EXHIBIT D

INTRODUCTION TO ANALYTICAL METHODS

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ILM05.3 D-2/Introduction
 Exhibit D - Analytical Methods

Table of Contents

Section Page

1.0 INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.1 Inorganic Methods Flow Chart . . . . . . . . . . . . . . . . . 5
1.2 Figure 1 - Inorganic Methods Flow Chart . . . . . . . . . . . . 6
1.3 Glassware Cleaning . . . . . . . . . . . . . . . . . . . . . . 6
1.4 Standard Stock Solutions . . . . . . . . . . . . . . . . . . . 6
1.5 Verification of Aqueous Sample Preservation . . . . . . . . . . 6
1.6 Percent Solids Determination Procedure . . . . . . . . . . . . 7
1.7 Insufficient Sample Volume . . . . . . . . . . . . . . . . . . 8
1.8 Sample Mixing . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.9 Undiluted Analysis . . . . . . . . . . . . . . . . . . . . . . 8
1.10 Dissolved Metals . . . . . . . . . . . . . . . . . . . . . . . 9
1.11 Replicate Exposure . . . . . . . . . . . . . . . . . . . . . . 9
1.12 Raw Data Requirements . . . . . . . . . . . . . . . . . . . . . 9
1.13 Quality Control Samples . . . . . . . . . . . . . . . . . . . . 9
1.14 Safety . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.15 Pollution Prevention . . . . . . . . . . . . . . . . . . . . . 10
1.16 Waste Management . . . . . . . . . . . . . . . . . . . . . . . 10

Part A - Analytical Methods for Inductively Coupled Plasma - Atomic Emission

Spectroscopy

Part B - Analytical Methods for Inductively Coupled Plasma - Mass Spectrometry

Part C - Analytical Methods for Cold Vapor Mercury Analysis

Part D - Analytical Methods for Total Cyanide Analysis

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ILM05.3 D-4/Introduction
 Exhibit D -– Section 1
Introduction

1.0 INTRODUCTION

The inorganic analytical service provides a contractual framework for

laboratories. This framework applies USEPA Contract Laboratory Program
(CLP) analytical methods for the isolation, detection, and quantitative
measurement of 23 metals (including mercury) and cyanide in water/
aqueous and/or soil/sediment samples.

The analytical methods that follow are designed to analyze water and
sediment/soil from hazardous waste sites for the presence of inorganic
analytes contained on the Inorganic Target Analyte List (TAL) (see
Exhibit C). The inorganic methods include alternative analysis
procedures for some analytes, multiple preparation procedures, and
Quality Control (QC) requirements. Analytical techniques in the
inorganic methodologies include Inductively Coupled Plasma - Atomic
Emission Spectroscopy (ICP-AES), Inductively Coupled Plasma - Mass
Spectrometry (ICP-MS), Cold Vapor Atomic Absorption Spectroscopy, and
Spectrophotometry. Graphite Furnace Atomic Absorption (GFAA) may be
requested by the modified analysis clause in the contract.

1.1 Inorganic Methods Flow Chart

Figure 1 outlines the general analytical scheme the Contractor shall

follow in performing standard trace metals and cyanide analyses under
this contract.

D-5/Introduction ILM05.3
Exhibit D -– Section 1
Introduction (Con’t)

1.2 Figure 1 - Inorganic Methods Flow Chart

1.3 Glassware Cleaning

Lab glassware to be used within the metals analysis must be acid cleaned
according to USEPA's manual, Methods for Chemical Analysis of Water and
Wastes or an equivalent procedure. An electronic version can be found
via USEPA's National Environmental Publications Internet Site (NEPIS) at
http://www.epa.gov/cincl.

1.4 Standard Stock Solutions

Stock solutions to be used for preparing instrument or method standards

may be purchased or prepared as described in the individual methods of
Exhibit D, Section 7 (Reagents and Standards).

1.5 Verification of Aqueous Sample Preservation

1.5.1 At the time of sample receipt, the Contractor shall check the pH of
the sample and note in a preparation log if the pH is less than 2 for
metals. In addition, it should be noted if the pH is greater than 12
for a cyanide sample. Unless instructed by the USEPA Regional CLP
Project Officer (CLP PO), the Contractor shall not perform any pH
adjustment action if the sample has not been properly preserved. If
the sample has not been properly preserved, contact Sample Management

ILM05.3 D-6/Introduction
 Exhibit D -– Section 1
Introduction (Con’t)

Office (SMO) for further instructions before proceeding with the

preparation and analysis. The Contractor may adjust the pH of a
sample for metals if SMO provides written documentation to the
Contractor from the USEPA Regional CLP PO or USEPA Office of
Superfund Remediation and Technology Innovation (OSRTI) Analytical
Services Branch (ASB) Inorganic Program Manager (ASB PM) authorizing
the adjustment.

1.5.2 Before preparation is initiated for an aqueous cyanide sample, the

Contractor shall test for the presence of sulfides and oxidizing
agents (e.g., residual chlorine). The test for sulfides shall be
performed by placing a drop of the sample on a strip of lead acetate
paper (which has been pre-moistened with pH 4 acetate buffer
solution). If the test strip turns black, the Contractor shall treat
the total volume of sample with powdered cadmium carbonate or lead
carbonate. Yellow cadmium sulfide precipitates when the sample
contains sulfide. This operation shall be repeated until a drop of
the treated sample solution does not darken the lead acetate test
paper. The solution shall be filtered through a dry filter paper
into a dry beaker, and the volume of sample to be used for analysis
shall be measured from the filtrate. It is recommended that the
Contractor avoid a large excess of cadmium carbonate and a long
contact time in order to minimize a loss by complexation or occlusion
of cyanide on the precipitated material. The test for oxidizing
agents shall be performed by placing a drop of the sample on a strip
of potassium iodide - starch test paper (KI - starch paper). If the
test strip turns blue, the Contractor shall contact SMO for further
instructions from the Region before proceeding with sample
preparation and analysis. The Contractor shall document the presence
of sulfides or oxidizing agents in the Sample Delivery Group (SDG)
Narrative.

1.6 Percent Solids Determination Procedure

1.6.1 Immediately following the weighing of the sample to be processed for

analysis, add 5-10 g of sample to a tared weighing dish. Weigh and
record the weight to the nearest 0.01 g.

1.6.2 Place weighing dish plus sample, with the cover tipped to allow for
moisture escape, in a drying oven maintained at 103-105°C. Sample
handling and drying should be conducted in a well-ventilated area.

1.6.3 Dry the sample overnight (12-24 hours) but no longer than 24 hours.
If dried less than 12 hours, it must be documented that constant
weight was attained.1 Remove the sample from the oven and cool in a
desiccator with the weighing dish cover in place before weighing.
Weigh and record weight to nearest 0.01 g. Do not analyze the dried
sample.

1.6.4 Duplicate percent solids determinations are required at the same

frequency as other analytical determinations. Duplicate results are
to be recorded on Form VI-IN.

1
Drying time is defined as the elapsed time in the oven; thus raw data
must record time in and out of the oven to document the 12-hour drying time
minimum. In the event it is necessary to demonstrate the attainment of
constant weight, data must be recorded for a minimum of two repetitive
weigh/dry/desiccate/weigh cycles with a minimum of 1-hour drying time in each
cycle. Constant weight would be defined as a loss in weight of no greater
than 0.01 g between the start weight and final weight of the last cycle.

D-7/Introduction ILM05.3
Exhibit D -– Section 1
Introduction (Con’t)

1.6.5 For the duplicate percent solids determination, designate one sample
aliquot as the “original” sample and the other aliquot as the
“duplicate” sample. Calculate dry weight using the results of the
“original” sample aliquot.

1.6.6 Calculate percent solids by the formula below. The value thus
obtained will be reported on the appropriate Forms I and, where
applicable, Forms VA-IN and VI-IN. This value will be used for
calculating analytical concentration on a dry weight basis.

EQ. 1 Percent Solids

1.6.7 If the sample contains less than 50% solids, the Contractor shall
notify SMO immediately of the samples impacted. After notification
to SMO, the Contractor shall proceed with sample analysis and
document the issue in the SDG Narrative.

1.7 Insufficient Sample Volume

If insufficient sample volume (less than the required amount) is

received to perform the analysis, the Contractor shall contact the SMO
to apprise them of the problem. SMO will contract the Region for
instructions. The Region will either approve that no sample analysis be
performed or will require that a reduced volume be used for the sample
analysis. No other changes in the analysis will be permitted. SMO will
notify the Contractor of the Region’s decision. The Contractor shall
document the Region’s decision in the SDG Narrative.

1.8 Sample Mixing

Unless instructed otherwise by the USEPA Regional CLP PO, all samples
shall be mixed thoroughly prior to aliquoting for digestion. There is
no specific procedure provided herein for homogenization of soil/
sediment samples; however, an effort should be made to obtain a
representative aliquot.

1.9 Undiluted Analysis

1.9.1 All samples shall be run undiluted for multi-analyte analysis (i.e.,
the final product of the sample preparation procedure) unless the
dilution adjusted detection limits for all analytes are below the
CRQL. When an analyte concentration exceeds the calibrated or linear
range, appropriate dilution (but not below the CRQL) and re-analysis
is required. The Contractor shall use the least dilution necessary
to bring the analyte(s) instrument reading within the upper 75% of
the calibrated or linear range and report the highest valid value for
each analyte as measured from the undiluted and diluted analyses.
Unless the Contractor can submit proof that dilution was required to
obtain valid results, both diluted and undiluted sample measurements
must be contained in the raw data.

1.9.2 For single analyte analysis, a diluted sample analysis may be the
only sample analysis performed if the analyte’s instrument result is
in the upper 75% of the calibrated or linear range. An undiluted
sample analysis does not have to be performed in this case. The
sample and its associated matrix spike and duplicate shall initially
be run at the same dilution.

ILM05.3 D-8/Introduction
 Exhibit D -– Section 1
Introduction (Con’t)

1.9.3 All sample dilutions shall be made with reagent water appropriately
acidified (except for cyanide) to maintain constant acid strength.

1.10 Dissolved Metals

1.10.1 If dissolved metals are requested by USEPA Regional Offices, the

Contractor shall follow the instructions provided on the Traffic
Report(s)/Chain of Custody Record(s). If there are no instructions
on the Traffic Report/Chain of Custody Record, the Contractor shall
digest the samples designated as dissolved metals.

1.10.2 If the Regional Office indicates on the Traffic Report/Chain of

Custody Record that a digestion is not to be performed when analyzing
field samples for dissolved metals, then a aqueous Laboratory Control
Sample (LCSW) and a post-digestion spike sample (hardcopy Form VB-IN
and diskette QC codes PDO and PDF) are not required.

1.11 Replicate Exposure

If the Contractor analyzes samples using multiple injections or

exposures, the Contractor must use the data obtained from all injections
or exposures to calculate the final sample result even if more than the
minimum number of injections or exposures are taken.

1.12 Raw Data Requirements

The Contractor is reminded and cautioned that the collection and

provision of raw data may or may not be referred to within the
individual methods of Exhibit D or the Quality Assurance (QA) protocol
of Exhibit E. The raw data deliverable requirements are specified in
Exhibit B, Section 2.5.2.3. Raw data collected and provided in
association with the performance of analyses under this contract shall
conform to the appropriate provisions of Exhibit B.

1.13 Quality Control Samples

If the Sampler designated two (or more) samples as QC for the same
matrix, and the QC samples are not specifically labeled with the
analysis they are to be used for (dissolved metals and total metals),
then the Contractor is to contact SMO to report the issue. SMO shall
then contact the Region and notify the Contractor of the Regional
decision.

1.14 Safety

The toxicity or carcinogenicity of each reagent used in this SOW has not
been precisely defined; however, each chemical compound should be
treated as a potential health hazard. From this viewpoint, exposure to
these chemicals must be reduced to the lowest possible level by whatever
means available. The laboratory is responsible for maintaining a
current awareness file of Occupational Safety and Health Administration
(OSHA) regulations regarding the safe handling of chemicals specified in
this method. A reference file of material handling data sheets should
also be made available to all personnel involved in the chemical
analysis.

D-9/Introduction ILM05.3
Exhibit D -– Section 1
Introduction (Con’t)

1.15 Pollution Prevention

1.15.1 Pollution prevention encompasses any technique that reduces or

eliminates the quantity or toxicity of waste at the point of
generation. Numerous opportunities for pollution prevention exist in
laboratory operation. USEPA has established a preferred hierarchy of
environmental management techniques that places pollution prevention
as the management option of first choice. Whenever feasible,
laboratory personnel should use pollution prevention techniques to
address their waste generation. When wastes cannot be feasibly
reduced at the source, USEPA recommends recycling as the next best
option.

