mountaineers, 2001.
6. Conyers, LB, Goodman D. Ground-Penetrating Radar: An Introduction for
Archaeologists. New York: Rowman & Littlefield, 1997.
7. Lunetta RS, Elvidge CD. Remote Sensing Change Detection: Environmental
Monitoring Methods and Applications. Chelsea, MI: Ann Arbor Press, 1998.
8. GSFC Earth Sciences (GES) Distributed Active Archive Center,
http://xtreme.gsfc.nasa.gov/.
9. Earth Observing System. http://edcimswww.cr.usgs.gov/pub/imswelcome/index.html.
10. Korte GB. The GIS Book. 5th ed. Albany, NY: OnWord Press, 2001.
11. Description and Sampling of Contaminated Soils: A Field Pocket Guide. EPA 625
1291002. Cincinnati, OH: National Center for Environmental Publications, 1991.
12. Bates TE. Soil handling and preparation. In: Carter MR, ed. Soil Sampling and
Methods of Analysis. Ann Arbor; MI: Lewis, 1993:1924.
13. 5th ed. Sample Handling and Transmittal Guide,
http://www.rdc.uscg.gov/msl/downloads1.html.
14. Dent D, Young A. Soil Survey and Land Evaluation. Boston: Allen & Unwin, 1981.

Field sampling

142

15. Koryta J, Stulik K. Ion Selective Electrodes. 2nd ed. Cambridge: Cambridge
University Press, 1984.
16. Hollands KR. Comparing Topography Soil Sampling with Other Known Precision
Ag Methods. http://www.sbreb.org/96/soilmgmt/96p98.htm.
17. Battaglin WA, Hay LE. Effects of sampling strategies on estimates of annual mean
herbicide concentrations in midwestern rivers. Environ Sci Tech. 1996; 30:889896.
18. Koziel JA, Noah J, Pawliszyn J. Field sampling and determination of formaldehyde in
indoor air with solid-phase microextraction and on-fiber derivatization. Environ Sci
Tech 2001; 35:14811486.
19. Brady NC, Weil R. The Nature and Properties of Soils. 12th ed. Upper Saddle River,
NJ: Prentice-Hall, 1999:656658.
20. Fisher MM, Brenner M, Reddy KR. A simple, inexpensive piston corer for collecting
undisturbed sediment/water interface profiles. J Paleolim 1992; 7:157161.
21. Hess-Kosa K, Hess K. Indoor Air Quality: Sampling Methodologies. New York:
Lewis, 2001.
22. Compilation of EPAs Sampling and Analysis Methods. 2nd ed. Keith LH, ed. New
York: Lewis, 1996.
23. National Field Manual of the Collection of Water-Quality Data. Techniques of WaterResource Investigations. Book 9. Handbooks for Water-Resource Investigations.
http://water.usgs.gov/owq/fieldmanual/ (search for Book 9).
24. Monitor Well Design, Installation and Documentation at Hazardous and/or Toxic
Waste Sites (Technical Engineering and Design Guides as adapted from the U.S. Army
Corps of Engineers, no. 17). American Society of Civil Engineers. Reston, VA: ASCE
Press, 1996.
25. Klesta EJ Jr, Bartz JK. Quality assurance and quality control. In: Klute A, ed.
Methods of Soil Analysis. Part 3Chemical Methods. Madison, WI: American
Society of Agronomy and Soil Science Society of America, 1996:1948.
26. Holkham T, Holkman T. Label Writing and Planning. New York: Aspen, 1996.
27. Bushnell R, Dooley T. Bar Code Compliance Labeling for the Supply Chain: How to
Do It. Surf City, NJ: Quad II, 2000.

6
Statistics
Statistics provide very powerful tools for analyzing data, including tools for analyzing
sampling activities. Some of these common tools are determining the number of samples
needed, standard deviation, regression analysis, and extraneous values, and predicting the
component values between sampled points. In all cases calculators or computers
equipped with standard software, including spreadsheets, can be used to do statistical
calculations. In order to understand what information the statistic is providing, however,
and to be able to explain this to others, it is important to know how the statistic is
calculated. This is also important when trying to understand what others are trying to
explain using statistics.
It is common to hear people talk about median, mean, average, one standard deviation,
and so on. When such conversations occur, are the speakers using the terms correctly?
How does what they are saying affect your sampling plan? On the other hand, can the
statistics being used in the sampling plan be explained to others?
There are a great many symbols used in statistics. It is important to be able to keep
these in mind while studying and interpreting statistical results. Table 6.1 gives some of
the most commonly used symbols and the terms they represent. These will be particularly
important, whether calculation of statistics is done by hand or using a computer, because
once the computer has done the calculation the experimenter must still interpret the
statistical results.
Statistics can be calculated by hand; however, in most cases calculations will be
carried out using computers and more or less complicated statistics programs. Although
for simple calculations a handheld calculator can be used, in all cases a computer will be
preferred. In the case of geostatistics the calculations are never done by hand or handheld
calculators because the equations are too complex. Keep in mind that some statistics
programs are difficult to learn and use, while others are not. In addition, some statistics
programs leave the experimenter in charge; some take charge.
For example, some statistics programs require setting up the statistics or the sampling
plan before obtaining or entering the data. Other programs allow the input of the data and
subsequent application of various statistical calculations. Because it is not always clear
what information will be needed or which statistic might need to be applied, the latter
approach is usually preferable. In Figure 6.1, after the data are entered it is found that two
data points are missing (X in A2 and Y in A6). If all the statistics had been set up
beforehand [e.g., the number of samples and the degrees of freedom (n and n1)], the
whole setup would have to be changed because of the missing data points.
If the data are entered and the statistics subsequently calculated, two possible
adjustments could be made. First the data could be calculated

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TABLE 6.1 Important Statistical Symbols and Their Meaning

Symbol

What it is

How is it obtained

Population mean

Add all data points and divide by the number of data points in the
population.

Sample mean

Add all sample data points and divide by the number of sample
data points taken.

s2

Sample variance

Obtained by taking the difference between the sample mean and

each sample and squaring and dividing by n1.

Sample standard
deviation

Take the square root of s2, the sample standard variance.

Hypothesis

The experimenter determines the null and alternate hypothesis.

t statistic

Obtained from table of t-values.

F statistic

Obtained from table of F-values.

FIGURE 6.1 Total petroleum hydrocarbons (TPH) levels in various areas of a

field.

without the missing data points using a smaller n and n1. On the other hand, it might be
decided to calculate the missing data points using kriging (described below). In either
case, being able to manipulate the data after they are entered would facilitate these
changes.

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6.1. RANDOM NUMBERS

In Chapter 5 random numbers were used to determine where samples were to be taken.
How does one obtain random numbers? A simple, unsophisticated way to do this is to
place little pieces of paper with numbers on them in a hat and pull them out one by one.
Random numbers can be more easily generated with many handheld calculators and with
all computers. Normally there will be a function called rand that will return random
numbers. Sometimes it will be necessary to multiply or truncate the numbers obtained to
produce numbers in the range you wish to have.
As long as the numbers are used as given by the program they are random, even if they
are multiplied by 10 or truncated to only one decimal place or a whole number. Table 6.2
is an example of random numbers generated by Excel using = rand()*10. The result of
this operation is the random numbers given in column 1. The truncated and rounded-up

TABLE 6.2 Random Numbers Generated by Excel Using=rand()* 10

Rand()*10

Rounded up

8.879528391

1.622723374

5.014714332

3.285093315

1.682229083

3.64113318

6.351850918

6.660649484

6.174987005

4.024443714

4.247216289

9.915704505

10

6.332125286

8.592222671

2.90158629

3.030321588

0.448112927

9.875606847

10

Note: Column 2 is the random numbers rounded to whole numbers.

numbers corresponding to these random numbers are given in column 2. Any time

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random numbers are needed this is the method best suited to obtaining them.

6.2. VARIATION
When dealing with environmental samples it is common to have variation that is much
larger than the chemist or mathematician would like. For some samples a variation of
1% might be acceptable; however, with environmental samples a variation of 10%
may represent a very accurate measurement.
For example, a soil core 1.9 cm in diameter was taken and the pH of each of three
subsamples was measured, first with the fresh sample, then the sample after it was dried,
and again after the sample was dried and mixed. In each case subsamples were mixed
with water (1:1 ratio), and the pH determined using a standardized pH meter. Table 6.3
gives the soil pHs

TABLE 6.3 The pH Measurements of Three Replicate Samples from a Soil Core in the
Original, Air-Dry, and Air-Dry Mixed Conditions

Sample
AC12a
AC12b
AC12c
Mean or average
Standard deviation

Fresh wet
sample

Dry-sieved
sample

5.30
5.03
5.01
5.11
0.16

5.32
5.41
5.27
5.33
0.07

Dry-sieved
mixed
5.23
5.28
5.30
5.27
0.04

Note: Unpublished data from senior research project of Luke Baker, Chemistry
Department, Wilmington College, Wilmington, Ohio.

found. The pH values in the second column were obtained after the core, which was
sealed in a plastic bag, was crushed by hand and mixed while still in the bag. The third
column is the same samples after air-drying and sieving (but no further mixing). The
fourth column is the same samples after mixing on a mixer overnight.
It will be noted that variation in the first set of measurements is quite large. Even
though the first measurement appears to be in error, including it gives a better estimation
of the mean than excluding it. Drying the sample leads to a decrease in acidity, while
sieving and mixing had little effect on the pH but decreased the variability. The
difference between a pH of 5.11 and a pH of 5.33 is so small that it would cause no
change in a remediation plan. Later in this chapter these pHs will be compared and their
relationship to each other examined [1].

6.3. POPULATION
In sampling groups of people or fields of corn the concept of sampling a population is

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self-evident. Air, water, and soil appear to be continuous media, however, and not related
to populations at all. In this case each sample is considered a member of a population.
One way of looking at this is to ask if the samples are part of a group of samples that are
the same or if they are from a different group of samples.
Soil scientists do define a soil individual; that is, a volume of soil that has well- and
precisely defined characteristics. Such a soil, which is 1 to 10 m2 and 1.5 to 2 meters
deep, is called a pedon, and a group of pedons in a field would be called a polypedon. It
is rare that a field to be sampled would consist of only one type of soil or pedon,
however. When soils are mapped, as in a soil survey (see Figure 1.2 in Chapter 1), the
different soils noted are not technically pedons, but soils of similar characteristics called
mapping units. Soil sampling thus is not sampling individuals in the soil science sense.
Both the atmosphere and hydrosphere are also seen to be continuous and homogenous.
When they are sampled, however, each sample is considered to be a member of a
population of samples, just as soil samples are.
Often three soil cores will be crushed and mixed to provide a sample for analysis. This
sample is also considered to be a member of a population of soil samples. This is true as
long as it is analyzed as one sample. It is expected that these samples will show the same
characteristics as any other sampling of this population or area; that is, plotting the
frequency of a characteristic versus, the number of individuals showing that the
characteristic will produce a standard, symmetrical bell-shaped curve. (See Figure 6.2.) A
characteristic that produces such a curve when measured and graphed is a normal random
variable. There are many similar curves with different absolute shapes that are considered
bell-shaped curves. The shape of the curve and the fact that the mean and median are the
same shows that its probability distribution is a normal distribution.
This same standard distribution argument can be made for other samples. A series of
air, water, or regolith material samples are all expected

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FIGURE 6.2 A bell-shaped curve. The line shows the median and the mean for
this set of data. (A true bell curve is calculated using the formula
).

to have this standard normal distribution characteristic. In all cases this assumes that a
large population is sampled; in most field sampling situations, however, neither a large
sample population nor a large number of samples is feasible for reasons of either time or
economics. Unless we know otherwise, the assumption is that the population is a normal
distribution and that the sample taken is representative of that normal distribution.
The shape of the curve will be significantly different for a population if the mean and
median are different. This will produce a bell curve that is not symmetrical (or it is
skewed). This would mean that on either side of the mean the curve would be different.
Such a situation is illustrated in Figure 6.3.

6.4. HYPOTHESIS
One of the first steps in using statistics is to develop a hypothesis that is used in
interpreting the results of the statistical analysis. Typically the hypothesis is that two
populations or sets of data represent two different populations or are from the same
population. In field sampling we are often interested in using statistics to determine if an
analyte is above or below some cutoff level. Another way in which hypotheses are used is
to determine if two areas being sampled have the same or different levels of
contamination. Two

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149

FIGURE 6.3 Graph showing a rightward-skewed distribution (series 2). The

dashed line is the median and the solid line the mean.

adjacent areas having the same level may be sampled as one unit rather than two, saving
time, effort, and money.
Examples of hypotheses are given in Table 6.4. The first two hypotheses state that the
population sample is equal to (in the first case) or not equal to (in the second case) the
sampled population, respectively. The second two equations state that the population is
larger than the sample population and smaller than the sample population, respectively.
Hypoth-eses are extremely valuable and powerful tools in any research. Whether or not a
hypothesis is correct is immaterial, because no matter which is the case, valuable
information about the samples and the populations being studied is obtained. Hypotheses
should never be looked at as being correct or incorrect.
Looking at the pHs in Table 6.3 we might have a hypothesis that the pHs are all from
the same population (i.e., all the samples are the same). This represents the first
hypothesis in Table 6.4 and is the one we will use to test whether or not the pHs are the
same. Another way to state this is that the method of determining the pH of soil does not
change the pH obtained. This hypothesis will be tested later in this chapter [2].

6.5. MEDIAN AND MEAN

Two essential pieces of information about a set of data is to determine the central
tendency, which is the median or the mean, and the standard deviation. These numbers
form the basis for all other calculations. The median is found by arranging the data in
ascending or descending order. If the number of data points n is odd, the middle number
is the median. If the number is even, the median is the average of the middle two
numbers. There are other ways of calculating the central tendency, such as the average

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(same

TABLE 6.4 Hypothesis Used in Statistical Analysis Where 0 is the Specified

Population Mean and Is the Actual Population Mean

Hypothesis

Meaning

t statistic

H0: =0

Populations are the same.

Two-tailed
t

H0: 0

Populations are not the same.

Two-tailed
t

o is larger than . Sampled population is smaller than

specified population.

One-tailed t

o is larger than . Sampled population is larger than

specified population.

One-tailed t

as mean) and mode. The value of the median, however, is that 50% of the values fall
above it and 50% below.
The other central tendency calculation is the mean, which is the same as the average
and is used to calculate other statistics. To obtain the mean of a group of numbers, the
numbers n are added together to find the total. This total is divided by the number of
numbers and the result is the mean. If the data set is large and evenly distributed, then all
the measures of central tendency will produce the same result. When the median and
mean are not the same, the data are said to be skewed. A graphical representation of such
data is given in Figure 6.3. If the mean is to the right of the median, the data are said to be
rightward skewed, as shown in Figure 6.3. If it is to the left, it is said to be leftward
skewed.
When discussing statistics it is important that everyone knows which measure of
central tendency is being used. As shown above, the relationship among the median,
mean, and the other values of central tendency can provide useful information about the
nature of the data.
As an example of the calculation of the mean, take the data from area A4 on the map in
Figure 6.1. These are the analytical results for the concentration in ppm of total petroleum
hydrocarbons (TPH) in the four surface core samples taken in this location. There are
four analytical results273, 286, 298, and 310 ppm, respectively. The mean is
represented by the term
which is called x bar. This term is found by adding numbers
and dividing the sum by n (n is the number of numbers)

or taking the values for area A4 in Figure 6.1 would give

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151

This number is found by rounding up.

The median for these same data is also 292 ppm. This is obtained by adding the central
two numbers (i.e., 286 and 298) and dividing by 2.
Carrying out the same calculation for B4, the mean
is found to be 909 ppm
(rounded up). Even though the means are different from those for A4 they do not provide
enough information to tell if the two areas have different amounts of TPH or not. For this
determination calculation of the standard deviation, shown below, is needed.
The average pHs given in the next to bottom row of Table 6.3 were also obtained in
this way. In this case each of the pHs shown was obtained by finding the mean of the
three determinations of the pH of the soil core shown in the column above it [3].

6.6. STANDARD DEVIATION

The first step in determining if the two average TPH levels or the average pHs calculated
above are different or not is to first calculate the sample variance s2 and the standard
deviation s. The first step in this process is to determine how far away from the mean
each of the data points is. To obtain this information each data point is subtracted from
the mean. From above the mean
and
273292=19 286292=6 298292=6 310292=18
Because this gives us a mixture of positive and negative numbers the mean of these
numbers is either 0 or very close to 0, and thus gives little information about the
variability.* To make the calculation more meaningful the differences are squared, which
makes all the numbers positive. Thus
(19)2=361 (6)2=36 62=36 182=324
A more useful mean is then determined for these squared numbers:

* If no

rounding is used in determining the mean, the sum of the deviations from the mean will be
0.
The letter is used to represent a summation. It tells us that the group of numbers represented by
are added together. The subscript i indicates that there are several different numbers. In
this case the first number, 273, is substituted for xi and the calculation is carried out. The second
number is then similarly taken, then the third, until all the numbers have been substituted for xi and

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the calculation carried out. Finally, all the numbers so obtained are added together. This is
summarized in the following equation:

This calculates the population variance (2). In mathematical terms what has been done in
the numerator is shown by the term

This term says that the difference

between the mean

and the value is
calculated then squared and the numbers added together to give the answer (numerator).
The final step is to divide this sum by n. This type of calculation is programmed into most
handheld calculators and computers. It is such a common term that it is part of the
standard keypad of many handheld calculators and the tool bar of Excel.
In calculating the sample variance n1 (or in this example, 3) would be used as the
divisor. The number n1 is sometimes called the degrees of freedom. The reason for
using this number rather than n will not be covered here, but can be found in all standard
statistics books, such as those given at the end of this chapter. When the sum of the
deviations is divided by n1 the number obtained is frequently represented by the symbol
s2, which is called the sample variance. The sample variance is used as an estimator of the
total population variance. The mathematical formula for carrying out the sample variance
calculation is

A shortcut or direct way to carry out this calculation would be to use the following
equation:

Although this equation looks complicated and is, using a computer it can easily be
programmed into the spreadsheet and used to make calculations. In most cases the
spreadsheet will already have the capability to calculate the standard deviation, and so
entering the equation is not necessary.
To calculate the standard deviation, represented by s, the square root of the variance
(i.e.,

) is determined. Thus

At this point we have the standard deviation, which is 15.87. This is also expressed as and
has the units ppm, just as the original data do. This is interpreted to mean that the actual

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value is most likely to be somewhere between 292+15 or 307 and 29215 or 277. The
smaller the standard deviation, the better the number or the more precise the
measurements.
The standard deviation can be used in many ways. In field sampling it is often used to
determine if a portion of a field is above or below a predetermined level of some
component. In the case of plant nutrients it may be used to tell if the nutrient is within a
desired range.
Another way to look at this is to ask how many measurements are within one standard
deviation of the mean. In this case one standard deviation is 15 ppm or 15 ppm; that is,
how many or what percentage of measurements are within one standard deviation above
and below the mean? Typically it would be expected that 68% of the measurements
would fall within one standard deviation. In the example used here a very small number
of measurements (only four) are used, and only 50% are within one standard deviations
(i.e., between 307 and 277).
In Table 6.3 the standard deviation for the pHs obtained for each sample is given. The
second and third samples are within one standard deviation of each other, while the first
sample is outside one standard deviation of the other two samples.

6.7. DIFFERENT OR SAME POPULATION?

There are a lot of statistical tools appropriate to the comparison of two sample means
Most of these are appropriate for a more complicated analysis. When only a relatively
simple analysis is needed, the statistic used is called the t statistic or student t. This is the
statistic that will commonly be used in almost all field and environmental sampling.
Is the average TPH concentration in area A4 the same or different from the
concentration in sample area A3? The first step is to decide on a null hypothesis. In this
case let the null hypothesis for A3 be H0: =457.5. The alternate hypothesis is that H0:
<457.5. For this calculation the degrees of freedom are 3 (i.e., n1 or 41). Is the of
A3 smaller or larger than the mean of A4, which is 291? To determine this, a t-value for
these data is calculated using the two-sample t-test using the following equation:

The for the area A4 is 291.75 and the 0 for A3 is taken to be 457.5.
How confident can one be that the two means are the same or different? Looking at
Table 6.5, there are confidence intervals for values of t. If a confidence interval of 95% is
chosen, this means that there is a 95% chance that the samples are the same if the t-value
is less than that given in Table 6.5. Looking at Table 6.5 it is seen that t at the 95%
confidence

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TABLE 6.5 Abbreviated Critical Values of t and Q

Percentage confidence intervals for t

n1

90%

95%

1
2
3
4
5

3.078
1.886
1.638
1.533
1.476

6.314
2.920
2.353
2.132
2.015

99%
31.821
6.965
4.541
3.747
3.365

99.5%
63.657
9.925
5.841
4.604
4.032

90% confidence interval for Q

Q0.90

0.941
0.765
0.642

interval is found to be 2.353. Because this value is less than the calculated t the null
hypothesis is rejected. This means that the two means are different and represent two
different populations.
This seems like an obvious outcome because the means are so different. The question
could be asked if areas A1 and C6 are different or the same. Again a null hypothesis is
needed. From Table 6.4 we let the null hypothesis be H0: =45. (The data are shown in
Table 6.6.) Then the calculation of t becomes

TABLE 6.6 TPH Means and Standard Deviations

Sample number
A1
A3
A4
A5
B1
B2
B3
B4
B5
B6
C5
C6
a

Mean (rounded)
44
455
292
165
31
324
1090
905
717
455
108
51

Standard deviationa
6
49
15
8
1
17
100
31
29
25
6
2

Truncated

This t-value is smaller than the t-value for the 95% confidence interval, and so the two

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are most likely (95% confident) to represent the same populations. If the confidence
interval was chosen to be 99.5% (see Table 6.5) the hypothesis would also be true, and
the two areas would be considered to be sampled from the same populations. However,
the confidence interval should always be chosen before the statistics are calculated,
should be used consistently, and should not be adjusted afterwards.
Keep in mind that the smallest number of measurements that can be treated statistically
is two. Less that this and n1 becomes 0. In realistic terms the smallest number most
people like to work with is three. This is a compromise between a large number of
samples (which would be prohibitively expensive, both in terms of time and money) and
so few samples that no inferences can be made.
The t statistic can also be used to determine if the true TPH level in any sampling area
is above or below the cutoff level. Looking at areas C3 and C4 it is obvious that the
levels are above the cutoff level, assuming this to be 500 ppm TPH, and that the sampling
plan needs to be amended to sample unsampled adjacent areas. You might wish to check
areas A3 and A6 to be sure that they are below the cutoff level. To do this a different t
statistic is used. This is the one-sample t statistic. This calculation would be carried out
using the equation below, where 0=500.

Also, areas A2 and A6 are missing data points, which need to be determined or estimated
using kriging. (See below.)
In the examples given here sample means and hypotheses are evaluated individually.
There are tools and methods for evaluating multiple sets of data points at the same time.
Analysis of variance is one of these methods and will be discussed below [4]. For the
data in Table 6.3 the t-test can be used to determine if the results from the various tests
are the same or different.

6.8. EXTRANEOUS VALUES

In all field sampling the results of analysis will contain values that are or appear to be
extraneous; that is, they appear to be larger or smaller than expected or are larger or
smaller than the general trend in the data would indicate is expected. In some cases the
term outliers may be used to mean the same thing. Another interpretation is that
extraneous values are those that do not come from the population, while outliers do come
from samples from the same population.
The first place to start in trying to determine if a value is extraneous is the project
notebook. Is there any indication that there is anything unusual about this sample site or
the sample when it was takenany color variation, any indication of compaction, any
unusual wetness, or any other observation that might indicate that the sample was
different? A second place to look would be the chain of custody. Did anything unusual
happen to the sample during transport or storage? Was there a change in temperature, was
the box dropped, was the sample stored for an unusually long period of time? Did

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anything unusual happen at the laboratory before the actual analytical procedure was
performed?
If some unusual situation occurred with the sample in question, the analytical data
from that sample can justifiably be discarded. It should be noted, however, that if any
other samples showed the same unusual characteristics or suffered the same conditions
and the analytical results appear to be normal, then these conditions cannot be used as a
reason to discard data.
If there is a mistake made during the analytical procedures, then it is reasonable to
expect that the data would be thrown out and not reported to the end user. We would
therefore not expect the actual analysis to be questionable.
When all other sources of variability are ruled out, the data can be checked using
statistical methods. Because of the large standard deviation in sample A3, it might be
suspected that one of the values is in error. The first step in estimating this is to find the
range of observations. This is the difference between the largest and smallest value, and
is represented by w, which is calculated as follows:
w=510410=100
Another way to think of this value is that it represents the dispersion of the values. A
simple statistic for deciding if a value is extraneous is the Q test.

The distance between the questionable value and its nearest neighbor is determined and
divided by w. If we were testing to see if 510 is an extraneous value in sample area A3,
this would be 510490, which equals 20.
Calculating Q

Because this value is less than the Q0.90 or the 90% confidence interval (see Table 6.5)
the value is not considered to be extraneous and is kept in the calculations.
In Table 6.3 the first pH value would appear to be extraneous or an outlier. Looking at
the mean pH values, the inclusion of this value is correct. After drying, sieving, and
mixing it is seen that the average calculated with the first value included (5.11) is much
closer to the one obtained after drying and mixing (5.27) than it would be if that value is
excluded from the calculation (i.e., 5.02).* This points out the importance of not
excluding values too hastily. We could also try to test this by finding w, which would be
5.305.01 =0.29. Then Q can be calculated.
* There are other methods of estimating the validity of a measurement. They will not be covered
here, but can be found in the references.

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From Table 6.5 we see that there is no value given for 31 or n=2; thus we cannot use
this method to make this determination.
Extreme care should be taken in disregarding or discarding data. It is very easy to
produce skewed or biased data by discarding data without a firm, unbiased basis for their
elimination. The best reason for discarding a data point is having recorded data showing
how, why, and where an error has occurred [5].

6.9. HOW MANY SAMPLES?

Another area of concern is to determine how many samples need to be taken. The
concern is both from the standpoint of obtaining an accurate description of the situation
occurring in the field and in minimizing the cost of sampling and analysis.
A simple method of calculating the needed number of samples is given by the equation

In this equation n=the number of samples to be taken. The t is from the t-table (Table 6.5)
for the confidence interval needed. The variability in the samples is represented by s2,
which is the variance. D is the acceptable variability in the mean estimate. There are two
ways of handling this equation. One is to assume that the area is to be remediated to no or
0 contamination. The other is to define the level to which the contaminant is to be
reduced.
This relationship can be handled in several ways, depending on the sampling needs.
One could specify a value for n and calculate either s2 or D2. On the other hand, s2 and
D2 may be known or assumed and n calculated. One way to estimate s2 is to use (R/n).
Here R is the expected range in the sampling, or in this example (R/4)2 is an estimator of
the true s2 for area B5.
The applicability of this equation is complicated by several factors. One is that the
variance or variability may be different at different places or depths in a field. If materials
are to be removed, only the number of samples needed to determine the boundary
between an acceptable and unacceptable level of a component needs be calculated. If this
is done and the cutoff is 500 ppm, then in B5 we could use 724.5500=224.5 as R. This
would then be used to calculate the number of samples to be taken. In this case, (224.5/4)
2 or (56.12)2 would be used as an estimator of s2.
If the samples have very different means and small standard deviations, it is not
necessary to take large numbers of samples. This is also true if the sample means are far
from the target level. Only when the level is close to or below the target or desired level
will one need to use this equation [6, 7].

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6.10. COMPARING AREAS

In some cases one might question if all the samples from a field or all the grids in a field
are the same or different. To answer this question one might think to carry out a t-test
comparing each grid with each other grid. This would be a tedious calculation. Rather
than do this, an analysis of variance (ANOVA) can be carried out. To do this the mean or
for all the areas or grids in the field is calculated. An for the two areas to be compared
is also calculated,* then as with previous calculations a hypothesis is needed. The null
hypothesis H0 is that all the areas are the same.
The two areas represented by B3 through B6 and C3 through C6 in Figure 6.1 can be
compared. The null hypothesis would be that the two areas are the same; that is,
H0=B3B6=C3c6. An alternate hypothesis Ha might be that the means are different
from each other.
The second step is to calculate what is called the sum of the squares for treatment
(SST). In this case we assume that grids B3 through B6 are one treatment and grids C3
through C6 are one treatment and that they are the same. The for all measurements is 600,
while the for area B3 through B6 is 796 and the for area C3 through C6 is 403. The
averages for these areas have been given as three digits without decimal for simplicity.
The general equation for calculating SST would be

In this equation, Xi is the mean of the ith group (i.e., B3 through B6 would be a group),
is the overall mean, and ni is the number of observations in the ith group. (This would be
16 for the B3 through B6 group.) The answer is calculated as follows:
=16(796600)2+16(403600)2=1235600
The next step is to calculate what is called the sum of squares of error (SSE). This is
based on the variability around the sample means (i.e., 796 and 403). The general
equation for this calculation is:

For area B3 through B6 the averages are 1090, 908, 724, and 463, and for area C3
through C6 they are 871, 586, 106, and 51. The averages for these
* All numbers have

been truncated to whole numbers for illustration. Decimals are kept when
working with actual data.
In this equation j is used in the same way i is used in previous equations.

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areas are 796 and 403, respectively, thus

The next step is to calculate a mean square for treatments (MST). This is done by
dividing the SST by the degrees of freedom. In this case there are two treatments (p is the
number of treatments and n the number of observations, which is 8), and so the degree of
freedom is 21, which is 1, thus

Next is the calculation of the mean square for error (MSE).

The last step is to calculate an F statistic.

At this point an F statistic shown in Table 6.7 that represents a 95% confidence interval
for H0 is consulted. The degree of freedom for the numerator (v1) is 1 and the degree of
freedom for the denominator (v2) is 6. Going to the F table the F statistic is 5.99. This
could be represented as
F.05=5.99 for v1=1 and v2=6
Because the calculated F statistic is more than that found in Table 6.7 it is concluded that
there are enough data to say that the two areas are different. This is an important
conclusion because it means that the two areas must be treated differently.
This type of calculation can be used to show areas in which the application of a single
method of remediation to the whole area as opposed to individual grids is reasonable. It
may also allow for reducing the number of samples and consequently the number of
analyses that need to be carried out [8].

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TABLE 6.7 Abbreviated Table of Critical F Values

Numerator degrees of freedom

1
1
2
3
4
5
6
7

2
161.4
18.51
10.13
7.71
6.61
5.59
5.59

199.5
19.0
9.55
6.94
5.79
5.14
4.74

aDenominator degrees of freedom.

The above calculation using eight means rather than the 32 observations is not a good
approach because it does not account for variability in the observations. It assumes that
grids B3 through B6 are equivalent and that grids C3 through C6 are equivalent, which is
a huge assumption. It is possible to use a more complicated version of ANOVA to test
both the differences among grids and between areas at the same time; however, such a
procedure is beyond the scope of this book. Two areas could be tested using the t-test;
however, it is subject to interpretation errors when applied to more than three areas.

6.11. LINEAR REGRESSION

Linear regression is used extensively in analytical procedures to determine the accuracy
of calibration curves. These calculations are thus extremely important because they
determine the accuracy of many analytical results. Because these are mostly used in the
commercial laboratory they will not be discussed here.

6.12. GEOSTATISTICS
There are many tools that have been and are used for estimating the unknown amount of
a component when it is between or surrounded by known amounts of the same
component. Simple linear interpolations using nearest neighbors, distance and a
weighting factor, and other methods have been developed and used. A method that has
gained much use and recognition is called kriging, which is based on geostatistics [9]. In
this discussion mathematics will be minimized and the results of various geostatistical
operations illustrated without the corresponding calculations.
The basic assumption of geostatistics is that samples taken close together are more
similar than those taken further apart; that is, there is a definable relationship between

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two components. Another way of thinking about this is that one component is correlated
to the value of another component. A further assumption is that the changes occurring in
the environment occur in a regular, describable fashion over definable distances. The
distances used can vary, depending on the component and the needs of the analysis.
Technically distances can be anywhere between the atomic and the km scale. The
distance over which this influence is active can be estimated and used in calculating the
value of the missing data.
For field sampling these assumptions are put into mathematical form so that
estimations can be made at unsampled locations. Note that geostatistics is closely related
to modeling, which will be discussed in detail in Chapter 7. Indeed, geostatistical
methodology and calculations are essential in many environmental models.
Determining the distance over which measured values are interdependent is essential if
these calculations are to be useful. Some reported values of the range of interdependence
for pH measurements in two locations are given in Table 6.8. As can be seen from these
data, interdependence can sometimes range for large distances [1012]. Interdependence
can also be scale-dependent in that it can be different, depending on the overall area of
interest.
Kriging could be used to estimate the missing values in A2 and A6 in Figure 6.1. In
this case the four nearest values could be used in the calculation; that is, for the missing
value X in A2 the value could be estimated using 190, 210, 510, and 321, and the missing
value Y in A6 could be estimated using 164, 94, 106, and 500. For this calculation the
distance between all points must also be known.
6.12.1. Correlograms
The first step is to think about how environmental measurements might change over a
distance. If there is a point source of contamination, we might expect that the level will
be high at the source and decrease with distance from the source. In Figure 6.1 the point
of contamination would appear to be area B3. A graph of the averages for each of the
areas from B1 to B6 is shown in Figure 6.4. The TPH values are seen to decrease with
distances from the source. This is true no matter which direction is taken away from area
B3. A regular decrease in the component over distance is thus one possible change.

TABLE 6.8 Ranges of pH Interdependence Reported for Two Locations

Location
Arizona

Soil

Range (m)

Conditions

Source

Pima clay
loam

1.5

Four 20-meter transects, 20-cm spaces, 50-cm Gajem [10]

depth

Pima clay
loam

21

Four 20-meter transects, 2-meter spacing, 50- Gajem [10]

cm depth

Pima clay
loam

260

One transect, 20-meter spacing, 100 points,

50-cm depth

Gajem [10]

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Hawaii

14,000
32,000

162

Transects on island of Hawaii, 1-to-2-km

spacing, 015 cm deep

Yost et al.
[11]

FIGURE 6.4 Decrease in TPH concentration from a point source.

Several other possibilities can exist; however, only two will be discussed here. One
would be that the concentration or characteristic does not change over the distance of a
transect or sampling blocks. For instance, it might be possible that within experimental
error the pH of a soil does not change over the entire area being sampled. In this case the
characteristic would follow a model with a slope of 0; that is, there is no change in the
value with a change in either the x or the y direction. In an absolute or realistic sense this
would not happen. What actually happens is that the pH varies around some mean and the
means at all places are not significantly different from each other.
The second would be that the characteristic changes in a regular fashion over the
distance of the transect. In Figure 6.5 soil bulk density changes in a regular pattern
because of wheeled traffic across the field. This type of graph may result from
measurement of any environmental characteristic or quantity, whether it is chemical or
physical.
In the types above, if the expected values are dependent on position, then universal
kriging, which uses variograms (see below) is used. It might also be noted that at a finite
variance both correlograms and variograms contain the same information.

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FIGURE 6.5 Recurrent pattern of soil bulk densities due to wheeled traffic
across a field.

6.12.2. Variograms
A variogram is a graphical representation of the variation in a measurement over distance
and is a basic component of any kriging. Four different types of variograms plotted as
variance versus distance are used as models.* (See Figures 6.66.9.) Except for Figure
6.8 (the linear model that does not have a corresponding covariance function), each of
these can have a covariance function, and this can be plotted and also used in
calculations. In Figure 6.6 the variance is 0 at a distance of 0. It increases linearly in a
straight line to a value at which it becomes a flat line, a slope of 0. The y value where the
line has a slope of 0 is called the sill. The distance from the start, x=0, y=0, to where the
slope becomes 0 or where the y axis reaches its maximum value, is called the range. The
range is the maximum distance at which components are still correlated. The graph in
Figure 6.6 is called a linear model with a sill.
A second linear model (Figure 6.7) has the variance at some value above 0 at 0
distance. The variance increases linearly to some value at which
* Although the term modeling is applied to these graphs they are not the same as the modeling we
will discuss in Chapter 7.

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FIGURE 6.6 Linear model with sill and range.

FIGURE 6.7 Linear model with nugget, sill, and range.

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FIGURE 6.8 Linear model without nugget, sill, or range.

FIGURE 6.9 Spherical model with range and sill.

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the line becomes flat with a slope of 0 or the y axis has a maximum value. The variance at
0 distance is called the nugget. The distance from 0 to where the slope becomes 0 is
called the range. In this case the variance at the point at which the line has a slope of 0 is
made up of the nugget and an additional variance, which is still called the sill. It is
important to remember that many of the components being sampled for in the
environment occur naturally at a low level. This natural low level and its variance will
lead to the occurrence of a nugget in the variogram of this component.
The third model is the linear model (Figure 6.8), which is simply a straight line with no
sill. A fourth model (Figure 6.9) is one that is curved between the 0 variance and 0
distance to a distance at which the line again has a slope of 0. The range is from 0 to the
place at which the slope becomes 0, and this is the sill. Typically one calculates the
variance and plots it versus the distance, and the curve is fitted to one of the appropriate
models.
When using data from field sampling the component variogram may not look like any
of those shown in Figures 6.6 through 6.9. There are a number of reasons for this. If the
concentration of the component goes to 0, there will be no variation, and so the variance
will also go to 0. This would be the case where there is a spill of a component that is not
commonly found in the environment. At some distance the concentration will be 0 and so
will the variance. In this case the variance will increase for some distance and at some
further distance fall back to 0. There are other situations that produce variograms
significantly different from those shown. In all these cases the graphed variogram is
compared to these idealized variograms. The one it fits best is the one used in carrying
out calculations.
To carry out a calculation using kriging the distance from the unknown point to all of
the known points must be known. The distances between all of the known points are also
needed, and thus must be calculated. Two tables are produced, one of which contains the
coordinates of each point and a table of distances between all known points. These
distances are used in the calculation of both a covariance function and a variogram, and
are the basis of the final weighting factors. The variogram is then fitted to a model
variogram.
Commercially available software packages are available that fit variograms to a model
variogram semiautomatically. However it is important for the researcher to know what is
being done, because a number of interpolation methods will be available to choose from.
Kriging can be chosen as one of the interpolation methods. (See Chapter 7 on modeling
and Appendix A for software sources.)
Kriging methods are used extensively in producing surface and subsurface maps of
contamination, thus this methodology will be associated with a wide variety of
commercial modeling programs. For these programs actual calculation is not necessary. It
will be beneficial to know something about the methods in interpreting the results of this
modeling, however. Some understanding of kriging will also help in understanding the
steps a commercial program is asking you to carry out.
6.12.3. Kriging Map
The values for a characteristic can be plotted on a map of the area sampled. The maps

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look like contour maps except they show lines of equal concentration or equal values of
some physical constant or chemical characteristic rather than elevations. The lines can be
found by using known values and using kriging to calculate the missing or unknown
values between the known values. A similar map can be drawn of the variance over the
same area, if desired. The type of map obtained is shown in Figure 6.10.

FIGURE 6.10 A map of kriged values. Both a point-kriged and block-kriged

map would look similar.

6.12.4. Verification of Kriging Results

An interesting characteristic of kriging is that it is possible to check calculations against
values that are later collected or from a group of values not used in the original
estimations. A missing value can be calculated using kriging, a sample can subsequently
be taken from the field at the missing site, and the analytical results compared to the
calculated results. If the geostatistical calculations are valid, then the calculated and new
measurements are reasonably close in value.
Another approach would be to use surrounding values to calculate a known value. At
this point we would assume a known point is missing and calculate its estimated value
from the previously developed equation. The two results should be found to be very close
in value. This method of checking the values is called jackknifing.

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6.12.5. Block Kriging

Analytical results from point sources are used in calculating kriging estimates; however,
the values from an area can also be averaged and these values used to produce a map of
that characteristic. For example, the data in the sample areas in Figure 6.1 can be
averaged, as shown in Table 6.7, and this average can be used in block kriging. A map
produced by block kriging is generally smoother than the map made from point values.
(See Figure 6.10.)