1.15.2 For information about pollution prevention that may be applicable to

laboratories and research institutions consult “Less is Better:
Laboratory Chemical Management for Waste Reduction,” available from
the American Chemical Society's Department of Government Relations
and Science Policy, 1155 16th Street, N.W., Washington D.C., 20036,
(202) 872-4477.

1.16 Waste Management

USEPA requires that laboratory waste management practices be conducted

consistent with all applicable rules and regulations. USEPA urges
laboratories to protect the air, water, and land by minimizing and
controlling all releases from hoods and bench operations, complying with
the letter and spirit of any sewer discharge permits and regulations,
and by complying with all solid and hazardous waste regulations,
particularly the hazardous waste identification rules and land disposal
restrictions. For further information on waste management consult “The
Waste Management Manual for Laboratory Personnel”, available from the
American Chemical Society at the address listed in Section 1.15.2.

ILM05.3 D-10/Introduction
 EXHIBIT D - PART A

ANALYTICAL METHODS

FOR

INDUCTIVELY COUPLED PLASMA -

ATOMIC EMISSION SPECTROSCOPY

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ILM05.3 D-2/ICP-AES
 Exhibit D - Analytical Methods for ICP-AES

Table of Contents

Section Page

1.0 SCOPE AND APPLICATION . . . . . . . . . . . . . . . . . . . . . . . . 5

2.0 SUMMARY OF METHOD . . . . . . . . . . . . . . . . . . . . . . . . . . 5

3.0 DEFINITIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

4.0 INTERFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

4.1 Spectral Interferences . . . . . . . . . . . . . . . . . . . . 6

4.2 Physical Interferences . . . . . . . . . . . . . . . . . . . . 6

4.3 Chemical Interferences . . . . . . . . . . . . . . . . . . . . 6

5.0 SAFETY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

6.0 EQUIPMENT AND SUPPLIES . . . . . . . . . . . . . . . . . . . . . . . 7

6.1 Glassware/Labware . . . . . . . . . . . . . . . . . . . . . . . 7

6.2 Inductively Coupled Plasma - Atomic Emission Spectrometer

(ICP-AES) . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

7.0 REAGENTS AND STANDARDS . . . . . . . . . . . . . . . . . . . . . . . 8

7.1 Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

7.2 Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE . . . . . . . . . . . . 12

8.1 Sample Collection and Preservation . . . . . . . . . . . . . . 12

8.2 Procedures for Sample Storage . . . . . . . . . . . . . . . . . 12

8.3 Procedure for Sample Digestate Storage . . . . . . . . . . . . 12

8.4 Contract Required Holding Time . . . . . . . . . . . . . . . . 12

9.0 CALIBRATION AND STANDARDIZATION . . . . . . . . . . . . . . . . . . . 13

9.1 Instrument Operating Parameters . . . . . . . . . . . . . . . . 13

9.2 Microwave Calibration Procedure . . . . . . . . . . . . . . . . 13

9.3 Inductively Coupled Plasma - Atomic Emission Spectrometer

(ICP-AES) Instrument Calibration Procedure . . . . . . . . . . 14

9.4 Initial Calibration Verification (ICV) . . . . . . . . . . . . 14

9.5 Continuing Calibration Verification (CCV) . . . . . . . . . . . 15

9.6 Initial and Continuing Calibration Blank (ICB/CCB) . . . . . . 15

10.0 PROCEDURE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

10.1 Sample Preparation . . . . . . . . . . . . . . . . . . . . . . 16

10.2 Microwave Digestion Cleaning Procedure . . . . . . . . . . . . 21

10.3 Sample Analysis . . . . . . . . . . . . . . . . . . . . . . . . 21

11.0 DATA ANALYSIS AND CALCULATIONS . . . . . . . . . . . . . . . . . . . 22

11.1 Water/Aqueous Sample Calculation . . . . . . . . . . . . . . . 22

11.2 Soil Sample Calculation . . . . . . . . . . . . . . . . . . . . 22

11.3 Adjusted Method Detection Limit (MDL)/Adjusted Contract

Required Quantitation Limit (CRQL) Calculation . . . . . . . . 23

12.0 QUALITY CONTROL (QC) . . . . . . . . . . . . . . . . . . . . . . . . 24

12.1 Initial Calibration Verification (ICV) . . . . . . . . . . . . 24

12.2 Continuing Calibration Verification (CCV) . . . . . . . . . . . 24

12.3 Contract Required Quantitation Limit (CRQL) Check Standard

(CRI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24

12.4 Blank Analyses . . . . . . . . . . . . . . . . . . . . . . . . 24

12.5 Interference Check Sample (ICS) . . . . . . . . . . . . . . . . 25

12.6 Spike Sample Analysis . . . . . . . . . . . . . . . . . . . . . 27

12.7 Duplicate Sample Analysis . . . . . . . . . . . . . . . . . . . 28

12.8 Laboratory Control Sample (LCS) Analysis . . . . . . . . . . . 29

D-3/ICP-AES ILM05.3
 Exhibit D - Analytical Methods for ICP-AES

Table of Contents (Con’t)

Section Page

12.9 ICP-AES Serial Dilution Analysis . . . . . . . . . . . . . . . 29

12.10 Method Detection Limit (MDL) Determination . . . . . . . . . . 30

12.11 Interelement Corrections . . . . . . . . . . . . . . . . . . . 30

12.12 Linear Range Standard (LRS) . . . . . . . . . . . . . . . . . . 31

12.13 Example Analytical Sequence for ICP-AES . . . . . . . . . . . . 31

13.0 METHOD PERFORMANCE . . . . . . . . . . . . . . . . . . . . . . . . . 32

14.0 POLLUTION PREVENTION . . . . . . . . . . . . . . . . . . . . . . . . 32

15.0 WASTE MANAGEMENT . . . . . . . . . . . . . . . . . . . . . . . . . . 32

16.0 REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32

17.0 TABLES/DIAGRAMS/FLOWCHARTS . . . . . . . . . . . . . . . . . . . . . 33

TABLE 1: Interferent and Analyte Elemental Concentrations Used

for ICP-AES Interference Check Sample (ICS) . . . . . . . 33

TABLE 2: Spiking Levels for Spike Sample Analysis . . . . . . . . 34

ILM05.3 D-4/ICP-AES
 Exhibit D (ICP-AES) -- Sections 1-3
Scope and Application

1.0 SCOPE AND APPLICATION

The following method is an inductively coupled atomic plasma-atomic

emission spectroscopy procedure that is used to analyze water, sediment,
sludge, and soil samples taken from hazardous waste sites. All metals
(except mercury) which are contained in the Inorganic Target Analyte
List (TAL) in Exhibit C are quantitated by this Inductively Coupled
Plasma - Atomic Emission Spectroscopy (ICP-AES) method.

2.0 SUMMARY OF METHOD

Water and soil samples are treated with acids and heat or microwave
energy to solubilize the metals present. These digestates are then
analyzed for trace metals by an atomic emission optical spectroscopic
technique. Samples are nebulized and the aerosol that is produced is
transported to a plasma torch where excitation occurs. Characteristic
atomic-line emission spectra are produced by a radio-frequency
inductively coupled plasma. The spectra are dispersed and the
intensities of the lines are monitored by a photosensitive device. The
signals from the photosensitive device are processed by a computer. A
background correction technique is required to compensate for variable
background contribution to the spectra of trace elements. Background
must be measured adjacent to analyte lines on samples during analysis.
The position selected for the background intensity measurement, on
either or both sides of the analytical line, will be determined by the
complexity of the spectrum adjacent to the analyte line. The position
used must be free of spectral interference and reflect the same change
in background intensity as occurs at the analyte wavelength measured.
Background correction is not required in cases of line broadening where
a background correction measurement would actually degrade the
analytical result.

3.0 DEFINITIONS

See Exhibit G for a complete list of definitions.

D-5/ICP-AES ILM05.3
Exhibit D (ICP-AES) -- Sections 4 & 5
Interferences

4.0 INTERFERENCES

Several types of interference effects may contribute to inaccuracies in

the determination of trace elements in water and soil/sediments. To
prevent this, appropriate steps must be taken in all analyses to ensure
that potential interferences are taken into account. This is especially
true when dissolved solids exceed 1500 milligrams per Liter (mg/L) and
when total elements are determined after the appropriate digestion
procedures are performed. Several types of interferences are summarized
below:

4.1 Spectral Interferences

Spectral interferences can be categorized as: overlap of a spectral line

from another element, unresolved overlap of molecular band spectra,
background contribution from continuous or recombination phenomena,
and/or background contribution from stray light from the line emission
of high concentration elements. The first of these effects can be
compensated by utilizing a computer correction of the raw data. This
would require the monitoring and measurement of the interfering element.
The second effect may require selection of an alternate wavelength. The
third and fourth effects can usually be compensated by a background
correction adjacent to the analyte line. In addition, users of
simultaneous multi-element instrumentation must assume the
responsibility of verifying the absence of spectral interference from an
element that could occur in a sample but for which there is no channel
in the instrument array.

4.2 Physical Interferences

Physical interferences are generally considered to be effects associated

with the sample nebulization and transport processes. Such properties
as change in viscosity and surface tension can cause significant
inaccuracies especially in samples which may contain high dissolved
solids and/or acid concentrations. The use of a peristaltic pump may
minimize these interferences. If these types of interferences are
present, they must be reduced by dilution of the sample.

Another problem which can occur from high dissolved solids is salt
buildup at the tip of the nebulizer. This affects aerosol flow rate
causing instrumental drift. Wetting the argon prior to nebulization,
the use of a tip washer, or sample dilution has been used to control
this problem. Also, it has been reported that better control of the
argon flow rate improves instrument performance. This is accomplished
with the use of mass flow controllers.

4.3 Chemical Interferences

Chemical interferences are characterized by molecular compound

formation, ionization effects and solute vaporization effects. Normally
these effects are not pronounced with the Inductively Coupled Plasma -
Atomic Emission Spectrometer (ICP-AES) technique; however, if observed
they can be minimized by careful selection of operating conditions (that
is, incident power, observation position, and so forth), by buffering of
the sample, and by matrix matching. These types of interferences can be
highly dependent on matrix type and the specific analyte element.

5.0 SAFETY

See Section 1.14 in Exhibit D - Introduction to Analytical Methods.

ILM05.3 D-6/ICP-AES
 Exhibit D (ICP-AES) -- Section 6
Equipment and Supplies

6.0 EQUIPMENT AND SUPPLIES

Brand names, suppliers, and part numbers are for illustrative purposes
only. No endorsement is implied. Equivalent performance may be
achieved using equipment and supplies other than those specified here,
however, a demonstration of equivalent performance meeting the
requirements of this Statement of Work (SOW) is the responsibility of
the Contractor. The Contractor shall document any use of alternate
equipment or supplies in the Sample Delivery Group (SDG) Narrative.

6.1 Glassware/Labware

6.1.1 250 milliliter (mL) beaker or other appropriate vessel

6.1.2 Watch glasses

6.1.3 Funnels

6.1.4 Graduated cylinders

6.1.5 Various volumetric flasks (Type A)

6.1.6 Thermometer that covers a range of 0-200°C

6.1.7 Whatman No. 42 filter paper or equivalent

6.1.8 Hot plate, block digester, or other heating source

6.1.9 Equipment and supplies for microwave digestion

6.1.9.1 Whatman No. 41 filter paper (or equivalent)

6.1.9.2 Disposable polypropylene filter funnel

6.1.9.3 Polyethylene bottles, 125 mL, with caps

6.1.9.4 Microwave oven with programmable power settings up to at least 600

watts.

6.1.9.5 The system must use PTFE PFA digestion vessels (120 mL capacity)
capable of withstanding pressure of up to 110 (±10) pounds per
square inch (psi) [7.5 (±0.7 atm)]. These vessels are capable of
controlled pressure relief at pressures exceeding 110 psi.

6.1.9.6 A rotating turntable must be used to ensure homogeneous

distribution of microwave radiation within the oven. The speed of
the turntable must be a minimum of 3 revolutions per minute (rpm).

6.1.10 Balances - Analytical Balance, 300 gram (g) capacity, and minimum
±0.01 g.

6.2 Inductively Coupled Plasma - Atomic Emission Spectrometer (ICP-AES)

consisting of a computer controlled atomic emission spectrometer with
background correction, a radio frequency generator, and a supply of
Argon gas, welding grade or better.

D-7/ICP-AES ILM05.3
Exhibit D (ICP-AES) -- Section 7
Reagents and Standards

7.0 REAGENTS AND STANDARDS

7.1 Reagents

7.1.1 Reagent water - The purity of this water must be equivalent to ASTM
Type II water (ASTM D1193-77). Use this preparation for all
reagents, standards, and dilutions of solutions.

7.1.2 Acetic acid - Concentrated (specific gravity 1.06).

7.1.3 Hydrochloric acid - Concentrated (specific gravity 1.19).

7.1.4 Hydrochloric acid, (1+1) - Add 500 milliliters (mL) conc. HCl
(specific gravity 1.19) to 400 mL reagent water and dilute to 1 Liter
(L).

7.1.5 Nitric acid - Concentrated (specific gravity 1.41).

7.1.6 Nitric acid, (1+1) - Add 500 mL conc. HNO3 (specific gravity 1.41) to
400 mL reagent water and dilute to 1 L.

7.1.7 Hydrogen peroxide (30%)

7.1.8 Nitric acid, 5% (v/v) - Add 50 mL conc. HNO3 to 500 mL reagent water;
dilute to 1 L.

7.2 Standards

7.2.1 Introduction

The Contractor must provide all standards to be used with this

contract. These standards may be used only after they have been
certified according to the procedure in Exhibit E, Section 8.0. The
Contractor must be able to verify that the standards are certified.
Manufacturer’s certificates of analysis must be retained by the
Contractor and presented upon request.

7.2.2 Stock Standard Solutions

7.2.2.1 Stock standard solutions may be purchased or prepared from reagent

grade chemicals or metals. All salts must be dried for 1 hour at
105°C unless otherwise specified.

(CAUTION: Many metal salts are extremely toxic and may be fatal if
swallowed. Wash hands thoroughly after handling) Typical stock
solution preparation procedures follow.

7.2.2.2 Aluminum solution, stock (1 mL = 100 µg Al) - Dissolve 0.100 grams

(g) of aluminum metal in an acid mixture of 4 mL of (1+1) HCl and
1 mL of conc. HNO3 in a beaker. Warm gently to effect solution.
When solution is complete, transfer quantitatively to a liter
flask, add an additional 10 mL of (1+1) HCl and dilute to 1000 mL
with reagent water.

7.2.2.3 Antimony solution, stock (1 mL = 100 µg Sb) - Dissolve 0.2669 g

K(SbO)C4H4O6 in reagent water, add 10 mL (1+1) HCl and dilute to
1000 mL with reagent water.

7.2.2.4 Arsenic solution, stock (1 mL = 100 µg As) - Dissolve 0.1320 g of

As2O3 in 100 mL of reagent water containing 0.4 g NaOH. Acidify
the solution with 2 mL conc. HNO3 and dilute to 1000 mL with
reagent water.

ILM05.3 D-8/ICP-AES
 Exhibit D (ICP-AES) -- Section 7
Reagents and Standards (Con’t)

7.2.2.5 Barium solution, stock (1 mL = 100 µg Ba) - Dissolve 0.1516 g

BaCl2 (dried at 250°C for 2 hours) in 10 mL reagent water with 1
mL (1+1) HCl. Add 10.0 mL (1+1) HCl and dilute to 1000 mL with
reagent water.

7.2.2.6 Beryllium solution, stock (1 mL = 100 µg Be) - Do not dry.

Dissolve 1.966 grams (g) BeSO4 C 4H2O, in reagent water, add 10.0
mL conc. HNO3 and dilute to 1000 mL with reagent water.

7.2.2.7 Cadmium solution, stock (1 mL = 100 µg Cd) - Dissolve 0.1142 g CdO

in a minimum amount of (1+1) HNO3. Heat to increase rate of
dissolution. Add 10.0 mL conc. HNO3 and dilute to 1000 mL with
reagent water.

7.2.2.8 Calcium solution, stock (1 mL = 100 µg Ca) - Suspend 0.2498 g

CaCO3 dried at 180°C for 1 hour before weighing in reagent water
and dissolve cautiously with a minimum amount of (1+1) HNO3. Add
10.0 mL conc. HNO3 and dilute to 1000 mL with reagent water.

7.2.2.9 Chromium solution, stock (1 mL = 100 µg Cr) - Dissolve 0.1923 g of

CrO3 in reagent water. When solution is complete acidify with 10
mL conc. HNO3 and dilute to 1000 mL with reagent water.

7.2.2.10 Cobalt solution, stock (1 mL = 100 µg Co) - Dissolve 0.1000 g of

cobalt metal in a minimum amount of (1+1) HNO3. Add 10.0 mL (1+1)
HCl and dilute to 1000 mL with reagent water.

7.2.2.11 Copper solution, stock (1 mL = 100 µg Cu) - Dissolve 0.1252 g CuO

in a minimum amount of (1+1) HNO3. Add 10.0 mL conc. HNO3 and
dilute to 1000 mL with reagent water.

7.2.2.12 Iron solution, stock (1 mL = 100 µg Fe) - Dissolve 0.1430 g Fe2O3

in a warm mixture of 20 mL (1+1) HCl and 2 mL of conc. HNO3.
Cool, add an additional 5 mL of conc. HNO3 and dilute to 1000 mL
with reagent water.

7.2.2.13 Lead solution, stock (1 mL = 100 µg Pb) - Dissolve 0.1599 g

Pb(NO3)2 in a minimum amount of (1+1) HNO3. Add 10.0 mL of conc.
HNO3 and dilute to 1000 mL with reagent water.

7.2.2.14 Magnesium solution, stock (1 mL = 100 µg Mg) - Dissolve 0.1658 g

MgO in a minimum amount of (1+1) HNO3. Add 10.0 mL conc. HNO3 and
dilute to 1000 mL with reagent water.

7.2.2.15 Manganese solution, stock (1 mL = 100 µg Mn) - Dissolve 0.1000 g

of manganese metal in the acid mixture, 10 mL conc. HCl and 1 mL
conc. HNO3, and dilute to 1000 mL with reagent water.

7.2.2.16 Nickel solution, stock (1 mL = 100 µg Ni) - Dissolve 0.1000 g of

nickel metal in 10 mL hot conc. HNO3, cool and dilute to 1000 mL
with reagent water.

7.2.2.17 Potassium solution, stock (1 mL = 100 µg K) - Dissolve 0.1907 g

KCl, dried at 110°C, in reagent water. Dilute to 1000 mL.

7.2.2.18 Selenium solution, stock (1 mL = 100 µg Se) - Do not dry.

Dissolve 0.1727 g H2SeO3 (actual assay 94.6%) in reagent water and
dilute to 1000 mL.

7.2.2.19 Silver solution, stock (1 mL = 100 µg Ag) - Dissolve 0.1575 g

AgNO3 in 100 mL of reagent water and 10 mL conc. HNO3. Dilute to
1000 mL with reagent water.

D-9/ICP-AES ILM05.3
Exhibit D (ICP-AES) -- Section 7
Reagents and Standards (Con’t)

7.2.2.20 Sodium solution, stock (1 mL = 100 µg Na) - Dissolve 0.2542 g NaCl

in reagent water. Add 10.0 mL conc. HNO3 and dilute to 1000 mL
with reagent water.

7.2.2.21 Thallium solution, stock (1 mL = 100 µg Tl) - Dissolve 0.1303 g

TlNO3 in reagent water. Add 10.0 mL conc. HNO3 and dilute to 1000
mL with reagent water.

7.2.2.22 Vanadium solution, stock (1 mL = 100 µg V) - Dissolve 0.2297

NH4VO3 in a minimum amount of conc. HNO3. Heat to increase rate of
dissolution. Add 10.0 mL conc. HNO3 and dilute to 1000 mL with
reagent water.

7.2.2.23 Zinc solution, stock (1 mL = 100 µg Zn) - Dissolve 0.1245 g ZnO in

a minimum amount of dilute HNO3. Add 10.0 mL conc. HNO3 and
dilute to 1000 mL with reagent water.

7.2.3 Secondary Dilution Standards

7.2.3.1 Mixed Secondary Dilution Standards

Prepare mixed secondary dilution standard solutions by diluting

the appropriate volumes of stock standards with acidified reagent
water to obtain the final volume. Mixed secondary dilution
standard solutions may be purchased. The purchased standards
shall meet the requirements in Section 7.2.1.

7.2.4 Working Standards

7.2.4.1 The calibration blank is prepared by diluting 2 mL of (1+1) HNO3

and 10 mL of (1+1) HCl to 100 mL with reagent water. Prepare a
sufficient quantity to be used to flush the system between
standards and samples.

7.2.4.2 Contract Required Quantitation Limit (CRQL) Check Standard (CRI)

The concentration of the analytes in the CRI shall be at the

respective CRQLs. Information regarding the CRI shall be reported
on Form IIB-IN.

7.2.4.3 Interference Check Sample (ICS) Solution

The ICS consists of two solutions: Solution A (ICSA) and Solution

AB (ICSAB). ICSA consists of the interferents and ICSAB consists
of the analytes mixed with the interferents.

7.2.4.4 Method Detection Limit (MDL) Solution

The MDL solution shall be at a concentration of 3 to 5 times the

expected MDL.

7.2.4.5 Mixed Calibration Standard Solutions

7.2.4.5.1 Prepare mixed calibration standard solutions by combining

appropriate volumes of the stock solutions in volumetric flasks
(see Sections 7.2.4.5.2 through 7.2.4.5.7). Add 2 mL of (1+1)
HNO3 and 10 mL of (1+1) HCl and dilute to 100 mL with reagent
water (see Note in Section 7.2.4.5.6). Prior to preparing the
mixed standards, each stock solution should be analyzed
separately to determine possible spectral interference or the
presence of impurities. Care should be taken when preparing
the mixed standards that the elements are compatible and

ILM05.3 D-10/ICP-AES
 Exhibit D (ICP-AES) -- Section 7
Reagents and Standards (Con’t)

stable. Transfer the mixed standard solutions to a FEP

fluorocarbon or unused polyethylene bottle for storage. Fresh
mixed standards should be prepared as needed with the
realization that concentration can change with aging. Although
not specifically required, some typical calibration standard
combinations follow.

7.2.4.5.2 Mixed standard solution I - manganese, beryllium, cadmium,

lead, and zinc.

7.2.4.5.3 Mixed standard solution II - barium, copper, iron, vanadium,

and cobalt.

7.2.4.5.4 Mixed standard solution III - arsenic and selenium.

7.2.4.5.5 Mixed standard solution IV - calcium, sodium, potassium,

aluminum, chromium, and nickel.

7.2.4.5.6 Mixed standard solution V - antimony, magnesium, silver and

thallium.

NOTE: If the addition of silver to the recommended acid

combination results in an initial precipitation, add 15 mL of
reagent water and warm the flask until the solution clears.
Cool and dilute to 100 mL with reagent water. For this acid
combination, the silver concentration should be limited to 2
milligrams per Liter (mg/L). Silver under these conditions is
stable in a tap water matrix for 30 days. Higher
concentrations of silver require additional HCl.

7.2.4.5.7 Protect all standards from light. Samples, sample digestates,

and standards must be stored separately.

D-11/ICP-AES ILM05.3
Exhibit D (ICP-AES) -- Section 8

Sample Collection, Preservation, and Storage

8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE

8.1 Sample Collection and Preservation

All samples must be collected in glass or polyethylene containers.

Water/aqueous samples must be preserved with nitric acid to pH less than
2 immediately after collection. All samples must be iced or
refrigerated at 4°C (±2°C) from the time of collection until digestion.

8.1.1 Dissolved Metals

For the determination of dissolved metals, the sample must be

filtered through a 0.45 micrometer (µm) pore diameter membrane filter
at the time of collection or as soon as possible. Use a portion of
the sample to rinse the filter flask, discard this portion, and
collect the required volume of filtrate. Preserve the filtrate with
nitric acid to pH less than 2 immediately after filtration.

8.2 Procedures for Sample Storage

The samples must be protected from light and refrigerated at 4°C (±2°C)
from the time of receipt until 60 days after delivery of a complete,
reconciled data package to USEPA. After 60 days the samples may be
disposed of in a manner that complies with all applicable regulations.

8.3 Procedure for Sample Digestate Storage

Sample digestates must be stored until 365 days after delivery of a

complete, reconciled data package to USEPA.

8.4 Contract Required Holding Time

The maximum holding time for metals is 180 days from Validated Time of
Sample Receipt (VTSR).

ILM05.3 D-12/ICP-AES
 Exhibit D (ICP-AES) -- Section 9
Calibration and Standardization

9.0 CALIBRATION AND STANDARDIZATION

9.1 Instrument Operating Parameters

Because of the differences between various makes and models of

satisfactory instruments, no detailed operating instructions can be
provided. Instead, the analyst should follow the instructions provided
by the manufacturer of the particular instrument. The Method Detection
Limit (MDL), precision, linear dynamic range, and interference effects
must be investigated and established for each individual analyte line on
that particular instrument. All measurements must be within the
instrument linear range where correction factors are valid. It is the
responsibility of the analyst to verify that the instrument
configuration and operating conditions used satisfy the analytical
requirements and to maintain Quality Control (QC) data confirming
instrument performance and analytical results.

9.2 Microwave Calibration Procedure

9.2.1 The calibration procedure is a critical step prior to the use of any
microwave unit. The microwave unit must be calibrated every six
months. The data for each calibration must be available for review
during on-site audits. In order that absolute power settings may be
interchanged from one microwave unit to another, the actual delivered
power must be determined.