6.13. COREGIONALIZATION
Sometimes two different properties are related to each other. For example, plant wilting
point and soil organic matter are closely related. When such a relationship exists, a
procedure called cokriging can be carried out. When two characteristics are closely
related additional information for predicting one characteristic based on measurements of
the second is possible. In some situations this is exactly what is done in modeling; that is,
a component related to or dependent on already known characteristics is used to estimate
the concentration and movement of the unknown component.
The whole area of geostatistics is mathematically intense, involving a great number of
variables and mathematical operations. The calculations themselves are not difficult, but
they do involve discrete mathematics and calculus. A number of computer programs are
available to carry out geostatistical calculations and can be purchased at reasonable cost
from firms such as RockWare. (Information for contacting this company is given in
Appendix B.)

6.14. GEOSTATISTICAL PROBLEMS

It would be nice if applying geostatistical methods could solve all environmental
problems. Unfortunately this is not the case. Geostatistics works best in areas that are
relatively homogeneous and the variables well known or studied. Applying kriging to a
field without knowing anything about it can be expected to lead to inaccurate estimations.
A 100-ha field uniformly made up of a sandy soil so that all the horizons and their
characteristics are the same or are well defined will be amenable to kriging. If the field
contains a compacted area, however, this area may not be amenable to kriging applied to
a transect line trough that area. This is particularly true in two instances.
The first instance would be where a compacted area smaller than the range is
encountered. If this range is used to identify sampling intervals, the compacted area may
be missed. In this case two problems can develop. First, if the compacted area is missed
its effects on the component of interest will not be taken into consideration in making a
management decision, such as a remediation plan. Second, the area on one side of the
compacted area may react very differently to the component of interest, and this
difference may be missed.
The second instance occurs where the subsurface changes dramatically, although the

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soil surface appears to be the same. If a sandy, textured soil is bordered by a field with
boulders and rocks just below the surface, the characteristics of that area will not be the
same as the field to which kriging is being applied. Application to this rocky area will
give inaccurate results.
The above situations should not present a problem if sufficient samples are taken and
used in the kriging estimation. It is essential that there be a number of component data
points representing the entire area of interest [1215].
I know of one example in which such a situation resulted in a catastrophic dam
collapse. A dam was built on an underlying rock layer. Unfortunately there was an area
of unconsolidated rock at a distance less than the range that was used in sampling, and
thus was not detected. This eventually led to undercutting of the dam and its collapse.
This resulted in massive flooding downstream.

6.15. CONCLUSIONS
Statistics is an essential tool in sampling. It is used to determine if two components have
the same or different levels of a component of interest. It is used to determine values of
interest at unsampled positions. It is also used to estimate the number and positions of
samples needed. Geostatistics is useful in estimating contours and missing values from
data sets. Various geostatistical methods are used in commercial modeling programs and
so are valuable in the modeling of environmental situations. It is highly recommended
that a statistician be consulted in using statistics in a sampling plan. It is also highly
recommended that appropriate computer statistical programs be used in carrying out all
statistical analyses.

QUESTIONS
1. Using a hand calculator or a computer generate 10 random numbers.
2. List and explain the four types of hypotheses.
3. Calculate the median and mean for the TPH values given for areas C1 through C6 in
Figure 6.1.
4. Calculate the standard variation of the TPH values given in sampling areas A1
through A6 in Figure 6.1.
5. Using the t statistic determine if the areas C1 and A6 represent the same or different
populations.
6. Determine if the value 346 ppm for TPH in sample area B2 is an outlier or is from
the same population for the area.

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7. The transect sampling of a field shows that the high TPH value is 2000 ppm. The
cutoff for TPH in this state is 500 ppm. How many samples will be needed to be sure that
all areas in which the TPH is above the allowed level are accounted for?
8. Describe the basic assumption of geostatistics.
9. Explain the terms nugget, range, and sill as applied to kriging.
10. What types of graphs illustrate the types of variations that can be found in
analytical results from samples taken over a distance?
11. In kriging, what are four models used to evaluate the component variation?
12. Describe some of the potential problems associated with kriging.

REFERENCES
1. Kempthorne O, Allmaras RR. Errors and variability of observations. In: Klute A, ed.
Methods of Soil Analysis: Part 1Physical and Mineralogical Methods. 2nd ed.
Madison, WI: American Society of Agronomy and Soil Science Society of America,
1986:131.
2. Freund JE, Simon GA. Statistics: A First Course. Englewood Cliffs, NJ: Prentice Hall,
1991:316322.
3. McClave JT, Benson PG. A First Course in Business Statistics. 4th ed. San Francisco:
Dellen, 1989:8083.
4. Freund, JE, Simon GA. Statistics: A First Course. Englewood Cliffs, NJ: Prentice Hall,
1991:340349.
5. Dixon WJ, Extraneous values. In: Klute A, ed. Methods of Soil Analysis: Part 1
Physical and Mineralogical Methods. 2nd ed. Madison: American Society of
Agronomy and Soil Science Society of America, 1986:8090.
6. Crpin J, Johnson RL. Soil sampling for environmental assessment. In: Carter MR, ed.
Soil Sampling and Methods of Analysis. Ann Arbor, MI: Lewis, 1993:518.
7. Freese F. Elementary Forest Sampling. Agriculture Handbook no. 232. U.S.
Department of Agriculture, Corvallis, OR: Oregon State University, 1962.
8. Freund JE, Simon GA. Statistics: A First Course. Englewood Cliffs, NJ: Prentice Hall,
1991:356365.
9. Myers DE. What Is Geostatistics?
http://www.u.arizona.edu/~donaldm/homepage/whatis.html.
10. Gajem YM. Spatial Structure of Physical Properties of a Typic Torrifluvent. M.S.
thesis, University of Arizona, Tucson, 1980.
11. Yost RS, Uehara G, Fox RL. Geostatistical analysis of soil chemical properties of
large land areas. I. Semi-Variograms. Soil Sci Soc Am J 1982; 46:10281032.
12. Warwick AW, Myers DE, Nielson DR. Geostatistical methods applied to soil science.
In: Klute A, ed. Analysis: Part 1Physical and Mineralogical Methods. 2nd ed.
Madison, WI: American Society of Agronomy and Soil Science Society of America,
1994:5382.

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13. Sharov A. 2.4 Elements of geostatistics.

http://www.gypsymoth.ento.vt.edu/~sharov/PopEcol/lec2/geostat.html.
14. Rossi RE, Mulla DJ, Journel AG, Franz EH. Geostatistical tools for modeling and
interpreting ecological spatial dependence. Ecol Monogr 1992; 62:277314.
15. Isaaks EH, Srivastava RM. Applied Geostatistics. New York: Oxford University
Press, 1989.

7
Modeling
Many types of models can be made of the environment; for example, a static physical
model, showing the different parts in three dimensions, or a similar dynamic model,
which actually models changes in the environment when conditions change. Another
approach is to develop a mathematical model that models the movement or actions and
reactions of a single component or multiple components in the environment. The ideal
would be to have this model be as simple as possible.
Today most mathematical models are developed using computer programs. The
advantage of using computers is that models incorporating many variables and complex
calculations can be developed and will run quickly and easily on a computer.
Mathematical models can be three-dimensional and be presented as relatively simple
three-dimensional graphs. On the other hand, the output may be a three-dimensional
diagram of the environment showing the surface and subsurface location of the
components of interest. These can also be dynamic models and can be used to predict and
quantify changes in the environment when conditions change.
All models have two basic valuable characteristics. The first is to allow the
visualization of the situation as it exists. Seeing the situation in even a static model can
help in the development or modification of a sampling plan. The second is that the model
allows the prediction or estimation of changes in the future. Dynamic models allow for
changes, which make it possible to predict how these changes would change the
dynamics of that portion of the environment being modeled. For instance, a model of soil
moisture levels might be developed for a certain rainfall, perhaps 500 mm of rain spread
over 6 months. The model would allow prediction of the changes that would be expected
if, for example, rainfall was 1000 mm or 250 mm over the same length of time.
Such changes in rainfall will affect sampling. A soluble pollutant will move further and
deeper under heavier rainfall conditions and thus require more sampling and deeper
sampling. Under reduced rainfall less movement would occur, and thus less sampling is
needed. The predictive nature of a model can thus be of great benefit in designing a field
sampling plan. In conjunction with sampling, such models can be used in decision
making, such as whether or not a contaminated groundwater plume requires cleanup.
Such models can guide the location of sampling sites and the drilling of monitoring wells.
Models should never be used as the sole basis for location of sampling sites and wells in
a field sampling plan, however.
Many constants are needed for any modeling. Some are chemical constants and others
are physical constants. A list of common constants and variables used in environmental
modeling are given in Table 7.1.

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TABLE 7.1 Common Constants and Variables Used in Modeling the Environment

Quantity/constant

Units

Common abbreviation

Water solubility

g/ml

Diffusion coefficient

cm2/s

Soil hydraulic conductivity

cm/s

cm2s1

Solar radiation

erg

Temperature

C or K
g1d1

R
C or K

Heat capacity

erg

Acceleration due to gravity

m/s2

c
g

Soil porosity

cm3/cm3

Volumetric water content

cm3/cm3

Soil matrix potential

kPa

Saturated soil water content

cm3/cm3

Volumetric air content

cm3/cm3

Air density

g/cm3

Soil bulk density

Mg/m3

B.D.

Note: Not an exhaustive list.

7.1. PHYSICAL MODELS

A physical model may be constructed in a number of different ways and may represent
one or several characteristics of the environment. The model may be static and only be a
scale model of the actual area, or it might be dynamic but qualitative in that several
components interact and the interactions are observed. In this case the model is used only
for visualization. The most sophisticated models will be both dynamic and quantitative,
allowing the calculation of the amount of change taking place over time. All of these
models may be valuable, depending on the system and the situation being investigated.
7.1.1. Static
The static model typically has all its components represented by various constructed
structures. Soil might be represented by fine sand. The sand might be colored to represent
various horizons. Fractured rock can be represented by gravel and consolidated rock by
colored clay. Water could be represented by water, colored clay, and the like. Such a
representation might also show caves, trees, and so forth. Often such a model is
constructed to scale. Such a scale might be something like 1:10,000 meaning 1 cm in the

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model represent 10,000 cm in the real landscape. Using a scale model allows one to
calculate distances between features.
Such a scale model can be used to locate sample sites and monitoring wells. In
addition, underground features (e.g., pipelines, caves, buried tanks) can be represented in
such a way that samples can be taken so as not to disturb or interact with them. Note that
in a scale model the position (north, south, east, west) and depth of the features must be
exactly known for their correct placement in the model and subsequent avoidance.
Another use of such models would be for comparisons before and after. In this case
two or more models can be constructed showing the present situation and the situation as
it is envisioned during the project and when the project is completed. This will allow the
involved parties to envision the changes so that they will not be surprised by proposed
changes or by their effect on the environment.
7.1.2. Dynamic
A dynamic model may be constructed in a manner similar to a static model. In this case,
however, the model is interactive in that it shows the interaction between components in
the environment. For the environment this type of model often involves observing the
interaction between water and soil. It might also show the interaction between air and soil
or all three, however.
Many qualitative models of the interaction of soil and water are available. In Chapter 2
there is a model that illustrates the movement of water through soils with horizons having
different textures. Another model is to drop water on soil peds held on a wire screen. The
stability of the peds can be seen by how they hold up to running water. If water is
allowed to drop from some height onto soil it will be splashed. The drops dislodge soil
particles that are then carried out of the soil for some distance. Water falling just a few
meters can cause soil to splatter a meter or more from the point of impact. (See landscape
modeling in Section 7.4.)
If a board with ridges on three sides is constructed and filled with soil, it can be used to
model stream movement and development. (See Figure 7.1.) To protect the wood from
water, the board is often covered with plastic before the soil from the area being
investigated is added. The board is placed at an angle to represent the slope of the area
being investigated. A source of water is allowed to flow across the soil. As the water
moves across the soil it will form a stream that mimics the actual movement and action
of natural streams. In this way the possible movement of contamination in a field may be
estimated before the field is sampled. It will also show where field offices and storage
facilities are best located.
This type of model is also valuable in observing the effects of flooding on an area. The
amount of water flowing across an area can be doubled, tripled, or made 10 times larger,
and the effect of these changes noted. If the area is particularly prone to periodic flooding
this type of model can be invaluable in locating both sampling sites and sites for
buildings. This type of model is shown in Figure 7.1.
Blowing air across soil or sand when it is wet or dry will model what happens during
wind erosion. Such a model can be used to design barriers or other structures to prevent
or lessen wind erosion. This can thus help in understanding how to design a sampling

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program during which wind could move pollution onto or off a contaminated field.
In developing and using models it is important to be aware of scaling. Some
characteristics may be different or act differently at different scales. What works at a 1meter scale may not work at a 100-meter scale. Sometimes it is possible to use
nondimensional representations so that the values are the same at all scales. Sometimes
the scaling problems are not readily obvious. They may even be hidden, so that they only
become apparent when the scale is applied to a larger or smaller area. This can be easily
demonstrated by filling a jar or glass full to the rim with water, placing a #10 sieve over
the mouth, and quickly flipping it upside down. The water will flow out. Repeat the
procedure using a #200 sieve, and it will be seen that the water does not flow out.
Predicting the movement of water in small pores from models using large pores will fail.

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FIGURE 7.1 Modeling stream formation and development. Note the

development of the stream channel and its path across the landscape.

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7.1.3. Quantitative
In many instances quantitative rather than simple qualitative models may be desirable.
Here again several types of physical models are commonly used. The most important and
commonly used among these is the soil column. Columns from several centimeters in
length and diameter to several meters in length and decimeters in diameter are frequently
constructed to model the movement of water and contaminants through soil. Glass,
plastic, and metal have been used to contain the column, with plastic being the material
of choice today. Such columns are often fitted with ports, electrodes, and other
monitoring devices so that the conditions in the column and the movement of
components through the column can be followed.
Columns can be constructed in a number of different ways. A retaining material, screen
covered with vermiculite, or coarse sand covers the bottom. This is often constructed so
that the flow out of the column can be controlled. Air-dried soil is added to the column
and then water is used to saturate it. Alternatively the column can be partially filled with
water, and soil can be slowly added. The latter method produces a more uniform soil
column, although it may be less representative of soil in the environment. Water,
contaminants, or solutions of contaminants in water can be added to the columns and
movement through the column followed. A column used for modeling water and
contaminant through soil is shown in Figure 7.2.
Soil columns constructed and used in this way can be very useful in determining the
fate of contaminants, insecticides, herbicides, and so on in soil. A graph of the movement
of ethers dissolved in water through the soil column shown in Figure 7.2 is shown in
Figure 7.3. The units of the x axis are apparent void volumes. The apparent void volume
is void space in soil. (See Chapter 2.) The more soluble methyl tertiary butyl ether
(MTBE) elutes from the column before the less soluble octyl ether. Note that the more
soluble compound comes out a little before one complete void volume. This is attributed
to preferential movement through large pores in the soil.
The data obtained from the graph in Figure 7.3 can be used to predict where a
contaminant is most likely to be found in a soil profile and how far and fast it will move,
and can be estimated on the basis of the mm of rainfall. From these data the breadth and
depth of needed sampling can be estimated. It should be noted that such column
conductivities are often lower than field conductivities. This can be due to plant cover,
soil structure, cracks, and animal holes. When needed, field studies using lysimeters can
be used to validate column studies.
Lysimeters are another dynamic physical way of modeling the environment. A
lysimeter is constructed by isolating an undisturbed volume of soil in the field. The soil is
isolated by concrete or metal dividers set in the

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FIGURE 7.2 Soil column for modeling water and solutes movement through a

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soil.

FIGURE 7.3 An example of the movement of ethers through the column

shown in Figure 7.2. The y axis is in arbitrary units. The x axis is in
column apparent void volumes. MTBE is methyl tertiary butyl ether.
(Data from senior research project of Dan Tener, Chemistry
Department, Wilmington College, Wilmington, Ohio.)

field. The bottom of the soil is retained by a metal grill supported by sand and gravel
underlain by a slanting, water-impervious layer of plastic, cement, or metal. This allows
water percolating through the soil to be collected. The big advantage of lysimeters is that
they contain a largely undisturbed column of soil. Because it is undisturbed it is expected
to more faithfully model the action and interactions of the soil as a whole. A diagram of a
typical arrangement of a lysimeter is shown in Figure 7.4.
Water collected at the bottom of the lysimeter can be pumped to the surface for
sampling and analysis. Alternately, an access tunnel can be constructed to allow samples
to be collected without pumping. There are too many different designs of lysimeters to
describe them all here. In some cases a soil water sampling methodology that collects soil
water at some depth may be called a lysimeter even when it does not involve a physical
lysimeter as such.
Movement of water and contaminants through a lysimeter can be followed under
natural rainfall or irrigation. The amount of water percolating through a soil versus the
amount lost through evapotranspiration can be measured and correlated to environmental
conditions. Knowing the amount of percolating water is essential when modeling soil
phenomena.

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FIGURE 7.4 A lysimeter containing an undisturbed soil and a water collection

sump.

7.1.4. Evapotranspiration
In the field, especially in a field with plants, measuring and separating evaporation and
transpiration is extremely difficult. Evaporation is the loss of water from the bare soil
surface. The soil surface is under continually varying conditions of cover, shade, direct
sunlight, and so on. Transpiration is the loss of water from stems and leaves. Stems and
leaves lose water at various rates, depending on air temperature, relative humidity,
sunlight intensity, wilting point, stage of plant growth, and so forth. At a minimum there
are six interdependent, constantly changing variables that must be measured to predict
water loss. It is much easier and more accurate to measure the total water loss during the
growth of the plants, called evapotranspiration, and even this is generally very
complicated.
To simplify estimating or modeling the loss of water during a period of time an open or
evaporation pan method is usually used. A pan filled with water is placed in the field and
the amount of water lost each day is measured. This is then related to environmental
conditions and water loss from evapotranspiration using a pan coefficient. The concept is
that the evaporation pan integrates the effects of temperature, wind, relative humidity,
solar radiation, and so on, and so can be used to estimate evapotranspiration. Today other
more sophisticated instrumentation is becoming more widely used.
The pan coefficient would seem to be unrelated to models needed or used in field
sampling. With volatile contaminants, however, loss from the surface may be significant.
Although it is often assumed that contaminants can only move deeper in soil, this is not
true. When evapotranspiration exceeds precipitation, components can move up the soil
profile. Evapotranspiration data can be used to predict where components will be in a soil

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or regolith profile. This in turn will be important in designing a sampling plan.

Also, the data obtained from evapotranspiration studies will be needed for some
mathematical models to be discussed below [1].

7.2. CHEMICAL MODELS

Chemical-type models of the environment usually rest or depend on some underlying
chemical principle. Kinetics, equilibrium, solubility, mass transfer, and partition between
organic and aqueous phases have all been used in modeling compounds in the
environment. These approaches work best with single chemical species or two or more
similar species that do not interact with each other. Many mathematical models are also
based on chemical phenomena.
Thermodynamics is the study of energy (heat), its movement, and its effect on its
surroundings. All systems generally move from conditions of higher energy to conditions
of lower energy. They also move from conditions of higher organization to areas of lower
organization. In thermodynamic terms this would be moving to conditions of greater
randomness. In the environment water moves downhill. Water also moves down through
soil and is held more strongly in small pores and less strongly in large pores. To move it
from small to large pores requires the input of energy. Organic matter in aerobic soil is
oxidized to carbon dioxide and water. In anaerobic soil organic matter is also broken
down; however, in this case the end product is methane. In both these cases energy is
given off and the compounds produced are smaller and more disorganized [2]. If a
reaction results in energy being given off and randomness increasing, then it can be
expected to take place.
Looking at the large scale, the soil is a medium designed to break down organic
compounds. It provides an intimate mix of solid surface, inorganic nutrients, water,
oxygen, and living organisms, and all of this is in the correct proportions to promote
rapid decomposition with the consequential release of energy and increase in
randomness. Using all of the above the fate of a component in the environment can be
modeled by knowing and following changes in its energy. The component will move
from situations of higher energy and more organization to situations of lower energy and
less organization.
Equilibrium is also used to develop models of the fate of components in the
environment. The concept of equilibrium is that at a macro scale a condition is reached at
which the concentrations of components on either side of a chemical equation do not
change. This situation is most often a dynamic equilibrium, however, in which reactants
and products are moving back and forth between these two conditions. A standard
representation of a chemical equilibrium reaction is shown and is said to be at
equilibrium when the rate k1 is balanced by the rate k1.

Equilibrium models such as the one given below are fairly simple and easy to calculate.

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In this equation the components are assumed to be at equilibrium. The total amount of the
component can be found by summing the amounts in the solid, liquid, and gaseous
phases.

Although over short periods of time the environment may appear to be in equilibrium, it
is never truly in equilibrium. Such equations may provide important information about a
component in the environment, however. They may also be included in more
comprehensive models of the environment [3].
Mass transfer is the movement of a mass of material through a medium. The medium
could be air, water, or soil. There are simple chemical equations for mass transfer;
however, in soil the situation is complicated because there is a limited amount of space
available for transfer. For this reason a capacity coefficient is needed. In soil some
volume containing solvent and solute is immobile and so does not contribute to mass
transfer. To complicate equations and models is the fact that solute can be sorbed to pore
surfaces. If the process is started with dry soil, some solute (water) will be sorbed to the
surface so tightly that it will be immobile. This amount of solute is also part of the
equation.
Two components of mass transfer are spherical diffusion and advective (horizontal)
dispersion. In spherical diffusion a point source of material will tend to diffuse outward
from that sphere in all directions equally. Conceptually there may be a number of spheres
and material diffusing out of them. Another possibility, advective dispersion, is
horizontal movement away from the source. This would be the case in a stratified
medium, in which a denser layer underlies a less dense horizon.
The combined soil-atmosphere model for evaluating the rate of loss of surface-applied
pesticides developed by Rivka Reichman, Rony Wallach, and Yitzhak Mahrer is an
example of this type of model and this type of modeling [4]. This model is specifically
designed to be used with the pesticides lindane, dieldrin, and trifluralin. It is developed
using thermo-chemical-type mass balance equations for water and contaminant in the
atmosphere and soil. Partial differential equations are used for heat, moisture, and
chemical transport. Other equations are used for surface and boundary conditions
between soil and the atmosphere. Once developed, the model can be run using a
computer after input of the appropriate data. The model is then compared to results from
an experimental study.
There is a rather large number of inputs used in most models, including the one above.
In this particular case the model involves 73 constants, variables, and assumed
conditions. In some cases once all the variables are known the answer is also known.
An example of a chemical kinetic model is a modification of the environmental model
called GLEAMS (groundwater loading effects of agricultural management systems) [5]
to simulate mercury transport. This model is called Hg-GLEAMS. Kinetics are used in
this model to represent the transformation of mercury between its various states. These
equations are used to measure the rate of conversion of mercury between Hg0, metallic
mercury, and Hg2+. Equations take the form of standard chemical rate equations. This

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model also requires meteorological, soil water partition coefficients, and kinetic rate
constants [6].
Kinetic models are useful when it is important to determine the rate of both production
and loss of a single species or component. Ammonia applied to soil is oxidized to nitrite
and subsequently to nitrate. The amount of nitrite existing at any one time will depend on
both these rates. Assuming a one-time contamination of a field and knowing the removal
rate of the contaminant, suitable sampling intervals can be developed that can reduce the
amount of sampling needed. If the rate of oxidation of nitrite is known, for instance, the
time needed for its level to decrease to acceptable levels or below action levels can be
calculated. In this case sampling and analysis can be done on the basis of the predicted
rate of loss rather than on an arbitrary schedule and consequently decrease the amount of
sampling needed.
Models will also incorporate such factors as vapor pressure and sorption and diffusion
characteristics, which are temperature-dependent, and thus the temperature becomes an
essential component of the equation. The soil characteristics (i.e., sandy or clayey), along
with dry and wet volumetric water contents, are important, along with solar radiation, air
temperature, relative humidity, and wind speed. All of these interact to moderate the
temperature changes in soil and so they also become part of the equation.
7.2.1. Computer Chemical Models
Computer models typically involve the use of numerical modeling discrete versions of
partial differential equations. This is particularly the case for modeling transport
processes. Table 7.2 gives a number of common computer programs used to model
chemicals in soil. In some cases these are used to model a single species and its form
under the conditions specified. In other cases they are intended to be more general. In
both cases the models use many assumed or inferred conditions, constants, and inputs. In
spite of the limitations many of the models can be useful in understanding the position
and movement of a contaminant in soil or in the environment in general.
Model usage involves three steps. The first step is to pick the appropriate model. This
may seem simple, but in some cases the suitability

TABLE 7.2 Common Soil Chemistry Models

Model

Source

GEOCHEM Mattigod SV, Sposito G. Chemical Modeling of Trace Metal in Contaminated Soil
Solutions Using Computer Program.
GEOCHEM. In: Chemical Modeling in Aqueous Systems.
ACS symp. ser. 93. Jenne EA, ed. Washington, DC: American Chemical Society,
1979:837856.
SOILCHEM Sposito G, Groves J. SOILCHEM on the MACINTOSH. In: Chemical Equilibrium
and Reaction Models. Loeppert RH, et al., eds SSSA spec. pub. 42. Madison, WI:
ASA and SSSA, 1990:271288.

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MINTEQ

Femy AR, Girivin DC, Jenne EA. MINTEQ: A Computer Program for Calculating
Aqueous Geochemical Equilibria. NTIS PB84157148, EPA-600/384032.
Springfield, VA: National Technical Information Service, 1984.

C-SALT

Smith GR, Tanji KK, Burau JJ. C-SALTA Chemical Equilibrium Model for
Multicomponent Solutions. Loeppert RH, et al., eds. SSSA spec. pub. 42. Madison,
WI: ASA and SSSA, 1990.

FITEQL

Westall JC, Morel EMM. FITEQL: A General Algorithm for the Determination of
Metal Ligand Complex Stability Constants from Experimental Data. tech. note 19.
Cambridge, MA: Ralph M. Parson Lab., Dept. Civil Eng., 1977.

Note: ASA, Agronomy Society of America; SSSA, Soil Science Society of America.

of a model may not be apparent until it is in use. The second step is calibration of the
model.
The third step is validation, which must be done in all cases; that is, if the model
actually predicts what will happen in the environment. Verification is usually done by
comparison of a model to a field situation. In restricted areas with uniform or very similar
soils models can often accurately predict the form and movement of a contaminant in the
environment. Caution is important, however. Often the model will not be as effective or
may not predict the field situation at all when it is applied to field situations in other
localities; thus for each new application of a model a validation experiment must be done.
This is especially true if the model is to be used to predict sampling site locations.
Most computer models contain empirical components that are varied by the researcher
to produce an acceptable result. Some models contain several such factors related to
various components. Another approach is to use weighting factors. These can be used to
increase or decrease the importance of a particular component of the equation so that the
results better correspond to what is actually happening in the environment.
All of these types of models suffer from the fact that they need large, sometimes vast,
arrays of inputs and variables to make them useful. In many cases these variables and
constants are not known. In these cases they can be obtained either by making field
measurements (measuring a soils porosity, bulk density, etc.) or using column and
lysimeter studies. Another approach is to estimate by various means the numbers from
other known characteristics of the soil or landscape. This is often done during a
calibration stage. For example, in groundwater (GW) modeling, well pumping, along
with pressure head measurements, might be taken to calibrate a GW model. In this case,
calibration is done by, for example, adjusting the value for soil conductivity. Once
calibration is completed other data are used for the verification phase. After the
verification phase and once all the data are collected or estimated a calculation can be
made.

7.3. SIMPLE MATHEMATICAL MODELS

A number of soil samples from differing soil types, specifically different soil orders from

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different places, can be used in a series of experiments determining different

characteristics. When all the data are collected and all the analysis completed a relatively
simple multiple regression analysis can be carried out using common statistical computer
programs. (See Chapter 6.) The results of such an analysis will relate the various
variables and show which are important in predicting a characteristic of a contaminant in
soil.
The sorption of chromium (CrIII) was investigated by Stewart et al. [7] in such a
manner. The analysis showed that sorption of chromium was related to a soils pH,
inorganic carbon, cation exchange capacity (CEC), and clay content. They were also able
to determine that the bioaccessability of CrIII was related to a soils clay and its inorganic
carbon content. Both of these were represented by relatively simple equations called
models of CrIII sorption and bioaccessability in soil.

7.4. LANDSCAPE MODELS

One of the most used environmental soils models is the universal soil loss equation
(USLE) or the updated revised universal soil loss equation (RUSLE). This model has
been developed for the United States; however, it and similar equations are used in other
countries. The use of this equation involves two components. The first part is an equation
that allows the calculation of the estimated amount of soil lost (eroded) from a field in a
year under a set of described conditions. The second part is a t-value for the soil or soils
in the field or fields. The T-value is the acceptable loss of soil in tons per year.
The USLE takes the form of
A=RKLSCP
A is the amount of soil lost in tons per year. This figure is compared to the acceptable
loss of tons per acre of soil from the soil types present in the field. The acceptable level is
the amount that can be lost without adverse affects on the soil or the surroundings. It is
important to know that even under the best vegetative cover soil is lost by erosion every
year. This is called geologic erosion. Accelerated erosion is above this natural level and is
caused by mans activities. The T-values to which A is usually compared range between
1 and 3 tons per ha per year.
The R factor is a storm erosivity factor. It takes into account the intensity of rainfall,
which is a measure of the energy in the raindrops and the rate of rainfall. The energy in
rainfall depends on the size and speed of the raindrop when it hits the soil surface. The
size of the raindrop is the main factor because the speed is determined in large measure
by gravity. Basically this means that rains that come in short, heavy downpours, with
large drops are more erosive than long, gentle rains. The rate of rainfall is the amount of
rain per unit of time. Typically this figure is in cm/min (in the United States in./hr). The
higher the rate of rainfall, the more erosive a rainfall event will be.
R factors are measured or interpolated. A common way to represent R factors is as
lines of isoerosivity on a map of the area being studied. In the United States such maps
are available for selected areas, and the whole country. The lines are separated by 50 R

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units. The R factor needed is obtained from this map and inserted into the equation.
The third factor in the equation is the erodability factor, or K. Because of differences in
infiltration and percolation rates and structural stability, different soils are more or less
resistant to erosion. This difference is reflected in the K factor. These factors have been
developed from field studies of numerous soils. Erosion by natural rainfall events from
field plots with definite area, length, and slope have been measured and related back to
soil characteristics. Either a soil will have an experimental K value or its K can be
calculated from the characteristics of the soils in the field.
The L factor is the length of the field and S is the slope. These two are combined to
give a single factor, LS. The body of the LS table contains the LS factors as a single
number. Factors are found by finding the slope on the left, length on the top, and LS
factor in the body of the table. (See Refs 8 and 9 for examples of a table.) From such a
table a soil with a slope of 4% and a length of 100 meters would have an LS of 0.64. A
soil with a slope of 16% and length of 200 meters would have an LS of 5.40.
Both the C and P factors are obtained from a table relating soil cover, organic matter,
vegetation, and management. A field in permanent pasture would have a C factor of
0.003, and with a corn-soybean rotation the factor would have a C of 0.53. The P factor is
the conservation practice or practices used in the field. Some examples would be grass
waterways, terraces, and contour strip cropping. Conservation practices control the
movement of water over the field or decrease the LS factor to lower erosion. A field with
a slope of 7% that is strip cropped has a P factor of 0.25, while this same field with 33meter-wide terraces without water outlets has a P factor of 0.6. All these factors can be
found on various Internet sites, such as those given in Refs. 8 and 9.
The appropriate factors from the tables are inserted into the equation and multiplied
together to obtain the estimated soil loss A. This is then compared to the T factor for the
soils in the field. If the A value is too high, management factors LS, C, and P are adjusted
so that a suitable soil loss is obtained. Note that the R and K factors cannot be changed
[8, 9]!
This equation can be used in a different fashion in field sampling. Here the information
needed is where the component of interest is most likely to be found. By knowing the rate
of erosion, the position and movement of the component along the surface can be
estimated. Places can be identified in which the component may be found deeper in the
soil profile because of the deposition of eroded soil. Areas in which the component is
closer to the surface because of the erosion of overlying soil can also be determined. The
likelihood and rate of soil and contaminant being eroded off the field can be calculated.
Also, if contaminated material is eroding onto the field the analytical results of field
sampling will constantly be changing, making the sampling program futile unless erosion
is taken into account.
The R and K factors can be used by themselves to estimate the amount of soil affected
by splash erosion. Splashing can lead to contamination of vehicles and buildings. It will
also expose sorbed contaminants to the atmosphere. This can lead to evaporation and loss
of material [10].
The RUSLE is the revised version of the USLE. This equation can easily be accessed
on the Internet. An explanation of the RUSLE is presented at this Internet site, along with
a computer program that allows the calculation of the A factor. The program is not

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Windows-friendly and is unconventional in its use of keys for moving through the
program and obtaining the data needed to make a calculation. It has some interesting
features, but will take some time to figure out if real use is to be made of it [9].
There is a similar equation for wind erosion. This equation takes the form
E=f(ICKLV)
It states that the amount of soil eroded by wind E is a function f of I soil erodability, C
climate, K soil ridge roughness, L width of field, and V vegetative cover factors. In this
case these factors are not simply multiplied together but are calculated using the
appropriate equation. This is the wind erosion equation (WEQ), and there is also a
revised wind erosion equation (RWEQ). Calculations using WEQ are carried out using a
computer program [11, 12].
Wind erosion can complicate field sampling by depositing or removing contaminants,
thus as with the USLE and RUSLE, the WEQ and RWEQ can be used to estimate where
contaminants are being exposed or buried by windblown soil. It is common for
contaminants from manufacturing to be carried in air. These contaminants can be
deposited on a field by simply falling out of the air or with rain when it occurs. Erection
of windbreaks to stop wind erosion will also allow pollutants to fall out of suspension.
This continuing source of contaminants can complicate the sampling and analysis of field
samples if not taken into account.

7.5. MODELING MOVEMENT OF PARTICLES THROUGH THE

ENVIRONMENT
Calculation or modeling the movement of particles in air may seem relatively simple, but
can be complex. There is a complex interaction of wind, field, and particle concentration.
There is also the question of the type of movement being considered. Is it by saltation or
suspended transport? Add to this the complexity of turbulent flow, and the system
becomes complex. In spite of this it is often the case that time in the air and distance
moved is relatively easy to determine. The glide path of a particle can be calculated once
the characteristics of the particle are known. This involves not only the pull of gravity but
also the shape of the particle. A flat particle will have a longer glide path than a round
particle and will take longer to reach the ground. Mass also comes into play in that as the
particle size increases the time in the air decreases until it reaches a value of 0 with
particles larger than sand.
Movement of suspended particles depends on wind speed and direction. High wind
speeds will keep particles in suspension for long distances. The direction of the wind will
determine the direction of movement of the particles, thus where the particles are
deposited will depend on both these factors, which are relatively easy to determine.
In many ways the movement of particles in water is similar to their movement in air.
The speed of particles settling will depend on their shape and mass and the flow of the
water they are suspended in. One difference is that some particles will be heavier than
water and settle; others can be less dense than water and thus float. Some particles will be

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so smallcolloidal in sizethat they will remain in suspension and not settle out.
Particles that are heavier than water can be modeled in a manner similar to modeling the
movement of the same particle in air. Particles that float or that initially float absorb
water and then sink can also easily be modeled.
Particles that remain suspended can be modeled, but the modeling is more complex.
Some components in water will be in equilibrium with the particles; others will be
irreversibly bound to them. In both cases modeling these particles is essential because
they carry contaminants.
There is one other common characteristic of air and water in regard to contaminants.
Gaseous and soluble contaminants will mix with and be dispersed throughout the air or
water in which they are mixed. There are initially concentration gradients, but over time
the solute or suspended material will be evenly distributed through the solvent [13].
Movement of components through soil, regolith, decomposed rock, fractured rock, and
whole rock is entirely different. In all these cases an agent (air or water) is necessary to
carry the component through the media. The movement will be tortuous, and solutes will
interact with the solid media through which the solvent is moving. The interaction may
be chemical, such as bonding to surface groups, or it may be physical, such as diffusion
into pores or filtering out. In either case the solute is slowed in its movement. Sometimes
its chemical composition is changed by interaction with solids or by being attacked by
microorganisms in the environment. Modeling this movement is thus very complex and
subject to a great deal of variability.

7.6. DYNAMIC MODELS

Dynamic modeling is complex in that it considers all the eventual fates of a component in
the environment. This includes the reservoir of the component, the sources that add to it,
and the mechanisms by which it is dissipated. If there are any feedback loops or
conditions, these will also be included. Simply knowing the components of the system
does not make a model dynamic. What does make it dynamic are the rates of all its
transformations, including feedback. Knowing the rates of the various transformations,
additions, and deletions allows the calculation of the fate and longevity of the component.
Several possible dynamic systems are illustrated in Figures 7.5 through 7.10. These
cases show in a general way how components interact with the environment. Figure 7.5
shows a logarithmic increase, which is very common for microbial growth when an easily
decomposed compound is added to soil. Figure 7.6 illustrates the increase with a
subsequent decrease in a component in the environment. This type of change is common
when an easily decomposed compound is added to soil, and microorganisms produce a
component toxic to themselves.
Figure 7.7 shows a cyclic change in a components occurrence in the environment.
Many phenomena follow this pattern, particularly plant and animal populations. Figure
7.8 shows a periodic decay that is characteristic of a microbial population decomposing
one component and releasing another that can be used by a different population. The
second population breaks down this component, releasing yet another component used by
another population. This process continues until all the material has been broken down

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into carbon dioxide and water.

Figures 7.9 and 7.10 show situations that are not sustainable and are not common,
although they may appear to be over short periods of time. Figure 7.9 shows a linear
increase or decrease in a component. Components, however, cannot be continuously
added or subtracted from the environment. Eventually a level will be reached at which
dissipation equals

FIGURE 7.5 Logarithmic increase in component in environment.

addition, or else in the case of dissipation the component either is present in very low
concentrations or is not present at all.

FIGURE 7.6 Increase followed by decrease of component in the environment.

Figure 7.10 shows a slow increase followed by a logarithmic increase in a component.

It also shows a logarithmic decrease in a component followed by a slow decrease. This

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last situation is common in soil in which some of a component is in solution and easily
decomposed while some portion is adsorbed on a surface and some is in small pores that
do not drain.

FIGURE 7.7 Cyclic increase and decrease in component in the environment.

FIGURE 7.8 Periodic decrease in component in the environment.

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FIGURE 7.9 Linear increase and linear decrease in a component in the

environment.

Components adsorbed on particle surfaces will decompose slowly because they are less
available when adsorbed. Components in small pores must diffuse out of the pore before
they can be decomposed. The rate of diffusion will depend on the concentration
difference between the bulk solution and the pore solution. When the concentration of
component in the bulk

FIGURE 7.10 Exponential increase and decrease of components in the

environment.

solution decreases to a point at which it is lower than that in the pore, then the component

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in the pore will diffuse out and be decomposed. Diffusion is a slow process and therefore
the decomposition process will appear to occur at a slow rate. A components
concentration cannot continuously increase or decrease exponentially. Eventually inputs
will cease or equal losses or the component will completely disappear from the
environment. Sensitive chemical instrumentation indicates that complete loss is not
likely.
A concrete example of looking at the changes in a component in soil is soil phosphate.
In soil it increases as organic matter decomposes and decreases as plants take it up and as
it reacts to form insoluble phosphates. Changes in phosphate in soil could be described by
a simple mathematical relationship:
Future levels of phosphate=previous levels of P+additions of P losses of P
or
P(t+t)=Pt+PiPo
where P(t+t) is the phosphate content at some time in the future (t is a change in t), Pt
is the phosphate at the present time t, Pi the inputs of phosphate, and Po the outputs or
loss of phosphate. This whole relationship can be represented by a simple flow diagram,
shown in Figure 7.11. In Figure 7.11 the central rectangle represents the pool of available
phosphate

FIGURE 7.11 A simple flow diagram for the input and loss of phosphate from
soil (triangles represent Pi (left) and Po (right).

while the arrows indicate the direction of flow. The circles represent the activity while
the oblong circles represent the rate of the activity happening. The rates are connected to
the process, indicating that the total flow over time is determined by the rate at which the
activity happens.
In developing a dynamic model inputs would be separated into those from fertilizer
application, organic matter breakdown, and release from minerals. In a like fashion losses

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would be separated into plant uptake, erosion, leaching, and precipitation. This would
lead to a much more complex but more realistic model. This increased complexity is
shown in Figure 7.12 [14].
This type of modeling can be very valuable in developing sampling plans that involve
determining natural attenuation, bio- or phytoremediation, or fertilizer use. The rate of
loss can be used to predict future levels of the component of interest and thus the need
and timing of future sampling.