9.2.2 Calibration of a laboratory microwave unit depends on the type of

electronic system used by the manufacturer. If the unit has a
precise and accurate linear relationship between the output power and
the scale used in controlling the microwave unit, then the
calibration can be a two-point calibration at maximum and 40% power.
If the unit is not accurate or precise for some portion of the
controlling scale, then a multiple-point calibration is necessary.
If the unit power calibration needs a multiple-point calibration,
then the point where linearity begins must be identified. For
example: a calibration at 100, 99, 98, 97, 95, 90, 80, 70, 60, 50,
and 40% power settings can be applied and the data plotted. The non-
linear portion of the calibration curve can be excluded or restricted
in use. Each percent is equivalent to approximately 5.5-6 watts and
becomes the smallest unit of power that can be controlled. If 20-40
watts are contained from 99-100%, that portion of the microwave
calibration is not controllable by 3-7 times that of the linear
portion of the control scale and will prevent duplication of precise
power conditions specified in that portion of the power scale.

9.2.3 The power available for heating is evaluated so that the absolute
power setting (watts) may be compared from one microwave to another.
This is accomplished by measuring the temperature rise in 1 kilogram
(kg) of water exposed to microwave radiation for a fixed period of
time. The water is placed in a PTFE beaker (or a beaker that is made
of some other material that does not absorb microwave energy) and
stirred before measuring the temperature. Glass beakers absorb
microwave energy and may not be used. The initial temperature of the
water must be between 19 and 25°C. The beaker is circulated
continuously through the field for at least two minutes at full
power. The beaker is removed from the microwave, the water is
stirred vigorously, and the final temperature is recorded. The final
reading is the maximum temperature reading after each energy
exposure. These measurements must be accurate to ±0.1°C and made
within 30 seconds of the end of heating. If more measurements are
needed, do not use the same water until it has cooled down to room
temperature. Otherwise, use a fresh water sample.

D-13/ICP-AES ILM05.3
Exhibit D (ICP-AES) -- Section 9
Calibration and Standardization (Con’t)

The absorbed power is determined by the following formula:

EQ. 1 Absorbed Power

WHERE, P = The apparent power absorbed by the sample in watts

(joules per second).
K = The conversion factor for thermochemical calories
per second to watts (=4.184).
Cp = The heat capacity, thermal capacity, or specific
heat (cal. g-1 °C-1) of water (=1.0).
m = The mass of the sample in grams (g).
DT = The final temperature minus the initial temperature
(°C).
t = The time in seconds (s).
Using 2 minutes and 1 kg of reagent water, the calibration equation
simplifies to:

The microwave user can now relate power in watts to the percent power
setting of the microwave.

9.3 Inductively Coupled Plasma - Atomic Emission Spectrometer (ICP-AES)

Instrument Calibration Procedure

9.3.1 Instruments shall be calibrated daily or once every 24 hours and each
time the instrument is set up. The instrument standardization date
and time shall be included in the raw data.

9.3.2 The calibration standards shall be prepared as in Section 7.2.4.5.

9.3.3 Calibrate the ICP-AES instruments according to instrument

manufacturer’s recommended procedures. At least two standards shall
be used for ICP-AES calibration. One of the standards shall be a
blank.

9.3.4 Any changes or corrections to the analytical system shall be followed

by recalibration.

9.4 Initial Calibration Verification (ICV)

9.4.1 Immediately after each of the ICP-AES systems have been calibrated,
the accuracy of the initial calibration shall be verified and
documented for every analyte by the analysis of the ICV solution(s)
at each wavelength used.

9.4.2 Only if the ICV solution(s) is(are) not available from USEPA, or
where a certified solution of an analyte is not available from any
source, analyses shall be conducted on an independent standard at a

ILM05.3 D-14/ICP-AES
 Exhibit D (ICP-AES) -- Section 9
Calibration and Standardization (Con’t)

concentration other than that used for instrument calibration, but

within the calibration range. An independent standard is defined as
a standard composed of the analytes from a different source than
those used in the standards for the instrument calibration.

9.4.3 The ICV solution(s) shall be run at each wavelength used for
analysis. The values for the ICV shall be reported on Form IIA-IN.

9.5 Continuing Calibration Verification (CCV)

9.5.1 To ensure calibration accuracy during each analysis run, one of the
following standards is to be used for the CCV and shall be analyzed
and reported for every wavelength used for the analysis of each
analyte, at a frequency of 10% or every 2 hours during an analysis
run, whichever is more frequent. The standard shall also be analyzed
and reported for every wavelength used for analysis at the beginning
of the run and after the last analytical sample. The analyte
concentrations in the CCV standard shall be different than the
concentration used for the ICV and shall be one of the following
solutions at or near one-half of the calibration standard:

C USEPA Solutions

C NIST Standards

C A Contractor-prepared standard solution

The same CCV standard shall be used throughout the analysis runs for
a Sample Delivery Group (SDG) of samples received.

9.5.2 Each CCV analyzed shall reflect the conditions of analysis of all
associated analytical samples (the preceding 10 analytical samples or
the preceding analytical samples up to the previous CCV). The
duration of analysis, rinses, and other related operations that may
affect the CCV measured result may not be applied to the CCV to a
greater extent than the extent applied to the associated analytical
samples. For instance, the difference in time between a CCV analysis
and the blank immediately following it, as well as the difference in
time between the CCV and the analytical sample immediately preceding
it, may not exceed the lowest difference in time between any two
consecutive analytical samples associated with the CCV.

9.5.3 Information regarding the CCV shall be reported on Form IIA-IN.

9.6 Initial and Continuing Calibration Blank (ICB/CCB)

A calibration blank shall be analyzed at each wavelength used for

analysis immediately after every ICV and CCV, at a frequency of 10% or
every 2 hours during the run, whichever is more frequent. The blank
shall be analyzed at the beginning of the run and after the last
analytical sample.

NOTE: A CCB shall be analyzed immediately after the last CCV, and the
last CCV shall be analyzed immediately after the last analytical sample
of the run. The results for the calibration blanks shall be reported on
Form III-IN.

D-15/ICP-AES ILM05.3
Exhibit D (ICP-AES) -- Section 10
Procedure

10.0 PROCEDURE

10.1 Sample Preparation

10.1.1 If insufficient sample amount (less than 90% of the required amount)
is received to perform the analyses, the Contractor shall contact the
Sample Management Office (SMO) to inform them of the problem. SMO
will contact the Region for instructions. The Region will either
require that no sample analyses be performed or will require that a
reduced volume be used for the sample analysis. No other changes in
the analyses will be permitted. The Contractor shall document the
Region’s decision in the Sample Delivery Group (SDG) Narrative.

10.1.2 If multiphase samples (e.g., two-phase liquid sample, oily

sludge/sandy soil sample) are received by the Contractor, the
Contractor shall contact SMO to apprise them of the type of sample
received. SMO will contact the Region. If all phases of the sample
are amenable to analysis, the Region may require the Contractor to do
any of the following:

C Mix the sample and analyze an aliquot from the homogenized

sample.

C Separate the phases of the sample and analyze one or more of

the phases, separately. SMO will provide EPA sample numbers
for the additional phases, if required.

C Do not analyze the sample.

10.1.2.1 If all of the phases are not amenable to analysis (i.e., outside
scope), the Region may require the Contractor to do any of the
following:

C Separate the phases and analyze the phase(s) that is(are)

amenable to analysis. SMO will provide EPA sample numbers
for the additional phases, if required.

C Do not analyze the sample.

10.1.2.2 No other changes in the analyses will be permitted. The

Contractor shall document the Region’s decision in the SDG
Narrative.

10.1.3 Water/Aqueous Sample Preparation

10.1.3.1 Preparation Method/Code (HW1) (USEPA Method 200.7, December 1982)

Shake sample and transfer 50-100 milliliter (mL) of well-mixed

sample to a 250 mL heating vessel, add 2 mL of (1+1) HNO3 and 10
mL of (1+1) HCl to the sample. Cover with watch glass or similar
cover and heat on a hot plate, block digester, or equivalent
heating source which is adjustable and capable of maintaining a
temperature of 92-95°C for 2 hours or until sample volume is
reduced to between 25 and 50 mL, making certain sample does not
boil. Cool sample and filter to remove insoluble material.

NOTE: In place of filtering, the sample, after dilution and

mixing, may be centrifuged or allowed to settle by gravity
overnight to remove insoluble material.

Adjust sample volume to 50-100 mL with reagent water. The sample

is now ready for analysis. Concentrations so determined shall be

ILM05.3 D-16/ICP-AES
 Exhibit D (ICP-AES) -- Section 10
Procedure (Con’t)

reported as “total”. If volumes less than 100 mL are used, all

other reagents shall be reduced appropriately (e.g., if 50 mL is
used, reduce reagent volumes by one-half). The final volume of
the digestate must equal the initial volume of the sample aliquot.

10.1.3.2 Preparation Method/Code (MW1) (USEPA SW-846 Method 3015)

10.1.3.2.1 A 45 mL aliquot of the sample is measured into PTFE digestion

vessels.

10.1.3.2.2 5 mL of concentrated HNO3 is added to the digestion vessels.

10.1.3.2.3 The caps with the pressure release valves are placed on the
vessels hand tight and then tightened, using constant torque,
to 12 ft/lbs. The weight of each vessel is recorded to
0.02 gram (g).

10.1.3.2.4 Place 5 sample vessels in the carousel, evenly spaced around

its periphery in the microwave unit. Venting tubes connect
each sample vessel with a collection vessel. Each sample
vessel is attached to a clean, double-ported overflow vessel to
collect any sample expelled from the sample vessel in the event
of over pressurization. Assembly of the vessels into the
carousel may be done inside or outside the microwave.

10.1.3.2.5 This procedure is energy balanced for five 45 mL water samples

(each with 5 mL of acid) to produce consistent conditions.
When fewer than five samples are digested, the remaining
vessels must be filled with 45 mL of tap, deionized, or reagent
water and 5 mL of concentrated nitric acid.

10.1.3.2.6 Newer microwave ovens may be capable of higher power settings

which may allow a larger number of samples. If the analyst
wishes to digest more than 5 samples at a time, the analyst may
use different power settings as long as they result in the same
time temperature conditions defined in the power programming
for this method.

10.1.3.2.7 The initial temperature of the samples should be 24°C (±1°C).

The Preparation Blank (PB) must have 45 mL of deionized water
and the same amount (5 mL) of acid that is added to the
samples.

10.1.3.2.8 The microwave unit first-stage program must be set to give 545
watts for 10 minutes and the second-stage program to give 344
watts for 10 minutes. This sequence brings the samples to
160°C (±4°C) in 10 minutes and permits a slow rise to 165-170°C
during the second 10 minutes.

10.1.3.2.9 Following the 20 minute program, the samples are left to cool
in the microwave unit for 5 minutes, with the exhaust fan on.
The samples and/or carousel may then be removed from the
microwave unit. Before opening the vessels, let cool until
they are no longer hot to the touch.

10.1.3.2.10 After the sample vessel has cooled, weigh the sample vessel and
compare to the initial weight as reported on the preparation
log. Any sample vessel exhibiting a less than or equal to
0.5 g loss into the overflow vessel must have any excess sample
from the associated collection vessel added to the original
sample vessel before proceeding with the sample preparation.

D-17/ICP-AES ILM05.3
Exhibit D (ICP-AES) -- Section 10
Procedure (Con’t)

Any sample vessel exhibiting a greater than 0.5 g loss must be

identified in the preparation log and the sample redigested.

10.1.3.2.11 Sample Filtration - The digested samples are shaken well to mix
in any condensate within the digestion vessel before being
opened. The digestates are then filtered into 50 mL glass
volumetric flasks through Whatman No. 41 (or equivalent) filter
paper and diluted to 50 mL (if necessary). The samples are now
ready for analysis. The sample results must be corrected by a
factor of 1.11 in order to report final concentration values
based on an initial volume of 45 mL. Concentrations so
determined shall be reported as “total”.

10.1.3.3 Preparation Method/Code (MW2) (ASTM Standard D4309-91)

10.1.3.3.1 A 50 mL aliquot of the sample is measured into PTFE digestion

vessels.

10.1.3.3.2 3 mL of concentrated HNO3 and 2 mL of concentrated HCl is added

to the digestion vessels.

10.1.3.3.3 Proceed as in Preparation Method/Code “MW1", Sections

10.1.3.2.3 through 10.1.3.2.11.

10.1.3.3.4 Sample Filtration - The digested samples are shaken well to mix
in any condensate within the digestion vessel before being
opened. If necessary, the digestates are then filtered through
filter paper and diluted to 55 mL. The samples are now ready
for analysis. The sample results must be corrected by a factor
of 1.1 in order to report final concentration values based on
an initial volume of 50 mL. Concentrations so determined shall
be reported as “total”.

10.1.4 Soil/Sediment Sample Preparation

10.1.4.1 Preparation Method/Code (HS1) (USEPA Method 200.7, December 1982)

10.1.4.1.1 Mix the sample thoroughly to achieve homogeneity. For each

digestion procedure, weigh (to the nearest 0.01 g) a 1.0 to
1.5 g portion of sample and transfer to a beaker.

10.1.4.1.2 Add 10 mL of 1:1 nitric acid (HNO3), mix the slurry, and cover
with a watch glass. Heat the sample to 92-95°C on hot plate or
block digester, and reflux for 10 minutes without boiling.
Allow the sample to cool, add 5 mL of concentrated HNO3,
replace the watch glass, as appropriate, and reflux for 30
minutes. Do not allow the volume to be reduced to less than 5
mL while maintaining a covering of solution over the bottom of
the heating vessel.

10.1.4.1.3 After the second reflux step has been completed and the sample
has cooled, add 2 mL of reagent water and 3 mL of 30% hydrogen
peroxide (H2O2). Return the heating vessel to the heat source
for warming to start the peroxide reaction. Care must be taken
to ensure that losses do not occur due to excessively vigorous
effervescence. Heat until effervescence subsides, and cool the
heating vessel.

ILM05.3 D-18/ICP-AES
 Exhibit D (ICP-AES) -- Section 10
Procedure (Con’t)

Continue to add 30% H2O2 in 1 mL aliquots with warming until

the effervescence is minimal or until the general sample
appearance is unchanged.

NOTE: Do not add more than a total of 10 mL 30% H2O2.

10.1.4.1.4 Add 5 mL of 1:1 HCl and 10 mL of reagent water, return the

covered heating vessel to the heat source, and heat for an
additional 10 minutes. After cooling, filter through Whatman
No. 42 filter paper (or equivalent) and dilute to 100 mL with
reagent water.

NOTE: In place of filtering, the sample (after dilution and

mixing) may be centrifuged or allowed to settle by gravity
overnight to remove insoluble material.

The sample is now ready for analysis.

10.1.4.2 Preparation Method/Code (HS2) (USEPA SW-846 Method 3050B)

10.1.4.2.1 Mix the sample thoroughly to achieve homogeneity. For each

digestion procedure, weigh (to the nearest 0.01 g) a 1.0 to 2.0
g portion of sample and transfer to a beaker.

10.1.4.2.2 Add 10 mL of 1:1 nitric acid (HNO3), mix the slurry, and cover
with a watch glass. Heat the sample to 92-95°C on hot plate,
block digester, or equivalent heating source, and reflux for 10
minutes without boiling. Allow the sample to cool, add 5 mL of
concentrated HNO3, replace the watch glass, as appropriate, and
reflux for 30 minutes. Do not allow the volume to be reduced
to less than 5 mL while maintaining a covering of solution over
the bottom of the heating vessel. Add an additional 5 mL of
concentrated HNO3 and reflux. Repeat this step until sample
oxidation is complete (no brown fumes generated).

10.1.4.2.3 After the reflux steps have been completed and the sample has
cooled, add 2 mL of reagent water and 3 mL of 30% hydrogen
peroxide (H2O2). Return the heating vessel to the heat source
for warming to start the peroxide reaction. Care must be taken
to ensure that losses do not occur due to excessively vigorous
effervescence. Heat until effervescence subsides, and cool the
heating vessel.

10.1.4.2.4 Continue to add 30% H2O2 in 1 mL aliquots with warming until

the effervescence is minimal or until the general sample
appearance is unchanged.

NOTE: Do not add more than a total of 10 mL 30% H2O2.

10.1.4.2.5 Add 10 mL of concentrated HCl and return the covered heating

vessel to the heat source and heat for an additional 10
minutes. After cooling, filter through Whatman No. 42 filter
paper (or equivalent) and dilute to 100 mL with reagent water.

NOTE: In place of filtering, the sample (after dilution and

mixing) may be centrifuged or allowed to settle by gravity
overnight to remove insoluble material.

The sample is now ready for analysis.

D-19/ICP-AES ILM05.3
Exhibit D (ICP-AES) -- Section 10
Procedure (Con’t)

10.1.4.3 Preparation Method/Code (MS1) (USEPA SW-846 Method 3051)

10.1.4.3.1 Add a representative 0.50 g (±0.01 g) of sample to the PTFE PFA

vessel.

10.1.4.3.2 Add 10 mL of concentrated nitric acid. If a vigorous reaction

occurs, allow the reaction to stop before capping the vessel.

10.1.4.3.3 Cap the vessel, then tighten using constant torque to 12

ft/lbs, according to the manufacturer’s direction.

10.1.4.3.4 Connect the sample vessel to the overflow vessel using PTFE PFA
tubing.

10.1.4.3.5 Weigh the vessel assembly to the nearest 0.01 g.

10.1.4.3.6 Place sample vessels in groups of 2 sample vessels or 6 sample

vessels in the carousel, evenly spaced around its periphery in
the microwave unit. If fewer than the recommended number of
samples are to be digested (i.e., 3 samples plus 1 blank) then
the remaining vessels must be filled with 10 mL of nitric acid
to achieve the full complement of vessels.

10.1.4.3.7 Each sample vessel must be attached to a clean, double-ported

vessel to collect any sample expelled from the sample vessel in
the event of over pressurization. Assembly of the vessels into
the carousel may be done inside or outside the microwave.
Connect the overflow vessel to the center well of the oven.

10.1.4.3.8 The PB must have 0.5 mL of reagent water and the same amount
(10 mL) of acid that is added to the samples. The PB must
later be diluted to 50 mL in the same manner as the samples.

10.1.4.3.9 Irradiate the 2 sample vessel group at 344 watts for 10

minutes, or the 6-sample vessel group at 574 watts for 10
minutes.

10.1.4.3.10 This program brings the samples to 175°C in 5.5 minutes; the
temperature remains between 170-180°C for the balance of the 10
minute irradiation period. The pressure should peak at less
than 6 atmospheres (atm) for most samples. The pressure may
exceed these limits in the case of high concentrations of
carbonate or organic compounds. In these cases, the pressure
will be limited by the relief pressure of the vessel to 7.5
(±0.7 atm).

10.1.4.3.11 Allow the vessels to cool for a minimum of 5 minutes before

removing them from the microwave unit, with exhaust fan on.
Allow the vessels to cool to room temperature before opening.
The vessels must be carefully vented and uncapped in a fume
hood.

10.1.4.3.12 Weigh each vessel assembly. If the weight of acid plus the
sample has decreased by more than 10% from the original weight,
discard the digests. Determine the reason for the loss.
Losses typically are attributed to use of digestion time longer
than ten minutes, using too large of a sample, or having
improper heating conditions. Once the source of the losses has
been corrected, prepare a new set of samples for digestion.

10.1.4.3.13 Sample Filtration: Shake the sample well to mix in any

condensate within the digestion vessel before being opened.

ILM05.3 D-20/ICP-AES
 Exhibit D (ICP-AES) -- Section 10
Procedure (Con’t)

Filter the digestion vessel into a 50 mL glass volumetric flask

through filter paper. Rinse the sample digestion vessel, cap,
connecting tube, and (if venting occurred) the overflow vessel
into the 50 mL glass flask. Dilute to 50 mL. The samples are
now ready for analysis. Concentrations so determined shall be
reported as “total”.

10.1.5 Non-Prepared Samples

10.1.5.1 Preparation Method/Code (NP1)

10.1.5.1.1 This code shall be used to report samples that are not digested
prior to analysis (e.g., dissolved metal samples that the
Contractor was instructed not to digest).

10.1.5.1.2 This Preparation Method/Code shall also be used to report the

non-prepared Method Detection Limit (MDL). The concentration
of this MDL shall be used to determine the appropriate
concentration qualifier for the results of non-prepared samples
and instrument Quality Control (QC) analyses.

10.2 Microwave Digestion Cleaning Procedure

10.2.1 Initial Cleaning of the PTFE PFA Digestion Vessels

10.2.1.1 Prior to first use - new vessels must be annealed before they are
used. A pretreatment/cleaning procedure must be followed. This
procedure calls for heating the vessels for 96 hours at 200°C.
The vessels must be disassembled during annealing and the sealing
surfaces (the top of the vessel or its rim) must not be used to
support the vessel during annealing.

10.2.1.2 Rinse in reagent water.

10.2.1.3 Immerse in 1:1 HCl for a minimum of 3 hours after the cleaning
bath has reached a temperature just below boiling.

10.2.1.4 Rinse in reagent water.

10.2.1.5 Immerse in 1:1 HNO3 for a minimum of 3 hours after the cleaning
bath has reached a temperature just below boiling.

10.2.1.6 The vessels are then rinsed with copious amounts of reagent water
prior to use for any analyses under this contract.

10.2.2 Cleaning Procedure between Sample Digestions

10.2.2.1 Wash entire vessel in hot water using laboratory-grade non-phos­

phate detergent.

10.2.2.2 Rinse with 1:1 nitric acid.

10.2.2.3 Rinse 3 times with reagent water.

10.3 Sample Analysis

10.3.1 Set up the instrument with proper operating parameters established in

Section 9.1. The instrument must be allowed to become thermally
stable before beginning. This usually requires at least 30 minutes
of operation prior to calibration.

10.3.2 Initiate appropriate operating configuration of computer.

D-21/ICP-AES ILM05.3
Exhibit D (ICP-AES) -- Sections 10 & 11
Data Analysis and Calculations

10.3.3 Profile and calibrate instrument according to instrument

manufacturer’s recommended procedures, using mixed calibration
standard solutions such as those described in Section 7.2.4.5.1.

10.3.4 A minimum of two replicate exposures is required for standardization

and all QC and sample analyses. The average result of the multiple
exposures for the standardization and all QC and sample analyses
shall be used.

11.0 DATA ANALYSIS AND CALCULATIONS

11.1 Water/Aqueous Sample Calculation

The concentrations determined in the digestate are to be reported in

units of microgram per Liter (µg/L):

EQ. 2 Aqueous Sample Concentration

WHERE, C = Instrument value in µg/L

Vf = Final digestion volume (mL)
Vi = Initial digestion volume (mL)
DF = Dilution Factor

11.2 Soil Sample Calculation

The concentrations determined in the digestate are to be reported on the

basis of the dry weight of the sample, in units of milligrams per
kilogram (mg/kg):

EQ. 3 Soil Sample Concentration

WHERE, C = Concentration (mg/L)

V = Final sample volume in Liters (L)
W = Wet sample weight (kg)
S = % Solids/100 (see Exhibit D - Introduction to
Analytical Methods, Section 1.6).
DF = Dilution Factor

ILM05.3 D-22/ICP-AES
 Exhibit D (ICP-AES) -- Section 11

Data Analysis and Calculations (Con’t)

11.3 Adjusted Method Detection Limit (MDL)/Adjusted Contract Required

Quantitation Limit (CRQL) Calculation

To calculate the adjusted MDL or adjusted CRQL for water/aqueous

samples, substitute the value of the MDL (µg/L) or CRQL (µg/L) into the
“C” term in Equation 2 above.

Calculate the adjusted MDL or adjusted CRQL for soil samples as follows:

EQ. 4 Adjusted Soil MDL/Adjusted Soil CRQL Concentration

WHERE, C = MDL or CRQL concentration (mg/kg)

WM = Minimum method required wet sample weight (g)
WR = Reported wet sample weight (g)
VM = Method required final sample volume (mL)
VR = Reported final sample volume (mL)
S = % Solids/100 (see Exhibit D - Introduction to
Analytical Methods, Section 1.6).
DF = Sample Dilution Factor

D-23/ICP-AES ILM05.3
Exhibit D (ICP-AES) -- Section 12
Quality Control

12.0 QUALITY CONTROL (QC)

12.1 Initial Calibration Verification (ICV)

The ICV standard shall be prepared in the same acid matrix as the
calibration standards and in accordance with the instructions provided
by the supplier. If measurements exceed the control limits of 90% (low)
and 110% (high), the analysis shall be terminated, the problem
corrected, the instrument recalibrated, and the calibration reverified.
Information regarding the ICV shall be reported on Form IIA-IN.

12.2 Continuing Calibration Verification (CCV)

The CCV standard shall be prepared by combining compatible elements at a

concentration equivalent to the mid-points of their respective
calibration curves. If the deviation of the CCV is greater than the
control limits specified of 90% (low) and 110% (high), the analysis
shall be stopped, the problem corrected, the instrument recalibrated,
the calibration verified, and the re-analysis of preceding 10 analytical
samples or all analytical samples analyzed since the last compliant
calibration verification shall be performed for the analytes affected.
Information regarding the CCV shall be reported on Form IIA-IN.