7.7. COMMERCIAL COMPUTER MODELING

Computers and computer modeling have become essential to the whole process of
environmental modeling and field sampling. Computer models

FIGURE 7.12 A complex flow diagram for phosphate in soil (upper triangle
might be fertilizer input, lower triangle might be plant uptake).

can make visualization of the landscape or part of the environment possible. Several
features make these models extremely valuable. First, they are easy to construct and easy
to change when necessary. New information can be added as it becomes available. The
new information can then be added to a visual representation of the area of concern.
Some programs allow analysis and correlation of data. Such questions as where the
contamination ends and how much area is covered by the contamination are questions
that the models can answer.
Figures 7.13 and 7.14 show two types of outputs that can be obtained by this type of
program. These are representations of the concentration of a pollutant in a field as

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calculated by a model. Figure 7.13 shows the surface spread of the component and its
decrease in concentration as it moves away from the source. Figure 7.14 shows a crosssectional view of the same contamination as it moves down through a soil profile. The
decrease in concentration as it moves away from the source is again shown. Both these
situations are relatively easy to model because of the uniformity of the soil and regolith.
An example of a commercial program used to model GW movement is Modflow,
which was developed by the United States Geological Survey

FIGURE 7.13 Surface view of the spread of a contaminant in soil. Lighter

areas indicate a lower concentration of the component.

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FIGURE 7.14 Model of subsurface movement of contaminant.

(USGS). It used finite-difference algorithms of the governing partial differential

equations to model GW flow. There are also contamination transport models that
interface with Modflow. (See Table 7.3 and Appendix B for more information about this
program.)

TABLE 7.3 Commercial Computer Modeling Programs

Program name/abbreviation

Type of modeling

GMS 3.1

Groundwater modeling

Modflow

Groundwater modeling

SMS

Surface water modeling

ChemFlux

Contaminant transport modeling

ARC ESRI GIS

Data visualization, query analysis, and integration

MrSID Geo

Image file handlinga

Note: All programs available from RockWare; see Appendix B.

A sample MrSID is available on the Web at no cost.

In Figure 7.15 there is a compacted layer and contaminant is leaking through the layer
into lower layers. This type of situation is impossible to model if the location of the

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holes in the compacted layer is not known. Even when the holes and their positions are
know they are hard to model. The figures shown are black and white; however, most if
not all computer modeling software will present these types of results in color. Different
colors will be used to show the concentration of the components of interest in various
locations. A color scale with reference will also be provided. Some common commercial
computer modeling programs are given in Table 7.3.
In developing a field sampling plan these models can help in directing sampling efforts
to areas with the greatest likelihood of being contaminated. Another way to use these is in
presentations designed to justify sampling plans and procedures to regulatory agencies.
The data can also be presented in a way that local populations can easily understand.

FIGURE 7.15 Model of contaminant through soil with a compacted layer.

Note that the contamination has moved through a hole in the
compacted layer and is contaminating lower layers.

7.8. GIS AND ENVIRONMENTAL MODELING

Because the Geographic Information System (GIS) is a powerful tool for relating and
displaying areas on and in the Earth, it has been proposed that it can be used in
environmental modeling. Some developments along these lines have been made, but GIS
is still used to display the environment as it is presently. It thus does not have predictive
capabilities, which are an important component of environmental modeling. By
displaying environmental conditions over a period of time, however, trends in the
movement of pollution or changes in the quality of the environment can be seen and

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predictions as to future changes can be made [15].

7.9. WHOLE PLANET MODEL

Koziol and Pudykiewicz have developed a model that is global in nature. It focuses on
organic pollutants and uses hexachlorocyclohexane as a model organic compound. The
model incorporates interactions among the atmosphere, hydrosphere, and lithosphere. In
terms of the hydrosphere, it includes ice and snow. In terms of the lithosphere, it includes
soil. All three of these are important because they are responsible for sorption of organic
components, some of which are released later. The release of previously sorbed
components is important to include in modeling because it will complicate modeling and
sampling. Verification of this model can be done by sampling. It is a particularly useful
model in that it takes into account all the components of the entire environment [16].

7.10. CONCLUSIONS
All types of modelsphysical, mathematical, chemical, statistical, dynamic, computer,
and whole Earthcan be useful in a sampling situation. Such models can predict the fate
of components in the environment. They can indicate the most important places and how
often sampling should be carried out. Such models can be useful in explaining sampling
strategies to both regulatory agencies and interested parties, including the general public.
Implementation of a modeling program can be very beneficial to any sampling project.

QUESTIONS
1. Describe two different types of physical models of the environment and tell what
characteristics they best model.
2. Discuss the advantages of quantification vs. qualification in sampling.
3. Explain the concept of evapotranspiration and how it can affect sampling.
4. What types of chemical phenomena are used in modeling the chemical activity of
components of the environment?
5. Simple mathematical models are often based on statistics. Explain.
6. Explain why computer models are useful in environmental modeling and relate this
to sampling.
7. There are two basic landscape models. What are they and how does each account for
the movement of soil and pollution?

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8. What do A and T refer to in USLE and how are they related?

9. Explain how particles move through air, water, and soil. How is movement in soil
different from that in water and air?
10. Make a simple dynamic model for the fate of nitrate in the environment. (Hint: see
Figure 7.5.)
11. Make a complex dynamic model for the fate of nitrate in the environment. (Hint:
see Figure 7.5.)
12. Write a simple equation for the future level of potassium in a body of water.
13. Look up the word colloidal as it applies to particle size. What is the upper limit to
colloidal-size particles? Why do they not settle out of suspension?
14. Explain how colloidal particles can affect the components dissolved in water.
15. A commercial environmental model can map horizons in soil and layers in the
regolith. The program can also estimate the depth to each horizon and layer between
sampled points. Explain how such a representation may be used in sampling.

REFERENCES
1. Brady NC, Weil RR. The Nature and Properties of Soils. Upper Saddle River, NJ:
Prentice-Hall, 1999:223234.
2. Svirezhev YM. Thermodynamics and theory of stability. In: Jrgensen SE, ed.
Thermodynamics and Ecological Modeling. New York: Lewis, 2000:115132.
3. Mattigod SV, Zachara JM. Equilibrium modeling in soil chemistry. In: Bartels JM, ed.
Methods of Soil Analysis: Part 3Chemical Methods. Madison, WI: Soil Science
Society of America and American Society of Agronomy, 1996:13091358.
4. Reichman R, Wallach R, Mahrer Y. A combined soil-atmosphere model for evaluating
the fate of surface applied pesticides. 1. Model development and verification. Environ
Sci Techn 2000; 34:13131320.
5. Leonard RA, Knisel WG, Still DA. GLEAMS: Groundwater loading effects on
agricultural management systems. Trans ASAE 1987; 30:14031418.
6. Tsiros IX, Ambrose RB. An environmental simulation model for transport and fate of
mercury in small rural catchments. Chemosphere 1999; 39:477492.
7. Stewart MA, Jardine PM, Barnett MO, Mehlhorn TL, Hyder LK, McKay LD.
Influence of soil geochemical and physical properties on the sorption and
bioaccessibility of chromium III. J Environ Qual 2003; 32:129137.
8. Universal Soil Loss Equation.
http://soils.ecn.purdue.edu/~wepphtml/wepp/wepptut/jhtml/usle.html.
9. Revised Universal Soil Loss Equation. http://www.sedlab.olemiss.edu/rusle/.
10. Brady NC, Weil RR. The Nature and Properties of Soils. Upper Saddle River, NJ:

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Prentice-Hall, 1999:668707.
11. Wind Erosion Simulation Models. http://www.weru.ksu.edu/weps.html.
12. Revised Wind Erosion Equation.
http://www.csrl.ars.usda.gov/wewc/rweq/readme.htm.
13. Zannetti P. Particle modeling and its application for simulating air pollution
phenomena. In: Melli P, Zannetti P, eds. Environmental Modeling. Boston:
Computational Mechanics Publications, 1992:211241.
14. Deaton ML. Winebrake JJ. Dynamic Modeling of Environmental Systems. New
York: Springer-Verlag, 2000.
15. Environmental Modeling with GIS. Goodchild ME, Parks BO, Steyaert LT, eds. New
York: Oxford University Press, 1993.
16. Koziol AS, Pudykiewicz JA. Global-scale environmental transport of persistent
organic pollutants. Chemosphere 2001; 45:11811200.

8
Sample Transport and Storage
As soon as the sample is removed from the medium in which it is located it is considered
to be in transit. During this process there are three main concerns. First is the integrity of
the sample. The sample must be secure from loss, tampering, or contamination. Second,
its identification must be maintained so that the results of analysis can be related back to
the field and site where the sample was taken. Third, the sample must not be allowed to
contaminate or be contaminated by the environments through which it travels. Particular
concern is for the personnel handling the sample, some of whom may know little about
the potential dangers in the sample.
Next to the actual taking of a sample, its transport and storage are most likely to cause
variation or inaccuracies in the analytical results. As mentioned both in previous chapters
and below, exposure to light, variations in temperature, wetting, and drying are all
storage and transport problems likely to cause variations in analytical results. It is not
sufficient to throw the samples in the back of the truck and get around to sending them
off for analysis when time permits.
A flow chart of the movement of sample from field to laboratory and analysis is given
in Figure 8.1. This is given as an example only, as various analytical laboratories and
different projects may have different flows of samples.

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FIGURE 8.1 Flow chart of movement of samples from field to commercial

laboratory to results returned to requesting agency. COC is the chain
of custody. RFA is the request for analysis.

8.1. SECURITY
There are many different components to maintaining the security of a sample. One is that
the sample container must not be broken or tampered with. This means that it cannot be
opened at any stage between the initial placement in the sample container and the final
opening of the container to take a sample for analysis. If there is a particular concern in

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this regard, some method of making the sample containers tamper-proof should be found.
One approach to this problem is to use fragile labels that are applied to a sample
container when filled out, so that tampering will damage them. If the individual
containers are not made tamper-proof, boxes or other containers of lots of samples can be
made tamper-proof by the use of seals or locks that indicate when they have been opened.
Another area of security is that the sample numbers be secure so that a sample can
always be identified. Sample identification numbers must be placed on the containers in
such a way that they cannot be erased or removed. Sometimes a little thought beforehand
is helpful in avoiding the loss of numbers. Labels inside a sample container with the
sample are not recommended in any case because they are a source of contamination and
often decompose (e.g., paper labels placed inside containers of moist soil will often
degenerate in several days). Under certain conditions labels on the outside can also be
lost. For instance, labels placed on the outside of soil drying cups often fall off during
drying. Lot containers, however, such as coolers used for shipping samples, will have
labels and other paperwork inside them. These are sealed in plastic bags and do not come
in contact with the samples.
There are several ways to avoid many labeling problems. Choose labels with highquality adhesive and write on them with indelible, nonsmearing ink. Place labels on areas
of the sample container that will receive little or no abrasion. One interesting place for a
label is on the bottom of sample bottles or containers. Often the middle of the bottle
bottoms are indented, and thus not subject to abrasion. A second reason this is a good
place is that dirty, wet fingers, water, and solvents can get on the top and sides of bottles
but often do not reach bottle bottoms. Some sample bags have fold-over tops secured by
tabs. The folded area is a good place to put a sample label. A third approach is to use
permanent markers to directly mark the sample container.
Samples must be secure from pests. During transport and storage in the field, samples
may attract rodents and other animals that can destroy or contaminate samples. Even
samples kept for only a short time may be attractive nesting and hiding places for rats and
mice. Rodents will attract snakes, and soon there is a whole host of animals in with the
samples. Even without opening the sample containers such intrusions may cause
contamination because some sample containers are porous and can allow contaminants
from animals to enter.
Samples will need to be protected from the deleterious effects of microorganisms in
addition to large animals. Because microorganisms can rapidly change the nature of
components in a sample, controlling their activity is important. Microbial activity is
minimized at low temperatures, and so storage at 4C is sometimes required. Also,
limiting the time between sampling and analysis will limit the development of this type of
problem.
Sample security means that samples are not exchanged for one another and two
different batches of samples are not intermixed. Samples must have designated space
during transportation and storage. Keeping samples in their designated transportation and
storage space will assure that they are not mixed with other samples, which is particularly
important when different samples or different sample batches require different analysis or
different analytical procedures. Once a sample has started an analytical procedure
extraction, for instanceit is usually not possible to use that same sample or extract in

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other analytical procedures.

At every step between the field and the final analysis an accounting of where the
sample is or has been needs to be kept. It is essential that there be no doubt about the
authenticity of the sample. It must be impossible for a sample to be contaminated,
switched for another sample, or mixed with another sample. In part this means that
samples are never left in the hands of persons not responsible for their transport and
storage. It also means having a detailed, well-documented chain of custody (discussed
below).
Security can also be thought of in terms of not allowing any sample to exit the
container and contaminate or be contaminated by its surroundings. This is dangerous for
the persons handling the samples and leads to contamination of the sample, making it
useless. Great care must be taken in making sure that the sample is well sealed in the
proper container. When several containers are packaged together this means that they
cannot interact with each other, either to break open an adjacent container or to exchange
components. Often a good approach is to have the samples double-contained. This would
be a plastic bag inside a plastic bag or a bottle inside a plastic bag. In addition, the
containers packaged together should be cushioned from each other by packing material.
A summary of security concerns is given in Table 8.1.

TABLE 8.1 Security Considerations for Field Samples

Container
integrity

Handling and package containers to minimize breakage

Sample numbers

Apply sample numbers in several places using high-quality labels and

permanent markings.

Pests

Samples must be secure from pests.

Sample mixing

Set up protocols that prevent mixing of samples from different batches or

mixing of batches.

Sample leakage

Package samples to prevent leakage during transportation and storage.

8.2. CONTAINERS
Sample containers must have three characteristics. First, the container material must be
compatible with the sample and the component or components of interest in the sample.
The container must not take away from or absorb any component in the sample, and it
must not add any component to the sample. This could be considered negative and
positive contamination of a sample. Characteristics of sample containers are covered in
more detail in Chapters 3 and 5.
The second characteristic is that the sample container be chosen so that it will not lose
components during shipment or transport. Losing components might take place by
breaking the container or by diffusion of material out of the container. Diffusion could be

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through the container walls, which is a common problem with plastic containers. Loss
might also be through septa in the tops of bottles. To assure that these types of losses do
not take place, both positive and negative control samples can be prepared in the field at
the time of sampling. If transportation and storage are of particular concern or are
particularly challenging, positive and negative standards or controls can be processed
through transportation and storage before actual samples (called transport controls). In
this way it is possible to determine if there are critical steps that need to be changed or
time constraints that need to be applied to ensure sample validity.
Sometimes samples will come under rigorous conditions during transport and storage.
Rigorous conditions are most often changes in pressure and temperature. Samples taken
at high altitude or in deep water and analyzed at low altitude or on the waters surface
will undergo significant pressure changes. Temperature changes cause pressure changes
in the sample container. If the sample contains volatile components or volatile organic
compounds (VOCs), component vapor pressures will change with temperature, and
appreciable pressure can build up when the sample is obtained under cold conditions and
is subsequently warmed to room temperature. Warm samples will lose components when
they are opened and the pressure is released. Likewise, a sample obtained at warm
temperatures and stored at cold temperatures can have considerable vacuum buildup in
the container. Opening the container while it is cold can result in contamination by
material moving into the container. Desert temperatures well over 40C and arctic
temperatures well below 0C can be encountered while sampling. Samples taken under
either of these extremes will undergo significant pressure changes when brought to room
temperature.
The third characteristic of a container is that it must not allow contamination of its
surroundings during transportation. This means that the outside of the container is clean
and that as discussed above, no part of the sample should be able to exit the container. A
common loss would be via breakage, which can be controlled by having sufficient and
proper packing material in the shipping container.

8.3. CONTROLS
To make sure that no changes occur during transport, storage controls are used. Common
types of controls are listed in Table 8.2. One type would simply be a known; that is, a
sample with a known concentration of the component of interest is transported and stored
with the test samples. Any change, loss, or gain would indicate a potential problem with
the transport

TABLE 8.2 Types of Sampling Controls

Name

Characteristics

Known samples A sample of known component concentration of interest is included with

samples collected in the field. Inclusion must be done in the field.

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205

Negative/blank A sample known not to contain the component of interest is included with
samples collected in the field. Can be either a field or trip blank.
Positive
(spiked)

A sample that contains more component of interest than is commonly found in

samples.

Surrogate

A sample containing a compound similar to that of interest is included with

samples.

Reference

Soil samples taken from similar soil in a different location known not to be
contaminated with the component of interest.

and storage procedures. Three other common types of controls are the negative and
positive or spiked (component of interest is added to the sample) and a sample containing
a surrogate compound.
A negative control would contain all the components found in the sample except the
one of interest and can be of two typesfield and transport. A field control follows the
whole path of samples, while transport controls are used as checks of the transportation
portion of the path of samples to the commercial laboratory. These allow for isolation of
the source of contamination problems if they occur. Negative controls are important for
two reasons. If they contain any of the component of interest serious contamination has
occurred, and this is the most serious concern. Any component detected in the negative
control that was not present originally also indicates a serious problem, however, and
makes the samples suspect. In such cases the analytical results should only be used after
verification by using other samples that they are representative of the field conditions.
A positive control contains the component of interest in a known concentration. If a
positive control has less of the component than it did in the field, it has lost material.
Again this means that all the samples taken, stored, and transported with this sample have
probably lost some of this component. One nice aspect of positive controls is that if they
all show a similar loss this can be used to estimate the loss from the samples. In this way
the original concentration of the component of interest in the samples can be estimated.
The sample information thus obtained may be useful; however, such samples and their
analytical results must be used with caution due to estimating the concentration of
components of interest using a fudge factor.
In some cases a surrogate is added to samples in place of the actual component of
interest. This is done when the component of interest is particularly toxic or otherwise
hard to handle. The surrogate is similar to the component of interest both chemically and
physically. Again it is assumed that if the surrogate concentration is unchanged during
storage and transportation, no loss of sample has occurred.
As discussed in previous chapters, controls consisting of samples adjacent to the
contaminated area need to be taken and sent through the storage and transportation
process. Also included would be samples from similar soils that are not from adjacent
areas. Both of these types of controls need to go through the same process.
Another type of control to consider is the archived sample. These are samples from
each step or stage of the sampling plan that are stored for later reference. They are
extremely useful if a question about analytical results or transport conditions arises later

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in the plan or in the remediation process.

8.4. TRANSPORT IN THE FIELD

Regardless of the sampleair, water, soil, or otherall are most susceptible to
contamination in the field. This happens because the sample is placed in the sample
container and is kept in the field with other samples while awaiting transport to the field
storage area. During this time samples are subject to light and changes in temperature. If
samples are taken while the sampler walks the field and samples are put in a backpack, it
may be several hours before the samples get to the field office.
Samples will be subject to jolts and bumping as the person or vehicle carrying them
traverses uneven ground between sampling sites. While in the field, samples will be
exposed to sunlight and variations in temperature. All of these factors will be controlled
once the samples are in the storage facility and boxed for shipment to the analytical
laboratory.
One good way to avoid some of these problems is to put the samples directly into the
lot shipment box that will be used to transport the samples to the analytical laboratory.
The box must be covered to keep out light and should be kept at a constant temperature
as much as possible. If cooling is called for, boxes will be filled with ice and kept filled at
all times. In this way samples are immediately cooled and stabilized in the field. During
this time containers must be kept isolated from each other, usually by packing material,
so they do not break.

8.5. TRANSPORT BOXES

Transport boxes are used to contain batches of samples and to transport these batches to
the commercial analytical laboratory. In some cases such boxes are best obtained from
the laboratory doing the analysis. A box supplied by the laboratory will come with
instructions for both packing and the conditions under which the samples must be kept. A
typical transport box is shown in Figure 8.2. The box shown contains a number of
different containers for different types of samples. Normally a box would only contain
the types of containers designated for the type of sample being collected.
Transport boxes are constructed of many different types of materials. Simple cardboard
boxes can be used but are not strong, and sample weights must be carefully monitored to
make sure that the box does not contain too many samples. Simple wooden, plastic, and
metal boxes are also used. These may be constructed with internal sample racks that keep
samples protected from each other. Insulated boxes are also used for some samples.
The box shown in Figure 8.2 is a relatively simple insulated plastic cooler. Typically
these are maintained at some lower temperature (4C is

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207

FIGURE 8.2 A typical sample transport box and various sample containers.
The container marked with A is used for checking sample box
temperature.

common) from placement of sample in them to removal of sample at the commercial

analytical laboratory. The internal temperature will be monitored by having a temperature
monitoring container, such as that shown in Figure 8.2 (i.e., the bottle labeled A, in the
box).* Measuring the temperature of the bottle contents upon arrival at the laboratory
serves as a check on the temperature of the sample box contents. If the temperature is
higher than required when the sample reaches the commercial laboratory, the sample may
be rejected or is at least suspect. It is also possible to have electrically refrigerated sample
boxes that have small electrical or mechanical cooling mechanisms and that can plug into
an electrical outlet or a vehicle electrical system. This type of sample transport container
will maintain the correct temperature in hot conditions as long as there is a source of
electricity.
* In many instances

temperature monitoring will be required by regulatory agencies.

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208

Various paper forms will come with the shipping container and must be filled out and
enclosed with the samples when they are returned to the analytical laboratory. Typical
forms are shown and discussed in Chapter 10.

8.6. TRANSPORT OUT OF FIELD

Care must be taken in transporting samples out of the field to the field storage facility.
Samples should not be thrown in the back of a pickup and left for several days before
being placed in the field office storage facility. This is of particular importance, because
samples banging around in the back of a pickup are prone to both breakage and picking
up contamination, as well as being exposed to light and variations in temperature. Any of
these variations alone or in combination can cause changes in the component or
components of interest.

8.7. STORAGE
There will almost always be time between taking a field sample and its field laboratory
and final analytical laboratory analysis. This will require a secure sample storage area at
or near the field office and at the analytical laboratory. The preference is to have this be a
separate building or at least an area separated from most or all of the other activities
occurring at the field office. As discussed above, this area must be secure from intrusion
by animals and unauthorized intrusion by persons working in the field or in the field
office. It must also be free of possible contaminants. Using a room that has previously
been used for the storage of feed, fertilizer, insecticides, solvents, or some unknown
purpose is not acceptable. Equally important, the stored samples must not be located in a
way that allows materials from samples to contaminate either the office area or the
personnel working there.
The room should be both humidity- and temperature-controlled. In some instances this
will require only heating or cooling, while in others maintaining a constant temperature
may require both a heating and a cooling unit. Constant temperatures are often best
achieved by having a heater and a refrigeration unit working against each other. In high
humidity areas removing some humidity may also be advisable. Air conditioners will
condense moisture out of the air, but this water must be drained to the outside of the
storage room.
The storage room may need to have several sections or different areas, depending on
the storage requirements of the samples taken and the components of interest they
contain. Some samples may need to be stored at 4C, while others may need to be kept at
20C. Yet others may need to be kept at room temperature. Also, some samples may
need to be stored dry, while others need to have the original moisture content maintained.
Ross and Bartlett [1] found that nitrate levels increased dramatically in forested
Spodosols stored at 3C after only 24 hr. On the other hand, Martens and Suarez found
little change in selenium species in air-dried soil samples. They found significant changes
in selenium oxidation states of air-dried alfalfa (Medicago sativa), however [2].

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209

Another aspect of storage temperatures is the effect on the physical condition of the
sample. Compounds in solution may precipitate at reduced temperatures and not go back
into solution when warmed. With some hydrocarbon samples cooling may result in
separation of various phases. This separation may not be reversed by heating, and may
produce analytical results that do not provide the information needed [3].
Some monitoring of the sample room needs to be done. The minimum acceptable
monitoring is to record the temperature and humidity in the room every time a sample or
batch of samples enters or leaves. This should be done on a sheet kept in the room. Each
different area of the room needs its own sheet, and all sheets must be filled in whenever a
sample is placed in the room, no matter which section it is placed in. Recording
thermometers and humidity indicators can be installed in such a way that a continuous
record of the rooms conditions can be kept. If this approach is taken, a separate
instrument is needed for each area of the storage room. Alternatively, sensors could be
connected to a computer and the computer could be used to record information about the
room. A connection can be made that is wireless or with wires. A single computer can
receive and store signals from many different sensors in different parts of the storage
room. Also, the computer can be set up to notify personnel when the storage room or any
part of it is not at the proper temperature or humidity. The storage room or area thus
needs to be versatile enough to allow for all the different storage requirements of
different samples and components of interest.
Locks on the doors will provide security, as will motion sensors and cameras so that all
movement into and out of the room is controlled and recorded. This provides added
security for the samples.

8.8. ARCHIVAL SAMPLES

It may be desirable to save some samples, called archival samples, until the end of the
project or even longer. They must be kept separately from all other samples and labeled
clearly as archival samples. These are duplicates or part of samples taken at a particular
time during sampling of a field. They can be used to check the accuracy and authenticity
or estimate the original condition of the samples at a later time during the project or even
years after the termination of the project. It must be kept in mind, however, that the
samples and the analyte of interest may have changed significantly during storage. For
this reason any use of archival samples in comparison studies must be done with extreme
caution.

8.9. SEPARATION OF SAMPLES AT THE FIELD OFFICE

Field analysis will be done in the field by the sampler or sampling crew. In some cases
this may not be feasible and the samples will be taken to the field office laboratory for
analysis, and some or all of the sample or samples will be analyzed and the rest shipped
to the commercial analytical laboratory. Separation is best done as the samples enter the
storage facility by immediately placing those to be analyzed in a different place from the

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210

samples to be shipped to the analytical laboratory. Samples will be analyzed immediately,

and thus will not need storage.

8.10. FIELD LABORATORY HANDLING

The analysis to be done immediately in the field or at the field laboratory is given in
Chapter 10. This includes such things as pH, electrical conductivity (EC), and dissolved
oxygen in the case of water samples. For pH and EC the analysis can be done directly on
the samples in the field as they are taken; that is, the samples need not be dried and
sieved. In some cases, however, it may be desirable to bring samples to the field
laboratory to sieve if they contain a lot of plant material or large rocks, gravel, and so
forth; otherwise a minimum of handling is recommended.
Although the above analyses are straightforward and not delicate, care still must be
taken to obtain accurate results. The word delicate is used to indicate that small changes
in the way the analysis is carried out will usually not result in a change in the results
obtained. For instance, slight dilution of the highly buffered solutions used for
standardizing a pH meter will cause little, no, or insignificant changes in the measured
pH. This does not mean that care need not be taken in doing the analysis, however. It
does.

8.11. TRANSPORT TO THE COMMERCIAL LABORATORY

A chain of custody (COC) form and other forms (see below) as required by the laboratory
must be started in the field as the samples are taken and be continued by the receiving
laboratory. Before shipping, however, the analytical laboratory is notified because it
needs to be ready to handle and store the samples in such a way that the components of
interest are preserved.
Commercial carriers are usually used to transport samples to the laboratory for
analysis. An ideal situation would be one in which the commercial analytical laboratory
is close enough to the field being sampled that the samples can be locally transported.
This situation does not often happen, and most often the samples will need to be shipped
to the laboratory using a commercial carrier. The carrier should be chosen so that the
transit time is no more than 1 day, if at all possible. Usually the project manager at the
analytical laboratory will be able to suggest carriers and shipping requirements.
Just as individual samples must have traceable numbers, so also must lots have
traceable shipping numbers. Registered or certified mail is traceable, but may not be
sufficient for the numbers and weights of samples that need to be shipped. Companies
such as Federal Express or UPS assign traceable numbers to shipments and will often
pick up samples at a designated location. This decreases handling and thus increases
security. Using one of these carriers the progress of the sample from pickup to delivery is
traceable, accessible, and can be followed using a computer and the Internet.
In many cases shipment will involve air transport. Very specific restrictions are applied
to samples shipped by air. Different types of samples (i.e., samples containing different

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211

types of contaminants) will have different restrictions. For instance, there are specific
requirements for packaging oil-contaminated samples. One of these is that the inside of
the box be fitted with an oil-resistant liner. There are also limits on the size and weight of
sample containers. All these restrictions must be strictly adhered to when shipping by air.
The shipment must be accompanied by a COC form updated by various persons
handling the shipment along the way and signed by the appropriate persons in the
appropriate places. This is particularly true if a national carrier such as UPS is not used to
ship the sample. This may seem simple, but a truck driver who takes the samples to the
local airport will handle samples, and this person needs to be known. Likewise, the
shipping department at the air shipment office will receive the samples and perhaps hand
them off to another person to get them to the airplane. Indeed, there may be three or four
different people handling the box between its arrival and being placed on the airplane.
When the plane lands, the same or a greater number of people may handle the sample box
before it gets to the laboratory receiving office. All of the people handling the container
of samples need to be identified, and the length of time the sample is in their possession
must be known. The greater the number of people handling the sample box the greater the
chance that something will happen that will render the samples unusable.

8.12. STORAGE AT THE COMMERCIAL ANALYTICAL

LABORATORY
Samples will be stored at the analytical laboratory, sometimes for very short periods of
time. Normally the laboratory will have standard operating procedures for sample
handling and appropriate storage facilities. A visit to the laboratory to see how samples
are handled is recommended. It is always advisable to ascertain how long and under what
conditions samples will be stored at the laboratory between receiving and analysis.
Second, a quick walk-through of the facility is necessary. Samples lying around in a
haphazard fashion in open containers are cause for concern. Such circumstances lead to
contamination and cross-contamination of samples.
A third concern is maintaining the proper environmental conditions during this time. If
the sample temperature is to be maintained at 4C, the appropriate cold room should be in
evidence. In some cases samples may need special environmental conditions for storage,
and the laboratory must be willing and able to provide these conditions.

8.13. CHAIN OF CUSTODY

The chain of custody (COC) is the most important component of the secure movement of
samples from the field to the laboratory to final receipt of the analytical results. Another
component associated with COC is the letter of transmittal. Such a letter is not typically a
COC, in that samples may have both a COC and a letter of transmittal. Also, a letter of
transmittal can mean different things to different people; a request for a new position in
an organization may be called a letter of transmittal, for example, and thus many of these
types of letters are unrelated to samples or safe sample movement. Although COCs may

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212

be thought of as being associated with evidentiary forensics samples, they are equally
valuable and important in environmental and geological sampling.
The COC accounts for where the sample originated, where it has been, who has
handled it, and what conditions it has been exposed to. It should prevent loss, misplacing,
and tampering with the sample in any way. It will also help prevent samples from either
being analyzed for the wrong constituents or being subject to the wrong procedures. To
accomplish this it is best to minimize the number of people involved in the COC and
sample handling. The more people handling a sample or container of samples, the greater
the likelihood of contamination, loss, or mislabeling of the samples. If one person is
sampling and is also responsible for storage, that person does not necessarily need to sign
the COC each time he or she handles the sample. Each time the sample or samples are
transferred to a new location, however, this needs to be fully noted. The dates, times, and
conditions of transfer need to be recorded, even if the same person is doing all the work
[3].
The COC starts in the field with taking the sample and putting it in the sample
container. The sample is recorded in the project notebook, given a number, and recorded
on a COC form. This form then stays with the sample until the analytical results are
reported back to the entity requesting the analysis. If bar codes are used, a code label can
be placed on the COC form [4]. If a group of samples are to be shipped as a batch, a
batch COC needs to be prepared. Individual sample COCs go in the batch box with the
samples, and the batch COC is signed as needed by persons handling the box. Again, if
bar codes are used a bar code for the box can be prepared and used to keep track of the
box. An illustration of the type of information needed for a COC form is given in Figure
8.3. (A more detailed COC is given in Chapter 10.)
At each step of this process a responsible person should be designated to receive
samples, sign the COC forms, and put samples in the appropriate storage area or
transmittal container. This person will also be the contact person during the time the
samples are in his or her possession. In small firms, in which there are a limited number
of employees, this may seem unnecessary. It is not; but it need not be a complicated
procedure. In large firms it is essential that persons handling samples be identified and all
the time the samples that are in their possession be accounted for.

8.14. COMPUTER CHAIN OF CUSTODY

A COC can and should be set up using computers. This should be done even though a
detailed paper COC is also maintained. One advantage of a computer COC is that it can
be quickly accessed from many locations when a problem occurs. Software can also
allow for the insertion of additional written descriptions and explanations in such a way
that they do not interrupt the flow of the COC because they are readily available as popup notes that appear with the push of a button. This is much more useful than shuffling
through numerous pages of information to find a needed explanation or description. The
information in the pop-up could be about storage facilities, changes in temperature, or
other conditions that might

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213

FIGURE 8.3 A suggested chain of custody form for field samples.

affect a samples integrity, and needs to be included with the COC. Software specifically
designed for COCs is available [5, 6].
An additional advantage is that computers can be accessed from remote locations if
they are connected to the Internet. They can also distribute or receive information from
several locations simultaneously. This means that the original COC can be accessed from
either the field in which the sampling is occurring or from the analytical laboratory in
which the analysis is occurring. It also means that at any time during transport changes in
the COC can be transmitted to both the field and to the analytical laboratory.
With computers there is always the danger of data loss. Acquiring and using an

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214

uninterruptible power supply (UPS) is a good way to help prevent data loss. These power
supplies will keep the computer running for a short period of time, which is usually long
enough to allow data to be saved, and the computer can be turned off when there is a
power failure. A safer strategy, however, is to constantly and conscientiously back up
data. Keep in mind that a UPS unit does not preclude the need for daily backup; it can fail
and it cannot prevent failure of other components of a computer.
There are five major ways to store data; 3.5 floppy disk, zip drives, hard drives, CDs,
and DVDs. A 3.5 floppy disk can be used and has the advantage that it can easily be
carried from place to place and can be kept with the COC. These disks, however, are
limited in the amount of data they can store. A hard drive is a convenient storage device
and can typically hold large amounts of date. Hard drives are usually internal to the
computer, however, so either data are transferred to the hard drive when the office
receives then or the computer must go with the sample. This obviously will not work with
a desktop computer containing a hard drive, but is feasible with a laptop. There are
external hard drives accessible through a computers USB port. This hard drive can be
carried from computer to computer, but transport is not easy because of its nature and its
susceptibility to damage and data loss.
Either internal or external zip drives are also available. These drives and their
removable disks hold a moderately large amount of data, and the disk can easily be
transported or kept with the COC. External zip drives are small enough to carry around
conveniently, and if they connect via a USB connector, can be connected to available
computers at any location. One important drawback to all the storage devices discussed
so far is that the data on them can be lost or erased.
For a permanent record, a CD or DVD recording can be made of the COC and the
accompanying information (usually referred to as burning). For a permanent record a
CD-R or DVD-R, (read only) must be used. There are CDs that can be rewritten, but
for COCs these are not recommended. Once a CD-R is burned, it is a permanent record of
the COC and accompanying explanations. A CD player/burner or DVD player can be
bought as an internal or external unit. An external unit would then be available to carry
between computers. DVDs hold a great deal more information than CDs, so a single
DVD may be all that is necessary to store all the information gathered about a particular
field, including maps and pictures.
Newer types of storage devices, flash memory, memory sticks, and flash cards, are also
available. These are used extensively on digital cameras, can also store data and are
relatively small. They hold about the same amount of data as a zip disk; that is, up to 256
megabites (MB) in a very small unit. They are particularly useful if a number of pictures
are to accompany the sampling plan, and can easily be carried from place to place and
used on any number of computers, both desk and laptop. A drawback is that some of
these devices require a special reader or port to transfer data from these devices to a
computer. Two other potential drawbacks are that some seem to use significant amounts
of energy, and this may be a problem when they are used with digital cameras, which
have dry cell batteries. The second drawback is that they can be erased, and so data can
accidentally be lost. A number of common computer storage devices are shown in Figure
8.4. Table 8.3 lists various storage devices and gives some information about their
characteristics.

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215

8.15. REQUEST FOR ANALYSIS

It is essential that samples leaving the field office for the analytical laboratory be
accompanied by a request for analysis (RFA) form, which will be different for different
laboratories. Both the COC and the RFA forms should have a contact person clearly and
easily identified on them. The

FIGURE 8.4 Some examples of computer storage media. From left to right:
CD, zip disk, and 3.5 floppy disk.

TABLE 8.3 Computer Storage Devices

Device

Type of media

Condition of stored data

Floppy drive

Floppy disk

Data easily stored and transported. Limited storage capacity.

Data can be erased or otherwise lost.

Zip drive

Zip disk

Data are easily stored and transported. Will hold more data
than floppy disk. Data can be erased or otherwise lost.

Memory stick Memory chip

and card

Data easily stored and transported. Holds about same amount

of data as zip drive, but is much smaller and more
transportable.

Hard drive

Nonremovable
hard disk

Holds large amount of data. Usually an integral part of a

computer. Not easy to transport. Data can be erased or
otherwise lost.

CD burner

CD-R

Holds large amount of data. Burner is usually integral part of

computer. Data cannot be erased.

CD burner

CD-RW

Same as above, but CD can be rewritten on, thus loss of data

is possible.

Field sampling

DVD burner

DVD-R, DVDRW

216

Similar to CD, but holds gigabytes (GB) of data. Can either

be write once or rewritable.

contact person needs to be identified as to position, mailing address, phone numbers, and
e-mail address. E-mail addresses are handy because an exchange of e-mails will often
facilitate phone contacts when needed. The reason this is so important is that the
laboratory needs to know of whom they should ask questions if there are problems with
the samples.
Discussion with the analytical laboratory personnel, particularly the project manager
assigned to the project, of the COC and RFA needs of the submitter is advisable and will
eliminate confusion in sample transfer, recording COC data, and processing the RFA. It
will also facilitate the return of analytical results to the contracting agency. Examples of
RFA and results of analysis forms are given in Figures 8.5 and 8.6. These figures do not
correspond to any commercial or government laboratory form; such forms will be more
detailed. (Additional forms of this type are given in Chapter 10.)
Request for analysis form (not related to any commercial or governmental
organization form)
Analytical laboratory informationname, address, contact person, address,
phone numbers, E-mail, etc.
Submitter informationname of organization, address, contact person, phone
numbers, E-mail, etc.
Requested organic analysis

Requested inorganic analysis

Analysis
requested

Analysis
requested

Check all that are

desired

TPH

Cr

VOC

Ni

DAPAL

Cu

PCB

AS

Total C

Se

CRN

Hg

Check all that are

desired

FIGURE 8.5 Example of the type of information needed for a request for
analysis. Actual forms will ask for more information and detail.

8.16. CONCLUSIONS
Handling samples between the field and final analysis is the second potential area of
sample loss or contamination. For this reason sample security is essential. Proper

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217

containers and controls must be used in sampling and shipping. The conditions that
samples are exposed to during shipping and storage must be controlled if the component
of interest is to be maintained in its original concentration and form. Chain of custody
forms must be scrupulously kept during the whole sampling and transportation process. It
is highly recommended that a computer-based COC be maintained, along with a paper
COC to accompany the samples. A request for analysis form must accompany the
samples to the analytical laboratory. Discussions with the analytical laboratorys project
manager assigned to the project is essential for successful sampling and analysis of
samples.
Request for analysis results form (not related to any commercial or government
form)
Analytical laboratory informationname, contact person, address, phone
numbers, E-mail, etc.
Submitter informationname of organization, contact person, address, phone
numbers, E-mail, etc.
Field sample Lab. sample Sample
number
number
amount

Sample
condition

Component analysis
requested
Cr Ni Cu As Se Hg

AC13a
AC13b
AC13c

FIGURE 8.6 Example of information provided in a request for analysis results

form. Actual forms will ask for more information and detail.