12.3 Contract Required Quantitation Limit (CRQL) Check Standard (CRI)

12.3.1 To verify linearity near the CRQL, a standard at the CRQL (CRI) shall
be prepared, in the same acid matrix as the calibration standards,
and analyzed at the beginning (immediately following the ICV/ICB) and
end of each sample analysis run, immediately preceding the
Interference Check Sample (ICS) analyses. In addition, the
Contractor shall analyze the CRI at a frequency of not less than once
per 20 analytical samples1 per analysis run. These analyses of the
CRI sample shall be immediately followed by the ICS analyses. [That
is, the analytical run sequence shall be CRI, ICS Solution A (ICSA),
ICS Solution AB (ICSAB), CCV and Continuing Calibration Blank (CCB),
in that order].

12.3.2 The CRI shall be run for every wavelength used for analysis, except
those for Al, Ba, Ca, Fe, Mg, Na, and K. Information regarding the
CRI shall be reported on Form IIB-IN.

12.3.3 If the percent recovery of the CRI falls outside the control limits
of 70-130% (50-150% for antimony, lead, and thallium) for one or more
analytes, the CRI shall be re-analyzed immediately for those analytes
only. If the results of the re-analysis for those analytes fall
within the control limits, no further corrective action is required.
If the results of the re-analysis for those analytes do not fall
within the control limits, the analysis shall be terminated, the
problem corrected, the instrument recalibrated, the CRI analyzed, and
the samples associated with the CRI re-analyzed.

12.4 Blank Analyses

There are two different types of blanks required by this method. The
calibration blank is used in establishing the analytical curve while the
Preparation Blank is used to monitor for possible contamination.

1
As defined in Exhibit G, CRI is an analytical sample.

ILM05.3 D-24/ICP-AES
 Exhibit D (ICP-AES) -- Section 12
Quality Control (Con’t)

12.4.1 Initial and Continuing Calibration Blank (ICB/CCB)

The ICB and CCB are prepared with acids and reagent water. If the
absolute value of the calibration blank (ICB/CCB) result exceeds the
CRQL (see Exhibit C), the analysis shall be terminated, the problem
corrected, the instrument recalibrated, the calibration verified, and
re-analysis of the preceding 10 analytical samples or all analytical
samples analyzed since the last compliant calibration blank shall be
performed for the elements affected.

12.4.2 Preparation Blank (PB)

12.4.2.1 The PB shall contain all the reagents and in the same volumes as
used in processing the samples. The PB shall be carried through
the complete procedure and contain the same acid concentration in
the final solution as the sample solution used for analysis.

12.4.2.2 At least one PB, consisting of reagent water processed through

each sample preparation and analysis procedure (see Section 10),
shall be prepared and analyzed with every Sample Delivery Group
(SDG), or with each batch2 of samples digested, whichever is more
frequent.

12.4.2.3 The first batch of samples in an SDG is to be assigned to

Preparation Blank one, the second batch to Preparation Blank two,
etc. (see Form III-IN). Each Sample Data Package shall contain
the results of all PB analyses associated with the samples in that
SDG.

12.4.2.4 The PB is to be reported for each SDG and used in all analyses to
ascertain whether sample concentrations reflect contamination in
the following manner:

12.4.2.4.1 If the absolute value of the concentration of the blank is less

than or equal to the CRQL (see Exhibit C), no further action is
required.

12.4.2.4.2 If any analyte concentration in the blank is above the CRQL,

the lowest concentration of that analyte in the associated
samples shall be greater than or equal to 10 times the blank
concentration. Otherwise, all samples associated with the
blank, with the analyte concentration less than 10 times the
blank concentration and above the CRQL, shall be redigested and
re-analyzed with appropriate new Quality Control (QC) for that
analyte. The only exception to this shall be an identified
field blank. The sample concentration is not to be corrected
for the blank value.

12.4.2.4.3 If the concentration of the blank is below the negative CRQL,

then all samples reported below 10 times the CRQL associated
with the blank, shall be redigested and re-analyzed with
appropriate new QC.

12.4.2.4.4 The values for the PB shall be reported on Form III-IN.

12.5 Interference Check Sample (ICS)

12.5.1 The ICS is prepared by the analyst or obtained from USEPA, if

available.

2
A group of samples prepared at the same time.

D-25/ICP-AES ILM05.3
Exhibit D (ICP-AES) -- Section 12
Quality Control (Con’t)

12.5.2 To verify interelement and background correction factors, the

Contractor shall analyze and report the results for the ICS, for all
elements on the Target Analyte List (TAL) and for all interferents
(target and non-target), at the beginning and end of each analysis
run, but not before the ICV. In addition, the Contractor shall
analyze and report the results for the ICS at a frequency of not less
than once per 20 analytical samples3 per analysis run. These
analyses of the ICS shall be immediately followed by the analysis of
a CCV/CCB pair. The ICS solutions shall be obtained from USEPA, if
available, and analyzed according to the instructions supplied with
the ICS. The Contractor shall not dilute the ICS more than is
necessary to meet the linear range values of the instrument.

12.5.3 The ICS consists of two solutions: Solution A and Solution AB.
Solution A consists of the interferents, and Solution AB consists of
the analytes mixed with the interferents. An ICS analysis consists
of analyzing both solutions consecutively, starting with Solution A.

12.5.4 The analytical results of ICS Solution A (ICSA) shall fall within the
control limit of ±2 times the CRQL of the analyte’s true value or
±20% of the analyte’s true value, whichever is greater (the true
value shall be zero unless otherwise stated) in the ICSA. For
example, if the analysis result(s) for Arsenic (CRQL = 10 µg/L, ICSA
true value = 0 µg/L) in the ICSA analysis during the run is 19 µg/L,
then the analytical result for Arsenic falls within the ±2 times the
CRQL window for Arsenic in the ICSA. If the analytical results of
the ICSA do not fall within the control limits, the analysis shall be
terminated, the problem corrected, the instrument recalibrated, and
re-analysis of the analytical samples analyzed since the last
compliant ICSA shall be performed. For analytes with CRQLs less than
5000 µg/L, the ICSA results shall be reported from an undiluted
sample analysis.

12.5.5 Results for the ICS Solution AB (ICSAB) during the analytical runs
shall fall within the control limit of ±2 times the CRQL of the true
value or ±20% of the true value, whichever is greater, for the
analytes included in the ICSAB. If the analytical results of the
ICSA do not fall within the control limits, the analysis shall be
terminated, the problem corrected, the instrument recalibrated, and
re-analysis of the analytical samples analyzed since the last
compliant ICSAB shall be performed.

NOTE: The control limits and concentrations for the ICSAB are being
monitored. These may be adjusted to provide greater control of
interferences.

12.5.6 If true values for analytes contained in the ICS are not supplied
with the solutions, the mean shall be determined by initially
analyzing the ICS at least five times repetitively for the particular
analytes. This mean determination shall be made during an analytical
run where the results for the previously supplied ICS met all
contract specifications. Additionally, the results of this initial
mean determination shall be used as the true value for the lifetime
of that solution (i.e., until the solution is exhausted). Only if
the ICS solutions are not available from USEPA, independent Check
Samples shall be prepared with interferent and analyte concentrations
at the levels specified in Table 1 - Interferent and Analyte
Elemental Concentrations Used for ICP-AES Interference Check Sample
(ICS). The mean value and standard deviation shall be established by

3
As defined in Exhibit G, ICSA and ICSAB are analytical samples.

ILM05.3 D-26/ICP-AES
 Exhibit D (ICP-AES) -- Section 12
Quality Control (Con’t)

initially analyzing the Check Samples at least five times

repetitively for each parameter on Form IVA-IN. Results shall fall
within the control limit of ±2 times the CRQL of the established mean
value or ±20% of the established mean value, whichever is greater.
The mean and standard deviation shall be reported in the raw data.
Results from the ICS analyses shall be reported on Form IVA-IN for
all Inductively Coupled Plasma - Atomic Emission Spectroscopy (ICP­
AES) analytes.

12.6 Spike Sample Analysis

12.6.1 The spike sample analysis is designed to provide information about

the effect of the sample matrix on the digestion and/or measurement
methodology. If a digestion is performed, the spike is added before
the digestion (i.e., prior to the addition of other reagents). At
least one spike sample analysis (matrix spike) shall be performed on
each group of samples of a similar matrix type (i.e., water, soil) or
for each SDG.4

12.6.2 If the spike analysis is performed on the same sample that is chosen
for the duplicate sample analysis, spike calculations shall be
performed using the results of the sample designated as the “original
sample” (see Section 12.7). The average of the duplicate results
cannot be used for the purpose of determining percent recovery.
Samples identified as field blanks and Performance Evaluation (PE)
samples shall not be used for spiked sample analysis. USEPA may
require that a specific sample be used for the spike sample analysis.

12.6.3 The analyte spike shall be added in the amount given in Table 2 -
Spiking Levels for Spike Sample Analysis, for each element analyzed.

NOTE: See Table 2 footnotes for concentration levels and

applications.

12.6.4 If the spike recovery is not at or within the limits of 75-125%, the
data of all samples received and associated with that spike sample
shall be flagged with the letter “N” on Forms IA/IB-IN and VA-IN. An
exception to this rule is granted when the sample concentration
exceeds the spike added concentration by a factor of four or more.
In such an event, the data shall be reported unflagged even if the
percent recovery does not meet the 75-125% recovery criteria.

12.6.5 When the matrix spike recovery falls outside the control limits and
the sample result does not exceed four times the spike added, a post-
digestion spike shall be performed for those elements that do not
meet the specified criteria (exception: Ag). Note that if a post-
digestion spike analysis is required for an analyte, the same EPA
sample that was used for the matrix spike analysis shall be used for
the post-digestion spike analysis. Spike the unspiked aliquot of the
sample at two times the indigenous level or two times the CRQL,
whichever is greater. Results of the post-digestion spike shall be
reported on Form VB-IN.

12.6.6 In the instance where there is more than one spike sample per matrix
per SDG, if one spike sample recovery is not within contract
criteria, flag all the samples of the same matrix and method in the
SDG. Individual component percent recoveries are calculated as
follows:

4
USEPA may require additional spike sample analyses, upon USEPA Regional
CLP Project Officer (CLP PO) request.

D-27/ICP-AES ILM05.3
Exhibit D (ICP-AES) -- Section 12
Quality Control (Con’t)

EQ. 5 Spike Percent Recovery

WHERE, SSR = Spiked Sample Result

SR = Sample Result
SA = Spike Added

12.6.7 When sample concentration is less than the Method Detection Limit
(MDL), use SR = 0 only for purposes of calculating percent recovery.
The Spike Sample Results (SSRs), Sample Results (SRs), Spike Added
(SA), and percent recovery (positive or negative) shall be reported
on Form VA-IN.

12.6.8 The units used for reporting SSRs will be identical to those used for
reporting sample results on Form IA-IN.

12.7 Duplicate Sample Analysis

12.7.1 One duplicate sample shall be analyzed from each group of samples of
a similar matrix type (i.e., water, soil) or for each SDG.5
Duplicates cannot be averaged for reporting on Form IA-IN.

12.7.2 Duplicate sample analyses are required for percent solids. Samples
identified as field blanks and PE samples shall not be used for
duplicate sample analysis. USEPA may require that a specific sample
be used for duplicate sample analysis. The Relative Percent
Difference (RPD) for each component is calculated as follows:

EQ. 6 Duplicate Sample Relative Percent Difference

WHERE, RPD = Relative Percent Difference

S = Sample Result (original)
D = Duplicate Result

12.7.3 The results of the duplicate sample analyses shall be reported on

Form VI-IN. A control limit of 20% for RPD shall be used for
original and duplicate sample values greater than or equal to five
times the CRQL (see Exhibit C). A control limit of the CRQL value
shall be entered in the “Control Limit” column on Form VI-IN if
either the sample or duplicate value is less than five times the
CRQL. If the sample and duplicate values are greater than or equal
to five times the CRQL, or if the sample and duplicate values are
less than the CRQL, the “Control Limit” field is left empty.

12.7.4 If one result is above five times the CRQL level and the other is
below, use the CRQL criteria to determine if the duplicate analysis
is in control. If both sample and duplicate values are less than the

5
USEPA may require additional duplicate sample analyses, upon USEPA
Regional CLP PO request.

ILM05.3 D-28/ICP-AES
 Exhibit D (ICP-AES) -- Section 12
Quality Control (Con’t)

MDL, the RPD is not calculated on Form VI-IN. For solid sample or
solid duplicate results less than five times the CRQL, enter the
value of the CRQL, corrected for sample weight and percent solids,
(i.e., original, not duplicate sample weight and percent solids), in
the “Control Limit” column. If the duplicate sample results are
outside the control limits, flag all the data for samples received
associated with that duplicate sample with an “*” on Forms IA/IB-IN
and VI-IN. In the instance where there is more than one duplicate
sample per SDG, if one duplicate result is not within contract
criteria, flag all samples of the same matrix in the SDG. The
percent difference data will be used by USEPA to evaluate the long-
term precision of the methods for each element. Specific control
limits for each element will be added to Form VI-IN at a later date
based on these precision results.

12.8 Laboratory Control Sample (LCS) Analysis

12.8.1 Water/aqueous and solid LCS shall be analyzed for each analyte using
the same sample preparations, analytical methods, and Quality
Assurance/Quality Control (QA/QC) procedures employed for the EPA
samples received.

12.8.1.1 The aqueous LCS solution (LCSW) shall be obtained from USEPA [if
unavailable, the ICV solution(s) may be used]. One LCSW shall be
prepared and analyzed for every group of aqueous samples in a SDG,
or for each batch of aqueous samples digested, whichever is more
frequent.

12.8.1.2 The USEPA provided solid LCS (LCSS) shall be prepared and analyzed
using each of the procedures applied to the solid samples received
(exception: percent solids determination not required). If the
USEPA LCSS is unavailable, other USEPA QC Check Samples or other
certified materials may be used. The control limits for these
materials and samples must be documented. One LCSS shall be
prepared and analyzed for every group of solid samples in a SDG,
or for each batch of samples digested, whichever is more frequent.

12.8.2 All LCS and percent recovery results shall be reported on Form VII-
IN. If the percent recovery for the LCSW falls outside the control
limits of 80-120% (exception: Ag and Sb), the analyses shall be
terminated, the problem corrected, and the samples associated with
that LCSW redigested and re-analyzed with appropriate new QC.

12.8.3 If the results for the LCSS fall outside the control limits
established by USEPA, the analyses shall be terminated, the problem
corrected, and the samples associated with that LCSS redigested and
re-analyzed with appropriate new QC.

12.9 ICP-AES Serial Dilution Analysis

12.9.1 Prior to reporting concentration data for the analyte elements, the
Contractor shall analyze and report the results of the ICP-AES serial
dilution analysis. The ICP-AES serial dilution analysis shall be
performed on a sample from each group of samples of a similar matrix
type (i.e., water, soil) or for each SDG, whichever is more frequent.
Samples identified as field blanks and PE samples shall not be used
for serial dilution analysis.

12.9.2 If the analyte concentration is sufficiently high (minimally a factor

of 50 above the MDL in the original sample), the serial dilution (a
five fold dilution) shall then agree within 10% of the original
determination after correction for dilution. If the dilution

D-29/ICP-AES ILM05.3
Exhibit D (ICP-AES) -- Section 12
Quality Control (Con’t)

analysis for one or more analytes is not within a control limit of

10%, a chemical or physical interference effect must be suspected,
and the data for all affected analytes in the samples received and
associated with that serial dilution must be flagged with an “E” on
Form VIII-IN and Forms IA/IB-IN.

12.9.3 The percent differences for each component are calculated as follows:

EQ. 7 Serial Dilution Percent Differences

WHERE, I = Initial Sample Result (Instrument reading)

S = Serial Dilution Result (Instrument reading x5)

12.9.4 In the instance where there is more than one serial dilution per SDG,
if one serial dilution result is not within contract criteria, flag
all the samples of the same matrix in the SDG. Serial dilution
results and “E” flags shall be reported on Form VIII-IN.

12.10 Method Detection Limit (MDL) Determination

12.10.1 Before any field samples are analyzed under this contract, the MDLs
shall be determined for non-prepared analyses (Preparation
Method/Code “NP1”), each digestion procedure and instrument used,
prior to the start of contract analyses, and annually thereafter, and
shall meet the levels specified in Exhibit C.

An MDL study shall be performed after major instrument maintenance,

or changes in instrumentation or instrumental conditions to verify
the current sensitivity of the analysis.

12.10.1.1 To determine the MDLs, the Contractor shall run MDL studies
following the procedures given in 40 CFR, Part 136. The
Contractor shall prepare the MDL samples by each digestion
procedure used and shall analyze these samples on each instrument
used. The Contractor shall also analyze the non-prepared MDL
samples on each instrument used.

12.10.1.2 The determined concentration of the MDL shall be less than half
the concentration of the CRQL listed in Exhibit C.

12.10.1.3 The concentration of the non-prepared MDL (Preparation Method/Code

“NP1”) shall be used to determine the appropriate concentration
qualifier for the results of non-prepared samples and instrument
QC analyses.

12.10.1.4 The results of the MDL determination studies shall be forwarded to

the USEPA Regional CLP PO, Sample Management Office (SMO), and
Quality Assurance Technical Support (QATS).

12.10.1.5 The MDL results shall be reported on Form IX-IN.

12.11 Interelement Corrections

12.11.1 Before any field samples are analyzed under this contract, the
interelement correction factors shall be determined prior to the
start of contract analyses and at least quarterly thereafter.
Correction factors for spectral interference due to Al, Ca, Fe, and
Mg shall be determined for all ICP-AES instruments at all wavelengths

ILM05.3 D-30/ICP-AES
 Exhibit D (ICP-AES) -- Section 12
Quality Control (Con’t)

used for each analyte reported by ICP-AES. Interelement correction

factors shall also be reported for any other elements (including
those on the TAL) that have been determined to interfere with the
requested target analyte(s).

NOTE: Depending on sample matrix and interferences, it may be

necessary to analyze interelement correction factors at a frequency
greater than quarterly and/or at multiple concentrations comparable
to the sample interferent levels.

12.11.2 If the instrument was adjusted in any way that may affect the ICP-AES
interelement correction factors, the factors shall be redetermined
and the results submitted for use. In addition, all data used for
the determination of the interelement correction factors shall be
available to the USEPA during an on-site laboratory evaluation.
Results from interelement correction factors determination shall be
reported on Form XA-IN and Form XB-IN for all ICP-AES analytes.

12.12 Linear Range Standard (LRS)

12.12.1 Before any field samples are analyzed under this contract, the linear
ranges shall be determined and reported prior to the start of
contract analyses, and at least quarterly thereafter by the analysis
of a linear range verification check standard, for each element on
Form XI-IN. The standard shall be analyzed during a routine
analytical run performed under this contract. The analytically
determined concentration of this standard shall be within 5% of the
true value. This concentration is the upper limit of the ICP-AES
linear range beyond which results cannot be reported under this
contract without dilution of the analytical sample.

12.13 Example Analytical Sequence for ICP-AES

S0

ICV

ICB

CRI

ICSA

ICSAB

CCV

CCB

10 samples

CCV

CCB

7 samples

CRI

ICSA

ICSAB

CCV

CCB

10 samples, etc.

D-31/ICP-AES ILM05.3
Exhibit D (ICP-AES) -- Sections 13-16
Method Performance

13.0 METHOD PERFORMANCE

Not applicable.

14.0 POLLUTION PREVENTION

See Section 1.15 in Exhibit D - Introduction to Analytical Methods.

15.0 WASTE MANAGEMENT

See Section 1.16 in Exhibit D - Introduction to Analytical Methods.

16.0 REFERENCES

16.1 US Environmental Protection Agency. Methods for Chemical Analysis of

Water and Wastes. Method 200.7. December 1982.

16.2 US Environmental Protection Agency. Test Methods for Evaluating Solid

Waste, Physical/Chemical Methods (SW-846). Method 3050B. Third Edition,
Update III. December 1996.

16.3 American Society for Testing and Materials. Standard Practice for Sample
Digestion Using Closed Vessel Microwave Heating Technique for the
Determination of Total Recoverable Metals in Water. D4309-91. October
1991.

16.4 US Government Printing Office. 40 Code of Federal Regulations, Part 136,

Section 1, Appendix B.

16.5 US Environmental Protection Agency. Test Methods for Evaluating Solid

Waste, Physical/Chemical Methods (SW-846). Method 3015. Third Edition,
Update II. September 1994.

16.6 US Environmental Protection Agency. Test Methods for Evaluating Solid

Waste, Physical/Chemical Methods (SW-846). Method 3051. Third Edition,
Update II. September 1994.

ILM05.3 D-32/ICP-AES
 Exhibit D (ICP-AES) -- Section 17
Tables/Diagrams/Flowcharts

17.0 TABLES/DIAGRAMS/FLOWCHARTS

TABLE 1: Interferent and Analyte Elemental Concentrations Used for

ICP-AES Interference Check Sample (ICS)

Analytes (mg/L) Interferents (mg/L)

Ag 0.2 Al 250
As 0.1 Ca 250
Ba 0.5 Fe 100
Be 0.5 Mg 250
Cd 1.0
Co 0.5
Cr 0.5
Cu 0.5
Mn 0.5
Ni 1.0
Pb 0.05
Sb 0.6
Se 0.05
Tl 0.1
V 0.5
Zn 1.0

NOTE: ICS Solution A (ICSA) contains the interferents at the indicated

concentrations. The ICSA may be analyzed at twice the concentration
indicated when interferences are present at higher concentrations in the
sample. ICS Solution AB (ICSAB) contains all of the analytes and
interferents listed above at the indicated concentrations.

D-33/ICP-AES ILM05.3
Exhibit D (ICP-AES) -- Section 17
Tables/Diagrams/Flowcharts

TABLE 2: Spiking Levels for Spike Sample Analysis

Water Soil(1) Water Soil(1)

Element (µg/L) (mg/kg) Element (µg/L) (mg/kg)
Aluminum 2,000 * Magnesium * *
Antimony 100 20 Manganese 500 100
Arsenic 40 8 Nickel 500 100
Barium 2,000 400 Potassium * *
Beryllium 50 10 Selenium 50 10
Cadmium 50 10 Silver 50 10
Calcium * * Sodium * *
Chromium 200 40 Thallium 50 10
Cobalt 500 100 Vanadium 500 100
Copper 250 50 Zinc 500 100
Iron 1,000 *
Lead 20 4

*
No spike required. NOTE: Elements without spike levels, and not
designated with an asterisk, shall be spiked at appropriate levels.
1
The levels shown indicate concentrations in the spike sample when the
wet weight of 1 gram of sample is taken for analysis. Adjustment shall be
made to maintain these spiking levels when the weight of sample taken deviates
by more than 10% of these values. Appropriate adjustment shall be made for
microwave digestion procedures where 0.5 grams of sample or 50 mL (45 mL of
sample plus 5 mL of acid) or 55 mL (50 mL of sample plus 5 mL of acid) of
aqueous sample are required for analysis.

EQ. 8 Spiking Level Adjustment

ILM05.3 D-34/ICP-AES
 EXHIBIT D - PART B

ANALYTICAL METHODS
FOR
INDUCTIVELY COUPLED PLASMA -
MASS SPECTROMETRY

D-1/ICP-MS ILM05.3
 THIS PAGE INTENTIONALLY LEFT BLANK

ILM05.3 D-2/ICP-MS
 Exhibit D - Analytical Methods for ICP-MS

Table of Contents

Section Page

1.0 SCOPE AND APPLICATION . . . . . . . . . . . . . . . . . . . . . . . . 5

2.0 SUMMARY OF METHOD . . . . . . . . . . . . . . . . . . . . . . . . . . 5

3.0 DEFINITIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

4.0 INTERFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4.1 Isobaric Elemental Interferences . . . . . . . . . . . . . . . 6
4.2 Abundance Sensitivity . . . . . . . . . . . . . . . . . . . . . 6
4.3 Isobaric Polyatomic Ion Interferences . . . . . . . . . . . . . 6
4.4 Physical Interferences . . . . . . . . . . . . . . . . . . . . 6
4.5 Memory Interferences . . . . . . . . . . . . . . . . . . . . . 7

5.0 SAFETY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

6.0 EQUIPMENT AND SUPPLIES . . . . . . . . . . . . . . . . . . . . . . . 8

6.1 Glassware/Labware . . . . . . . . . . . . . . . . . . . . . . . 8
6.2 Inductively Coupled Plasma Mass Spectrometer (ICP-MS) . . . . . 8

7.0 REAGENTS AND STANDARDS . . . . . . . . . . . . . . . . . . . . . . . 9

7.1 Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
7.2 Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
7.3 Blanks . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE . . . . . . . . . . . . 13

8.1 Sample Collection and Preservation . . . . . . . . . . . . . . 13
8.2 Procedures for Sample Storage . . . . . . . . . . . . . . . . . 13
8.3 Procedure for Sample Digestate Storage . . . . . . . . . . . . 13
8.4 Contract Required Holding Time . . . . . . . . . . . . . . . . 13

9.0 CALIBRATION AND STANDARDIZATION . . . . . . . . . . . . . . . . . . . 14

9.1 Instrument Operating Parameters . . . . . . . . . . . . . . . . 14
9.2 Inductively Coupled Plasma - Mass Spectrometry (ICP-MS)
Instrument Calibration Procedure . . . . . . . . . . . . . . . 14
9.3 Initial Calibration Verification (ICV) . . . . . . . . . . . . 15
9.4 Continuing Calibration Verification (CCV) . . . . . . . . . . . 15
9.5 Initial and Continuing Calibration Blank (ICB/CCB) . . . . . . 16