QUESTIONS
1. Explain three reasons why security of samples is important. What security
precautions are needed?
2. Describe the characteristics that a sample container must have. What must the

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218

container do and what must it not do?

3. In terms of transporting samples, what considerations about sample containers
should be taken into account?
4. What are two types of common controls and what information about samples and
sample handling does each provide?
5. Explain how samples can be contaminated in the field.
6. What characteristics must a sample transport box have?
7. Describe the characteristics that a sample storage facility must have.
8. What steps are followed in separating and handling samples at the field sample
laboratory?
9. What are archival samples and why may they be important? What factor must be
remembered if the archival samples are used to derive data to compare with the current
samples?
10. Describe the characteristics of a chain of custody.
11. What information is called for in a request for analysis?
12. What is the difference between a chain of custody and a letter of transmittal?
13. What are the advantages of using computers in maintaining a chain of custody?
14. Using the Internet, look up the shipping requirement for air shipment of water or
soil contaminated with oil or hydrocarbons.

REFERENCES
1. Ross DS, Bartlett RJ. Effects of extraction methods and sample storage on properties
of solutions obtained from forested spodosols. J Environ Qual 1990; 19:108113.
2. Martens DA, Suarez DL. Changes in the distribution of selenium oxidation states with
sample storage. J Environ Qual 1997; 26:17111714.
3. Marine Safety Laboratory, http://www.rdc.uscg.gov/msl/downloadsl.html. Pp. 813.
4. Bar Code PrimerIntroduction to Barcoding. http://barcodehq.com/primer.html.
5. Murphy C, Briggs P, Adrian B, Wilson S, Hageman P, Theodorakos P. Chain of
CustodyRecommendations for Acceptance and Analysis of Evidentiary
Geochemical Samples. U.S. Geological Survey circular 1138. Washington, DC: United
States Government Printing Office, 1997.
6. e-Chain. http://www/enabl.com/p_echain.html.

9
What Is Present
Analytical results having unexpected amounts or types of components
are not necessarily in error

The environment is made up of the atmosphere, hydrosphere, and lithosphere. The

atmosphere is relatively simple and its composition is relatively stable. Only those
elements, compounds, ions, and molecules that are gases or that can remain suspended in
the atmosphere will stay there for a significant period of time. The hydrosphere is more
complex, having various levels of salts and other compounds that originate in the
lithosphere containing it. The lithosphere is far more complex and can contain all the
elements, compounds, molecules, and ions present in the Earth. The three parts of the
environment cannot be separated from each other. Components occurring in one sphere
can and do move into the other spheres.
The three spheres are sampled for contaminants on a regular basis. For the most part
components occurring in the atmosphere are either its natural components or components
put there as a result of the activities of man. With few exceptions, such as reactions
among chlorine, ozone, and nitrogen oxides, the number and complexity of reactions
producing compounds, ions, and molecules in the atmosphere are both limited and
relatively simple.
Both the hydrosphere and lithosphere, particularly the soil, are different. Soil is
intimately connected to water because rain falls on it, infiltrates, percolates, and finally is
released into bodies of water. During these processes water picks up molecules, ions, and
elements from the soil. The soil is a great reactor, producing all manner of inorganic,
organic, and biochemical molecules, as well as ions, some of which will be dissolved by
the water moving through it. The question then becomes what types of compounds are
common and commonly produced in this reactor.
Added to the natural components produced by normal soil reactions will be
components produced by man and either unintentionally or intentionally added to soil and
water. Both these groups of compounds are important because they will show up in
samples taken from soil and water and because it is important not to confuse naturally
made and occurring components with contaminants added to soil and water by man.
Soil is a mixture of inorganic and organic solids plus a solution of inorganic and
organic ions, molecules, gases, and elements in water. It also has a gas phase made up of
nitrogen, oxygen, carbon dioxide, water vapor, argon, methane, and a number of other
minor gaseous constituents. Many think of the inorganic fraction as being inert and
unchanging. This is not true. The variety of inorganic components, their structure, and
their composition is vast. Likewise, the organic fraction is large and immensely varied.

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This in turn leads to a complex solution of these components in water and the occurrence
of many unexpected components in the environment.
The inorganic phase is mostly silicon, aluminum, and oxygen. The organic fraction is
made up mostly of carbon, hydrogen, nitrogen, and oxygen. Neither of these
characterizations provides any useful information about the composition and activity of
soil, however. Even small amounts of clay particles, particularly the very active clay
fractions, can make a large difference in a soils characteristics. This includes how easily
a soil is sampled. A sandy soil with small amounts of clay can be sampled using a core
sampler. Sandy soils without any clay must be sampled using a bucket-type sampler. The
same thing can be said for the other components in soil, including organic matter.
The soil solution is made up of water. In most cases it contains a complex mixture of
inorganic and organic ions and molecules and dissolved gases. Relatively small changes
in any of these constituents can have a pronounced effect on the soil solutions
characteristics. At pH 7 the soil solution contains 0.0000001 moles of H+ per liter.* This
is not very much! A slight increase in H+ to 0.000001 moles/liter makes the solution
acidic, while a change to 0.00000001 H+ moles/liter makes the soil solution basic.
In like fashion, small changes in the gaseous content of soil can dramatically affect its
characteristics. An increase in the carbon dioxide concentration in soil air will change the
soil solution pH. It can also cause the precipitation of various ions as carbonates.
All of this leads to three important considerations in sampling. First, changing soil
conditions will change the amount of a component that is found. In some cases it may
even determine if a component is found or not. Because such a variety of components is
present, sampling must always be accompanied by controls. It is not good enough to
simply say that lead, chromium, arsenic, or any one of innumerable other inorganic and
organic compounds is found in a soil sample. The concentration at which it is found is
critical because it must also be determined if this level is natural for the soil or not. Is the
component significantly above background levels or not? Another important question
concerns the biological availability of the component. Is the component in a form that is
biologically available or unavailable? Only when these questions have been answered can
one begin to assess the need for further sampling and, potentially, remediation.

9.1. IN TOTAL
The three spheres of the environment have very different compositions when looked at
from the perspective of gas, liquid, and solid phases. The atmosphere is predominantly a
gaseous phase. Relatively small amounts of liquids and solids are suspended in it. The
hydrosphere is predominantly a liquid phase. It has variable amounts of salt, relatively
small amounts of gas dissolved in it, and small amounts of solid suspended in it. On the
other hand, soil has relatively large amounts of gaseous, liquid, and solid phases in
intimate contact with each other.
* It is

more accurate to call this the hydrogen ion activity in soil rather than concentration;
however, for our purposes here concentration illustrates the point better.

What is present?

221

A sample of soil has three phasessolid, liquid, and gasintimately mixed together.
It is roughly half solid and half void space. The solid phase in many soils is 98%
inorganic and 2% organic, or 49% and 1% of the total volume. The void space is roughly
half air and half filled with water. (See Figure 9.1.) The inorganic component has an
elemental composition of aluminum, silicon, iron, titanium, and oxygen if only the major
components are considered. The relative amounts of these three and other major elements
change as soil develops.
As can be seen in Figure 9.2, rock is composed primarily of silicon and aluminum. It
also contains appreciable amounts of iron, potassium, and sodium with smaller amounts
of calcium and magnesium. The more soluble

FIGURE 9.1 Percentage composition of a soil sample by volume. Water and

air contents vary with moisture content.

components are leached out of the soil parent material or regolith over time and the more
resistant materials are left behind. In the pie chart of weathered rock there is thus an
increase in aluminum and a decrease in silicon content. Iron and magnesium increase, in
concentration, and calcium, potassium, and sodium decrease. Along with this is a
dramatic increase in the amount of water held by the inorganic components. The
composition of the inorganic phase of soil is thus constantly changing, and the relative
amounts of components present will be different at different times.
The organic constituents are composed of carbon and hydrogen with some nitrogen
and oxygen. On a weight bases the hydrogen is not appreciable; its atomic mass is 1
atomic mass unit (AMU). On a molar basis, however, it is extremely important because
there are approximately 2 moles of hydrogen for every mole of carbon.
The soil solution phase is primarily water or H2O. In this case elemental analysis
would show this phase to be made up primarily of oxygen with some hydrogen. All other
constituents would be at low concentrations.
The gaseous phase of soil is mostly nitrogen (N2), oxygen (O2), and water. Because of
its low concentration, carbon from carbon dioxide or other sources might not show up as
being important. Methane and hydrogen may also be present in low concentration in
flooded soils. This type of description of the soil atmosphere is similar to that commonly
given for atmospheric air, which is said to be composed of nitrogen, oxygen, and carbon

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dioxide. Nitrogen represents approximately 80% of air and oxygen 20%, with carbon
dioxide being 0.003%. Note that argon, which is never mentioned, makes up 1% [1]!
Additionally, water can be as much as 5% of the soil atmosphere.

FIGURE 9.2 Inorganic composition of rock and soil before and after
weathering. Data taken from Ref. 10.

9.2. THE INORGANIC COMPONENTS

When discussing the specific inorganic contents it might be good to start with those
present in elemental form. The gaseous phase contains nitrogen, oxygen, argon, and in
the regolith, radon. Both nitrogen and argon are considered to be inert in the
environment. On the other hand, oxygen is very reactive and necessary for respiration by
most organisms and plant roots. Helium and radon can also be found in the soil
atmosphere and are particularly apparent near geologic fault lines [2, 3]. Even mercury
gas (Hg gas) has been reported in the regolith atmosphere [4]! There is little in the way of
elements in the hydrosphere, soil solution, and water in either the regolith or in rock

What is present?

223

except for the dissolved gases nitrogen, oxygen, argon, hydrogen, and so on. In some
cases colloidal-size carbon particles may be present and may be of particular concern
because of their high sorptive capacity [5].
The solid phase of soil, regolith, and rock will contain very small amounts of noble
metals in the elemental state [6]. There will be some elemental carbon present, much of it
as a result of fire, either natural or man-made [5]. There may also be some gaseous
elements trapped in solid matrices in soil. The overwhelming amounts of the inorganic
components are in the form of ions and molecules.
In some places the soil, regolith, and rock may contain arsenic and uranium. Radon
when found comes from the decomposition of uranium in the regolith. It is of note
because of its diffusion into house basements [7 10].
9.2.1. Elements in Combination
Many more elements than those mentioned above are commonly found in the
environment but are present as compounds or ions rather than in the elemental state.
Of the 110 or so elements in the periodic table, 36or 33%are common and
important in the lithosphere. Their importance comes either because they are essential for
plants or are needed in the diets of animals, or because they or one of their forms is toxic.
In addition there are other elements, such as silver, gold, argon, and helium, found in low
concentrations, that are not essential to plants or animals and are not toxic. Because of
their environmental and economic importance all have had specific analytical procedures
developed for their detection and measurement.
In Table 9.1 the elements commonly analyzed for are arranged in three columns. The
first column shows elements essential to plants and animals. The second shows elements
toxic to plants and animals at high concentrations but essential at low concentrations. The
third contains elements generally considered to be toxic. Not all elements listed in
column 1 are essential for all plants and animals. For instance, cobalt (Co) is generally
not needed by plants, but is essential in the nutrition of animals. Likewise, silicon is not
essential to animals, but is for some plants. The same thing can be said in column 2. As
shown in column 3, some elements, such as aluminum (A1), are toxic to plants but not to
animals. On the other hand, lead (Pb) is toxic to humans but is not especially toxic to
plants [11]. The last

TABLE 9.1 Elements Found in Soil

Plant and animal essential

elements found as ions

Essential and
toxic

Potentially
toxic

Found in elemental
form

Macroa

Se

Al

H2

Li

O2

As

Ba

N2

Na

Rb

Rn

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224

Cs

He

Be

Ar

Sr

Mg

Cd

Cu

Ca

Pb

Pb

Si

Hg

Ag

Fe

Br

Au

Microa

Feb

Cr

Rn

Mn

Cu
Zn
Mo
Co
Ni
P
Cl
aMacro elements are present at relatively large levels
bFe only counts if you consider meteorites.

and micro are relatively low levels.

column gives the elements sometimes found in elemental form in the environment.
All the natural elements are found someplace on the Earth. The elements mentioned
above, however, are common in all areas, while other elements are found in detectable
amounts only in restricted locations.
As stated above, these elements are found as ions combined with other ions in the
environment. In the case of inorganic compounds these are generally salts. The metals are
found as positive ions, or cations, and the nonmetals as negative ions, or anions, and in
some cases both can form negatively charged oxyanions when combined with oxygen.
(See below.) Carbon in organic compounds is not ionic, but forms compounds that do not
generally have full positive or negative charges.*
* Exceptions to this are organic acids, which

cations when they associate with protons.

can ionize to form anions, and amines, which act as

What is present?

225

9.2.2. Nonmetal Compounds in Soil

The nonmetals in soil include compounds of carbon, oxygen, nitrogen, chlorine, silicon,
phosphorous, sulfur, bromine, iodine, arsenic, fluorine, and selenium. A number of
inorganic carbon compounds, such as carbon dioxide and carbonates, occur in soil. The
vast majority of carbon compounds in soil are organic, however, and will be discussed in
the section on organic compounds below. Oxygen occurs in carbon dioxide, but also
more importantly in water. Water is a unique and critical component in the environment
and will be discussed in the next section. Oxygen occurs in carbon monoxide and ozone,
which is important in both the upper and lower atmosphere. Oxygen also occurs in all the
oxyanions.
Nitrogen can occur in several different types of inorganic compounds in the
environment. These will commonly be compounds of ammonia, ammonium, nitrite or
nitrate, and various nitrogen oxides. Although other nitrogen compounds have been
reported in the environment, they are generally in low concentration and do not gain
much attention from environmentalists. Any time an unusual amount of any type of
nitrogen compound is found in any environmental sample there is cause for concern.
Phosphorus is found bonded to oxygen, forming phosphates. Most often phosphates
are formed as combinations with calcium to produce various calcium phosphates. These
may also have other elements associated with them, such as hydrogen, fluorine,
aluminum, and iron, forming other naturally occurring phosphates.
Both chlorine and bromine are commonly found in the environment. Their
concentrations increase as one moves toward the oceans or salt deposits. Both are
commonly combined with alkali metals to form salts. These salts are highly water soluble
and are easily and rapidly leached from soil during its formation. Eventually these salts
are deposited in the oceans [12].
Silicon is almost exclusively found as silicon dioxide (SiO2) and silicates in the
environment. In silicates it takes a tetrahedral form in the center of four oxygens, which
bond to other constituents, such as aluminum. In this way it is an integral part of soil
minerals in the sand, silt, and clay fractions.
9.2.3. Metal Cations
The alkali and alkaline earth elements form simple positive cations. The alkali metals
lithium (Li+), sodium (Na+), potassium (K+), rubidium (Rb+), and cesium (Cs+) form ions
with a single positive charge or oxidation state. The alkaline earth metals magnesium
(Mg2+), calcium (Ca2+), strontium (Sr2+), and barium (Ba2+) occur as simple cations with
two positive charges or an oxidation state of 2+. Aluminum is found only in the 3+
oxidation state. Other metals, such as chromium, manganese, iron, cobalt, nickel, and
copper can occur in two or more oxidation states. For these elements not only is their
presence important but also their oxidation state. Iron II (Fe2+) is more soluble than iron
III (Fe3+). Chromium IV (Cr6+) is considered to be more toxic than chromium III (Cr3+),
thus the form or species of an element is as important or more important than simply its
presence.
High concentrations of lithium, sodium, and potassium are associated with high soil

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226

pH. Normally soil pHs do not go above 9, thus higher pHs may indicate that there are
high levels of the alkali metals and that something unusual is happening and needs to be
investigated further.
Aluminum is associated with acid soil conditions. Soils with low pHs will be found to
have high levels of available Al3+. This is of concern because this cation is toxic to most
plants. The exceptions are the so-called acid-loving plants, such as rhododendron and
blueberries [13].
Elements found in multiple oxidation states will generally be found in the state
appropriate for the conditions existing at that time. Under reducing conditions iron will
be found as Fe2+, and under oxidizing conditions it will be in the Fe3+ oxidation state.
This is generally true for all the cations, which exist in several oxidation states (i.e., lower
oxidation state under reducing conditions and higher oxidation state under oxidizing
conditions). Manganese is found as 2+, 3+, and 4+ in soil and acts as if it is between
oxidation states because of this mixture [14].
Another exception is molybdenum (Mo). It is an exception not because of multiple
oxidation states, but because it is found as an oxyanion, molybdate (MoO42), rather than
a cation in soil [15].
When sampling and analyzing soil it is important to keep the oxidation states of the
metals of interest in mind. Samples from reducing conditions will typically show higher
levels of soluble transition metal cations than those taken from oxidizing conditions. A
second component of this is that during the sampling, samples are usually exposed to
oxygen. Such exposure can lead to changes in the oxidation states of the metals the soils
contain. This would also happen if these samples were exposed to air during storage or
transport. Oxidation at any step can have a pronounced effect on the analysis and the
apparent biological availability of a metal.
9.2.4. Nonmetal Cations
There are two common nonmetal cations found in soil. The first is the H+, a proton,
which does not really occur as H+ but as the hydronium ion H3O+. The second is
ammonium
Both of these can be important indicators of unusual soil conditions.
The hydronium ion is associated with acidity in all media and is only present in
appreciable amounts when the pH is acidic; that is, below 7. Because of its size and
hydration it does not fit easily into any scheme designed to describe cations in soil.
Soil pH is rarely below 4.0, thus when pHs occur appreciably below 4 they indicate an
unusual situation. Usually such low pHs are associated with some cold region forest soils
or with sulfur and its oxidation to sulfuric acid. This is particularly likely in and around
mining operations, in which sulfur is brought into oxidizing conditions, especially when
it is mixed with soil or water. Whenever very low pHs are found in soil, the source
should be found, because low environmental pHs indicate a serious problem that needs to
be found and corrected. Very low pHs can solubilize otherwise inert toxic minerals and
can ultimately lead to the total destruction of the soil itself.
The second common nonmetal cation is ammonium
Ammonium is important
because plants use it as a source of nitrogen for plant growth and development. Ammonia
is also important because it can be oxidized to both nitrite and nitrate.

What is present?

227

Both H+ and
act as cations in soil and become exchangeable cations on the
cation exchange capacity. Although protons H+, or H3O+ are cations, it is hard to define
their exact cation exchange activity. Ammonium
however, acts like any other
cation in the soil and can readily be identified as an exchangeable cation. Both these
cations can affect cation availability and exchangeability in soil analysis. Exposure of
samples to either changes in pH or ammonia thus can change analytical results.
9.2.5. Cation Exchange Capacity
Clay and organic matter in soil usually have a negative charge and thus attract and hold
cations. This results in the soil having cation exchange capacity (CEC). It should be
expected that a portion of all cations in soil will be associated with the cation exchange
sites. This includes both metal and nonmetal cations.
Analytical methods cannot directly measure the amount of cations on the exchange
sites; they must be removed from the sites and brought into solution before analysis. This
means that some replacing cation must be used to exchange with them and move them
into solution. A cation that has higher oxidation states (2+ and 3+) or that is present at
high concentration will replace cations with lower oxidation states or lower
concentrations.
Some cations are not attracted to CEC sites in soil. Most iron (Fe3+), aluminum,
titanium, and manganese precipitate as oxides and thus are not available to act as soluble
or exchangeable cations. On the other hand, Fe2+ forms soluble complexes with organic
compounds, and thus it also does not act as a simple cation. It should be expected,
however, that both oxidation states of iron will be found in most soils.
Although cation exchange capacity is most often discussed, some soils also show
appreciable anion exchange capacity. Some tropical and highly weathered soils are
particularly noted for this characteristic. Just as in cation exchange, an anion must be
removed from anion exchange sites to be analyzed. It is also important to remember that
not all anions (e.g., phosphate) are either excluded or attracted to soil particles in an
exchangeable fashion [16].
9.2.6. Anions
Anions in soil are single oxidation state species, such as the halogens and the
multioxidation state oxyanions. Only the halogens are commonly found in the
environment as simple anions and are found with an oxidation state of negative one.
Because most soil particles and the simple anions have negative charges they repel each
other. Thus the simple anions are readily leached lower in the soil or out of it altogether
[17]. The oxy anions may or may not be readily leached out of soil, depending on their
ability to chemical react with other ions or species.
Many oxyanions occur naturally in the environment. The most important of these are
carbonate, nitrate, phosphate, and sulfate. There are many others, however, that are in
lower concentration but are nevertheless extremely important. Important oxyanions, their
structures, and their biological importance are given in Table 9.2.

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228

9.2.6.1. Carbonate and Bicarbonate

In addition to their biological importance, carbonate and bicarbonate are important in
determining the buffering and pH of soil and soil solutions. Carbon dioxide from
respiration in plant roots and microorganisms is released into the soil atmosphere. Some
dissolves in water, forming bicarbonate ions.

If the existing soil solution becomes acidic, bicarbonate will accept a proton-

TABLE 9.2 Common Environmental Oxyanions

Name

Formula

Source and biological importance

Carbonate

Counter and exchange ion in root uptake of cations and anions

Bicarbonate

Counter and exchange ion in root uptake of cations and anions

Sulfate

Source of sulfur for plants

Nitrate

Source of nitrogen for plants

Nitrite

Source of nitrate in soil

Phosphate

Source of phosphorus for plants

Molybdenate

Source of molybdenum for plants and microorganisms; important in

nitrogen fixation

Arsenate

Toxic component in the environment

Selenate

Source of selenium for plants and animals

Borate

Source of boron for plants

producing carbon dioxide and water, the reverse of the equation above. The common test
for carbonate minerals is
CaCO +2H+2ClCO +Ca2++2Cl+H O
3
2
2
to treat them with dilute hydrochloric acid. The release of gas in the form of bubbles is a
positive test for carbonate. Soil carbonates form in soil by the following reaction:
2H O+CO +Ca2+CaCO +2H+
2
2
3
In basic environments protons are released from bicarbonate and carbonate is formed as
shown above. If this takes place where there is an excess of calcium or some other base

What is present?

229

cation, a carbonate such as calcium carbonate is formed. Carbonates are not very soluble
in water, and this reaction results in deposition or precipitation.
Because of its involvement in maintaining or controlling pH, carbonate is an important
oxyanion. Exposure of samples to carbon dioxide may affect the pH of the sample and
consequently the availability and solubility of many components in that sample. Exposure
to high levels of carbon dioxide during sampling or sample transport is thus expected to
have an effect on the analytical results.
9.2.6.2. Sulfur and Sulfate
Sulfur can occur as an element in nature. In soil and water, however, it does not remain in
the elemental form long. Under reducing conditions it is reduced to hydrogen sulfide
(H2S), and under oxidizing conditions it is oxidized to sulfuric acid (H2SO4). Soils and
soil samples exposed to elemental sulfur, most commonly labeled as flowers of sulfur,
will suffer a dramatic decrease in their pH. This in turn can lead to the release of
materials into the soil solutions that are not normally found there. Soil sulfur, however, in
the form of sulfate as the anion
is always present, is stable, and does not affect
pH.
Sulfur is an essential element in the nutrition of plants, animals, and microorganisms.
Plants can take in many different forms of sulfursulfate being one of themand
incorporate it into various needed organic sulfur compounds. Calcium and magnesium
sulfates are commonly used to ameliorate various soil conditions caused by poor soil
structure and are also used as a source of calcium under conditions in which it is not
desirable to change a soils pH [17].
9.2.6.3. Phosphate
The oxyanion phosphate
is a common and essential component of life. It occurs
in different forms, depending on the pH of its surroundings and associated metals.
Commonly one or two of its negative charges are satisfied by protons, and thus it occurs
as
or as
These are the two most common forms occurring in the
normal pH range of water and soil. The 1 and 2 charges on these forms are typically
satisfied by sodium, potassium, calcium, or magnesium.
Under very acid conditions phosphate occurs as phosphoric acid (H3PO4), while under
very basic conditions it occurs as phosphate
Because of the extreme pHs under
which these forms are found, their occurrence indicates unusual soil or environmental
conditions.
Looking at phosphate it would be assumed that this oxyanion would act as all anions
are expected to act. It does not. All species of phosphates react with metals to form
insoluble, plant-unavailable phosphates. Under acid conditions either monobasic
or dibasic phosphate
reacts with iron and aluminum to forminsoluble and unavailable iron and aluminum phosphates. Under basic conditions
insoluble and unavailable calcium phosphates form. Phosphate species can also react with

Field sampling

230

both solid inorganic surfaces and organic components, and thus are also removed from
solution by these mechanisms. For these reasons phosphate does not typically move in
soil unless unusual conditions, such as extremely high levels of phosphate or very sandy
soils, occur [18].
High levels of plant-available phosphate in soil and water can occur naturally. In
Florida, where phosphate is mined and soils are sandy, soil phosphate can be so high that
it readily leaches into water. In any area in which phosphate is mined the Earths surface
may have high concentrations of phosphate. Both of these cases are easily explained.
Such situations are unusual, however, and any time high levels of phosphate are found
the source of phosphate needs to be determined.
9.2.6.4. Oxides of Nitrogen
The two most common oxides of nitrogen are the oxyanions nitrite and nitrate. Table 9.3
provides a list of all the common environmental oxides of nitrogen. Nitrogen is added in
large amounts to agricultural land as nitrogen fertilizer, anhydrous ammonia, aqueous
ammonia solutions, and various nitrates, including ammonium nitrate. Ammonium added
to the soil when temperatures are above 5C and in the presence of moist but not
saturated water conditions is quickly oxidized to nitrite and then nitrate. Nitrite is usually
present in small amounts because oxidation of nitrite to nitrate is faster than the oxidation
of ammonia to nitrite. During the oxidation of ammonia to nitrate protons are released
into the surroundings. Thus both soil and water may become acidic during this
transformation.
Both nitrite and nitrate carry a negative charge. They are mobile in soil, and their
compounds are very soluble. When either nitrite or nitrate are present in soil they can
leach into the ground water. However this only occurs as long as they are under oxidizing
conditions. Under reducing conditions nitrate is reduced to N2, NO, and N2O gases. The
occurrence of nitrate along with the various oxides of nitrogen in environmental samples
should be expected. When they are found, increased acidity may also be found. The
occurrence of large amounts of nitrite in environmental samples indicates an unusual
situation that needs further investigation [19].

TABLE 9.3 Common Environmental Oxides of Nitrogen

Name

Chemical formula

Common occurrence

Nitric oxide

NO

During denitrification

Nitrous oxide

N2O

During denitrification

Nitrogen dioxide

NO2

During denitrification

Nitrite

First oxidation product of ammonia

Nitrate

Final product in oxidation of nitrite

What is present?

231

9.2.6.5. Molybdate
Molybdate is extremely important in biological nitrogen fixation. Molybdate is present in
relatively low concentrations in soil, however. Acid soils with appreciable leaching may
have total molybdate levels around 0.5 mg/ kg. Basic soils having low rainfall may have
levels 10 times that amount. Soils to which sewage sludge has been added may have
significant increases in molybdate concentration. Because of its negative charge
molybdate would be expected to move readily through the environment. It reacts with
many constituents, however, and thus does not move as readily as expected [20].
9.2.6.6. Borate
Boron is present in soil and is taken up by plants as HsBO3. It can also occur as borate
and
however. The boron oxyanions are generally present in very low
concentrations in soil. Boron can move by both mass flow and diffusion in the soil
solution. Because it is both an essential nutrient for and is toxic to plants it is of particular
environmental concern. There is a very narrow range over which it is sufficient but not
toxic. High levels of boron in soil can result from coal ash disposal and represent a cause
for concern when revegetation and bioremediation are undertaken [20].

9.3. THE ORGANIC COMPONENT

Organic compounds in the environment range from the very simple to the very complex.
From methane, which is released during anaerobic decomposition of organic matter, to
humus, which is the organic matter that is produced during organic matter decomposition
and remains afterwards. Compounds of intermediate complexity are also formed during
the organic matter decomposition process. All organic functional groups can be found in
the organic components in the environment, and all of these are in addition to inorganic
elemental carbon, carbon dioxide, and carbonate.
To be an organic compound a molecule must be made up of carbon and hydrogen. It
may also contain several other different kinds of atoms, the most important of which are
oxygen and nitrogen. Other atoms, however, are common, such as sulfur, phosphorus,
and the halogens, particularly chlorine and bromine. When these other atoms are present,
their position and arrangement in the molecule are extremely important. They form the
functional groups that control a compounds interaction with the environment. Solubility
in water, movement, reactions, and toxicity are all related to a compounds functional
groups.
Halogens substituted on any organic compound have a dramatic effect on both their
physical and chemical properties. Halogens are heavy, and substituting a halogen for a
hydrogen on an organic compound increases the compounds density, sometimes making
it denser than water. Halogens also make the compounds less soluble in water. On the
other hand, many oxygenand nitrogen-containing functional groups increase a
compounds solubility in water.

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9.3.1. Hydrocarbons
The backbone of all organic compounds is carbon atoms bonded together. The most
highly reduced compounds are alkanes, which contain only carbon and hydrogen and are
part of a group of compounds called hydrocarbons. As the name implies, these
compounds contain only carbon and hydrogen. This group is composed of three families
of compounds that are used as fuels, are common in the environment, and are common
pollutants. The three families are the alkanes, alkenes, and alkynes. Alkenes have at least
one double bond, and alkynes have at least one triple bond in addition to carbon,
hydrogen and single bonds.
The hydrocarbons are less dense than water and are insoluble in water. Because of
these characteristics they move with water through the environment by floating on it.
When analyzing soil for hydrocarbon contamination, it is common to treat any
combination of hydrocarbons as a single unit or entity. In analytical results they are
reported as the total amount of all of these types of compounds, and thus they are referred
to as total petroleum hydrocarbons (TPH). This analysis thus gives no indication of the
types of compounds present or their relative concentration. Indeed, a gas
chromatographic analysis of hydrocarbon fuels gives a very complex and poorly resolved
chromatogram with a large number of peaks showing the presence of a large number of
compounds.
Groups that contain only carbon and hydrogen are called alkyl groups and are
represented by the letter R. This represents a group of any configuration that contains
only carbon and hydrogen and is attached to another, usually larger, component. In some
cases an R group may be used to represent other constituents in a molecule. If this is the
case, however, this usage must be expressly and distinctly shown.
In addition to compounds that contain only carbon and hydrogen are numerous
environmentally sensitive compounds that contain carbon, hydrogen, and one or more
halogen atoms. The halogens are substituted for hydrogens in these compounds and are
generally called halocarbons. They are similar to hydrocarbons in that they are nonpolar,
insoluble in water, sometimes denser than water, and generally slowly biodegradable.
When denser than water halocarbons will be at the bottom rather than at the top of
aqueous environments and aqueous extracts of soil.
Most halocarbons are man-made or the result of mans activities, some examples of
which are given in Table 9.4. There are, however, a large number (over 1,500), of natural
halogenated organic compounds occurring in the environment. A small amount of
chlorinated organic compounds are produced by such common soil microorganisms as
the bacteria Pseudomo-

TABLE 9.4 Common Environmentally Important Halogen-Containing Organic

Compounds

Name

Structure

Chloromethane

C1CH3

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233

Dichloromethane

C12CH2

Trichloromethane (chloroform)

Cl3CH

Tetrachloromethane (carbon tetrachloride)

C14C

Dichlorodifluoromethane (a

CFC)a

C12CF2

1,2-Dichloroethane

1,2-Dichloroethene

Freonsa (used as refrigerants)

Trichloroethylene

Vinyl chloride (monomer used in the production of plastics)

aNumbers of chlorines and fluorines varies in chlorofluorocarbons (CFCs).

Note: Most of these compounds are used as solvents.

nas and Bacillus, the actinomycetes Streptomyces and Saccarothrix, and the fungi
Aspergillus and Penicillium. It thus cannot be assumed that all halogenated organic
compounds are anthropogenic, nor can it be assumed that all halogenated organic
compounds are resistant to degradation in the environment [21].
9.3.2. Aromatic Compounds
Another group of compounds with the characteristics of hydrocarbons are those
containing benzene rings. Another name for these hydrocarbons is aromatic, although
they often do not have a sweet or spicy fragrance. Many aromatic compounds are of
environmental concern as toxins or carcinogens; however, an equal or greater number of
compounds containing benzene rings are inert or even beneficial. Tryosine, an amino
acid, cinnamonaldehyde, a component of cinnamon responsible for its smell and taste,
and aspirin, an analgesic, are but three benzene ring-containing compounds regularly
used by humans. Phenylalanine, another amino acid that contains a benzene ring, is an
essential dietary amino acid.
Compounds containing a benzene ring can be classified as belonging to one of three
groups. A relatively simple group is those compounds that contain only one benzene ring
having some group attached to it. Examples are the benzene itself, along with toluene,

Field sampling

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ethylbenzene, and the xylenes. This group of compounds is often referred to as BTEX,
meaning some combination of all of these compounds. Any benzene ring with an alkyl
group may also be referred to as an alkylbenzene. Compounds of this type are shown at
the top of Figure 9.3. Hydrogen atoms are at each corner of the hexagon rings, as shown
for benzene C6H6, but they are omitted in the other diagrams for simplicity.
A second group of compounds is made up of benzene rings bonded to each other by a
single bond or where two or more rings share carbons. An example of the first type of
compound is biphenyl, which has two benzene rings joined by a single bond. Compounds
containing only the benzene rings carbon hydrogen and halogens can be either toxic or
carcinogenic. One important group of these compounds is the polychlorinated biphenyls
(PCBs). An example of a polychlorinated biphenyl is shown in Figure 9.3. There are 10
carbons that can have a chlorine substituted for hydrogen on either or both of the two
rings. There are thus a large number of possible PCBs.
Examples of the second type of compound are situations in which the benzene rings
share two carbons (e.g., naphthalene or anthracene). These condensed ring compounds
may have the rings joined in many different ways, as shown in Figure 9.3, producing
different compounds. The

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235

FIGURE 9.3 Common aromatic compounds containing one and several

benzene rings bonded together. Hydrogen atoms are at the corners of
the hexagons, as shown for benzene, but are omitted in the others for
simplicity. DDT is dichlorodiphenyltrichloroethane.

benzo[]pyrenes are examples of a type of compound sometimes called a chicken wire

compound. Many of these compounds, such as benzo[]pyrene itself, are carcinogenic
and thus are of environmental concern.
A third group is compounds containing two or more benzene rings separated by
nonbenzene groups. This includes a large number of compounds that contain benzene
rings separated by a variety of substituted and unsubstituted alkyl groups. The connecting
groups thus may have other functional groups attached to them. Of particular concern are
those types of compounds containing halogens. Some of these, such as DDT, are of
general environmental concern; others are of particular human health concern. Two
chlorinated aromatic compounds of this type are given later in Figure 9.5.

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9.3.3. Oxidized Functional Groups

The partially oxidized organic compounds contain acid, aldehyde, ketone, ether, and
alcohol functional groups. (See Table 9.5.) Each functional group makes up a family of
compounds having different reactivity, solubility, and interaction with various
constituents in the environment. They are generally more soluble in water and move more
readily in the environment than do hydrocarbons. In many cases they are also more easily
decomposed by microorganisms to CO2 and water.
Organic molecules can contain more than one functional group. Common examples are
sugars (hexoses), which contain five alcohol (OH) groups, and one aldehyde (CH=O)
group, as seen in Figure 9.4. Another common example is unsaturated fatty acids, which
contain one acid functional group and one or more double bonds. Amino acids contain at
minimum one acid functional group and one amine group.
Increasing the number of oxygen- or nitrogen-containing functional groups in a
compound increases its solubility. In Figure 9.4 six carbon hexane is very insoluble in
water, while the six carbon hexose sugar is very soluble. Sugars are polymerized into
starch and cellulose, fatty acids polymerize into fats, and amino acids polymerize into
proteins, and when this happens the size of the polymer and its linkages will control
solubility rather than numerous oxygen- or nitrogen-containing functional groups.
When larger organic compounds degrade in the environment, they undergo a series of
decomposition steps during which a number of different intermediate organic compounds
are produced. These often contain a number of different functional groups. The rate of
decomposition of starting and intermediate compounds is related to the functional groups
they contain. Functional groups control a compounds solubility in water. They also
control its rate of decomposition, because generally, the more water-soluble a compound
is the faster it is degraded. The more soluble a compound is, however, the more likely it
is to move in the environment, and thus there will be an increased need for sampling.
This also means that when looking for a particular organic contaminant in soil or water
its natural occurrence must be established and quantified. It cannot be assumed that the
compound of interest is not naturally or commonly present in a particular environment.
This even means that highly reduced compounds such as alkanes, alkenes, and alkynes
may be present even though their formation in aerobic environments is

TABLE 9.5 Organic Functional Groups

Group
Alkanes

Structure
CH3(CH2)nCH3

Characteristics
Contains only carbon and hydrogen. Gases and liquids
insoluble in water, flammable.

Alkenes

Contains at least one double bond. Gases and liquids

insoluble in water, flammable.

Alkynes

Contains at least one triple bond. Gases and liquids

insoluble in water, flammable.

What is present?

237

Alcohols

CH3CH2OHEtnanol

Ethers

CH3CH2OCH2CH3 Contains at least one ROR group. Gases and liquids

Diethyl ether
insoluble in water and flammable.

Contains at least oneOH group. Low molecular weight

alcohols are soluble in water, liquids and solids.

Aldehydes
Contains at least one

group, liquids and solids.

Ketones
Contains at least one

group, liquids and solids.

Contains at least one

solids.

group, liquids and

Acids

Amines

CH3CH2NH2
Ethyl amine

Contains at least one (R)3N group, liquids and solids.

FIGURE 9.4 Structure of some common multifunctional organic compounds

and hexane.

unlikely. On the other hand, partially oxidized compounds are also possible. Two
examples not naturally found in the environment are 2,3,5-trichlorophenoxyacetic acid
(2,4,5-T), an herbicide, and 2,3,7,8-tetrachlorobenzo-p-dioxin. The structures of these
compounds are given in Figure 9.5.
A number of abbreviations and acronyms are used in discussing organic compounds in
soil. BTEX and PCB have already been discussed. In addition, all volatile organic
compounds will be grouped together and called VOCs, through this term usually refers to
environmentally hazardous volatile compounds. Compounds that do not dissolve in water
can be called nonaqueous phase liquid (NAPL). Aromatic compounds containing two or
more benzene rings will be referred to as polyaromatic hydrocarbons (PAH). Other

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abbreviations and acronyms also are in common use. (See Chapter 1 and Appendix A.)
9.3.4. Humus
As stated above, during the process of microbial decomposition new organic matter is
synthesized. This results in the formation of humus, which is a

FIGURE 9.5 Examples of compounds containing a variety of alkyl, benzene,

and functional groups. Hydrogen atoms are omitted for simplicity.

complex compound composed of a large number of diverse groups. Some have said that
humus is a polymer. No monomer or mer* had ever been identified, however, and so it
cannot really be said to be a true polymer. It is a large, complex molecule, that is dark in
color and resistant to decomposition.
Soil scientists and others routinely separate humus into a number of different
components: humic acid is extracted with alkali, fulvic acid is soluble in acid, and humin
is not soluble in any solvents. Being able to separate humus into different components
has not generally led to an illumination of its structure. Knowing the structure of these
separate parts also does not shed much light on the chemical characteristics of humus,
and humus as a whole has characteristics that are different from those of any one of these
components. In spite of not knowing its structure it is known that humus has a
pronounced effect on water and soil and their characteristics. This is particularly true
when trying to describe humus and soil interaction with environmental pollutants.
Because of its complex organic structure and numerous functional groups, humus has a
high affinity for many organic compounds and metals. (See chelation below.) It does not
act like it has a surface, but as if it has organic compounds dissolved in it. In some cases
it may be hard to tell when the dissolved contaminant ends and the humus begins. Humus
will hold many different types of organic compounds containing many different types of
functional groups. Once adsorbed by humus, compounds are generally slower to move in
soil.
Colloidal organic matter and humus may remain suspended in water, sorb components,
and move through the environment. This may result in movement of components not
expected to move and result in their being present in higher than expected concentrations.
Humus has a strong affinity for metals because of its cation exchange sites, and so it will
attract and hold cations by cation exchange mechanisms. The two groups most often sited
as being responsible for cation exchange in humus are acid and phenolic groups. Phenolic
*A

mer is the individual unit or units of which a polymer is made.

What is present?

239

groups are benzene rings with an OH group. Both acid and phenol groups can ionize,
leaving a negative charge on the group and thus attracting cations.
Another mechanism of attraction is through its oxygen-containing groups, by which
humus can hold metal cations in structures resembling chelates, as shown in Figure 9.6.
(Chela is Latin for crab.) In this case association with lone pairs of electrons on oxygen
and nitrogen hold the metal. The term chelate indicates that there are several parts of one
organic

FIGURE 9.6 Ethylenediaminetetraacetic acid with a chelated metal ion (M+).

compound involved in the association. An example of a simple organic chelate is

ethylenediaminetetraacetic acid (EDTA). In this case the functional groups act like claws
associated with the metal. Humus also has a high affinity for metals and holds them by
both cation exchange and chelation mechanisms. These mechanisms hold metals in forms
that are available to plants [22, 23].

9.4. THE BIOCHEMICAL COMPONENT

In addition to simple and complex organic compounds, soil also contains compounds that
are biochemical. These occur from two different sources. First, many organisms exude
enzymes to decompose compounds outside the cell. In most if not all cases this is done so
that molecules that are too large to bring inside the cell for digestion can be broken down.
For instance, cells cannot use cellulose until it is broken down into its individual sugar
monomers (e.g., fungi), which are the primary cellulose degraders and exude
extracellular enzymes, cellulases, to break down cellulose.
Extracellular enzymes are most often discussed as being exuded by microorganisms;
however, there is evidence that they are also exuded by plants and even some animals.
Plant roots have been shown to exude the enzymes invertase, phosphoratase, and
amylase. Animals, particularly earthworms, have been shown to contribute invertase to
the soil solution. This is similar to our secreting invertase in saliva to break down starch
to sugar in our mouths. Little is known about the overall importance of animal-released
enzymes in soil, however.
Extracellular enzymes are of particular interest because of their involvement in soil

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chemical reactions, and consequently they have been extensively studied. They can
catalyze numerous reactions and result in both decomposition and intermediate
compounds being present. Extracellular enzymes, which decompose proteins, fats,
hydrocarbons, and cellulose, should be expected to occur in any soil that has these
components in it. Some common examples of enzymes found in soil and their source are
given in Table 9.6.
Enzymes are often associated with the mineral fraction in soil. The association of
enzymes with clay minerals in particular has been extensively investigated. Often such
associations are more active catalytically than are the enzymes alone, thus even when the
enzymes do not occur freely in the soil solution they may still be present and active [24].
Some inorganic and even some organic components in soil may catalyze the same
reactions as enzymes, however. Peroxide decomposition and hydrolysis can be promoted
by inorganic ions, exchange sites, and organic molecules at normal soil temperatures
[24], thus the observation of a reaction occurring in soil may not always be clearly related
to enzymes alone.
Other compounds may also be exuded into the environment by organisms. Some may
be simple organic waste products and others complex molecules that the organism cannot
use. These may include intermediate decomposition products from the breakdown of
pesticides and insecticides.
Microbial, plant, and animal cells in or added to the soil both exude material and break
open, releasing their contents. Any intercellular component may thus be found in soil at
any time. Many of these compounds are easily decomposed by other organisms and so do
not last long in the soil environment. Some compounds may become associated with clay
particles and become a little more resistant to further decay. In the decomposition process
many intermediates are found and may be part of a mix of compounds found in a soil
analysis.
Cellular components that are not easily decomposed will also be present. These may
include both organic compounds and inorganic compounds. Microorganisms can reduce
sulfate, nitrate, selenium, and

TABLE 9.6 Some Common Extracellular Enzymes and Their Common Source

Enzyme

Source

Proteases, cellulases, and pectic and

proteolytic enzymes

Numerous bacteria and fungi

Cellulase

Fungi

Lipases

Fungi and other microorganisms

Phosphatase

Bacillus, Fusarium, Saccharomyces, and many other

soil bacteria and fungi

Source: Taken from Ref. 24.

other elements to their elemental form, and these may thus be present in soil from this

What is present?

241

source. They may also be present in combined form as a result of microbial activity. Cell
walls, compounds with long hydrocarbon moieties such as lignin, and other structures
resistant to decomposition may persist in the soil for significant amounts of time [25].

9.5. THE LIVING COMPONENT

All soil has organisms living in it, including animals, plants, and microorganisms. The
number of microbes varies with the counting method, and is as high as 109 per g of soil.
The activities of these organisms will affect the sampling plan and analytical procedures.
One affect is soil component decomposition, and another is their movement through soil.
Such organisms as ants and termites can move large amounts of soil. Often this means
moving soil from some depth to the soil surface. This is important because it might be
assumed that the A horizon is being sampled when in reality it is the C or B horizon that
is really being sampled and analyzed.
In some cases the reverse may be true. Groundhogs dig sizable tunnels down and
through the soil profile. When the animals abandon these holes they may fill with soil
washed into them from the surface. In this case samples assumed to be from the B or
lower horizons may actually be from the surface. This may not be evident by observing a
single sample, but would be obvious when observing a soil profile. The same type of
thing can happen with other animals and animal holes in soil.
Where a spill has happened in this type of environment, contaminants can move deep
into the soil through these types of holes. In this case sampling must be deeper than the
holes if an accurate determination of the extent of contamination is to be known. In both
of these cases knowing that borrowing animals are common and that burrows have been
filled in is essential. Such information is available in a soil survey.
The above examples are for groundhogs, ants, and termites; however, in different parts
of the world different animals will be living in soil and making it their home. It should
not be assumed that because groundhogs do not live in a particular area this type of soil
mixing cannot happen. It can.
Plants change the soil in a more dramatic way. As roots grow through the soil they
change its physical and chemical properties. Roots push soil particles together, allowing
them to be held together by cations, clay, organic matter, and microbial gums to form
secondary particles, or peds. Secondary particles have distinct areas of weakness and void
volumes between them that increase infiltration and percolation. This in turn will increase
contaminant movement through the soil. Sampling will need to take these changes into
consideration.
Roots exude acids and give off carbon dioxide. Both of these make the soil more acid.
The roots also deplete the soil around them of water and base cations. As it moves toward
the roots, water can carry components, including contaminants, to plants that either
collect at the root surface or are taken into the roots and transported to the plant leaves.
Soils with a dense plant cover such as sod* will have characteristics that are different
* Sod refers to any situation in which soil has a continuous grass cover (e.g. lawns, golf courses,
hay fields).

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from soils that have row crops or soils which are sparsely vegetated.
Microorganisms can also change soils physical and chemical characteristics. Through
the production of microbial gums, sand, silt, and clay particles can be cemented together
and change infiltration and percolation through soil. More important, microorganisms can
dramatically change the chemical characteristics of soil. Rapid decomposition of organic
matter can deplete soil air of oxygen, creating anaerobic conditions. Microorganisms can
also change the oxidation state of inorganic ions around them. In this way
microorganisms can dramatically change the components present and therefore the
components one is looking for may be dramatically changed. Final and intermediate
decomposition products may be present in the same sample.
Because of these differences sampling will be different for different environments.
Typically sod can be sampled on a random basis. Pastures with animals will be a little
different because of animal tracks and manure, both of which should be avoided when
sampling. In tree-covered areas there may or may not be vegetation between the trees. In
any case sampling must be done between trees as randomly as possible. In industrial
areas the same concepts must be observed; that is, plants may accumulate contaminants.
Animal holes and other soil cracks will allow components to move rapidly into and
through soil; thus all these potential sampling considerations need to be kept in mind.
In addition to animals being present their activity is also important. Any environmental
condition that changes the activity of animals may also change the occurrence of the
compounds associated with them. Unusually wet, dry, hot, or cool conditions and the
seasons will change animal and plant activity, thus weather conditions and the date can
change the types of compounds found, and this should be noted in the project notebook
and taken into consideration when interpreting analytical results [26].

9.6. CONCLUSIONS
Soil contains a large and diverse number of inorganic, organic, and biological molecules.
The inorganic component comes from the breakdown and leaching of rock and minerals.
The organic components come from organic matter added to the soil by plants, animals,
and microorganisms. This same group provides biochemical molecules, enzymes,
proteins, fats, carbohydrates, nucleic acids, and lignins to the soil. In addition, the
breakdown of animal and plant tissue releases intracellular constituents to the
environment, particularly the soil solution. Because of the intimate relationship between
soil and water, these compounds may be found in water. Any of these compounds that are
gaseous can also be found in the atmosphere. In addition to chemical change plants,
animals and micro-organisms can create physical changes in soil that affect sampling.
It would simplify things greatly if all the reactions taking place in soil could be
elucidated and described fully. There are always new and often unexpected reactions
being discovered, however. For instance, microorganisms can carry out both
transhalogenation and chlorine bromine exchange in halomethane. This complicates both
the quantification and the understanding of the source and fate of these compounds in the
environment [27].

What is present?

243

QUESTIONS
1. List the 10 most common elements and inorganic compounds found in soil.
2. What are the two nonmetal cations found in soil, and why are they particularly
important?
3. Phosphate is an oxyanion, but it does not move in soil. Explain why it does not
move.
4. All organic compounds are composed of what two elements?
5. Organic molecules made up of only carbon and hydrogen are known by what
general name?
6. Compounds containing benzene rings are of particular concern in the environment.
Give examples of three groups of compounds containing benzene rings. Why are these
groups of particular environmental concern?
7. Draw the structures for four common oxidized functional groups found in organic
compounds. These functional groups result in the compounds containing them having
increased water solubility. Explain how this happens.
8. One group of extremely important biochemical component in soil are enzymes.
What are enzymes and how do they function in soil?
9. Explain how animals change soil and how they can affect sampling plans.

REFERENCES
1. Brady NC, Weil RR. The Nature and Properties of Soils. 12th ed. Upper Saddle River,
NJ: Prentice-Hall, 1999:268269.
2. Sato M, Sutton AJ, McGee KA, Russell-Robinson S. Monitoring of hydrogen along
the San Andreas and Calaveras Faults in central California in 19801984. J Geophys
Res Gas Geochem Volcan Earthquakes Resource Explor Earth Inter 1986; 91:12315
12326.
3. Virk HS, Walia V, Kumar N. Helium/radon precursory anomalies of Chamoli
Earthquake, Garhwal Himalaya, India. J Geodyn 2001; 31:201210.
4. Poissant L, Casimir A. Water-air and soil-air exchange rate of total gaseous mercury
measured at background sites. Atmosph Environ 1998; 32:883893.
5. Glaser B, Haumaier L, Guggenberger G, Zech W. Black carbon in soils: The use of
benzenecarboxylic acids as specific markers. Org Geochem 1998; 29:811819.
6. Sergeev NB, Gray DJ, Scott KM. Gold mass balance in the regolith, Mystery Zone,
Mt. Percy, Kalgoorlie, Western Australia. Geochem Explor Environ Anal 2001; 1:307

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312.
7. Alma MGM, Tokunaga S, Maekawa T. Extraction of arsenic in the synthetic arseniccontaminated soil using phosphate. Chemosphere 2001; 43:10351041.
8. Papachristodoulou CA, Assimakopoulos PA, Patronis NE, Ioannides KG. Use of
HPGe -ray spectrometry to assess the isotopic composition of uranium in soils. J
Environ Radioact 2003; 64:195203.
9. Raju KK, Raju AN. Biogeochemical investigation in south eastern Andhra Pradesh:
The distribution of rare earths, thorium and uranium in plants and soils. Environ Geol
2000; 39:11021106.
10. Konrad KB, Introduction to Geochemistry. New York: McGraw-Hill, 1967:99105.
11. Strojan ST, Philips CJC. The detection and avoidance of lead-contaminated herbage
by dairy cows. J Dairy Sci 2002; 85:30453053.
12. Foth H. Fundamentals of Soil Science. 8th ed. New York: Wiley, 1990:14.
13. Shuman LM, Chelate and pH effects on aluminum determined by differential pulse
polarography and plant root bioassay. J Environ Sci Health, pt A: Environ Sci Eng
Toxic Hazard Subst. Control 1994; 29:14231438.
14. Nico PS, Anastasio C, Zasoski RJ, Rapid photo-oxidation of Mn(II) mediated by
humic substances. Geochimica et Cosmochimica Acta 2002; 66:40474056.
15. Campillo N, Lopez-Garcia I, Vinas P, Arnau-Jerez I, Hernandez-Cordoba M.
Determination of vanadium, molybdenum and chromium in soils, sediments and
sludges by electrothermal atomic absorption spectroscopy with slurry sample
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16. Becquer T, Ptard J, Duwig C, Bourbon E, Moreau R, Herbillon AJ. Mineralogical,
chemical and charge properties of geric ferralsols from New Caledonia. Geoderma
2001; 103:291306.
17. Havlin JL, Tisdale SL, Nelson WL, Beaton JD. Soil Fertility and Fertilizers: An
Introduction to Nutrient Management. 6th ed. Upper Saddle River, NJ: Prentice-Hall,
1999:222230.
18. Donahue RL, Miller RW, Shickluna JC, Soils: An Introduction to Soil and Plant
Growth. 4th ed. Englewood Cliffs, NJ: Prentice-Hall, 1977:131133.
19. Brady NC, Weil RR, The Nature and Properties of Soils. 12th ed. Upper Saddle
River, NJ: Prentice-Hall, 1999:495519.
20. Havlin JL, Tisdale SL, Nelson WL, Beaton JD, Soil Fertility and Fertilizers: An
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1999:276281, 286291.
21. berg G. The natural chlorine cycleFitting the scattered pieces. Appl Microbio
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22. Swift RS, Organic matter characterization. In: Bartels JM, ed. Methods of Soil
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24. Skujins JJ. Enzymes in soil. In: McLaren AD, Peterson GH, eds. Soil Biochemistry.
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27. Harper DB, Kalin RM, Larkin MJ, Hamilton JTG, Coulter C. Microbial
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bromomethane budgets. Environ Sci Tech 2000; 34:25252527.

10
An Overview of Basic Principles of Analytical
Methods
Rolf Meinholtz

The planning for an analytical strategy begins with the original question asked by the
client and runs through sampling of the field in question, subsequent characterization of
the sample, sample analysis, and data reduction to create the final report. During this
process it is necessary to ask some essential questions at a fundamental level. The first is,
What is the original question that is being asked by the client? Two basic factors must be
considered here. The first is the amount and nature of the sample; that is, is it solid,
liquid, or gas? The second is the potential concentration levels of components in the
sample. Once these questions are considered and an analytical strategy is developed, it is
time to take a sample. The entire process from initial question to final report is seen in the
flow chart in Figure 10.1.
Once the sample has been taken some of it is enclosed in containers and sent to the
commercial analytical laboratory for analysis. The rest is used to perform what are
termed field parameters, field tests, or field analyses. Field analyses are those that
because the analytes change rapidlymust be measured immediately and directly [e.g.,
dissolved oxygen (DO)]. (See Tables 10.1 and 10.2 for examples of analyses done in the
field, those done in the commercial laboratory, and hold times.) These are general lists,
and in some cases additional field analyses may be dictated by the client or the analytical
laboratory, depending on the analytical

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FIGURE 10.1 Flow of sample through analytical laboratory.

TABLE 10.1 Analytical Procedures Which Can Be Carried Out in the Field or Properly
Equipped Field Laboratory
Color

Dissolved oxygen

Iodine

Odor

pH

Sulfite

Temperature Chlorine

Total dissolved solids

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TABLE 10.2 Recommended Maximum Holding Times for Samples Between Sampling
and Analysisa

Time from sampling

Analysis

Immediate

pH

6 hr

Fecal coliform
Standard plate count
Ground and wastewater total coliform

24 hr

502/524 (unpreserved)
Hexavalent chromium
Odor
Residual chlorine
THM and HAA formation potential

30 hr

Total coliform in DW

36 hr

Bioassay

48 hr

Asbestos
BOD/CBOD
Chlorophyll A
Color
Dissolved oxygen (modified Winkler method)
Nitrate/nitrite
Orthophosphate
Surfactants
Turbidity
UV254

72 hr

EPA 18 (air)

7 days

Most extractable organics

Radon

Sulfide
TDS/TSS
VOC aromatics (unpreserved)
aSee

EPA web site http://epa.gov/ for specifics of analysis.

Note: Holding times start at the time of taking the sample!

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measurements requested. Once the field analyses are performed and the data recorded on
what are termed field calibration or data sheets (Figure 10.2), this sample is usually
discarded. These data sheets must be submitted to the laboratory with the associated
samples since these results can change the analytical procedures used, as well as having
an effect on the analytical results obtained [1].
Once the sample has been received and logged into the testing laboratory, the next step
is sample preparation. In rare cases what are termed direct methodswhich allow sample
analysis without prior

FIGURE 10.2 Field calibration form.

preparationmight be used. However, for the majority of samples some preparation will

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be necessary before analysis.

Sample preparation can be considered to be the removal of interfering matrix
components from the sample before analysis. It might involve modification of the sample
using extraction, concentration, and/or other

steps that change the original or raw sample into a form that can be analyzed using
chemical or instrumental methods. For example, a liquid/ liquid separation of organic
components from a water sample and their subsequent concentration to permit trace-level
detection by an analytical method might be conducted. Another example is the chemical
decomposition of a soil or solid sample using grinding and acidic reduction to free metal
species present for analysis.
The sample preparation methods described above are used to produce the actual
sample or extract that is analyzed using selective physical or chemical methods. Physical
methods include all spectroscopic analysis (e.g., spectrometry, molecular, and atomic
spectroscopy) and chemical methods include titrations, other volumetric methods, and
precipitation reactions.
The analytical result is used for the determination of the qualitative and/or quantitative
composition and concentration of the analyte in the raw sample. After the analysis is
complete, critical consideration of the resulting data is carried out, looking for mistakes
deriving from preparation and process errors. This is followed by analysis of the raw data
for possible interferences. These may be from the method, the nature of the sample or

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problems from transport. When this is completed the raw data are processed and
documented. Finally, the results from all the tests performed are considered together as a
whole. Complex matrices and difficult testing problems can all require a combination of
methods and analytical procedures to arrive at the final analytical report, so it is
important that all the data from a field or project be considered together as a whole at
some point.
Considering all data as a whole is also a form of error check; for example, checking for
impossible numbers or for sample mismatch of fractions between lab groups. At this
point the fundamental question asked in the beginning must again be considered in the
light of whether or not the data answer the original question posed by the client. If so, the
process is complete; if not, the process must continue until the original question has been
answered to everyones satisfaction.

10.1. DETERMINING THE PROBLEM

Problem determination is a fundamental part of the sampling and testing process and
there are multiple aspects to be considered. Since all of the aspects of these two activities
can have a dramatic impact on not only the nature of the sampling event but also the
sample analysis, it is a very good idea to spend time at the beginning asking simple and
basic questions. What does the client want, and what is the question that is being asked?
This could be as simple as what the pH and total organic carbon (TOC) level of a
groundwater sample is, or as complex as what all the compounds and concentration levels
are of all contamination in a soil or water sample.
After the original question is posed it is time to determine the limits of the testing and
sampling process by asking yet more questions. The limiting factors for the selection of
an analytical method will often be the amount of sample available for sampling and
subsequent analysis, and the form or state of the sample to be analyzed. The nature of the
sample taken will determine many of the procedures for the sampling event, as well as
sample transport, storage, and preparative process and many of the analytical methods
and procedures.
As an example of the importance of the sample characteristics the first question asked
would be the physical state of the sample to be taken; that is, is it a solid, liquid, or gas?
Is the sample homogeneous throughout the field to be sampled? Will the sample be able
to be taken in such a way as to maintain homogeneity during transport and sample
preparation and analysis? These questions all have distinct and far-reaching effects upon
the sampling process and the sample taken (e.g., the process and container used to take
and transport an air sample will be much different in form and type from that used to
obtain a solid or liquid sample).
The three generally found phases of natural matter on the Earth are gas, liquid, and
solid, each having its own sampling techniques and requirements, and each of which will
be discussed separately. The fourth phase of matter, plasma, is not usually seen outside
an extreme laboratory environment, and while it can be a part of some of the analytical
methods [i.e., inductively coupled plasma (ICP) analysis] it is really not a state of matter
that can be sampled, much less transported or stored. For these reasons it is outside the

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scope of this chapter and will not be discussed.

The analytical laboratorys project manger (PM) will ask the above questions of the
client. This works as a check to make sure that the test being requested will answer the
clients question. The PM maintains direct contact with the client and is responsible for
communication between the client and the laboratory. Therefore the PM is the vital link
in the initial chain of questions by both the lab and the client. While the PM does not
have to be a chemist, he or she will have a broad level of experience and knowledge of
the laboratorys methods and processes as well as a detailed knowledge of the specific
criteria of the various analytical procedures. This is especially important when it is
considered that the PM is acting as a twoway check (e.g., both on the client and his or her
requested analysis as well as on the laboratorys response, generated data, and resultant
report).

10.2. WHAT IS THE NATURE OF THE SAMPLE?

The nature of the sample or the sample matrix is part of the first general questions asked;
however, because of the profound effects this answer has on sampling and subsequent
sample preparation and analysis it important to consider it again. Indeed, it is a question
that must be asked more than once and be considered throughout the planning of the
analytical strategy. The characterization of the sample matrix will often automatically
determine many sampling and analytical parameters. For example, the sampling process
for a soil is dramatically different from that for groundwater or air. Also, the type and
nature of the sample containers are often driven by this question. Precleaned glass
containers with Teflon seals and various preservatives are needed for many organic test
methods. Alternately, for metals analysis, plastic or Nalgene-type containers are needed.
Although the three states of mattergases, liquids, and solidshave their own
individual sampling requirements and techniques, there are several key factors in regard
to taking a sample that are universal to the sampling process. The first common point is
the consistency in sampling. Regardless of the accuracy and precision of the analytical
process used, the analytical result can be no better than the quality of the original sample
submitted for analysis. Therefore one of the primary concerns of the sampler must be the
collection of a true and representative sample. The second point is that once taken,
correct and clearly labeled documentation of the samples is essential, as is the accuracy
of the data recorded in the field information sheets (Figure 10.3) and in the project
notebook.

10.3. THE SAMPLING PROCESS

The sampling event is the first significant result-determining step in the analytical
process. The main goal of sampling is to obtain a sample that is representative of the
field. The other side of this is to maintain or preserve the sample as a valid example of
the field conditions. The possibility of error at that point and the effect of that error are
greater than within the analytical methodology [1, 2].

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One of the most important factors to be considered and maintained in the field
sampling process is cleanliness. This factor, along with sample integrity and
documentation, is critical to the valid and accurate sampling process. All the sampling
equipment used must be thoroughly cleaned (and sterilized if necessary) and stored in
such a way as to ensure cleanliness upon initial use in the field. Also, all equipment must
be thoroughly cleaned and rinsed between each sampling event if the equipment is reused
in the field. It is imperative that sample integrity be maintained both in terms of
cleanliness and correctness in composition from site to site. It is very easy to contaminate
a whole sampling event with one poor equipment cleaning or by failure to change gloves
between sampling a badly contaminated field, a field with low levels of contaminant, or a
field that is clean.
Maintaining sample integrity requires that care be taken at all steps of the sampling
event to ensure a representative sample is obtained and sent to the laboratory to be
analyzed. For water or liquid samples, this may simply require checking for immiscible
layers or fractions in the liquid sample. For soil it may require subsampling from various
places and thoroughly mixing the subsamples before the final analytical sample is taken.
Unless great care

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FIGURE 10.3 An example of a field information form.

An overview of basic principles of analytical methods

255

is taken, however, this method can introduce or compound errors when a comparison is
attempted between the subsamples and the field conditions.

10.4. WHAT IS TO BE SAMPLED AND HOW IS IT TO BE SAMPLED?

Once the PM has determined what the client needs to sample and what volume of sample
is required for the requested analysis, a bottle kit is prepared and sent to the client or the
field for sampling. The bottle kit includes the proper containers as determined by the
method used for the requested analysis. (See Figure 8.2 in Chapter 8.) Also included are a
set of instructions for sampling and filling out of the chain of custody (COC) forms
(Figure 10.4).
Once the sampler receives the sample kit, it is important that it be checked for
breakage or content errors before the sampling team goes to the field and begins
sampling. Specific instructions will come with the field sampling kit. After the sampling
event, the now filled containers are placed in the transport container, often an ice chest.

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Chain of custody forms, field calibration sheets, field information forms (Figures 10.4,
10.2, and 10.3, respectively), and notes or comments from the sampling event are
enclosed in watertight containers (heavy-weight industrial-style Ziploc-type bags work
well) and placed in the container. Packing or temperature blanks and enough ice, if
cooling is called for, to prevent breakage while in transit is added. Since ice or some
other form of cooling is used for most types of samples, it is very important that the lab
receive the cooler before the ice melts or the other cooling mechanism is lost. If the
sampling takes longer than a day, the samples can be held in the coolers until completion
of the sampling event; however, it is vital that the first set of samples taken be maintained
in ice during this time.
If samples are held for any length of time, it is important that the hold times as
determined by the method are not exceeded (e.g., time from sampling to analysis). Some
specific methods as well as many of the wet chemistry methods have hold times that are
measured in hours. Most organic methods (analysis for organic contaminants) as well
as metal analysis methods have allowable sample hold times of days. Table 10.2 gives
maximum sampling to analysis elapse times. Once all sampling is complete and the
samples are ready to be sent, the contents of all of the coolers must be checked to make
sure they are complete. The COC sheets (see Figure 10.4) must also be checked for
completeness. This form is then enclosed in its respective individual cooler. The ice level
is checked and topped off with ice as needed, and the coolers are sealed. Coolers can
often be sent as is via a shipper such as United Parcel Service (UPS) or Federal
Express, or if necessary can be encased in an outer cardboard shell for shipment to the
laboratory.

FIGURE 10.4 Sample chain of custody record form.

Usually the only time there are problems with shipping are when not enough ice has
been added to the cooler or the cooler has been held up in shipping and is received by the
lab after much of the ice has melted, resulting in the temperature of samples exceeding

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the accepted limits. Another possibility is that not enough ice was added before shipping
so the sample containers are not well padded, resulting in container breakage and sample
loss.

These types of problems must be noted by the lab as soon as the cooler is received and
opened. It is vital that any questions, problems, or discrepancies in the coolers and their
contents be noted and resolved at the earliest possible time. Often the PM will be able to
answer many of the questions as a result of discussions and knowledge of the clients
needs without having to contact the client; otherwise, it is necessary to contact the client
or field sampler to resolve questions and discrepancies. By doing this at the beginning of
the laboratorys log-in process, it is often possible to resolve problems before the sample
is released to the various laboratory sections for analysis.
Noting problems early will prevent the sample from being misprepared or analyzed
using the wrong methods or otherwise being consumed. It is important to remember that
typically field sampling is limited in both time and volume. Often the amount of the
sample sent to the laboratory is enough to perform the requested analysis and enough for
laboratory quality control needs plus a little more. Therefore there may not be enough
sample available to perform multiple preparations and analysis on the sample in question,
and thus it is important that the preparation and analysis to be done right the first time.
Other problems in regard to shipping or sample transport could be termed catastrophic
loss; for example, the cooler falls from the back of the sampling truck on the highway
while at speed, resulting in cooler disintegration, or the tractor at the landfill runs over the
cooler, resulting in a very flat cooler. For these types of problems the only answer is to

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note the loss and resample.

10.5. DOCUMENTATION
As already stated, it is vital that the sample field analysis, project notebook, field
calibration, field information, and the COC forms be filled out completely, and in real
time. (See Chapter 8 for considerations of the completion of COC sample labeling and
documentation.) It is very difficult to remember all the details in a sampling event while
dealing with the sample containers, test equipment, coolers, and all the other associated
paraphernalia. To expect to remember all the details correctly and record them later is the
height of folly. This folly can have a vast impact on the samples, the data obtained from
them, and the final results of the analysis due to field data or sample mislabeling errors.
Figure 10.2 is an example of a field calibration sheet for recording analyses such as pH,
conductivity, turbidity, and dissolved oxygen. Figures 10.3 and 10.4 are field information
sheets and COC record sheets. The field information form (Figure 10.3) and the project
notebook are the places in which anything and everything about the field can and should
be recorded.

10.6. SAMPLE PREPARATION FOR ANALYSIS

Sample preparation before analysis can range from simple to very complex. A drinking
water sample for volatile organic compound analysis might only require the addition of
internal and surrogate reference compounds before being introduced into an instrument
for analysis. Sample preparation for a more complex sample matrix such as a clayey soil
might require grinding, mixing, and subsequent extraction using an organic solvent that
produces a concentrated extract for analysis. Preparation might also entail the extraction
of the original sample into an organic solvent, this solvent being subsequently extracted
with a different solvent that is compatible with the instrument to be used for analysis.
Other cases will involve the separation of different fractions of soil or of immiscible
liquid fractions and their subsequent separate analysis. The results of the separate
analysis are combined on a proportional basis to yield a result representative of the whole
original sample. While these are all based on the principles of general chemistry, the
specific steps used or performed on the sample are usually specified by a regulatory or
government agency that provides the laboratorys certifications and license. (See Ref. 3.)

10.7. ANALYTICAL TESTING

Generally speaking, the natural laws of chemistry and physics serve as the basis for an
analytical method. Natural laws are those such as the absorption of a specific wavelength
of energy, be it visible, infrared, or ultraviolet, by a specific chemical element or
compound. It could also be the ability of a specific chemical compound to be precipitated
out of a solution using a specific chemical reaction and subsequently the product being

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weighed. While the principles used in a method range from the general to the specific,
they are all derived from natural laws. This means that an analysis done in one location
will give the same reproducible results when done the same way in a different location.
Analytical methods consist of a series of intermediate steps that, when combined, make
up the analytical procedure. Therefore, the analytical method could be considered as a set
of steps that are determined by the process of measurement, which is in turn based on
natural scientific laws. It can include some of the intermediate steps of sample
preparation and evaluation and represents the overall concept for the acquisition of data
from the sample. The analytical procedure consists of (a) instructions for the initial
sampling event, (b) the sample preparation with directions or indications for required
equipment and chemicals, and (c) the analytical instrumentation and instrument settings
used. The method also gives the required analytical calibration, the area or scope of
application, and possible selectivity and/or interferences [4].
On this basis two types of quantitative analysis can be defined: the classic wet
chemical methods and instrumental methods. Many of the classic analytical methods still
in use today are simple yet reliable wet chemistry procedures, including gravimetry
(analysis by weight) and volumetric or titrimetry methods. Instrumental methods are
based on the chemical nature of the compounds and elements being analyzed for and are
separated into organic and inorganic methods. Organic methods are those analytical
procedures for compounds that are mostly made of carbon and hydrogen (e.g.,
pesticides), and generally man-made chemical compounds. Inorganic methods are for
non-carbon-containing compounds and such natural elements as the metals.
10.7.1. Gravimetry
If the analytical procedure used to quantify a substance is based on weight, it belongs to
the field of gravimetry. This involves precipitating a compound out of the sample or an
extract of the sample, drying, and weighing. It is preferred over other methods for
microanalysis using sample amounts in the gram range. Its advantages over the
instrumental methods to be discussed later include the absence of calibration, thus
making it an absolute method. It is a high-precision method and requires limited
apparatus. Its disadvantage in a production environment is the large expenditure of time
and effort required to perform an analysis. A general procedure for a gravimetric method
is as follows: (a) taking of a subsample and weighing, (b) dissolution of the sample, (c)
subsequent precipitation of the component of interest according to a prescribed
procedure, (d) filtering and washing of the precipitate, (e) drying, and (f) weighing.
A second gravimetric method is called thermal analysis (TA), which is a general term
for methods whereby a physical or chemical change in the properties of a substance or
mixture is measured as a function of time or temperature. The sample is subjected to a
controlled increase in temperature and its change in mass is measured over the course of
a preset temperature/ time program. A mass change occurs when a volatile component is
released from the sample (water vapor, carbon dioxide, organic contaminants, or other
similar substances). In addition to decomposition, oxidation can occur, depending on the
atmosphere surrounding the sample. Weight measurements are made using a special
thermal balance and the resultant data are graphed in terms of temperature versus time

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and are called thermograms. Each point of change in the thermograph corresponds to a
particular reaction of the sample; therefore the thermograph can be unique for a particular
sample and thus used as a form of identification.
Anything done to a sampleduring sampling in the field, transportation, or storage
that affects potentially volatile components can change the sample, leading to
misidentification (e.g., leaving a sample in a sun-heated vehicle could lead to the loss of
organic compounds, which could lead to this type of error when a thermal analysis is
carried out) [5].
10.7.2. Titrimetry
In titrimetry, compounds or groups of compounds are quantified by measuring the
volume of a reagent solution of known concentrationtermed the titrimetric solution or
titrantthat is required for a defined, complete chemical conversion of the compounds to
be determined. Titrant is added until an end point is indicated, and the whole procedure is
termed a titration. Chemical conditions required for a titrimetric determination are a
defined course of the reaction between the sample and the titrant and the ability to
recognize the equivalence point (the titration end point). The type of titration is specified
on the basis of the type of reaction occurring [e.g., acidmetry (titrations with acids),
alkalimetry (titration with bases), redox titration (transfer of electrons), precipitation
titrations (also a form of gravimetry), and complexometric titrations, which are the
formation of complexes between the sample and the titrant]. End points are found by a
change in an indicator, usually a color change; by measuring pH or changes in pH using a
pH meter; or by measuring some other electrical characteristic of the solution being
titrated.
10.7.3. Instrumental
As the name implies, instrumental methods require special analytical instrumentation
techniques and knowledge beyond the use of balances, burettes, and other glassware.
Instrumental analysis consists of a number of steps in two phases: the extraction or
sample preparation phase and the analytical or quantitative phase, which is where the
sample extract is characterized. The last step is to relate these results back to the original
sample and field.
Instrumental methods can be divided into three main groups based on the principle
involved. The first group is based on the emission or absorption of electromagnetic
radiation (light). Interactions among atoms, molecules, ions, and electromagnetic fields
and radiation are used to produce analytical data. These methods are often grouped
together as either atomic or molecular spectroscopy, both of which can be either emission
or absorption in nature. Atomic spectrometric methods, used for analyzing metals,
include atomic absorption spectrometry (AA), atomic emission spectrometry, flame
emission photometry, and X-ray fluorescence. Molecular spectroscopic methods, used
mostly for organic compounds, include ultraviolet and visible (UV-Vis), infrared (IR),
mass (MS), and nuclear magnetic resonance spectrometry (NMR). Mass spectrometry is
most often used in combination with a separation method, such as gas chromatography

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(GC); in this case the method is called gas chromatography/mass spectrometry (GC/MS).
This methodology allows the simultaneous separation of a complex sample into its
component compounds and the characterization and identification of these isolated
individual components.
The second group of methods is based on separation or extraction principles. A sample
is prepared and used in the instrumental portion of the method. Many organic methods
are based on a chromatographic method for sample speciation and characterization.
Chromatography requires the use of a detection method (usually one of the preceding
spectrometric methods) for a complete analytical procedure. This means the sample
extract is prepared using an extraction method, loaded onto a gas chromatograph for
separation, characterization, and speciation of the complex sample components. Once
separated, these components are detected and quantitated using a detector.
All extraction methods are based on the physical/chemical separation between different
phases, such as partition between liquid/liquid or liquid/ solid phases. Separation
principles are based on the extraction of a group of compounds from the sample using the
principle of differing solubility (e.g., a group of organic compounds will have a greater
affinity for a strong nonpolar or less polar solvent that is immiscible with the sample
matrix being extracted). An example of this would be a water or soil sample that is
extracted using methylene chloride as the extraction solvent. Methylene chloride is not
soluble in water, and so organic compounds extracted into it are separated from their
original matrix. Table 10.3 summarizes the various types of extraction methods in
common use today.
Separation conditions can be varied by changing the pH of the sample being extracted
or by using a different solvent. Changing the pH of water changes the protonation [H+] of
the solutes contained in it. For instance, acidification increases the chance that the solute
will be protonated, and this means that the solute will have a different net charge. This
change in the charge is the reason that the solute compounds have a greater affinity for a
solvent of different polarity. This is also an example of the importance of the pH of the
original sample during analysis.

TABLE 10.3 Extraction Methods

Name

Abbreviation

Aqueous samples
Classic
Solid phase
SPE
Supercritical
SCF
fluid
Nonaqueous samples
Solution
Phase separated

Phases
Liquid/liquid, solid/liquid
Absorbent column
Liquefied gas used in the liquid state under
pressure
Aqueous or organic solvent

Matrix
Liquid or solid
Liquid only
Solids

Homogeneous
liquid
Separate phases and extract using one of the Two separate
above
phases

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10.7.3.1. Atomic Spectrometric Methods

Atomic absorption spectrometry methods can be of two typesabsorption and emission.
If a single wavelength of light (monochromatic) passes through a hot gas that contains
metal* in an atomic state, some will be absorbed. The specific wavelength of needed light
is produced by a hollow cathode lamp (HCL), which has a cathode made of the metal of
interest. A sample is passed through an atomizer and into a flame, which produces the hot
gas through which the light is passed. The intensity of the analytical wavelength of light
is decreased by absorption of the light by the metal in the flame. Any wavelengths not
absorbed by the metal are not affected by it. The decrease in the recorded light intensity
is proportional to the amount of metal present. Thus, the amount of light absorbed can be
related back to the metal present in the sample and from there back to the field.
In atomic emission spectrometry, a wavelength of light characteristic of the metal
being analyzed is isolated and recorded. As described above, the sample is passed
through an atomizer into a flame where the metal is excited and gives off wavelengths of
light specific for that metal. The wavelength of light of interest is isolated using a
monochromator and recorded. The amount of light recorded is proportional to the amount
of metal in the flame and can be related back to its concentration in the sample and the
field.
In both absorption and emission spectroscopy the metal must be excited in a flame. For
many elements the hotter the flame the more sensitive the analysis. There are, however,
some similar techniques using the same basic instrument that do not require a flame,
although the sample is still heated to high temperature. In all cases a wavelength of light,
which may be either in the ultraviolet or visible region of the spectrum, specific to the
metal being analyzed for is used in the analysis.
There is another way in which an atom can be excited so that it gives off light of
specific wavelengths, and this is by being bombarded by X rays. In this method, called Xray fluorescence spectrometry, a sample is placed in a beam of high-energy X rays and
irradiated. The metals in the sample are excited, absorb energy, and reradiate this
absorbed energy as light of specific wavelengths. The wavelength of light given off is
specific for specific elements, and the amount of light produced can be related back to the
amount of metal present in the sample. In addition to X rays, neutron and gamma
radiation can also be used, although the instrumentation is different.
Anything done during sampling, transportation, and storage that changes the metal
content of the sample will change the results of this analytical method. This can happen
anytime the sample comes in contact with any metal because almost all metals in
common use are mixtures. Even if the analysis is not for iron, exposure of the sample to
iron could cause it to be contaminated with other metals in the iron. Chromium, nickel,
and manganese are commonly found in materials made from iron and could contaminate
a sample left in contact with it. Any contact between the sample and any metal should be
avoided [6].
* Although this discussion

method.

only considers metals, some nonmetals can also be analyzed by this

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263

The preceding discussion indicates that metals and elements only absorb or emit one
wavelength of light. This is not the case. All elements absorb and emit many different
wavelengths of light. In some cases, wavelengths from two different elements may
overlap or be so close together that they interfere with each other. For this reason it is
important for the person doing the analysis to know all the elements likely to be present
so that these possible interferences can be controlled or eliminated.
10.7.3.2. Molecular Spectroscopic Methods
Colorimetry includes all the physical-chemical methods that make use of the light
absorption of colored solutions for the quantitative analysis of dissolved substances.
Colorimetry is based on the direct color comparison without any measuring device
beyond the human eye. When light passes through a colored solution its intensity is
reduced due to absorption of light of a specific wavelength by the colored substance. This
change is used in direct color comparison between the test solution and either vials
containing known concentrations of the component of interest or a color chart. The
amount of material present is recorded from the reference vial or chart to which it most
closely compares.
Two types of colorimetry are commonone in which the solution is colored and one
in which a reagent that reacts with the component of interest to form a colored complex is
produced. This second method is commonly used in pH determination of soil and water
and the levels of chlorine in swimming pool water.
10.7.3.3. Spectrophotometry
Spectrophotometry is similar in principle to colorimetry, except an instrument is used to
measure or compare the amount of light absorbed. The instrument consists of a light
source and an optical system to isolate the wavelengths of light of interest and pass the
light through the sample to a detector. In Spectrophotometry light in both the UV and IR
regions of the spectrum is used in addition to visible light. This means that components of
interest do not have to have perceivable color in order to be detected. In UV
spectroscopy, the UV region of the spectrum is used, and absorption of light is caused by
the movement of electrons in the molecule. In the IR region of the spectrum, the vibration
of bonds in molecules is determined.
10.7.3.4. General Spectroscopy Considerations
From the above discussion it is obvious that any additions, subtractions, or changes in the
sample can change the absorption of light and thus change the spectrophotometric results.
This is especially the case for colorimetry, in which contamination of the sample with a
dye or other colored compound can have a dramatic effect on the quantitative results.
Also in such analyses, if the cells used to hold the sample in the instrument are dirty, they
can interfere with the analysis. Likewise, a cloudy sample will give an erroneous result.
All analytical methods that depend on the absorption or emission of light have several
requirements in common. They all need blank solutions that contain all the components

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in the test solution except the component of interest. These blanks are used to zero the
instrument before readings are made. The second requirement is a standard or calibration
curve. These are prepared by making a series of solutions containing different known
amounts of the component of interest. These are then measured and a graph of the
amount of component present versus the instrument response is prepared. Using this
graph the concentration of analyte in an unknown can be determined. Statistically this
standard curve should have a regression coefficient r2 of 0.99 or 99%. This shows that
the graph is nearly a straight line and that there is a good relationship between the actual
amount of material present and the instrument reading [7].
10.7.3.5. Mass Spectroscopy
Mass spectroscopy is different from other Spectroscopy techniques in that it measures the
mass of molecular ions or fragments produced by ionizing the sample. The fragments
produced from a compound are unique, and can thus be used for its identification. A
sample of a compound is introduced into the mass spectrometer, and the ions formed are
separated in the analyzer using either a magnetic or an electrical field. The separated ions
and fragments are recorded and their unique fragmentation pattern is used for
identification. When this same fragmentation pattern is obtained from an unknown in a
mass spectrum, it shows that this compound is present. Because mass spectroscopy is
best used to determine the composition of a pure single molecule, it is often used after
chromatographic separation of a mixture into it component parts [8, 9].
10.7.4. Separation Methods
Initial physical and chemical separation may be necessary as adjuncts to final separation
and determination methods. Two reasons for separation are:
1. If the selectivity of the determination method is insufficient and interfering impurities
must be separated out and the sample concentrated before analysis.
2. If as many substances as possible are to be qualified and quantified in a single
procedure. In this case, the sample must be separated into its respective components
(e.g., aqueous/nonaqueous, solid/liquid).
Separation methods can be initially divided into two groups, depending on whether or not
they act on the basis of analyte transformation. Transformation includes the classic
gravimetry, electrogravimetry, which is when a substance is transformed with the aid of
an electric current, and volatization of a substance in an aqueous phase.
Separation without substance transformation can be accomplished by partitioning on
the basis of partial charges, masses, sizes, or shapes, and different vapor pressures of the
compounds of interest. Separations caused by partitioning between two immiscible
phases are also very important. Depending on the types of components and solvents
involved one differentiates adsorption or desorption processes (solid-liquid or solid-gas),
liquid-liquid partitioning (usually as liquid extraction), ion exchange (between a solid ion
exchange matrix with a substitutable charge group and a liquid phase), and liquidsolid
extractions.

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Specific methods of separation based upon particle charge depend on the differences in
the migration of free charged particles while in an electrical field. Differences in the
particle mass, size, and shape also make it possible to separate substances by such
methods as gel filtration or centrifugation. Separations can also be based on vapor
pressure differences between compounds using distillation, condensation, sublimation,
and crystallization.
For extraction of solids, extraction desorption concepts apply and may be of several
different types. An aqueous solution may be used to extract inorganic components and
ions from a solid material for subsequent analysis, or an organic solvent may be added to
a soil or solid matrix either before or after the sample has been dried with a chemical
agent such as anhydrous sodium sulfate. To ensure good chemical mixing and extraction
the sample/solvent combination is mixed for a period of time either on a mixer or using
an ultrasonic device. Ultrasonic mixing is performed using either an ultrasonic bath or
horn. During this procedure solvent aliquots are alternately added to and decanted from
the sample after each period of sonication, and placed into a single vessel for future
concentration.
Aqueous extracts are often used as is, while organic extracts are often concentrated.
Organic sample extracts are concentrated using a blow down device where a regulated
stream of dry, pure gas is passed over the vessel top in such a way as to promote
evaporation of the solvent without disturbing the liquid surface. The gas blow down
method of concentration is better than the older methods of cooking off the excess
solvent using special glassware and a distillation column on a warm water bath. Boiling
methods are time- and labor-intensive, and even when used with great care, are prone to
catastrophic loss through bumping or explosive boiling and leaking or broken
glassware. After the sample extract has been concentrated to a set volume (usually 1 ml),
it is stored in a small vial sealed with a Teflon-faced septum or cap at 4C until
instrument analysis takes place.
Another general form of extraction is what is termed gas/liquid or gas/ solid extraction.
These are both variations upon the principle of headspace analysis. Headspace analysis is
the analysis of a gas that has been in contact with a liquid or solid sample and is used to
draw conclusions about the nature and/or composition of the underlying sample. There
are two general variations of headspace extraction; the first and most frequently used
form is where an inert gas, such as helium, is bubbled through a liquid sample, thereby
stripping volatile analytes from it. This is often referred to as purge and trap (P&T) or
dynamic headspace analysis. The stripped gas sample is passed through an absorbent
trap, which retains the volatile analytes. The collected analytes are analyzed by rapidly
releasing them from the absorbent trap (usually by heating and back flushing) and
introducing them as a band or slug into a gas chromatograph.
Gas chromatography, discussed below, is particularly well suited for this analytical
method because the extracted sample is already in a vapor or gas phase and can be
directly introduced into the GCs carrier gas stream for the separation.
The other form of headspace extraction is where the samplebe it liquid or solidis
placed in a sealed container with a gas volume above it. The container is then heated to a
set temperature and allowed to come to equilibrium between the two phases (i.e., solid
and gas). After a prescribed period of time a fixed volume of the containers gas phase is

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removed and introduced into the GCs carrier gas stream and analyzed [10].
The last general form of extraction is known as solid phase extraction (SPE). The use
of this form of extraction is rapidly increasing because of the smaller volumes of solvent
used in the extraction and the concurrent ease of sample concentration due to the smaller
original volumes involved. It allows for high selectivity in the components extracted and
retained and on the elution solvents, which are used to remove the component of interest.
A liquid sample is passed through a short disposable column containing an absorbent
material using either pressure to push or vacuum to pull the liquid through the column
(Figure 10.5). By choosing suitable column material and solvent, the selective retention
and subsequent elution of analytes of interest can be obtained, providing both sample
cleanup and concentration in one or two steps. This extraction method is only usable for
liquid samples (usually water) that have little or no particulate matter because suspended
solids will clog the extraction column before the entire sample has passed through.

FIGURE 10.5 An extraction column used for purification of analyte before

analysis.

Any material accidentally added to a sample during sampling, transportation, or storage,

or any error in sampling would also be concentrated during the above procedures. Even
small, seemingly inconsequential contamination can be magnified 10 or 100 times during
concentration steps. When this happens it can have a pronounced detrimental effect on
the analytical results and may produce entirely erroneous results, resulting in dramatically
increased costs of analysis and remediation [1113].
10.7.5. Chromatographic Separation
There are a myriad of chromatographic methods in common use, all of which are
extremely powerful separation techniques and all of which operate on the same basic
principles. They have a stationary phase over which a mobile phase moves. When a
complex mixture of components is introduced into a chromatographic procedure, the
components are differentially partitioned between the two phases. Differential
partitioning results in separation of the components as they move under the influence of
the mobile phase. Once separated the individual pure components are identified and
quantified.
Two specific types, liquid chromatography (LC) and GC, are most commonly used in
environmental analysis. Liquid chromatography, also known as column chromatography,

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is performed in columns using only the pull of gravity to move the mobile phase. The
columns used have an inner diameter of 1 cm or greater and a stationary phase with
particles between 100 to 300 m in diameter. The second kind of LC uses high pressure
to move the mobile phase through the column. Because of this it is called high pressure
or high performance LC (HPLC). High performance LC uses narrow columns 2 to 4 mm
in inner diameter with particles of 3 to 10 m in diameter as the stationary phase and
mobile phase pressures up to 4 MPa. High performance LC achieves considerably higher
separation efficiencies than does column chromatography.
As with the SPE method discussed above, particle-free samples are required for either
of these methods. Suspended solids will be filtered out on the top of the column and
prevent the movement of mobile phase through it.
The other chromatographic method commonly used in environmental analysis is GC.
In this method, a carrier gas such as helium, nitrogen, or hydrogen is used as the mobile
phase to drive the sample through a column that contains the stationary liquid phase. The
samplewhich must be in either a gaseous or a vapor state, vaporization being
accomplished by heating the sample when it is injected into the GCis then separated by
partitioning between a liquid phase and the carrier gas. A limitation of this method is that
the sample must be able to be converted to a gas or vapor state with minimal loss or
degradation.
The sensitivity of modern gas chromatographic methods cannot be overemphasized.
Solvents being used in a part of a laboratory several roomsor in some cases several
floorsaway may be detected in a sample being analyzed. Thus great care must be taken
to ensure that samples are not exposed to any vapors during sampling, transportation, and
storage. This is also why both positive and negative controls are needed for all methods.
In both HPLC and GC it is possible to identify a compound by its retention time
(e.g., the time between when a compound is introduced into a column and when it
emerges). If repetitive analysis of samples that all have the same constituents and the
instrument is set up the same way retention times can be a very good indication of the
type and amount of compound present. However, two compounds can have the same
retention times, and so an independent separate identification method is always
appropriate. Gas chromatography/MS is extremely valuable to the analyst and laboratory
because the compounds can be identified conclusively during the analysis and it does not
require costly and time-consuming conformation using a second method.
Introduction of samples that will not vaporize or decompose when heated will destroy
the chromatographic column. Any material in the sample having these characteristics will
invalidate the analytical results, prevent further analysis, and prevent the use of the
instrument for several days. Also, gas chromatographic columns are not cheap,
sometimes costing over $1000, and thus care needs to be exercised in the preparation and
introduction of samples into a GC to ensure its suitability and continued operation [14,
15].
10.7.6. Combined Methods
In modern instrumental analysis it is common to use a combination of instrumentation in
tandem or sequentially. The most common is GC coupled with MS (GC/MS). As

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separated compounds exit a gas chromatographic column they are introduced into a mass
spectrometer. This method thus not only separates a complex mixture into its component
parts but also identifies the components, making it an extremely powerful analytical tool.
The output from a GC/MS is sent to a computer, where it is recorded and displayed.
The computer also contains a library of the unique fragments of a wide range of
compounds. It can be used to search this library for compounds with the same
fragmentation patterns as the unknown component from the chromatographic column and
thus identify it. In one analytical procedure taking little time, a very complex mixture can
be separated and its component parts identified.
There are two very important limitations to this method that must be kept in mind at all
times. It is possible that two different compounds will come out of a chromatographic
column at the same time. It is also possible that these two compounds will have similar
fragmentation patterns. When this happens the computer output can misidentify the
compound exiting the chromatographic column. This is a particular problem when the
GC and MS are set up for a particular analysis and, without changing the instrument
parameters, it is used for a very different analysis [9, 16].
10.7.7. Electroanalytical Analysis
Electroanalytical methods use an electric current (i.e., amperage and voltage) or a change
in potential to produce an analytical result. These methods are often based on the change
in a material that occurs upon the application of an electrical potential. They are
commonly used as the indication method in such classic wet chemistry methods as
titration processes. Electroanalytical methods use ion and electron movement and phase
interfaces of electrodes and ions to obtain information about the type and concentration
of organic or inorganic material present in a solution.
The two main electroanalytical forms are transformation of electrical energy into
chemical energy (i.e., electrolysis with current flow across a cell) and the transformation
of chemical energy into electrical energy using a galvanic cell. As an example,
electrolysis takes place when current is applied to a copper rod immersed in a copper
solution and is connected with a second half cell made up of a platinum rod immersed in
an acidic solution. Copper ions will take up electrons and be deposited as metal on the
cathode. A galvanic cell (wet cell) is made when of two half cells, each consisting of a
metal electrode immersed in its cationic solution, are connected to each other. The
measured potential of this cell is the difference between the individual potentials of the
electrodes in their solutions. If one cell is copper ions in a copper sulfate solution and the
other a zinc rod in a zinc sulfate solution, the connection between the solutions and rods
makes a galvanic cell. The reduction of copper ions to metallic copper at the copper rod
and the oxidation of the zinc metal to zinc ions at the zinc rod takes place. This combined
reaction generates a current.
Testing methods employing the principles of electroanalytical chemistry are mainly
limited to the two forms known as potentiometry and conductometry.
In potentiometry, the characterization of the amounts and types of the materials present
are determined by measuring the potential differences between a measuring or indicator
electrode and a reference electrode using a constant potential. This is the principle used to

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measure the pH of a sample. The hydrogen ion concentration of a sample is measured

using a pH electrode in combination with a reference electrode or solution. The pH
electrode usually consists of a glass tube that contains a buffer solution of a known pH
and a reference electrode. In operation, pH measurements are made using a single-tube
measuring device, containing both a pH and reference electrode, which is immersed in
the sample to be tested. The glass wall of the electrode at the end of the tube acts as a
complex membrane and allows hydrogen ions from the sample to penetrate into the glass
electrode. Sodium ions are displaced by hydrogen ions and a potential difference
develops at the glass/water interface. The exchange rate between the sodium and
hydrogen ions on the surface of the glass of the electrode is pH-dependent. Therefore the
different potentials between the reference solution and the sample are linked to different
pH values, and it is this difference that is measured and interpreted as the pH of the
sample [4].
In conductometry, the presence of ions in solution allows a current to flow when an
alternating current voltage is applied. The conductance or resistance of the cell is the sum
of the ions across the sides of a reference cell in comparison to the sample cell.
Measurements using conductometry are mostly used in analytical methods in which a
large change in conductance of a sample cell is compared to a reference conductance.
Conductance measurements are used to measure the salt content of aqueous solutions or
extracts.
Any error in sampling that changes the pH or salt content of the sample will adversely
affect these measurements. It will also affect the proposed cleanup and remediation
procedures, and it may interfere with other analytical procedures [17].

10.8. ANALYTICAL METHODSSOME SPECIFICS

In determining the actual methods (described above) to be used in the sample analysis the
first thing to consider is the nature of the sample; that is, is it solid or liquid and what is
the clients question? This consideration is a way to start the logic tree for the analysis,
which is a relatively simple, logical consideration of the sample and what you want to
learn from it. Historically it has been repeatedly found that a few minutes time given to
such a basic consideration of common sense before the sample is taken (much less logged
in for analysis) can save time, effort, and frustration later.
Ideally this consideration should be second nature to the PM in discussing the problem
or analysis needed with the client. (Remember that the PM is the first and last contact
with the client and hopefully can get the complete picture.) If a client thinks his well is
contaminated with organics from the next-door neighbor or some governmental or
regulatory agency has requested monitoring of an underground storage tank (UST) the
base method to be used for analysis of the sample is determined by this request. If the
sample is being submitted for initial characterization (i.e., what it is or what is in it), basic
analytical methods for the general component determination are used. The use of GC/MS
methods in both these cases is highly recommended because of the ability of this method
to isolate and determine many different analytes with one analysis.

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10.8.1. Methods for Liquid Samples

Water or liquid samples are measured by volume, the pH is adjusted, and an extraction
reference is added. (This extraction reference is traditionally called a surrogate, and is a
known compound or group of compounds with similar characteristics as the target
compounds.) This way there is a measure of extraction efficiency for the sample; that is,
if X amount of a surrogate with the same or similar characteristics to your target analyte
is added to the sample and after extraction the analysis of the sample extract shows a 90%
extraction efficiency it could be assumed that there was a 90% recovery of the target
compound. Unfortunately this does not hold to true for many compounds. Usually
extraction efficiency should not be used to correct the analytical results for extraction
efficiency; rather, the surrogate recoveries are used in comparison to the methoddetermined limits to validate it. In the case of an invalid testing event the sample may
require reanalysis to confirm matrix or method interference. If enough of the original
sample remains, the entire sample preparation and analysis process may be repeated.
10.8.1.1. Extracting Liquid Samples
Liquid samples are extracted in one of the following ways, depending on whether they
are aqueous or nonaqueous. (Extraction methods are summarized in Table 10.3.)
Aqueous Samples:
ClassicLiquid/liquid or solid/liquid (i.e., liquid sample matrix/ organic
solvent or solid matrix/organic solvent).
Solid phaseA liquid sample is passed through an absorbent that retains the
analyte, which is flushed from the column for analysis.
Supercritical fluidA sample is extracted by the use of a gas that has been
compressed to its liquid phase. This is usually carried out using liquid carbon
dioxide (CO2) [10].
Nonaqueous Liquid Samples:
Small quantities of oil or some other nonwater miscible matrix
extracted with either water or an organic solvent.
Large quantities of oils or nonwater immiscible matrixes
separated from any water phase either by decanting or by using a
and then extracting the remaining material, usually with either
organic solvent.

or a solid
are usually
drying agent
water or an

10.8.1.2. Multiple Extractions

Multiple sample extractions can be carried out in two ways. The first is the extraction of
the sample with multiple aliquots of solvent, usually three times. For example, three 50ml aliquots of methylene chloride are added to 1 liter of water sample, each aliquot is
shaken for 2 min, is allowed to separate, and is collected combined with other extracts for

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concentration in a common container. Theoretically 5075% of the sample contaminant

will be extracted by the first aliquot. Lighter or less complex sample matrixes might have
an extraction efficiency of upwards of 90% in the first fraction, while heavy molecular
weight compounds or complex matrixes or soils may have a far lower efficiency. This
will be indicated by recovery of the extraction surrogate. The standardized use of three
solvent aliquots with a fixed solvent contact time of 1 or 2 min acts as a point of
standardization for the extraction process, hopefully ensuring that if you have x amount
of a compound in your sample you will have extracted it all. If 100% is not extracted
because of matrix interference you will be aware of the decreased extraction efficiency
by the monitoring surrogate extraction.
10.8.2. Methods for Extracting Solid Samples
Solid samples are extracted by adding an extractant, then mixing and either decanting the
extractant or filtering to separate solids from the extractant.
10.8.2.1. Methods for Solid Samples
Individual samples are taken from the field using a predetermined pattern and extracted.
The extracts are then analyzed. The handling of these solid samples will be illustrated
using soil as an example.
A soil sample is characterized and mixed to assure a uniform sample from the sample
container. A subsample is weighed and the original weight being extracted is recorded in
the laboratory logbook. A portion of the sample must be analyzed for its percentage of
solids because this factor must be applied to the resultant data for the soil sample to yield
the fields true component concentration. Extraction surrogates are added and the sample
is mixed to ensure even distribution. Mixing with a drying agent, such as sodium sulfate,
dries the sample.
An aliquot of the extraction solution is added and the sample is mixed for a fixed time,
either by stirring or through the use of an ultrasonic extraction device. Solvent is poured
off through a piece of filter paper into a flask and the sample is re-extracted twice more
for a total of three solvent aliquots. The extract can be passed through a cleanup phase;
that is, a fluorasile cleanup column (see Figure 10.5) that has been prerinsed with the
solvent used for the extraction. This or the original solvent extract is reduced in volume
to 1 or 2 ml and analyzed.

10.9. DATA ASSESSMENT

The data produced using one of the analytical procedures described above is what is
termed raw data and must be related to some standard or reference to determine the
relationship of the analytical response to an actual value. This is usually done by
comparing the raw response to the response obtained from the instrument or method
when a series of known standards is analyzed. The instrument responses from these
standards are used to prepare a response or calibration curve for the instrument that

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encompasses the linear response range of the method. Often the range and number of
these calibration standards as well as the statistical form used to generate the response
curve will be dictated by published method conditions.
Ideally, the raw sample response will fall within the range of responses used in
determination of the instrument or method calibration range. If the raw response is
outside this range, there are two factors to consider. The first is what the concentration
limit is for the particular component or compound in the analytical method used. If the
analyte in question exceeds the calibration range of the analytical method or instrument,
the answer may be to dilute the sample by an accepted factor and reanalyze.
Diluting and rerunning a sample can introduce contamination from the diluting agent,
and it will introduce a dilution factor that must be added to the calculation when deriving
the true concentration of the sample. Dilution may mask or reduce other important
analytes in the sample to such an extent that they are not accurately determined using the
analytical method. Thus, great care and high-accuracy glassware and measurement must
be used in making dilutions. A general rule related to all analysis is that any additional
manipulation of the sample will introduce error.
Usually there are also other points to consider as part of this. One of these points is the
question of how far above the instrument limit the analysis went. This is important
because the instrument may now be contaminated. Contamination can be determined by
running a method blank to see if it is below detection levels for the compound in
question. If it is, there is no problem. However, if it is above detection limits, the
analytical system requires cleanup or maintenance to bring the level back below the
detection threshold for the compound in question. Finally, the system must be thoroughly
checked using a series of system blanks to ensure conformity to method requirements. In
extreme cases the system might require further cleaning or component replacement
before the instrument system is clean.
Another question to be considered is if the level of the analyte interferes with other
compounds that might be present. If so, the other compounds may not be reliably seen or
reportable. The sample in this case may need either dilution or further separation and
reanalysis with the reporting levels modified to reflect the dilution factor.
In extreme cases, the level of a compound may exceed its solubility in a sample or
solution. When saturation occurs excess material will separate out, as in the case of oil or
gasoline contamination of groundwater. Compounds that make up the gasoline dissolve
in water until saturation occurs, and the remainder of the gasoline then pools or forms a
layer on the top of the water sample. This can cause errors in the characterization of a
sample if part of the nonuniform sample is taken to represent the entire sample. This is an
example often seen in groundwater samples from a field contaminated by a leaking
gasoline storage tank. While the layer of free product on the surface may lead to very
high concentrations for compounds such as benzene or toluene in the analysis of the
water sample, they are often not the true concentrations of the compounds actually
dissolved in the water.
This is an example of a sample with multiple layers in which the concentration will
vary between the layers of the liquid sample. In the case of a soil, the analytes may, in
extreme cases, be seen as deposits within the soil matrix as a whole. Because this is not a
characteristic sample, it can lead to analytical problems unless care is taken in the

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original sampling of the site and the subsequent sample preparation, extraction, and
analysis.
In some cases the level of contamination may be below the maximum contamination
level (MCL), and in this case further action beyond continued monitoring and assessment
is usually not required. If the component is below detectable levels it is probably also
below MCL. If not, the sample extract may need to be concentrated to obtain analyte for
analysis. As with diluting, as discussed above extreme care must be exercised in the
concentration of samples.

10.10. REPORT GENERATION AND DOCUMENTATION

What is the overall report produced by the laboratory as a whole? It can be as simple as a
handwritten or typed transcription of the verbally reported results discussed with the
client by the PM. However, most analytical testing labs today use some form of computer
database to produce the reports. Generally these are known as a laboratory information
management system (LIMS), and act as an aid both in handling the large volume of
samples received and the data generated and in collating and generating reports. One soil
sample for a general screening for organic and inorganic components may have several
hundred individual results linked to it. Because the chance for transcription errors
increases every time the data are copied, it is better from a data integrity standpoint to
enter the data into the LIMS either directly from the instruments or from the original data
sheets. The data are then double-checked, peer reviewed, and subsequently checked by a
supervisor or a group leader to ensure accuracy. The importance of double-checking the
results and the data entered into the LIMS system cannot be stressed enough.
Once all the requested analysis is done and all the data have been entered into the
LIMS system, the PM should review it for gross errors and impossible numbers. After
this is done and any problems are resolved, a draft report is generated and reviewed. If all
is acceptable, a final draft is printed and again checked for errors or inconsistencies by
the quality assurance/quality control (QA/QC) offices and finally by the lab manager or
director who is the final check on and ultimately responsible for the data and the report
produced by the lab. If everything is acceptable, the report is signed by the final review
authority and is released for delivery to the client.
Often in todays work environment the report is sent as a faxed copy or an electronic
data deliverable form (EDD) via the Internet or data media. However, it is still important
that a hard copy be sent to the client unless specifically directed otherwise. The reason for
this is that the final hard copy is the legally accepted copy of the data if there are any
complications or problems. The laboratory results can have far-reaching and often very
expensive effects. For example, the ruling of a drinking water system out of compliance
because of contamination could result in legal action and fines. The classification of a
field as contaminated can result in the current and possibly prior landowners being liable
both legally and financially for the contamination and the subsequent cleanup costs.
Because of the potential ramifications of the labs results, it is imperative that the lab
maintains internal records and documentation of the methods and results and the actual
raw data, both in electronic and hard form, as well as any problems or variations from the

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accepted methods and procedures that might have occurred. Many regulatory agencies
require that the data associated with a drinking water system be available in time frames
of multiple decades. Also, it may take months for the client to get all of the data (results)
from field sampling and to collate and generate its own report. This means that the actual
data must be available for a time frame of at least a year [18].

10.11. DO THE RESULTS ANSWER THE CLIENTS QUESTION?

While this question may seem redundant, as stated earlier, it is important to consider it
often during the testing and report-generation process. This is due to the fact that the
answer to the clients original question will often lead to many more questions and
problems that will need to be considered and answered in turn. Thus it is important to
come back to the original question and be certain that it is answered.

10.12. SOME GENERAL QUESTIONS AND CONSIDERATIONS

What if the concentration is above the MCLs? Traditionally this means that there is a
contamination problem that must be resolved. Usually a government or regulating agency
at the local, state, or federal level will become involved. For instance, in the United States
a department of the Environmental Protection Agency (EPA) will have already acted to
set levels of acceptable contamination. These levels will vary with the compound in
question according to the nature and potential danger of the contaminant, and are often
termed the maximum levels of contamination. Another term often used is that of action
level; that is, that concentration level above which some form of remediation or site
cleanup is mandated. If the level of a contaminant exceeds the MCL level, the field will
often require mandatory cleanup according to the various state or federal regulations.
Once the federal or state-level EPA becomes involved and the levels are confirmed, the
source of contamination is determined, along with the extent of contamination and its
possible hazards. Fines are levied via the courtshopefully, to pay for the required site
cleanup and to prevent future spillage or accident by encouraging better management,
technology, or systems.
States and countries other than the United States can and do set MCL levels that are
different from those of the United States Environmental Protection Agency (USEPA). It
is always essential to determine the locally applicable rules and regulations.

10.13. CONCLUSIONS
The first question to ask before analysis of a sample can occur is what it is that the client
wishes to learn and what the nature of the sample is. There are both simple and complex
analytical procedures that can be applied to samples in order to answer the clients
questions. Some are methods carried out in the field and some are done in the commercial
laboratory. Field analysis such as pH and dissolved oxygen are simple and quick and

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require simple instruments. More complex analysis involving extraction, concentration,

and instrumental analysis are done in the commercial laboratory. In any analytical
procedure sample preparation is an essential first step that is often followed by extraction
and finally by analysis. Analytical procedures may be standard wet chemical methods or
more complex instrumental methods. Commonly the instruments used fall into two
groupsthose based on spectroscopy and those based on chromatography. In some cases
a combination of spectrophotometric and chromatographic methods will be used in the
analysis. Once all the analysis is completed the data are checked and a final report is
prepared and presented to the client.
The final data and resultant report can be no better than the original simple submitted
for analysis, and this also applies to all steps of the analytical procedure. If care is not
taken at every stepsampling, transport, storage, and during the analytical processes
errors will be compounded and the resultant data will be flawed. The ultimate result is
that the data do not accurately reflect the true nature of the field being tested.

QUESTIONS
1. What are the limiting factors for the determination of sampling and testing methods?
2. Insulated ice chests are often used to transport samples from the field to the
laboratory. What must the ice chest or cooler contain in addition to the samples? What
two purposes does the ice serve?
3. What is one of the most important factors in obtaining a representative sample in the
field? What two factors go along with this point?
4. Name three common methods used for sample preparation.
5. What laws are fundamental as applied to an analytical procedure?
6. What are the two types of quantitative analyses and three groups of instrumental
techniques? Name each and give a short description of how they work.
7. What does PM stand for? What is this persons role?
8. When the concentration of an analyte of interest is far beyond the range of the
instrument or method, what must be done to analyze it? How can analyzing samples
containing too much of an analyte adversely affect the subsequent analytical procedures?
9. What is the sampling logic tree and how is it used in sampling and sample analysis?
10. What is an extraction reference or surrogate and how is it used in the sample
analysis process?

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11. What are three common methods of sample extraction?

REFERENCES
1. Description and Sampling of Contaminated Soils: A Field Pocket Guide. EPA 625
1291002. Cincinnati, OH: National Service Center for Environmental Publications.
Fed Reg 1991.
2. Corbitt RA, ed. Standard Handbook of Environmental Engineering. New York:
McGraw-Hill, 1988.
3. Sampling: When, Why, How.
http://www.epa.gov/region/offices/oea/ieu/manual/inspect08.htm.
4. Brady JE, Humiston GE. General Chemistry: Principles and Structures. New York:
Wiley, 1982.
5. Haines P, ed. Principles of Thermal Analysis and Calorimetry. London: Royal Society
of Chemistry, 2002.
6. Dean JR, Ando DJ. Atomic Absorption and Plasma Spectroscopy. New York: Wiley,
1997.
7. Pavia DL, Lampman GM, Kriz GS. Introduction to Spectroscopy. Ann Arbor, MI:
Brooks Cole, 2000.
8. De Hoffmann E, Stroobant V. Mass Spectrometry: Principles and Applications. New
York: Wiley, 2001.
9. McMaster MC, McMaster C. GC/MS: A Practical Users Guide. New York: Wiley,
1998.
10. Kolb B, Ettre LS. Static Headspace-Gas Chromatography: Theory and Practice. New
York: Wiley-VCH, 1997.
11. Dean JR. Extraction Methods for Environmental Analysis. New York: Wiley, 1999.
12. Taylor L. Supercritical Fluid Extraction. New York; Wiley-Interscience, 1996.
13. Simpson NJK, ed. Solid-Phase Extraction: Principles, Techniques, and Applications.
New York: Marcel Dekker, 2000.
14. Poole CF. The Essence of Chromatography. New York: Elsevier Health Science,
2002.
15. Kitson FG, Larsan BS, McEwen CN. Gas Chromatography and Mass Spectrometry.
New York: Academic, 1996.
16. Bard AJ, ed. Electroanalytical Chemistry. New York: Marcel Dekker, 1999.
17. Nakagawa AS. Lims: Implementation and Management. London: Springer Verlag,
1994.

11
Traps, Mistakes, and Errors
Alfred R.Conklin, Jr., and Rolf Meinholtz

Traps, mistakes, and errors can occur at any stage in sampling and analysis; for example,
in the field, during transport and storage, during analysis, and in the interpretation and
communication of analytical results. Traps occur when incomplete data about a sampling
activity, including the history and characteristics of a field, have been collected or
something unusual happens. Mistakes often are the result of untrained or inexperienced
personnel who do not understand the procedure, the importance of each step, how it
works, and what results are reasonable and expected. Mistakes could also be made by
personnel who simply do not pay attention to what they are doing.
Most traps, mistakes, and errors associated with environmental sampling occur with
the physical sampling process as it occurs in the field. Fewer occur during transport and
analysis, and the least with chemical and statistical analysis and reporting of data. In
some cases errors are caused by the heterogeneous nature of the environment. In most
cases they are caused by personnel [1]. Unfortunately nothing will completely eliminate
errors and mistakes, but they can be minimized by having checks at each stage of the
process, by having good communication between samplers and laboratory personnel, and
by using statistical tools. To be effective these must be carried out with careful attention
to detail.
The first place in which personnel have trouble is in reading maps and judging
distances. A way around these problems is the extensive use of a global positioning
system (GPS). The second place in which problems occur is in transporting and storing
samples. The thoughtful use of chain of custody forms and procedures will minimize
problems associated with these activities. The third place will be in carrying out the
analysis, and the last in reporting the results. Extensive and continuing training in
analytical procedures and reporting protocols will minimize these problems. Good
communication between personnel involved at each stage is also crucial in minimizing
errors.
During transportation and storage, problems arise due to mixing samples and putting
the wrong paperwork in the sample transport box, along with breakage and the loss of
temperature control. Carefully choosing sample containers and packing materials, paying
attention to details in completing paperwork, including labeling, and including the correct
paperwork with the proper samples will all go a long way toward minimizing problems.
Checks and double checks at this point can prevent the loss of samples and incorrect
laboratory analysis.
In the analytical process there are also a number of traps and errors that can be made.
Samples may be extracted using the wrong extractant, or the correct extractant might be
used but with the wrong instrument. Interfering compounds or species present in the

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original samples or added later may result in inaccurate results or hide the compounds of
interest altogether. The laboratory technician may incorrectly read or record data. With
sufficient numbers of controlsboth positive and negativethese types of problems can
be caught and rectified.
In searching for errors often the first approach is to apply statistics rigorously to the
field samples and their analytical results. While statistical analysis is critical in any
sampling program, it is not sufficient in and of itself to ferret out all problems. An
example of statistics not being applicable to a specific set of data is given in Section 11.2.
A better first approach is to look for possible sources of errors recorded in the project
notebook and in the chain of custody, field calibration, and field information forms. A
summary of errors and mistakes made both in sampling and in analyzing samples is given
in Table 11.1.

11.1. HISTORY OF THE AREA

Because it is one of the first pieces of information obtained about a field, its history is a
beginning source of mistakes. Failing to obtain a complete history of an area can result in
costly and time-consuming errors in interpreting data and developing remediation plans.
A complete and thorough investigation of all aspects of an area will be invaluable in

TABLE 11.1 Sources of Mistakes and Errors Made in Sampling and Analyzing
Environmental Samples

Activity

Sources of error

Field
sampling

Incorrect field, incorrect position in field, inconsistent sample size, failure to

record in field notebook (also see Table 11.3), incorrect labeling, failure to fill out
proper forms, improper or failure to preserve (e.g. acidification, cooling)

Transportation Incorrect sample container, loss of sample, contamination from other samples or
surroundings, incorrect labeling, incorrect shipping container and container
conditions
Storage

Incorrect storage conditions (e.g. temperature, isolation, sunlight, time)

Analysis

Incorrect storage conditions, incorrect handling (e.g. wetting, drying, heating and
cooling, exposure to contamination, loss of contaminant), incorrect sample
preparation, wrong extraction method, incorrect solvent used

Reporting

Incorrect input of data, incorrect mathematical and statistical analysis

explaining both expected and unexpected analytical results. Examples of the importance
of obtaining the history of the field to be sampled have been given in previous chapters.
(See particularly Section 3.6 in Chapter 3.)
A field history can be of great help in determining what potential contaminants may be
present. For example, if the groundwater is being tested at the site of an old gasoline

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station, it is within reason that gasoline contamination may be found. Also, and just as
important as the initial field characterization, is the ongoing history of a site. This can be
as fundamental as a field map indicating where the sample points are located to as
complex as the field sample history plotted as a thread over time with reference to field
soil characteristics and hydrology.
The biggest mistake made in obtaining the history of an area is the assumption that it
was not or could not have been used for a specific or general activity that would lead to
contamination. These assumptions are often made by looking at the area as it is presently
and seeing no indication of human activity. Of course this view leaves out the possibility
that somewhere below the surface is information about previous uses, which may be
indicated by the occurrence of some common soil components. The occurrence of higher
than normal levels of elemental carbon may indicate the existence of campfires or other
burning in the area. This might be caused by normal occurrences, but may also indicate
human habitation. Higher than expected levels of phosphorous in soil may indicate the
same thing.
Thus, exploration of the history of an area must be done with an open mind, and it
must never be assumed that the area is not and never has been contaminated. The most
unlikely fields, often remote from populated areas, are contaminated in one way or
another. A small area enclosed in trees in a remote field on a farm was found to be an
area in which a farmer had dumped both empty and partially filled containers of excess
agricultural chemicals, including toxic compounds, some dilute and some concentrated.
Such an area is a source of contamination to surrounding land and water supplies.
Another remote field surrounded by trees was found to contain a pit being used as a
dump. The area was both remote from a population center and screened from surrounding
roads by the trees. Gullies are commonly used as places to dump unwanted materials.
Often this is done for two purposes. One is a mistaken idea that this activity will decrease
erosion and slow or stop the development of the gully. The other reason is that the
material is not visible to the casual passerby. Even if the discarded material is buried it
will be exposed later when further erosion has occurred.
In terms of human occupation, some chemicals are commonly found, that were used in
earlier times but would be restricted today. A simple example is arsenic, which although
still commonly used in small amounts, was previously used much more extensively. The
same is true for lead, which was commonly used for water pipes and in paint. Both of
these elements, in various combinations, may be found in soil on which humans have
built towns and businesses. Thus these chemicals may be present in appreciable amounts
even if there is no indication that someone is living on or using the land at the present
time.
It is also not safe to assume that contamination must be only at the surface or at a
certain depth and no deeper. Material becomes buried for all kinds of reasons and by all
kinds of activities, and so all sources of information about an area must be investigated,
including historical accounts of activities, such as battles and settlements, that may have
been located in the area.

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11.2. AREA GEOLOGY

Knowledge of the geology of an area can be important in developing and carrying out a
successful sampling plan and avoiding traps and mistakes. Two dramatic examples of this
would be volcanic ash and karst landscapes. Both of these situations are unusual and can
dramatically affect a sampling plan. Volcanic material may contain high levels of gravelsized particles that facilitate movement of contaminants under saturated flow conditions.
These soils often have very small amounts of clay, and this also leads to rapid movement
of contaminants.
Karst landscapes develop in limestone rock and result in surface sinkholes and
subsurface cave systems. In this type of landscape water, soil, and contaminants can
move both on the surface and below it. Material can move to the underground cave
system and then long distances until it emerges in a well, stream, river, or lake. Samplers
need to be aware of the geology of the area in which the sampling is taking place and take
into account the movement of material in different geological localities when developing
a sampling plan.
It might be assumed that water and pollutants cannot move through solid rock, but
exceptions exist. One is sandstone, which can be very porous and allow water to pass
through it as rapidly as it passes through soil or sand. The second is the fact that in many
cases underlying rock is not solid but fractured; that is, it contains many cracks through
which water and pollutants can readily pass. Not knowing the type of underlying rock
and its condition can lead to misunderstanding the fate of a component or contaminant in
the environment.
In certain localities it is possible to have both soil and water move long distances. Soil
can erode from sloping fields, in which case the amount of erosion and the final
deposition of the eroded soil will affect the sampling plan. In addition to the erosion, soil
can move downhill under the pull of gravity. This is termed colluvial movement and can
result in the movement of large amounts of soil and regolith or underlying glacial till
down a hillside, further resulting in significant movement of contamination if present.
Both of these potential sources of movement must be accounted for in a sampling plan. If
they are not, it is likely that not all the contamination will be discovered.
Table 11.2 shows soil analytical results that would be typical for a farm in central Ohio.
At first glance, Table 11.2 does not look unusual except that sample WC-15c has a pH of
7.4, while all the other samples have acid pHs. One might then question the validity of
this pH measurement. Statistical analysis would say that this is an outlier and could be
discarded. However, knowing the geology of this area one would know that the regolith
is basic while the overlying soil is acidic. This indicates that the sample is from an area in
the field that has suffered severe erosion. An inspection of the field would show that this
is indeed the case. Not knowing the geology of an area one would not be aware of this,
and thus accurate data would be discarded without regard to its importance to sampling
and analysis.
Another area of concern is water movement. Water can move rapidly over the surface
of soil and carry contaminants into nearby streams, rivers,

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TABLE 11.2 Soil Analysis Results for a Field in Central Ohio

Soil sample number

1:1

cmolc/kg

pH

CEC

kg/ha
Ca

Mg

WC-15a

5.6

1,200

230

15

200

WC-15b

6.1

10

1,100

340

22

195

WC-15c

7.4

10

1,500

550

10

156

WC-15d

5.9

1,000

320

23

250

WC-15e

6.2

1,100

360

25

245

lakes, and other bodies of water or onto uncontaminated land. It is also possible to have
water moving underground for some distance only to emerge aboveground at some other
locality. All of the area in which the water is moving both below- and aboveground is
important to sample and monitor. In addition to water carrying contaminants out of an
area it can also carry contaminants into an area. Recognizing the potential for movement
of contaminates out of and into an area will greatly simplify sampling.

11.3. KNOWING WHAT IS OR IS LIKELY TO BE PRESENT

For both safety and sampling it is essential to have some idea of the type and amount of
contamination that is known or suspected to be present. The type and amount of
protective equipment and clothing needed by sampling personnel will be dictated by this
information. Relatively innocuous contaminants that do not produce hazardous fumes and
are not toxic will require minimal safety equipment and precautions. On the other hand,
high levels of contamination and contamination with highly toxic materials will require
the maximum in safety equipment and precautions.
The type of sampler and sample container used will be determined by the type of
contaminant thought to be present. Samples thought to contain volatile organic
compounds (VOCs) need to be sampled and placed in sealed containers without
headspace.* This is necessary to prevent the loss of VOCs before the analysis can be
completed. On the other hand, soil to be analyzed for metals need not be stored in
containers that are airtight. However, in this case they must be kept away from metal
contamination, which might occur if they were stored in metal sample containers. Also,
samples stored for metal analysis may lose other contaminants (e.g., VOCs), and thus
borrowing a portion of this sample for some other analysis is not possible.
* Headspace is

the space (air space) between the sample and the top of the container closure.

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11.4. NOT ACCOUNTING FOR INPUTS, LOSSES, AND MOVEMENT

The level of a contaminant in water or soil will depend on the amount added to it, the
losses, and its movement through or out of the field. Although this seems simple and it is,
it is not the total story. It may be that the addition of a contaminant is a single, one-time
event. On the other hand, there may be a continuing addition of contamination. This can
be very confusing if the occurrence, source, and amounts of contamination being added
are not known.
Additions can be made by spillage, but may also be due to water invading the area or
by windborne material. A spill is likely to be known and may indeed be the reason for
sampling. However, if additional material is being brought into the area by water or wind
movement, it will make the sampling seem bad. Samples may show a continuing increase
in contamination when there is no additional spill. The movement of water onto an area
may be evident; however, the fact that it is carrying contaminant may not. On the other
hand, wind may not seem a possible source of contamination when, through the
deposition of airborne dust, it may well be. Analysis of water entering and air over a field
may be essential in understanding what is happening.
Losses of contaminant through percolation, leaching, and erosion may be evident and
measurable. Certainly there will be monitoring wells around the contaminated field, and
from the analysis of the water in these wells the movement of contaminant out of the field
will be known. However, erosion of contaminated soil may not be as easily identified. A
hectare furrow slice of soil weighs approximately 2,000,000 kg, and thus the loss of 500
kg of soil will not be observable. For this reason, losses from this source may go
unnoticed. Likewise, it may be that a small but significant amount of contaminant is
escaping into the atmosphere. This also may be missed.
Mass movement of soil (as in sliding down a hill) can cause movement of associated
contamination. This may mean that the area originally sampled no longer contains the
contaminant, thus requiring samples to be collected downhill from the original sampling
area. Sampling thus needs to follow the direction of the movement of the contaminated
medium. Failure to take this into account can result in an area being declared free of
contamination when all that has happened is that the contamination has moved to a new
location. This can come back to haunt both samplers and remediators.

11.5. PERSONNEL
Businesses will always prefer to hire the least expensive labor they can. Because field
sampling appears to be simple it seems reasonable to hire samplers who have little
education and no background in field sampling. This can and will lead to sampling
inconsistencies that will cause severe and sometimes costly or even deadly mistakes.
These mistakes will be made in six areas. The first and simplest is that the correct field
will not be found or the incorrect field will be sampled. The second set of mistakes will
occur in reading maps and judging distances. The third will occur because representative,
consistent, uniform samples will not be taken. Observing of environmental

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characteristics, maintaining sample integrity, and observing safety rules will be three
more problems associated with inexperienced samplers. It is hoped that only one of these
is the major problem and can easily be rectified. Unfortunately, several of these may
occur in the same sampling event.
For the inexperienced samplers problems start with not finding the correct field, and it
is often the case that inexperienced samplers will sample the wrong field. However, this
can also happen with trained personnel if they are not careful. Often fields and their
extent are not easily recognizable. They will not have GPS references associated with
them. Personnel must rely on tree lines, streams, roads, buildings, and their relationship
to each other to find the correct field.
Assuming the person finds the correct field, how is he or she to set up the sampling
grid? Experienced samplers will be able to accurately judge a grid in a field by picking
out reference points around the field. Inexperienced samplers will take all their samples
from a relatively small, unrepresentative area in a large field. If multiple grids are to be
sampled and multiple subsamples taken from each grid, then such persons will fail to
sample all the grids appropriately. Upon completion of sampling the position of the
samples in the grided area will be unknown.
If samples are not taken from representative places in the field, are taken to different
depths at different places, or are not taken in the prescribed place in the field, the analysis
of these samples will be accurate but may not be representative of the field. These
eventualities will come about because areas are hard to get to, it is harder to insert the
sampler in some places than in others, and some designated places in the field will not be
found.
Another concern is that samplers understand environmental factors affecting sampling.
Often variations in layers and direction of movement of the medium being sampled are
not taken into account. This leads to mixing of samples from different layers in one
sample container. Other mistakes would be not noting changes in layer thickness or
density in the project notebook and not taking these into consideration in obtaining the
sample. For instance, if the A horizon is specifically being sampled and it becomes thin
in an area, it is not acceptable to include the B horizon in the sample just to make it the
same depth of other sample cores. In this case, this variation needs to be detailed in the
project notebook so that later evaluation of variations in the A horizon and how they
affect sampling and analytical results can be made.
The inexperienced sampler will often not be careful in maintaining the integrity of the
samples. This may mean that the sampling tool is not cleaned between samples, that care
is not taken in getting all the sample in the container, or that the container is not sealed or
is not placed in the proper transportation box. It might also mean not taking care to
protect the sample from heat, cold, light, and contamination after sampling or not
transporting it rapidly to the analytical laboratory. An additional problem with the
inexperienced sampler is in not being careful to make sure that all data are carefully
recorded in the project notebook. Careful recording of field notes is essential in later
interpretation of analytical results and applying them to the remediation of a field
problem. These notes are also essential in deciding if data are correct and if extraneous or
suspicious data need to be kept or discarded. This is especially important during
statistical analysis of analytical results.

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11.5.1. Using GPS

A particularly effective way to solve many of these problems is with the use of GPS.
Fields can be unequivocally located using GPS, and waypoints or sampling sites can be
located and their positions programmed into the GPS instrument being used. In this way
the location of the field and sample sites therein are known and the sampler can locate
them by referring to the GPS unit. Both experienced samplers and inexperienced
samplers will need training in reading, interpreting, and recording GPS data. It is
essential that the person sampling be able to accurately read and record GPS data in the
project notebook. This is particularly important if the sample is not taken at the exact
location specified but nearby, or if the field is to be repeatedly sampled. While learning to
use a GPS instrument it is important that samplers practice sampling under the
supervision of an experienced sampler.
It might be thought that having the sampler physically mark the sampled sites would
solve this problemit does not. With inexperienced samplers, checking sampling
markers placed at the sampling sites will show that the field was not sampled correctly.
The solution to this problem would be for the field to be resampled correctly. Time is an
important component of sampling, and resampling may not be possible for several weeks
after the original sampling event because of weather or work schedules. Thus, the
original samples will not be comparable to the later samples. For some situations it may
be critical for the success of the sampling and remediation process that samples be taken
at a particular time. In this case resampling can have a large detrimental impact on the
whole sampling project [2]. Common mistakes made by inexperienced samplers are
summarized in Table 11.3.
11.5.2. Safety
Safety will also be of special concern, especially for inexperienced field samplers, and
the first concern is for the safety of the person doing the sampling. This is due to the fact
that some samples or fields can be dangerous to human health, and this fact may only be
discovered after analysis is complete. All workers must observe all safety rules at all
times. In addition to this being important for the person doing the sampling, it is also
important for persons helping with the sampling. The second concern is for the safety of
sampling equipment and the samples already taken. In the sampling process money and
time is expended in purchasing and maintaining sampling tools and in obtaining the
samples.

TABLE 11.3 Mistakes Made by the Inexperienced Sampler

Field

Not finding the field and the corresponding field map

Sampling

Taking samples from the incorrect places in the field

Sample size

Not taking samples from the same depth at each site

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285

Horizons

Not noting changes in horizons and direction of movement

Project notebook

Not recording all observations in the field notebook

Safety

Two aspects
1. Not following safety rules
2. Not operating and maintaining equipment safely

Sample handling

Not handling samples in the prescribed manner

11.6. ANALYZING OR SAMPLING FOR THE WRONG COMPONENT

An ammonia spill occurs in an open field. The weather and soil are warm and there is a
gentle misting rain each evening keeping the soil moistened at field capacity. Several
weeks after the spill, soil and water samples are taken. Ammonia levels are found to be at
acceptable levels and so the assumption is made that there should be no concern about the
spilled ammonia. It is obvious that much less ammonia has been spilled than was
reported. A week after the sampling, analysis, and declaration that no problem exists,
several babies in nearby houses that use well water for drinking come down with blue
baby syndrome [3]. Could there be a connection?
Under the soil and environmental conditions described above ammonia is rapidly
oxidized, first to nitrite and then to nitrate, which subsequently leaches into the
groundwater. Under the conditions described soil bacteria can convert kg of ammonia to
nitrate per day. Thus in a very short period of time the level of ammonia is back to its
background level. In this case analysis should be not only for ammonia, but also for
nitrate.
A company is accused of dumping chromate, specifically chromate(VI), which has
many adverse health affects, on a field. Soil analysis shows only the occurrence of small
amounts of Cr(VI). In this case it is important to know that Cr(VI) is quickly converted to
Cr(III) in soil, and so this is the species for which the soil should be analyzed.
The types of changes illustrated above can also occur with organic contamination. For
example, a monitoring well at a landfill that had been closed and capped years before was
observed to have rapidly increasing levels of vinyl chloride, which had some other
contaminants associated with it. It was hypothesized that illegally dumped or lost drums
of vinly chloride were the source of this chemical in the wells. However, all compounds
were found to be chemical and biological decomposition products of solvent mixtures in
decomposing drums 10 ft deep in the landfill.

11.7. ANTAGONISMS AND INTERFERENCES

There are numerous antagonisms between analytes and between analytes and matrices.
For instance, it is possible for two different compounds to elute from a gas
chromatograph column at the same time, thus obscuring the occurrence of both
compounds. Often a matrix will mask the occurrence of an analyte, making it appear not

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to be present. The analytical laboratory can change analytical and extraction procedures
to take into account different retention times or other confusing interactions with
analytical methods so that an accurate measurement of the analyte can be made.
These types of method adjustments cannot be made without the laboratory having a
complete history of the field as well as the nature and levels of contamination present.
However, in some cases, well-meaning but sometimes not well thought out actions of the
persons submitting a sample will result in interferences. A good example of this is a field
that was used as a wood treatment facility and was heavily contaminated with both
organic and inorganic contaminants. Soil cleanup was being done by arc furnace, which
reduced the soil to ash. The ash was analyzed for such compounds as benzene,
naphthalene, polyaromatic hydrocarbons (PAHs), and pyrenes to ascertain if they were
within regulatory limits. Purge and trap was used for benzene, the other components were
analyzed by extraction, and initially none of these compounds was found in the ash.
After 2 months and hundreds of samples benzene started to be observed in samples.
However, its recovery was poor and the observed concentrations inconsistent, varying
from sub-ppb to 50150 ppb levels. Little change happened during the following 2 weeks
of checking and further testing except that the recovery levels got worse and more erratic.
During this time the client asserted that no change had been made in its sampling
procedures and so the problem had to be in the laboratory procedures. After another 2
weeks the client admitted that it had started adding lime to the samples before
incineration.
It was determined that the poor recoveries and inconsistent analytical results were
attributable to this lime addition. During incineration lime was reduced and when mixed
with the ash produced cement. Thus when water was added to the samples during
extraction the contents were solidifying and this interfered with the purge and trap
process. This explained the erratic results, but not the occurrence of benzene in the
sample because it should have been destroyed during incineration. At this point the client
again said that nothing had changed in its procedures that would account for the
appearance of benzene.
It turned out that the client had begun using water to cool the ash when it exited the
furnace. The cooling water was being taken from an open pit at the field, and was
contaminated with various chemicals leached from the contaminated fields soil and into
the water in the pit. Benzene was the most mobile of these chemicals and so was the first
to show up during analysis. Water in the pit was found to contain benzene in excess of
several hundred ppb. The good intention of cooling the waste ash to speed the process
resulted in several hundred tons of ash and soil being passed through the furnace, again at
considerable expense.
This illustrates the incompatibility of procedures being used at the sampling field with
those being used in the analytical laboratory. Note here that a detailed description in a
project notebook of procedures being carried out in the field would have greatly
facilitated finding the source of the problem and correcting it and would have saved
considerable time and money.

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11.8. SAMPLE ANALYSIS MISMATCH

Two of the most common mistakes in the commercial laboratory are not considering
either all the aspects of the sample that is being analyzed or the basic question that is
being asked; that is, can the sample be tested for the analyte in question or will the
sample preparation or analysis introduce too many problems? An example would be
looking for VOCs in a solid sample that needs to be ground before sample extraction. The
extra sample preparation and handling required will result in VOC loss unless steps are
taken to prevent it. The sample may have to be handled under an inert gas, at a reduced
temperature, or by manipulation within a sealed environment. The resulting headspace as
well as the original sample then needs to be analyzed.
Another example of a sample and test mismatch would be the extraction of a plastic or
resin polymer sample with an organic solvent that could partially or fully dissolve the
underlying polymer base. A sample that contains plastic fragments may have some
plastic dissolve while it is being extracted using a large volume of methylene chloride,
and this may interfere with subsequent analysis. Some of the dissolved plastic will
precipitate when using solvent evaporation methods to concentrate the solution to the
final analytical volume. This may result in a sample being impossible to analyze because
either the whole sample solidified or part of the component of interest is dissolved in or
sorbed by the precipitated plastic.

11.9. EXTRACTION OR METHOD ERRORS

Analyzing a sample for a target analyte may require solvent extraction and subsequent
concentration. At this point in the analysis the concentrated solvent may be incompatible
with the instrument or detector stipulated in the original method. As an example, a water
sample analyzed for pesticides is extracted using diethyl ether and is then concentrated
and dissolved in methyl tertiary butyl ether (MTBE). This concentrated extract is then
analyzed using a gas chromatograph and an electron capture detector. For ether extracts
and solvents detector response is acceptable and there is no interference with target
compounds.
If on the other hand an equally common extracting solvent, methylene chloride, is used
in the extraction and subsequent concentration, an acceptable detector response will not
be obtained with this prescribed detector. The extraction and concentration steps will
proceed well and the final concentrated analytical sample will look good. Indeed, it may
even look like the MTBE extract described above. However, when the sample is injected
into the gas chromatograph the electron capture detector, which is not compatible with
this solvent, will become saturated with methylene chloride, requiring several hours of
cleaning before it can again be used for the desired analysis.

Field sampling

288

11.10. SAMPLE/TEST CONTAINER ERRORS

Sampling one type of matrix using the wrong type of container or preservative can have
dramatic and catastrophic effects on the data obtained from the sample. An example of
this is the use of plastic containers to transport and store samples to be analyzed for
organic contaminants. Plastics commonly contain phthalates, which are a class of organic
compounds used to give a plastic flexibility. Small amounts of these compounds can
readily leach out of plastics and interfere with subsequent analytical procedures.
Phthalates could also be extracted by the organic compounds in the sample being
analyzed.
Samples can also be contaminated by using a batch of sample containers that are not
properly cleaned and by not cleaning sampling equipment thoroughly between uses.

11.11. IMPROPER SAMPLING TECHNIQUES

Inattention to sampling methods can lead to errors in sample analysis. An example would
be leaving headspace in a sampling container intended for VOC analysis. Sample
components will volatilize into the headspace at different rates, depending on their vapor
pressures. This leads to an uncharacteristic sample and erroneous data, which can lead to
inappropriate actions being taken in the cleanup of the field.
When sampling soils, great care needs to be taken to ensure that the threads, the lid of
the container, and the seals are clean and free of particles. Such particles can prevent
proper sealing and subsequent loss of sample through vapor loss, evaporation, or leakage.
It is imperative that care be taken to make sure that a representative sample is
collected. This point is especially important for soil or other solid samples, especially
when distinct layers are present. It is equally important in situations in which liquid
samples are made up of several immiscible layers. Failure to note this and ensure that a
representative sample or samples comprising all the fractions or layers is taken will result
in erroneous data and analytical results.
One way to handle this problem is to sample each of the distinct layers or fractions
individually and separately. Each of these fractions would be analyzed using the
procedure appropriate to either the type of material or the contaminants it contains. The
resultant analytical data can be put together to produce a composite picture of the
contamination in the field; for example, if the samples are taken from a pile of excavated
soil, the outside of which may be lower in contaminant because of exposure to light and
air. In this case samples can be taken immediately after excavation or from both surface
and subsurface layers in the pile. The resulting analytical results can be combined to
describe the concentration gradients in the pile.

11.12. VARIATIONS IN METHOD

Variations in extraction techniques can change analytical results and interpretation. This

Traps, mistakes, and errors

289

could be almost anything, such as using the wrong solvent or even using a different
amount of solvent at some stage in the extraction. Variation in the time of extraction, not
using prerinsed glassware, and not using prerinsed drying agent can also lead to sample
contamination or loss. This is one reason for extraction surrogates. They provide a
reference for extraction efficiency. Most extraction methods have set limits for the
extraction efficiency of the surrogates as per the method. When the efficiency is within
limits the data will be readily acceptable. If the solvent recoveries are outside acceptable
limits the extraction is suspect and must be redone.
For clean and relatively low viscosity samples extracts will produce good results. Dirty
or highly viscous samples are problematic and may produce erratic results. For a number
of reasons potential problems from dirty or viscous samples should be considered before,
during, and after analysis and review to determine the usefulness of the data.

11.13. MOVEMENT OF A CONTAMINANT

The movement of a contaminant is usually derived from the sites underlying hydrology.
The water table will move the contaminant plume mainly in the direction of the water
flow. This is especially true for those chemical compounds with very high solubility, for
example, MTBE. For contaminants with low solubility in water the diffusion rate from
the point of contamination will be much lower. Soil, water, and air sampling must always
be carried out downstream from the point of contamination. This does not mean that
sampling to the side, uphill, upstream, and upwind from the contamination is not
necessary. It is. This goes along with mass movement of soil as noted above, which must
also be kept in mind.

11.14. STATISTICAL ERRORS

In looking for sources of sampling errors most literature searches will provide a multitude
of references that are primarily statistical analyses. These are books and papers that show
how statistics can be used to detect such things as errors. However, the use of the
incorrect statistical tool or method, including the incorrect use of hypothesis or method of
calculation, the use of an incorrect table, or the incorrect interpretation of the statistical
results in the analysis of data, are dangerous traps which must be avoided. To do this it is
highly recommended that an experienced statistician be part of the investigatory team or
be used in doing the statistical analysis on the data [4, 5].

11.15. CONCLUSIONS
Many traps, mistakes, and errors can take place during sampling and analysis of
environmental samples. Personnel and activities in the field are the two biggest sources of
errors in sampling and analysis. Knowing the history of an area, its geology, what is
present, and the rates of inputs, losses, and movement is also important to accurate

Field sampling

290

sampling. In the analytical procedures, analysis for the wrong component, antagonisms
between analytes, sample analysis mismatches, and extraction using the wrong method
are important sources of errors. The characteristics of the environment and movement of
contaminants in that environment are important considerations. The use of proper
statistical tools is essential in obtaining good sampling results.

QUESTIONS
1. Describe the training personnel should have before beginning to field sample.
Include all aspects of sampling.
2. Think of an example in which knowledge of the history of a field would be
important in developing a sampling plan for that field.
3. A soil sample reported to be contaminated with lead is sampled and the analysis
shows a lead level of 10 ppm. What would you need to know before deciding that the
field from which the sample came needed to be remediated to remove lead?
4. A soil supposed to be contaminated with hydrocarbons is extracted with aqua regia
(a strong acid). The result is a solution that cannot be analyzed for hydrocarbons. Explain
why this is the case. What would aqua regia be expected to extract from a soil sample?
5. The results of analysis show that in week 1 the level of zinc in a field was 120 ppm.
The sample from a week later showed a level of 140 ppm. It is assumed that the analysis
is in error. What other explanation could there be for this increase, assuming it is not an
error?
6. Iron (Fe) in soil reacts with phosphate to form insoluble precipitates. After the
application of phosphate fertilizer to a field what would be expected to happen to the
level of soluble iron in the soil?
7. A field is contaminated with large amounts of nitrate. A 0-to-20-cm surface sample
from this field shows little nitrate. Does this mean that the nitrate has disappeared from
the soil? Where would you sample to make sure the nitrate is not in the soil? If the nitrate
is not in the soil, where might it be?
8. A sample extract used to remove VOCs from a sample is analyzed by atomic
absorption. An absence of metals is seen in the results of the analysis. Can you explain
why this might be the case?
9. A statistical analysis of the results of a series of extracts of the same soil shows a
large variation in the results. Is this to be expected?

Traps, mistakes, and errors

291

REFERENCES
1. Leschber R. Sampling: Fundamental aspects. In: Gomez A, Leschber R, LHermite P,
eds. Sampling Problems for the Chemical Analysis of Sludge, Soils and Plants. New
York: Elsevier Applied Science, 1986:2.
2. Gomez A, Leschber R, Colin F. Sampling techniques for sludge, soil and plants. In:
Gomez A, Leschber R, LHermite P, eds. Sampling Problems for the Chemical
Analysis of Sludge, Soils and Plants. New York: Elsevier Applied Science, 1986:80,
81.
3. Nitrates and Blue Baby Disease. Florida Department of Health,
http://www.doh.state.fl.us/environment/water/SUPER_Act_website/watertox/nitrate.htm
2003.
4. Myers JC. Geostistical Error Management: Quantifying Uncertainty for Environmental
Sampling and Mapping. New York: Wiley, 1997.
5. Smith PL. A Primer for Sampling Solids, Liquids, and Gases: Based on the Seven
Sampling Errors of Pierre Gy. Asa-Siam Series on Statistics and Applied Probability.
Philadelphia: Society for Industrial & Applied Mathematics, 2001.

Appendix A
Abbreviations and Acronyms
A

Estimated soil loss using the USLE

afs

Acre furrow slice

AM/FM

Automated mapping/facilities management

AMU

Atomic mass unit

APHA

American Public Health Association

ATT

Abbreviations and acronyms and terms

AWWA

American Water Works Association

BMP

Best management practice(s)

CADD

Computer-aided design and drafting

CD

Compact disk

CD-R

CD-record only

CFC

Chlorofluorocarbon

CHP

Chemical hygiene plan

COC

Chain of custody

DAAC

Distributed active archive centers

DGPS

Differential global positioning system

DI

Deionized (usually water)

DO

Dissolved oxygen

DOQ

Digital orthophoto quadrangle

DOQQ

Digital orthophoto quarter quadrangle

DOT

Department of Transportation

DVD

Digital video disk

DVD-R

DVD-record only

EDD

Electronic data deliverable

EH&S (EHS)

Environmental health and safety

EOS

Earth observatory system

EPA

Environmental Protection Agency

EROS

Earth resources observation systems

F statistic

FAA

Federal Aviation Administration

GIS

Geographic information system

Appendix A

293

GMT

Greenwich mean time

GPO

Government Printing Office

GPR

Ground-penetrating radar

GPS

Global positioning system

hafs

Hectare furrow slice

HMIS

Hazardous material identification system

ISE

Ion selective electrode

Hydraulic conductivity

LD50

The dose at which 50% of test animals die

LIMS

Laboratory information management system

MCL

Maximum contamination level

MDL

Minimum detection limit

MSDS

Material safety data sheets

MSE

Mean square for error

MST

Mean square for treatments

NAD-27

North American Datum-1927

NAD-83

North American Datum-1983

NAPL

Nonaqueous phase liquid

NASA

National Aeronautics and Space Administration

O3

Ozone

OSHA

Occupational Safety and Health Administration

PAH

Polyaromatic hydrocarbons

PCB

Polychlorinated biphenyls

PM

Project manager

PM10

Particulate matter 10 m or smaller

ppa

Parts per quintillion

ppb

Parts per billion

PPE

Personal protective equipment

ppm

Parts per million

ppq

Parts per quadrillion

ppt

Parts per trillion

RCRA

Resource Conservation and Recovery Act

RFA

Request for analysis

RUSLE

Revised universal soil loss equation

RWEQ

Revised wind erosion equation

Standard deviation

s2

Sample variance

Appendix A

294

SCF

Supercritical fluid (extraction)

SPE

Solid phase extraction

SSE

Sum of squares for error

SST

Sum of squares for treatment

STP

Standard temperature and pressure

t-statistic

TCP

Transport control plan

theta

Effective porosities

TPH

Total petroleum hydrocarbon

TOPO

Refers to topographical map

USB

Universal serial bus

USEPA

United States Environmental Protection Agency

USLE

Universal soil loss equation

UTC

Universal time coordinate

UTM

Universal transverse mercator

VOC

Volatile organic compound

WAAS

Wide area augmentation system

WEF

Water Environment Federation

WEQ

Wind erosion equation

Appendix B
Sources
SAMPLERS
Clements Associates Inc.
1992 Hunter Avenue
Newton, IA 50208
Giddings Machine Company, Inc.
401 Pine Street
P.O. Drawer 2024
Fort Collins, CO 80522
MODELING
Rock Ware
2221 East Street
Suite 101
Golden, CO 80401
ERSI
380 New York Street
Redlands, CA 923738100
GENERAL SUPPLIES AND CONTAINERS
Eijelkamp
P.O. Box 4, 6987 ZG Giesbeek
Mijverheidsstraat 30
6987 EM Giesbeek
The Netherlands
Spectrum Laboratory Products
14422 South San Pedro Street
Gardena, CA 902482027
Gemplers
100 Country Side Drive
P.O. Box 270
Bellsville, WI 53508
SAMPLE ANALYSIS
Elabs, Inc.
8 East Tower Circle
Ormond Beach, FL 32174
SAFETY

Appendix B

296

Ullom Safety Resources, Inc.

P.O. Box 340601
Beaver Creek, OH 454340601
REFERENCE SOURCES FOR SAMPLING METHODS AND SAMPLE
ANALYSIS
USEPAhttp://www.epa.gov/epaoswer/hazwaste/test/main
ASTMhttp://www.astm.org
APHAhttp://www.apha.org/media/
AWWAhttp://www.awwa.org/
WEFhttp://www.wef.org/
OSHAhttp://www.osha.gov/
ASTMhttp://www.astm.org/

Index

Abandoned city, 79
Abandoned village, 79
Abbreviations, 17
see also appendix A, 299
Abrasion resistant glove, 73
Absorption through skin, 93
Accelerated erosion, 189
Acetone, 18
Acid, 9, 14, 32, 226, 2346
Acid fumes, 93
Acidic reduction, 256
Acidification, 9, 26
Acids, 9, 14, 88, 93
Acre, 17
Acronyms, 17
Actinomycetes, 239
Action levels, 187, 280
Advective dispersion, 186
Aeration, 42
Aerial maps, 109
Aerial photograph, 10, 21, 63
Aerobic, 9, 27
Aerobic environment 241
Aerobic soil, 184
Africa, 26
Afs, 17
Agriculture, 4, 5, 14, 20, 36, 63
Agricultural chemicals, 1313, 141, 286
Agricultural fertilizer, 131
Agricultural field, 66, 131, 134, 236
Agricultural sampling, 140
Aircraft, 10, 18, 19, 79, 120
Air sampling, 70
Air shipment, 215
Alaska, 35
Alcohol, 14, 242
Aldehyde, 242
Alfisol, 8
A-line, 40
Alkali metals, 231

Index

298

Alkanes, 238, 242

Alkenes, 238, 242
Alkylbenzene, 240
Alkynes, 238, 242
Alluvial fans, 47
Altitude, 20, 111, 115
Aluminum, 2267, 229, 231, 233, 235
Aluminum oxides, 36
Amalyase, 245
Amendments, 48
American Public Health Association, 110
American Society for Testing Materials, 110
American Water Works Association, 110
Amines, 99
Amino acids, 239, 242
Ammonia, 5, 27, 55, 187, 231, 236, 292
Ammonia gas, safety, 98
Ammonium, 231, 232
Ammonium hydroxide, 88
Ammonium nitrate, 236
Amount of sample, 1235, 252, 257
Amylase, 245
Anaerobic, 5, 24, 27, 29, 35, 93, 137, 185, 237, 248
Analysis of data, 296
Analysis of variance, 158, 160, 163
Analyte, 5, 132, 151, 252, 257, 292, 293
Analytical data, 11, 13, 15
Analytical laboratory, 13, 14, 15, 54, 55, 75, 76, 2112, 215, 218, 219, 221, 253, 293
Analytical measurements, 2523
Analytical methods, 2, 15, 30, 36, 109, 125, 127, 132, 135, 233, 264, 292
detailed, 15
metals, 15
organics 15
pH and 15
rapid, 15
Analytical procedure, 14, 28, 36, 53, 64, 76, 159, 208, 247, 253, 257, 265
Analytical report, 257
Analytical sample, 294
Analytical specifics, 2758
Analytical strategy, 252
Analytical testing, 265
Analyzing for wrong component 292
Andisol, 6, 35
Anhydrous ammonia, 102
Anhydrous sodium sulfate, 271
Animal(s), 5, 31, 32, 133, 192, 207, 213, 229, 235, 247, 248
Animal cells, 246
Animal holes, 181, 247

Index

299

Animal released enzymes, 245

Animal tracks, 247
Anion exchange capacity, 136, 233
Anions, 233
ANOVA, 161, 163
Anoxic, 29
Antagonisms, 292
Antennas, 18, 114
Anthracene, 240
Anthropogenic, 239
Antibiotics, 54
Ants, 247
Aqueous environment, 238
Aqueous phase, 185
Archival samples, 213
Arc View, 79, 139
Argon, 26, 27, 225, 228
Aridisol, 6, 35
Armed forces, 19, 79
Aromatic compounds, 14, 239
Arsenic, 14, 100, 226, 229, 286
Aspergillus, 239
Aspirin, 239
Assumed conditions, 186
Atmosphere, 9, 245, 28, 150, 186, 190, 202, 225, 226, 227, 248
Atmospheric air, 9
Atmospheric samples, 137, 138
Atomic absorption spectrometry, 267
Atomic emission spectrometry, 267
Atomic spectrometric methods, 2679
Atomic spectroscopy, 256
Attenburgh limits, 40
Auger samplers, 68, 70
Automatic sampler, 73
Average, 146, 152
Average concentration, 136
Bacillus, 239
Background level, 226
Backup, 77
Bacteria, 238
Balance, 55
Bar code, 59, 73, 76, 143, 217
Barium, 231
Basalt, 31
Base:
cations, 247
fumes, ammonia, 93

Index
Basic, 226
soils, 236
Basic safety, 87
Batch Chain of Custody, 217
Bathroom, 53
Bats, 31
Batteries, 114, 219
Beakers, 55
Bedrock, 24
Bell-shaped curve, 150, 151
Below detection limits, 279
Benzene, 239, 240, 293
Benzene rings, 239
Benzo[a]pyrenes, 241
Biased data, 158, 162
Bicarbonate, 234
Bioaccessability, 189, 226
Biochemical molecules, 225, 245
Biological availability, 226
Biological characteristics, 2, 5, 8, 36
Biological component, 245
Biological condition, 24, 27, 29
Biological decomposition, 238, 292
Biological nitrogen fixation, 236
Bioremediation, 128, 141, 197, 237
Biphenyl, 240
Bleeding, 99
Block kriging, 171
Boron, 237, 242
Bottle kit, 212, 261
Broadcasted chemicals, 131
Bromine, 230, 237, 249
BTEX, 240, 243
Bulk density, 16, 424, 64, 129
Buried objects, 4, 19, 47, 79
tank, 4, 79, 178
soil, 33
waste, 190, 286
Cables, 4, 79
Cadastral questions, 119
Calcium, 131, 227, 231, 234, 235
Calcium carbonate, 27, 118, 234
Calculators, 146
Calibration of model, 188
Canada, 35
Capacity coefficient, 186
Capillaries, 48

300

Index

301

Carbohydrates, 248
Carbon, 225, 227, 228, 230, 237
Carbonate, 118, 230, 233, 234, 237
Carbon dioxide, 9, 26, 27, 32, 185, 193, 2257, 230, 233, 234, 236, 242
Carbonic acid, 27
Carbon monoxide, 9, 230
Carcinogenic materials, 4, 240
Caribbean, 26
Catastrophic lake turnover, 29
Catastrophic loss, 264
Cation exchange, 131, 136, 189, 232, 244
Caves, 31, 79, 177, 287
CD recordings, 77, 219
Cellular components, 246
Cellulose, 242, 245, 246
Cell walls, 247
Cement, 293
Center frequency wavelength, 117
Central tendency 152
Cesium, 231
Chain of custody, 14, 53, 59, 76, 81, 143, 158, 206, 208, 21522, 261, 262, 264, 284
Charged molecules, 28
Checks, 284
Chelates, 245
Chemical characteristics of soil, 5, 32
Chemical condition, 24
Chemical decomposition, 256
Chemical environment, 137
Chemical equation, 185
Chemical equilibrium, 185
Chemical flux, 200
Chemical hygiene plans, 73, 84, 104
Chemical instrumentation, 196
Chemical integrity, 30, 70
Chemical methods, 256
Chemical model, 184, 186
Chemical phenomena, 185
Chemical principles, 185
Chemical properties, 247
Chemical rate, 186
Chemical reaction, 32, 245
Chemical resistant gloves, 73
Chemical species, 27, 185
Chemical storage, 53
Chemical transport, 186
Chemical type, 185
Chemicals in soil, 4, 5, 192
Chlorinated compounds, 238

Index

302

Chlorine, 225, 230, 237

Chlorofluorocarbon, 239
Chromatography, 2723
Chromium, 189, 231
species, 292
Cinders, 35
Cinnamonaldehyde, 239
Clay, 4, 8, 246, 34, 3644, 64, 110, 177, 187, 189, 226, 231, 233, 247, 287
Clay minerals, 246
Clayey soil, 66, 110, 137, 186
Cleanliness, 259
Cleanup plan, 64, 65
Climate, 32
Coal ash, 237
Coarse sandy soil, 50
Cobalt, 229, 231
Cobbles, 39
Coefficient of linear extensibility (COLE), 40
Colloidal, 30, 192
Colloidal carbon, 228
Colloidal organic matter, 244
Colluvial, 47, 287
Color, 10, 58
Color scale, 201
Commercial carriers, 215
Commercial computer models, 197200
Commercial laboratory, 15, 58, 76, 252, 253
Commercial resources, 80
Communication, 95, 284
Communication lines, 19, 116, 117
Compacted layer, 17, 48, 58, 201
Comparing areas, 161
Comparing sample means, 155
Compasses, 115
Complex matrices, 257
Component characteristics, 4
Composite samples, 125, 126
Computer, 53, 59, 77, 79, 118, 119, 120, 146, 176, 186, 191, 197, 200, 21820
Computer chain of custody, 2179
software, 80, 217
Computer models, 13, 197
Computer monitoring, 214
Computer simulation, 80
Computer software programs, 80
Conductivities, 181
Confidence interval, 1568, 160
Confidence level, 141
Conifer, 36

Index

303

Conservation practice, 190

Constants, 186
chemical, 176
physical, 176
contact person, 220
Container errors, 294
Containers, 10, 12, 13, 14, 53, 715, 123, 125, 207, 208, 252, 294
Contaminants, 45, 8, 10, 11, 13, 14, 15, 19, 246, 35, 403, 49, 53, 54, 67, 79, 84, 120, 126, 136
8, 142, 181, 184, 190, 200, 225, 247, 285, 287
additions, 289
level, 288
loss, 288
metal, 121
movement, 13, 110, 287, 288, 289, 296
organic, 122
type, 67
Contaminated area, 4, 11, 72, 127, 138, 140, 141
Contamination, 4, 6, 11, 14, 15, 19, 31, 44, 58, 65, 66, 70, 75, 76, 95, 12830, 178, 198, 200, 270,
293, 295
concentrations, 103
episodic, 131
MSDS sheets, 84, 86, 1046
natural levels, 103
protective equipment, 288
route into body, 103, 104
types, 67, 103
VOC, 104
Continuous core, 68
Contour strip cropping, 190
Controls, 127, 20910, 226, 285
Coordinates, 111, 113
Copper, 55, 229, 231
Coregionalization, 172
Core sampler, 67, 68, 71, 121, 122, 125, 226
Corrected signals, 78
Correlation, 119
Correlation of data, 198
Correlograms, 1645
Corrosive, 73
Counties, 120
Creosote, 64
Crimp on caps, 73
Crimping tool, 73
Crop, 5, 8, 72, 131, 132
Cross-contaminates, 54, 122
Cross-sectional view, 198, 199
Currents, 8, 138
Cutoff level, 158

Index

304

Cyanide, 55
Cyclic change, 192
DAAC, 79
Dam, 173
Data assessment, 278, 279
Data reduction, 252
Datum, 113, 115
DDT, 241
Dead Sea, 32
Decompose, 73, 192
Decomposing rock, 31, 192
Decomposition, 185, 246, 247
Decontamination, 73, 94, 99, 101
Deeds of sale, 65
Definitions, 17
Degrees of freedom, 146, 155
Deionized water, 54, 55
Delta, 47
Density, 424, 48, 237, 238
Department of transportation, 78
Depressional area, 16, 32, 130
Desktop computer, 218
Detailed sampling, 1279
Detergents, 55
DGPS, 78, 114
Dibasic phosphate, 235
Dieldrin 186
Diethyl ether, 18, 294
Differential GPS, 77, 78, 113
Differential partitioning, 273
Diffusion, 27, 186, 196
Digital cameras, 219
Digital orthophoto quarter quadrangles, 10, 61, 63, 139
Direct methods, 255
Dirty glassware, 295
Disinfection, 53
Dispersion, 159, 193
Dissolved gases, 28
Dissolved oxygen (DO), 252
Distillation, 54
Distributed Active Archive Center, 79
Documentation, 264
DOQQ, 11, 61, 62, 139
Dose, 106
Drainage tiles, 79
Drying, 54, 205
Dump sites, 65, 286

Index

305

Duplicate samples, 125

Dust bowl, 26
DVD recording, 77, 219
Dynamic complex models, 1927
Dynamic equilibrium, 185
Dynamic model, 177, 192, 197
Earth Observing System, 79
Earth Resources Observation Systems, 79
Earths surface, 5, 10, 12, 1920, 256, 30, 31, 39, 63, 111, 113, 11820, 142, 201, 225, 230, 236
Earthworms, 245
Easements, 119
EDD, 280
EDTA, 245
Effective porosities, 13
Electrical conductivity, 64
Electric lines, 116, 117
Electrical power substation, 64
Electricity, 53, 54
Electroanalytical analysis, 274, 275
Electrodes, 181
Electromagnetic radiation, 19, 117
Electromagnetic spectrum, 19, 118, 120
Electron capture detector, 294
Electronic deliverable form, 279
Element, 18, 2258
Elemental carbon, 237, 286
El Nio, 120
Emergency equipment, 66
Emergency numbers, 73
Empirical components, 188
Energy source, 49, 185, 189
Engineering, 5, 8, 36
Engineering classification of soil, 39
Entisol, 8, 35
Environmental abbreviations, acronyms, and terms, 17, 172
see also appendix A, 299
Environmental analysis, 273
Environmental characteristics, 4, 15, 24
Environmental conditions, 3, 113, 292
Environmental harm, 141
Environmental Health and Safety, 86
Environmental measurements, 164
Environmental modeling, 164, 1835, 192, 197, 201
Environmental pollutants, 244
Environmental problems, 172
Environmental protection, 105
Environmental Protection Agency, 80, 110, 281

Index
Environmental sampling, 134, 284
Enzymes, 245, 246, 248
EOS, 79
EPA, 81, 281
Equal mass samples, 43, 44
Equilibrium, 185, 192
Erodability, 190
Eroding soil, 15, 65, 190
EROS, 79
Erosion, 4, 8, 15, 32, 34, 47, 189, 197, 286, 287
Erosion control, 63, 18990
Erosive factor, 189
Error check, 257
Errors, 3, 110, 115, 141, 284, 285, 288, 294, 296
concentration, 272, 273
reflected multipath, 115
plastic containers and, 294
Escarpments, 61
Estimated soil loss, 189
Ether, 18, 30, 181, 241, 242
Ethylbenzene, 240
Ethylenediaminetetraactetic acid, 245
Evaporation, 26, 27, 32, 184, 190
Evaporation pan, 184
Evapotranspiration, 1834
Exchange resins, 136
Exchange sites, 246
Exosphere, 26
Expanding clay, 35
Explosion proof fan, 54
Explosive, 19, 79, 87
Extracellular enzymes, 245
Extraneous values, 128, 146, 158
Extraction, 256, 265
concentration, 272, 293
efficiency, 295
errors, 294
methods, 267, 268
surrogates, 295
FAA, 78
Face mask, 96, 97
Farm building, 53
Farmland, 131
Farm-setting, 20, 54
Fats, 246, 248
Fatty acids, 242
Federal Aviation Administration, 78

306

Index

307

Federal Express, 215, 262

Feed, 213
Feedback loops, 192
Fertilizer(s), 16, 54, 118, 131, 132, 141, 197, 189, 213, 236
Field, 25, 10, 14, 15, 19, 84, 189, 190, 191
Field analysis, 252, 253
Field calibration, 284, 253, 264
Field characteristics, 2, 64, 284
Field history, 65, 78, 284, 287, 293
Field information sheets, 259, 264
Field map, 5963, 285
Field office, 10, 47, 53, 75, 80, 178, 219
Field office laboratory, 15, 53, 545, 76
Field office laboratory samples analysis of, 214
Field parameters, 252
Field safety, 1013
Field sampling, 2, 3, 16, 17, 54, 151, 184, 190, 201
Field site, 2
Field test, 188, 252
Final report, 252
Fine sand, 38
Fine-textured soil, 67
Finite-difference algorithims, 200
Flame emission photometry, 267
Flammable, 4, 87
Flammable gas detectors, 55
Flash cards, 219
Flash memory, 219
Flat field, 130
Flat plane, 32
Float, 192
Flood, 5, 24, 47, 119, 178
Flood plane, 47
Flood waters, 29
Flooding, 24, 178
Floppy disks, 219
Florida, 236
Flow diagram, 196
Fluid layers, 25
Fluorine, 230
Forest soils, 232
Fractured rock, 13, 30, 177, 192, 287
Frozen, 6, 35
F-statistic, 162, 163
F-table, 163
Fuels, 18, 55, 66, 238
Full face shields, 73
Fulvic acid, 244

Index

308

Fumes, 87, 92
Functional groups, 237, 244
Fungi, 239, 245
Fungicides, 133
Furnace, 293
Gas chromatograph, 238, 267, 271, 272, 292, 294
errors, and, 274
Gas chromatographic/mass spectral analysis, 14, 267, 274
Gaseous contaminants, 191
Gases, 18, 185, 225, 226, 228, 252, 258
Gas law, 27
Gasmask, 72, 97, 101
Gas phase, 185, 226, 228
Gates, 133
Gelisol, 6, 35
Geographic Information System, 10, 12, 20, 59, 63, 65, 76, 79, 11820, 143, 201
modeling, and, 109, 11820, 201
Geological sampling, 134
Geologic erosion, 189
Geologic fault lines, 228
Geologists, 30
Geology, 287
Geostatistical problems, 172
Geostatistical tools, 77
Geostatistics, 13, 163, 16572
Geothermal activity, 29
GIS, 11, 13, 20, 60, 63, 65, 77, 79, 11920, 143, 201
Glacial till, 34, 287
Glaciers, 44
Glass electrode, 275
GLEAMS, 186
Glide path, 191
Global model, 201
Global Positioning System, 12, 19, 53, 5863, 65, 767, 109, 1115, 135, 139, 284, 289, 290
accuracy, 105, 115
Gloves, 66, 73, 98, 139
GMT, 113
Goggles, 73, 95, 96
Gold, 229
Golf courses, 132
Government, 79, 80
Governmental records, 65
GPR, 19, 53, 77, 78, 109, 1168, 143
GPS, 13, 20, 53, 5963, 65, 77, 109, 1115, 136, 139, 284, 290
pollution monitoring, 20
precision, and, 20
surveying tool, 20

Index

309

unit, 78
Grab samples, 3, 11, 130
Graduated cylinders, 55
Granite, 31
Grain sampler, 70
Granular sampler, 70
Grass, 32, 132
Grass waterways, 190
Gravel, 10, 368, 40, 44, 48, 58, 177, 183
soils, 50
Gravimetry, 265
Gravity, 47, 189, 191
Grease, 64
Greek symbols, 130, 142
Greenwich Mean Time (GMT), 113
Grid, 71, 118, 123, 126, 139, 141
three-dimensional, 128
horizontal, 130
Grinding, 256
Groundhogs, 32, 247
Ground penetrating radar, 19, 53, 768, 109, 1168, 143, 284, 290, 289
Groundwater, 131, 176, 188, 198, 200, 257, 292
Groundwater modeling, 200
Gullies, 286
Hafs, 17, 288
Halocarbons, 238
Halogenated organic compounds, 238, 239
Halogens, 233, 237, 240
Halomethane, 249
Hard drives, 77, 219
Hay field, 132
Hazard, 4, 84, 281
Hazardous fumes, 288
Hazardous gas, 97
Hazardous liquids:
acids, 93
aqueous mixtures, 99
bases, 93
caustic, 92
ether, 93
flammable, 92, 93
hydrides, 93
methyl mercury, 93
nonvolatile 92
organic amines, 93
pure, 92
volatile, 92

Index

310

Hazardous Material Identification System, 8791

Hazardous materials, 47, 55
Hazardous solids, 93
Hazardous situations, 87
Hazardous waste field, 119
Hazard warning label, 8791
Headspace, 125, 288, 294
Headspace analysis, 267, 271
Heat, 185, 186
Heavy metal, 18, 27, 64
Heavy soils, 38
Hectare furrow slice, 17, 289
Helium, 228, 273
Herbicide, 133, 135, 181, 243
Heterogeneous environment, 284
Hexachlorocyclohexanes, 201
Hexane, 18
Hexose, 242
Hg-GLEAMS, 186
High clay plasticity, 8
High pressure, 137
High viscosity, 296
Hillsides, 32
History in sampling, 2, 3, 4, 10, 11, 14, 15, 66, 72, 118, 2846
Histosol, 8, 35
HMIS, 8791
Hold times, 252, 254, 262
Homogeneous materials, 150, 257
Horizon, 5, 6, 8, 24, 313, 47, 48, 134, 177, 178, 186, 290
A, 5, 33, 110
B, 5, 34, 110
Bt, 36
C, 5, 6, 32, 34
E, 33, 110
O, 32, 33
R, 32, 34
Horizonation, 25
HOT, 18
Housing, 14
Human activity, 285
Humic acid, 244
Humic materials, 14
Humin, 244
Humus, 244
Hydraulic conductivity, 13
Hydrides, 93
Hydrocarbons, 2389, 246
Hydrochloric acid, 234

Index
Hydrogen, 88, 93, 226, 227, 229, 231, 232, 237, 273
Hydrogen bonding, 28
Hydrogen sulfide, 235
Hydrology, 119, 286, 296
Hydronium ion, 232
Hydrosphere, 25, 26, 28, 150, 202, 2257, 229
Hypothesis, 151, 152, 157, 161
Ice, 32, 44, 202
Igneous rock, 30
Illegal dumping, 292
Illuviated, 31
Immiscible layers, 259
Immiscible liquid fraction, 265
Improper sampling techniques, 293
Inaccurate results, 284
Inceptisol, 8
Incineration, 293
Incomplete data, 284
Incorrect recording of data, 284
Indelible ink, 207
Inductively coupled plasma (ICP), 258
Inert gas, 294
Inexperienced personnel, 284
Infiltration, 35, 50, 190, 225, 247
Infrared, 20, 267
Inorganic carbon, 189
Inorganic clay, 40
Inorganic components, 76, 136
Inorganic compounds, 63, 246
Inorganic contaminant, 67
Inorganic ions, 28, 246, 247
Inorganic molecules, 28, 225, 248
Inorganic nutrients, 185
Inorganic phase, 226, 227
Inorganic silt, 40
Insecticides, 133, 135, 181, 213
Instrumental methods, 109, 256
Instrumentation, 30
Intercellular components, 246, 248
Interferences, 257, 292
Interfering compounds, 285
Interfering matrix, 256
Internet, 190, 215, 218
Interpretation of analytical results, 284
Interstitial water, 29
Invasive sampling, 109
Invertase, 245

311

Index
Inverted soil, 6, 35
Investigative team, 296
Iodine, 230
Ionosphere, 26
Ions, 4, 225
Ion selective electrode (ISE), 127
Iron, 118, 137, 226, 228, 230, 233
Iron oxides, 36
Irrigation, 183
ISE, 128
Isoerosivity map, 189
Karst, 27, 31, 287
Kentucky, 31
Ketone, 242
Kinetics, 185, 186
Kriging, 115, 147, 158, 163, 165, 1702
Labels, 11, 13, 18, 59, 1423, 207, 258, 284
Laboratory, 11, 13, 14, 81, 123, 125
Laboratory information management system, 279
Lake, 25, 287
Lake turnover, 29
Landfills, 55, 292
Landsat TM, 120
Landscape, 2, 47, 61, 63, 129, 177, 188, 198, 287
Landscape models, 189
La Nia, 120
Lateral movement, 48
Latitude, 60, 113, 115, 139
Lava, 30
Layers, 9, 11, 25, 29, 127, 129, 201, 279, 290
LD50, 106
Leach, 9, 24, 126, 133, 197, 231, 233, 236, 292
Lead, 14, 55, 226, 229, 286
Letter of transmittal, 216
Light soil, 38
Lightning strikes, 120
Lignin, 247
Lime, 133, 293
Limestone, 24, 27, 30, 31, 287
Limiting factor, 257
LIMS, 280
Lindane, 186
Linear increase, 192
Linear model, 165
Liner, 70, 73
Liquefied gases, 87

312

Index

313

Liquid ammonia, 92
Liquid limit, 8, 39, 40
Liquid/liquid separation, 256
Liquid phase, 185, 226, 227
Lithium, 231
Lithosphere, 24, 26, 2931, 202, 225, 229
Load carrying, 39
Loam, 38
Logarithmic decrease, 193
Logarithmic growth, 192, 193
Longitude, 60, 113, 115, 139
Loss to atmosphere, 288
Lot number, 73
Lysimeters, 181, 183
Magma, 30
Magnesium, 131, 227, 231, 235
Magnetic materials, 118
Magnetic susceptibility, 19
Magnetite, 118
Mammoth caves, 31
Manganese, 231, 233
Manure, 133, 134, 248
Map, 10, 13, 19, 21, 53, 56, 59, 60, 62, 63, 79, 111, 115, 119, 120, 127, 129, 139, 219
aerial photographs, 59
area, 10
cross-sectional 60
detailed, 10
simple, 59
soils, 10
soil survey, 10
surface, 59
three-dimensional 21, 59
topographical topo, 59, 61
Map reading, 284
Marble, 31
Markers, 78
Mass, 16, 191
Mass balance, 42, 186
Mass flow, 27
Mass soil movement, 288, 296
Mass spectrometry, 267, 270
Mass spectrometry/gas chromatography, 274, 277
limitations, 274
Mass transfer, 185
Material Safety Data Sheets, 84, 86, 1046
Matrices, 292
Maximum contamination level (MCL), 279, 280

Index

314

Mean, 77, 146, 152

Mean square for treatments (MST), 162
Median, 146, 152, 153
Medical treatment, 84
Medium movement, 290
Medium sand, 38
Memory sticks, 219
Merck Index, 84, 86, 106
Mercury, 186, 228
Mesosphere, 26
Metal(s), 19, 55, 67, 76, 88, 229, 244, 245, 256, 268, 288
Metal cations, 27, 55, 231
Metal contamination, 288
Metamorphic rock, 30
Meters:
dissolved oxygen, 55
ion selective electrode, 55
pH, 54, 55, 128
temperature, 55
Methane, 9, 185, 225, 227, 237
Methylene chloride, 294
Methylethylketone, 18
Methyl mercury, 99
Methyl tertiary butyl ether, 181, 183, 2945
Mice, 207
Microbial activity, 247
Microbial cells, 246
Microbial decomposition, 244
Microbial growth, 192
Microbial gums, 42, 247
Micronutrients, 131
Microorganisms, 9, 27, 192, 207, 234, 245, 246, 247, 248
Microwaves, 19, 116
Minerals, 9, 197, 248
Model(s), 13, 183, 197, 200, 201
chemical 1858
computer, 176, 201
computer chemical, 201
dynamic, 13, 80, 1767, 181, 1927, 200, 202
equilibrium, 185
evapotranspiration, 1834
kinetic, 186
landscape, 18990
mathematical, 13, 176, 185, 188, 189
physical, 13, 80, 17781
quantitative, 177, 181
scale, 177
soil-atmosphere, 185

Index

315

thermodynamic, 185
Modeling, 13, 67, 80, 164, 192
complex, 13
dynamic, 13, 80, 192
environmental system, 12, 201
mathematical 13189
physical 13, 80, 17781
whole planet, 202
Model validation, 188
Modem, 53
Modflow, 198, 200
Moisture, 71, 186
Molecular spectroscopic imethods, 256, 269, 270
Moles, 32
Mollisol, 8
Molybdate, 237
Molybdenum, 232
Monitoring, 92, 101, 103
personnel, 101
Monitoring wells, 95, 138, 143, 176, 178, 289, 292
Monobasic phosphate, 235
Mountains, 25
MrSID GeoViewer, 63, 200
MSDS, 84, 86, 105, 106
MTBE, 181, 2946
Muddy soil, 67
Municipal dump, 14
Municipalities, 120
Naphthalene, 240, 293
National Aeronautics and Space Administration (NASA), 79, 118
National Safety Council, 86
Natural attenuation, 197
Natural halogenated organic compounds, 238
Natural laws, 265
Natural level, 63
Nature of the sample, 252, 257
Nickel, 231
Nitrate, 5, 27, 55, 187, 213, 231, 232, 236, 246, 292
Nitrite, 5, 27, 55, 187, 231, 232, 236, 292
Nitrogen, 5, 9, 267, 87, 131, 135, 225, 227, 228, 230, 2367, 245, 273
Nitrogen compounds, 5, 27, 236, 244
Nitrogen fertilizer, 133, 236
Nitrogen oxides, 225, 230, 236
Nitrogen oxyanions, 236
Noble metals, 229
Nonaqueous phase liquid (NAPL), 243
Nondimensional representation, 179

Index

316

Noninvasive sampling, 109

Nonmetal cations, 232
Nonmetals, 19, 230
Non-point source, 66
Nonrepresentative sample, 289
Nonsmearing ink, 59, 207
North American Datum, 61, 113
Noxious fumes, 95
Nucleic acids, 248
Nugget, 169
Null hypothesis, 152, 156, 161
Number changes, 58
Number of s amples, 71, 127, 138, 146, 159
Occupational Safety and Health Administration, 2, 84, 86, 87, 110
Oceans, 25, 31, 119, 120
Octyl ether, 181
Off field protection, 104
Off field safety, 84
Ohio farm, area study, 287
Organic acids, 242, 244
Organic compounds, 14, 63, 74, 202, 236, 244, 245, 246
Organic contaminants, 15, 67, 292
Organic fraction, 2257
Organic functional groups, 241, 242
Organic ions, 28
Organic matter, 5, 28, 33, 34, 35, 39, 41, 42, 64, 130, 131, 133, 134, 185, 189, 197, 225, 227, 233,
236, 242, 243, 2468
Organic methods, 267
Organic phase, 185, 226
Organic pollutants, 202
Organic silts, 40
Organic soil, 16, 34
Organic sulfur, 235
Organic vapors, 74
Organisms, 27, 185, 245, 246
OSHA, 2, 85, 86, 87, 111
Outlier, 158
Owner records, 65
Oxidation, 5, 27, 184, 187, 292
species, 27
Oxidation state, 27, 231, 233, 248
Oxidative reactions, 29
Oxidized functional groups, 241
Oxidizer, 88, 90
Oxidizing, 28, 137, 184
Oxidizing conditions, 5, 22932, 235
Oxisol, 8, 35

Index

317

Oxyanion, 2302, 2335

Oxygen, 9, 26, 27, 29, 185, 22531, 235, 237, 245, 248
Oxygen-containing groups, 244
Oxygen-free water, 29
Oxygen rich water, 28
Ozone, 225, 231
Packing materials, 75, 284
PAH, 244, 293
Pan coefficient, 184
Partial differential equations, 186, 200
Particle concentration, 191
Particle density, 16, 42, 191
Particle movement, 191
Particulate matter, 24, 26
Partition, 185, 187
Parts of the environment, 197
Pasture, 131, 133, 248
PCBs, 64, 240, 243
Ped, 41, 178, 247
Pedology, 72
Pedon, 150
Peer review, 280
Penicillum, 239
Percolation, 27, 32, 35, 42, 47, 183, 190, 225, 247
Periodic decay, 192
Permafrost, 35
Permitting, 80
Peroxide, 246
Personal Protective Hazard Assessment Worksheet, 85, 86
Personnel, 11, 289
Personnel contamination, 94
Personnel exposure, 91, 92
Personnel monitoring, 101
Personnel protection, 94101
Personnel protective equipment, 84, 85, 91, 959
Personnel protective hazard assessment, 85, 86
Pesticides, 16, 54, 133, 186, 243, 294
Pests, 207
Petroleum, 5, 18
pH, 15, 26, 27, 64, 128, 131, 148, 149, 152, 153, 156, 165, 189, 214, 225, 226, 2315, 257, 266,
267, 275, 287
Phenols, 14, 244
Phenylalanine, 239
Philippines, 31
pH meter, 53, 128
Phosphatase, 246
Phosphate, 15, 65, 196, 231, 233, 235, 236, 241

Index

318

Phosphorus, 131, 135, 235

Photographs, 10, 63
Phthalates, 294
Physical characteristics of soils, 5, 32
Physical chemical separation, 267
Physical environment, 137
Physical integrity, 70
Physical properties, 5, 27, 30, 237, 247
Physically marked sites, 20, 291
Phytoremediation, 197
Pickup truck, 70, 122
Pipelines, 4, 19, 79, 178
Plant activity, 247
Plant cells, 246
Plant enzymes, 245
Plant growth, 184
Plant leaves, 247
Plant nutrients, 102, 128, 134, 141
Plant roots, 27, 245
Plants, 32, 36, 42, 50, 181, 184, 192, 196, 197, 228, 229, 234, 235, 245, 247, 248
Plastic, 26, 39, 183, 248
Plastic coated liners, 73
Plastic extraction, 293
Plastic limit, 8, 39
Plastic sieve, 54
Plasticity index, 8, 39, 40
Plateau, 130
Platy structure, 41
Point source, 66
Poisonous snakes, 95
Pollutant, 13, 21, 35, 176, 178, 191, 198, 202, 238, 287
Pollution, 19, 20, 66, 202
concentration, 138
Polyaromatic hydrocarbons, 244, 293
Polychlorinated biphenyls, 64, 240
Polymer, 136
Polypedon, 150
Polystyrene cooler, 75
Population, 14951, 158, 192
densities, 120
variance, 154
Pore size, 13
Pores, 42, 179, 181, 185, 196
Postprocessing, 78
Potassium, 135, 227, 231, 235
Power lines, 19
Power station, 64
Powered samplers, 66

Index

319

Precipitated plastic, 294

Precipitation, 184, 197
Precipitation reactions, 257
Predicting component values, 146, 176
Preliminary field survey, 63
Preliminary nitrate sampling, 127
Preparation errors, 257
Pre-sampling activity, 10, 66
Pressure, 30
Problem determination, 257
Process errors, 257
Processing center, 118
Project manager, 76, 221, 257, 260, 264, 275, 280
Project notebook, 2, 10, 45, 53, 5559, 65, 76, 110, 130, 139, 142, 143, 158, 217, 248, 264, 285,
290, 293
Protecting sample, 290
Protective equipment, 66
Proteins, 242, 246, 248
Protons, 234
Prudent use, 100
Pseudomonas, 238, 239
Pumice, 31
Pump, 71, 183
Purge and trap, 272, 293
Pyrenes, 293
QA/QC, 280
Quality assurance, 141, 280
Quality control, 141, 280
Quantitative analysis, 257, 265
Quantitative composition, 257
Quartzite, 31
Q-test, 158, 159
Radar, 19, 116
Radon, 228
Railroad, 64
Rain, 10, 20, 24, 26, 27, 312, 133, 189, 190, 225
Raindrops, 189
Rainfall, 4, 14, 20, 101, 176, 183, 189
RAM requirements, 77
Randomness, 15, 185
Random number generation, 140, 147, 148
Random sampling, 128, 129, 132, 138, 139, 140
three-dimensional, 128
Random variable, 150
Rate, 192, 197
Rats, 207

Index

320

Raw sample, 256, 257

Real time, 78
Red Cross first aid course, 87
Reduced chemical species, 27, 28
Reducing conditions, 29, 58, 235
Regolith, 31, 32, 41, 117, 129, 185, 192, 198, 2278, 270, 287
Regression analysis, 146, 189
Regression coefficient, 270
Regulating government agency, 265
Regulatory agencies, 201
Relative dielectric permitivity (RDP), 116
Remediation, 124, 24, 35, 41, 64, 66, 79, 80, 109, 127, 128, 138, 141, 172, 211, 290, 291
Remediation plans, 13
Remote sensing, 3, 19, 20, 79, 118
Report documentation 279
Report generation, 279
Representative sample, 258, 294
Request for analysis, 21921, 261
Resampling, 291
Reservoir, 192
Resin extraction, 293
Resistivity, 19
Resources, 80
Respirators, 66, 73, 978, 101
Retention time, 292
Revegetation, 237
Revised universal soil loss esquation (RUSLE), 18990
Revised wind erosion equation (RWEQ), 190
RFA, 2201
Right of way, 119
River bottom, 130
Rivers, 25, 33, 45, 130, 287
River terraces, 34, 130
Roads, 25, 63
Rock, 5, 13, 24, 302, 33, 41, 44, 48, 67, 134, 138, 172, 177, 192, 227, 228, 257, 287
decomposition, 32
RockWare, 172
Rocky soil, 66, 67
Roots, 9, 10, 32, 64, 247
acids, 247
enzymes, 245
exudates, 247
Row crops, 131, 132, 247
Rubber, 73
Rubidium, 231
Russia, 35
Saccarothrix, 239

Index

321

Safety, 2, 5, 112, 14, 66, 72, 81, 84, 913, 130, 291
during sampling, 291
Environmental health and safety, 86
food/drink, 100
information, 84
personnel, 11
plan, 84
resources, 84
training, 73
Safety concerns, 846
Safety consultants, 86, 87
Safety courses, 86, 87
Safety equipment, 11, 66, 72, 90, 94
shower, 90
eye wash, 90
glasses, 66, 73, 91, 92
Safety in agricultural fields, 102
Safety in an industrial waste field, 102, 103
Safety labels, 90
Safety materials, 94
Safety resources, 84, 867
Safety sampling, 10
Safety shipping labels, 90
Saliva, 245
Saltation, 191
Salt deposits, 31, 32, 48, 110, 118, 225, 226, 230
Sample analysis, 24, 252, 26470
Sample bottles, 706
Sample consistency, 258
Sample containers, 5, 9, 13, 14, 715, 207, 257, 287
analysis mismatch, 293
glass 72, 125
paper, 73, 125
plastic, 73, 125
Sample contamination, 217
Sample contents, 14
Sample drying, 271
Sample handling, 2, 13, 80, 109, 138, 141, 142
Sample holding times, 252, 253
Sample identification, 205
Sample integrity, 138, 205, 258
Sample labeling, 13, 56, 58, 59, 127, 130, 139, 142, 264
Sample layers, 294
Sample location, 10, 138
Sample loss, 205, 207, 209
Sample matrix, 257, 264
Sample mislabling, 217
Sample mismatch, 293

Index

322

Sample number, 559, 76, 142, 143, 206

Sample physical state, 257, 264
Sample preparation, 255, 257, 264
Sample rigorous conditions, 208
Sample security, 2068
Sample site, 58, 60, 63, 139, 140, 188, 290
Sample storage, 10, 53, 284
commercial laboratory and, 216
Sample temperature change, 208, 209, 211
Sample transport, 2, 4, 13, 80, 2058, 235, 257, 269, 284
Sample type, 125, 126
Sample variance, 126
Sampler(s), 12, 14, 17, 41, 53, 66, 70, 76, 109, 120, 139, 134, 136, 264, 287, 290
Sampler types:
alloy, 121
auger, 68, 122
brass, 122
bucket, 17, 68, 123
core, 68, 1213
handheld, 120, 122
hydraulic, 122
iron, 122
material, 120, 121
metal, 121
plastic, 121
power, 70
sediment, 71
stainless steel, 122
steel, 122
Teflon, 122
truck mounted, 70, 120
types, 66, 70, 121, 122
well drilling, 123
Samples, 2, 13, 15, 16, 24, 26, 54, 57, 59, 66, 72, 75, 126, 132, 133, 178, 208, 210, 252, 255, 264
amount, 1235
authenticity, 76
composite, 125
container, 5, 9, 715, 125
depth, 126
duplicate, 125
negative control, 208
positive control, 208
split, 125, 126
subsurface, 127, 130
subsamples, 126
surface, 124, 126, 127, 130
transport, 130
Sampling, 2, 35, 105, 1620, 29, 32, 34, 35, 44, 47, 58, 59, 63, 65, 66, 67, 76, 78, 80, 81, 105,

Index

323

109111, 119, 129, 1313, 135, 138, 140, 150, 158, 1768, 183, 187, 190, 197, 201, 226, 232, 235,
242, 247, 252, 257, 265, 284, 288, 289
activity, 284
alone, 95
data, 63
depressional area, 16
depth, 15, 71
direction of movement and, 288
equipment, 6770, 84, 1201
erosion, and 15
error, 259, 261, 289, 291, 296
exchange, 207
for wrong component, 292
GPS, 139
grab, 11
grid, 126, 12930, 290
handling 2, 12, 13, 222
history, 16
immiscible layers, 295
kit, 261
latitude/longitude, 139
needs, 3
permits, 80
process, 258
site, 139, 178
tool(s), 9, 58, 6770, 1201
transect, 138
UTM, 139
Sampling pattern, 71
Sampling personnel, 287
Sampling plan, 2, 3, 4, 11, 12, 13, 53, 12637, 176, 178, 187, 197, 201, 211, 287
Sand, 4, 246, 36, 38, 402, 44, 48, 67, 127, 177, 178, 181, 183, 187, 231, 248
Sandy layer, 58
Sandstone, 24, 30, 287
Sandy soil, 4, 35, 38, 40, 42, 44, 47, 66, 67, 137, 225, 235, 236
Satellite, 1920, 78, 111, 113, 118, 120
Saturated zones, 273, 287
Scale, 177, 178
Screw tops, 73
Sediment, 27, 29
Sediment samplers, 70
Sedimentary rock, 30
Seeds, 71
Selenium, 104, 205, 230, 246
Sensor, 19, 120
Separation methods, 270, 271
Serial number, 73
Sewage sludge, 237

Index
Shaker, 55
Shale, 24, 30
Shipping, 58, 90, 215, 262
Shipping boxes, 76, 90
Shipping conditions, 317
Shipping kits, 76, 212
Shipping numbers, 215
Shrinkage, 8, 40
Sieve, 39, 54, 142, 179
Signage, 8891
Silicates, 231
Silicon, 226, 227, 229, 230
Sill, 166, 169
Silt, 24, 26, 36, 3942, 44, 50, 137, 231, 248
Silt loam, 37, 45, 127
Silver, 55, 229
Simple mathematical models, 188
Sinkholes, 27, 31, 287
Site, 2, 12, 27
sampling, 119
Skewed, 151, 153, 158
Sloping fields, 130, 287
Sloping layers, 134
Snakes, 207
Soap, 30
Socks, 73
Sod, 248
Sodium, 227, 229, 231, 235, 290
Software, 59, 77, 79, 201
Soil air, 9, 16, 27, 32, 186, 226, 227, 233, 242, 247
Soil amendments, 117
Soil analysis, 14, 131
Soil atmosphere, 27, 32, 186
Soil-atmosphere model, 186
Soil bacteria, 292
Soil bulk density, 36, 414
Soil chemical characteristics, 127, 247
Soil chemistry models, 247
Soil color, 10
Soil column, 181, 188
Soil conductivity, 188
Soil conservation, 34, 190, 279
Soil cracks, 247
Soil engineering description, 8, 3841
Soil environment, 8, 246
Soil forming factors, 5, 314
Soil individual, 149
Soil liquid limit, 8

324

Index
Soil map, 6, 149
Soil matrix, 267
Soil microorganisms, 238
Soil moisture, 122
Soil orders, 6
Soil parent material, 5
Soil ped, 39
Soil physical characteristics, 247
Soil plasticity, 8, 39, 40
Soil plastic limit, 8, 39, 40
Soil pores, 27
Soil porosity, 188
Soil profile, 6, 9, 32, 34, 41, 47, 1814, 189, 247
Soil sample, 14, 57
Soil samplers, 6770
Soil science, 40, 150
Soil scientist, 58, 34, 35, 36, 122, 244
Soil separate, 36
Soil solution, 228, 248
Soil structure, 32, 41, 181
Soil surface, 19, 66, 189
Soil survey, 6, 10, 63, 66, 110, 150, 247
Soil taxonomy, 34, 35
Soil texture, 368
Soil type, 58, 11, 34, 36, 79, 127, 139
Soil use, 5
Soil void space, 9, 414
Soil water, 448, 183
minerals, 9
pH, 9
Solar radiation, 26, 187
Solid phase, 185, 226
Solid phase extraction, 272
Solubility, 185
Soluble contaminants, 191
Solum, 5, 41
Solute, 30, 186, 192
Solvents, 135, 185, 191, 192, 203, 207, 213, 294
Solvent mixtures, 292
Solvent evaporation, 294
Solvent extraction, 293
Spectrometers, 20, 267
Spectrometry, 256, 26770
Spectrophotometry, 270
Spectroscopic analysis, 256
Spectroscopy, 267
Spectroscopy errors, 270
Spectrum, 20, 118

325

Index

326

Spherical diffusion, 186

Spiked, 141
Spill, 20, 48, 87, 247
Spillage, 74, 289
Splash erosion, 190
Split sample, 125
Spodic horizon, 35
Spodosol, 8, 36
Spreadsheet, 146
Squares of error (SSE), 161, 162
Stainless steel, 55
Standard deviation, 77, 146, 1525
Standard distribution, 151
Standardizing solutions, 55
Standard Methods for the Examination or Water and Wastewater, 110
Standard temperature and pressure, 99
Standard variance, 99
Starch, 242, 245
Statistical errors, 296
Statistical programs, 77, 146, 189
Statistical tools, 3, 12, 77, 146, 296
Statisticians, 76, 296
Statistics, 3, 12, 77, 109, 127, 128, 140, 188, 285, 290
Stone, 5, 36, 123
Stony soil, 66
Storage, 11, 14, 48, 58, 75, 81, 141, 178, 2078, 213, 232, 284
Storage area, 53
Storage facility, 178, 217
Storage locks, 213
Storage monitoring, 213
Storage room, 75
Storage temperature, 212, 213
STP, 98
Strata, 129
Stratified medium, 186
Stratosphere, 26
Stream movement, 178
Streams, 25, 45, 130, 178, 179, 287
Stream terraces, 34
Streptomyces, 239
Strontium, 231
Structures, 41, 47, 177
Student t, 1567
Subsample(s), 142, 149, 290
Subsoil, 11, 12, 31, 42
Subsurface conditions, 20
Subsurface horizons, 5
Sugar, 242, 245

Index
Sugar cane, 15
Sulfate, 26, 235, 246
Sulfur, 230, 232, 235, 237
Sulfuric acid, 232, 235
Sum of the squares for treatment (SST), 161
Sunlight, 26, 74, 184
Superfund field, 64
Surface water model, 199
Surfactants, 30
Surprises, 66
Surrogate, 142, 265
Surveying, 20, 72
Suspended transport, 9, 191
Swelling, 40
Symbols, 146
Systematic sampling, 11, 140
also see Sampling
Tamper proof, 207
Tampering, 73
Tank car, 66
Tanks, 4
Tar, 64
Teflon, 73
Temperature, 14, 20, 32, 184, 187, 207
control, 75, 261, 284
Temperature blanks, 211, 262
Temperature change, 211, 284
Termites, 32, 247
Terms of Environment, 17
Terraces, 34, 190
Testing, 257
Textural triangle, 36, 38
Texture, 13, 36, 41, 48, 58, 67, 178
Thawing, 35
Thematic, 119
Thematic map, 63, 119
Thermochemical, 334
Thermodynamics, 185
Thermosphere, 26
Three-dimensional sampling, 126
Threshold values, 72
Time, 31, 32, 113, 136
Time-weighted average sampling, 134, 135
Titanium, 227, 233
Titrations, 256
Titrimetry, 266
Toluene, 239, 240

327

Index

328

Tool cleaning, 290

Topography, 32, 79, 119, 129
Total organic carbon (TOC), 257
Total petroleum hydrocarbon, 18, 147, 153, 155, 157, 163, 165, 237
Toxic compound, 4, 14, 15, 20, 27, 80, 97, 141, 192, 210, 229, 231, 232, 234, 236, 286, 288
fumes 100
inorganic 14
organic, 14
Toxins, 239
TPH, 18, 147, 153, 154, 156, 157, 164, 165, 238
Trace level detection, 256
Transect, 126, 127, 172
Transect sampling, 11, 15, 55, 70, 81, 1268, 137
Transformation, 192
Transhalogenation, 249
Transition horizons, 33
Transparent overlays, 119
Transpiration, 11, 183
Transport, 2, 11, 14, 53, 75, 183, 211, 232, 284
Transportation route, 75
Transport boxes, 75, 211, 2156, 262, 284
electrically cooled, 211
forms, and, 212
plastic, 211
temperature monitoring, 211
Transport in field, 211
Transport out of field, 212
Transport temperature, 217
Transport to commercial laboratory, 214
Traps, 15, 79, 125, 2848, 2923, 296
Trees, 32, 177, 248
2, 3, 5-Trichlorophenoxyacetic acid, 243
Trifluralin, 186
Triple bond, 238
Troposphere, 26
Truncate, 148
Tryosine, 239
T-statistic, 1558
T-table, 160
T-test, 156, 161, 163
Tunnels, 79, 183
Turbulent flow, 191
T-value, 155, 157, 189
Twelve soil orders, 6, 34
Ultisol, 8
Ultrasonic mixing, 271
Ultraviolet, 26, 267

Index

329

Uncontaminated reference soils, 14, 139

Underground features, 19, 79
Underground storage tank (UST), 66, 276
Under water samle, 137
Uninterruptible power supply, 219
United Parcel Service, 215, 262
United States, 2, 6, 17, 80, 189
Units, 16
Universal Soil Loss Equation (USLE), 189
Universal solvent, 28
Universal Time Coordinate (UTC), 113
Universal Transverse Mercator (UTM), 61, 113
Unknowns, 93
USB port, 219
U.S. Environmental Protection Agency (USEPA), 17, 86, 110, 281
U.S. Geological Survey (USGS), 61, 198, 200
U.S. Occupational Safety and Health Administration, 84, 86, 87
Uranium, 229
Utilities, 116, 117, 119
Vadose zone, 32, 41
Vaporization, 26
Vapor loss, 294
Vapor pressure, 18, 187, 294
Variable, 76, 110, 176, 186
Variability, 160
Variance, 160, 165, 169
Variations in method, 295
Variograms, 16570
Vegetation, 63, 79, 119, 120, 189, 190, 248
Vehicles, 19, 70
Vermiculite, 181
Vertisol, 6, 35
Vinyl chloride, 292
Visual evaluation, 4
Visual representation, 198
VOC (volatile organic compound), 17, 67, 99, 125, 209, 243, 288, 293, 294
Void space, 9, 17, 42
Void volume, 17, 181, 247
Volatile component, 141, 265
Volatile contaminants, 184
Volatile liquid, 4, 87
Volatile organic compound, 17, 67, 99, 125, 209, 243, 288, 293, 294
Volcanic ash, 6, 34, 287
Volcanos, 26
Volumetric methods, 256
Volumetric water content, 186

Index

330

WAAS (wide area augmentation system), 77, 78, 113

Wash area, 53
Wash bottles, 55
Washing, 73
Waste, 55, 66
Water:
currents, 3, 8
flow, 119, 296
horizons, 8
layers, 9
lines, 116, 117
monitoring, 287
sample, 70, 293
saturated, 27, 35, 41
table, 24
Water Environment Federation, 110
Waterfalls, 31
Water plume, 107200
Water safety, 103
Watershed, 119
Water vapor, 8, 9, 26, 27, 225
Waterways, 63
Waypoints, 115, 291
Weather, 20, 90, 119, 248, 291, 292
Weighing paper, 55
Weighting factor, 188
Well, 24, 31, 70, 188
Well-graded gravels, 8, 39
WEQ (wind erosion equation), 190
Wetting, 205
Whole planet model, 201
Wide area augmentation system, 77, 78, 113
Wilting point, 184
Wind, 9, 24, 26, 184, 191
Wind-blown soil, 190
Wind-borne contaminant, 288
Wind-borne dust, 289
Windbreaks, 191
Wind direction, 191
Wind erosion, 178, 190
Wind speed, 190, 191
Wood-drill bit, 68
Wood treatment facility, 293
Worms, 32
Wrong extractant, 284, 285
Wrong instrument, 284, 285
Wrong paper work, 284, 285
Wrong solvent, 285, 295

Index

X-ray fluorescence, 267, 269

Xylenes, 240
Zimbabwe, 26
Zinc, 55, 67
Zip disk, 219
Zip drives, 219
(Z)-3, 7, 8-tetrachlorobenzo-p-dioxin, 243

331