10.0 PROCEDURE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
10.1 Sample Preparation . . . . . . . . . . . . . . . . . . . . . . 16
10.2 Sample Analysis . . . . . . . . . . . . . . . . . . . . . . . . 17

11.0 DATA ANALYSIS AND CALCULATIONS . . . . . . . . . . . . . . . . . . . 19

11.1 Recommended Elemental Equations . . . . . . . . . . . . . . . . 19
11.2 Data Value Corrections . . . . . . . . . . . . . . . . . . . . 19
11.3 Multiple Monitored Isotopes . . . . . . . . . . . . . . . . . . 19
11.4 Prepared Sample Analysis . . . . . . . . . . . . . . . . . . . 19
11.5 Prepared Sample Analysis (HW3) . . . . . . . . . . . . . . . . 20
11.6 Adjusted Method Detection Limit (MDL)/Adjusted Contract
Required Quantitation Limit (CRQL) Calculation . . . . . . . . 20

12.0 QUALITY CONTROL (QC) . . . . . . . . . . . . . . . . . . . . . . . . 21

12.1 Tune Standard . . . . . . . . . . . . . . . . . . . . . . . . . 21
12.2 Initial Calibration Verification (ICV) . . . . . . . . . . . . 21
12.3 Continuing Calibration Verification (CCV) . . . . . . . . . . . 21
12.4 Contract Required Quantitation Limit (CRQL) Check
Standard (CRI) . . . . . . . . . . . . . . . . . . . . . . . . 21
12.5 Blank Analyses . . . . . . . . . . . . . . . . . . . . . . . . 22
12.6 Interference Check Sample (ICS) . . . . . . . . . . . . . . . . 23

D-3/ICP-MS ILM05.3
 Exhibit D - Analytical Methods for ICP-MS

Table of Contents (Con’t)

Section Page

12.7 Spike Sample Analysis . . . . . . . . . . . . . . . . . . . . . 24

12.8 Duplicate Sample Analysis . . . . . . . . . . . . . . . . . . . 25
12.9 Laboratory Control Sample (LCS) Analysis . . . . . . . . . . . 26
12.10 ICP-MS Serial Dilution Analysis . . . . . . . . . . . . . . . . 26
12.11 Internal Standards . . . . . . . . . . . . . . . . . . . . . . 27
12.12 Method Detection Limit (MDL) Determination . . . . . . . . . . 27
12.13 Linear Dynamic Range (LDR) . . . . . . . . . . . . . . . . . . 27
12.14 Example Analytical Sequence for ICP-MS . . . . . . . . . . . . 28

13.0 METHOD PERFORMANCE . . . . . . . . . . . . . . . . . . . . . . . . . 29

14.0 POLLUTION PREVENTION . . . . . . . . . . . . . . . . . . . . . . . . 29

15.0 WASTE MANAGEMENT . . . . . . . . . . . . . . . . . . . . . . . . . . 29

16.0 REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29

17.0 TABLES/DIAGRAMS/FLOWCHARTS . . . . . . . . . . . . . . . . . . . . . 30
Table 1. Isobaric Molecular-Ion Interferences . . . . . . . . . . 30
Table 2. Mass Choices for Elements that Must Be Monitored
During the Analytical Run . . . . . . . . . . . . . . . . 33
Table 3. Recommended Elemental Expressions for Isobaric
Interferences . . . . . . . . . . . . . . . . . . . . . . 34
Table 4. Internal Standards . . . . . . . . . . . . . . . . . . . 35
Table 5. Spiking Levels for Spike Sample Analysis . . . . . . . . 35

ILM05.3 D-4/ICP-MS
 Exhibit D (ICP-MS) -- Sections 1-3
Scope and Application

1.0 SCOPE AND APPLICATION

This method provides procedures for the use of Inductively Coupled

Plasma - Mass Spectrometry (ICP-MS) to determine the concentration of
dissolved and total recoverable elements in water/aqueous samples taken
from hazardous waste sites. This method is applicable to all metals in
the Target Analyte List (TAL) for ICP-MS in Exhibit C.

2.0 SUMMARY OF METHOD

This method describes the multi-element determination of trace elements

by Inductively Coupled Plasma - Mass Spectrometry (ICP-MS). Sample
material in solution is introduced by nebulization into a radio
frequency plasma where energy transfer processes cause desolvation,
atomization, and ionization. The ions are extracted from the plasma
through a differentially pumped vacuum interface and separated on the
basis of their mass-to-charge ratio. The separated ions are detected
and the ion information processed by a data handling system.
Interferences related to the technique must be recognized and corrected.
Such corrections may include compensation for isobaric elemental
interferences and interferences from polyatomic ions derived from plasma
gas, reagents, or sample matrix. Instrumental drift, as well as
suppressions or enhancements of instrument response, must be corrected
for the use of internal standards.

3.0 DEFINITIONS

See Exhibit G for a complete list of definitions.

D-5/ICP-MS ILM05.3
Exhibit D (ICP-MS) -- Section 4
Interferences

4.0 INTERFERENCES

Several types of interferences may cause inaccuracies in the

determination of trace elements by Inductively Coupled Plasma - Mass
Spectrometry (ICP-MS). To prevent this, appropriate steps must be taken
in all analyses to ensure that potential interferences are taken into
account. Possible interferences are in Sections 4.1 through 4.5.

4.1 Isobaric Elemental Interferences

Isobaric Elemental Interferences are caused by isotopes of different

elements which form singly or doubly charged ions of the same nominal
mass-to-charge ratio, and which cannot be resolved by the mass
spectrometer. All elements determined by this method have, at minimum,
one isotope free of isobaric elemental interference. Of the analytical
isotopes recommended for use with this method, only selenium-82
(krypton) has an isobaric elemental interference. If alternative
analytical isotopes having higher natural abundances are selected, in
order to achieve greater sensitivity, an isobaric interference may
occur. All data obtained under such conditions must be corrected by
measuring the signal from another isotope of the interfering element and
subtracting the appropriate signal ratio from the isotope of interest.
A record of this correction process should be included with the report
of the data. It should be noted that such corrections will only be as
accurate as the accuracy of the isotope ratio used in the elemental
equation for data calculations. Relevant isotope ratios should be
established prior to the application of any corrections.

4.2 Abundance Sensitivity

Abundance Sensitivity is a property defining the degree to which the

wings of a mass peak contribute to adjacent masses. The abundance
sensitivity is affected by ion energy and mass filter operating
pressure. Wing overlap interferences may result when a small ion peak
is being measured adjacent to a large one. The potential for these
interferences should be recognized and the spectrometer resolution
should be adjusted to minimize.

4.3 Isobaric Polyatomic Ion Interferences

These are caused by ions consisting of more than one atom which have the
same nominal mass-to-charge ratio as the isotope of interest, and which
cannot be resolved by the mass spectrometer. These ions are commonly
formed in the plasma or interface system from support gases or sample
components. Most of the common interferences have been identified and
are listed in Table 1 - Isobaric Molecular-Ion Interferences, with the
target analytes affected. Such interferences must be recognized, and
when they cannot be avoided by the selection of alternative analytical
isotopes, appropriate corrections must be made to the data. Equations
for the correction of data should be established at the time of the
analytical run sequence, since the polyatomic ion interferences will be
highly dependent on the sample matrix and chosen instrument conditions.

4.4 Physical Interferences

These are associated with the physical processes which govern the
transport of the sample into the plasma, sample conversion processes in
the plasma, and the transmission of ions through the plasma-mass
spectrometer interface. These interferences may result in differences
between instrument responses for the sample and the calibration
standards. Physical interferences may occur in the transfer of solution
to the nebulizer (e.g., viscosity effects), at the point of aerosol
formation and transport to the plasma (e.g., surface tension), or during

ILM05.3 D-6/ICP-MS
 Exhibit D (ICP-MS) -- Sections 4 & 5
Safety

the excitation and ionization processes within the plasma itself. High
levels of dissolved solids in the sample may contribute to deposits of
material on the extraction and/or skimmer cones. Deposits can reduce
the effective diameter of the orifices and therefore ion transmission.
Dissolved solid levels not exceeding 0.2% (w/v) have been recommended to
reduce such effects. Internal standardization may be effectively used
to compensate for many physical interference effects. Internal
standards ideally should have similar analytical behavior to the
elements being determined.

4.5 Memory Interferences

Memory Interferences result when isotopes of elements in a previous

sample contribute to the signals measured in a new sample. Memory
effects, or carryover, can result from sample deposition on the sampler
and skimmer cones, as well as from the buildup of sample material in the
plasma torch and spray chamber. The site where these effects occur is
dependent on the element and can be minimized by flushing the system
with a rinse blank between samples (see Section 7.3.3). The possibility
of memory interferences should be recognized within an analytical run
and suitable rinse times should be used to reduce them. The rinse times
necessary for a particular element should be estimated prior to
analysis. This may be achieved by aspirating a standard, containing the
elements corresponding to ten times the upper end of the linear range
for a normal sample analysis period, followed by analysis of the rinse
blank at designated intervals. The length of time required to reduce
analyte signals to within a factor of ten of the Method Detection Limit
(MDL) should be noted. Memory interferences may also be assessed within
an analytical run by using a minimum of three replicate integrations for
data acquisition. If the integrated signal values drop consecutively,
the analyst should be alerted to the possibility of a memory effect, and
should examine the analyte concentration in the previous sample to
identify if it was high. If a memory interference is suspected, the
sample should be re-analyzed after a long rinse period.

5.0 SAFETY

See Section 1.14 in Exhibit D - Introduction to Analytical Methods.

D-7/ICP-MS ILM05.3
Exhibit D (ICP-MS) -- Section 6
Equipment and Supplies

6.0 EQUIPMENT AND SUPPLIES

Brand names, suppliers, and part numbers are for illustrative purposes
only. No endorsement is implied. Equivalent performance may be
achieved using equipment and supplies other than those specified here,
however, a demonstration of equivalent performance meeting the
requirements of this Statement of Work (SOW) is the responsibility of
the Contractor. The Contractor shall document any use of alternate
equipment or supplies in the Sample Delivery Group (SDG) Narrative.

6.1 Glassware/Labware

6.1.1 250 milliliter (mL) beaker or other appropriate vessel (glass or

plastic)

6.1.2 Watch glasses (glass or plastic)

6.1.3 Funnels

6.1.4 Graduated cylinders

6.1.5 Various volumetric flasks (Type A)

6.1.6 Thermometer that covers range of 0-200°C

6.1.7 Whatman No. 42 filter paper or equivalent

6.1.8 Hot plate, block digester, or other heating source capable of

maintaining 92-95°C.

6.1.9 Balances - Analytical Balance, 300 gram (g) capacity, and minimum
±0.1 milligram (mg).

6.2 Inductively Coupled Plasma Mass Spectrometer (ICP-MS) consisting of:

C An instrument capable of scanning the mass range 5-250 atomic mass

unit (amu) with a minimum resolution capability of 1 amu peak
width at 5% peak height and either a conventional or extended
dynamic range detector.

C A radio-frequency generator compliant with Federal Communications

Commission (FCC) regulations.

C A high purity (99.99%) argon gas supply.

C A variable speed peristaltic pump to deliver sample solution to

the nebulizer.

C A mass-flow controller on the nebulizer gas supply is required.

ILM05.3 D-8/ICP-MS
 Exhibit D (ICP-MS) -- Section 7
Reagents and Standards

7.0 REAGENTS AND STANDARDS

7.1 Reagents

Reagents may contain elemental impurities that might affect the

integrity of analytical data. Owing to the high sensitivity of
Inductively Coupled Plasma - Mass Spectrometry (ICP-MS), high-purity
reagents should be used whenever possible. Suitable acids are available
from a number of manufacturers or may be prepared by sub-boiling
distillation. Nitric acid is preferred for ICP-MS in order to minimize
polyatomic ion interferences. Several polyatomic ion interferences
result when hydrochloric acid (HCl) is used, however, it should be noted
that HCl is required to maintain stability in solutions containing
antimony and silver. When HCl is used, corrections for the chloride
polyatomic ion interferences must be applied to all data.

7.1.1 Reagent Water - The purity of this water must be equivalent to ASTM
Type II water (ASTM D1193-77). Use this preparation for all
reagents, standards, and dilutions of solutions.

7.1.2 Nitric Acid - Concentrated (specific gravity 1.41).

7.1.3 Nitric acid (1+1) - Add 500 milliliters (mL) conc. HNO3 to 400 mL of
reagent water and dilute to 1 Liter (L).

7.1.4 Nitric acid (1+9) - Add 100 mL conc. nitric acid to 400 mL of reagent
water and dilute to 1 L.

7.1.5 Hydrochloric acid - Concentrated (specific gravity 1.19).

7.1.6 Hydrochloric acid (1+1) - Add 500 mL conc. HCl to 400 mL of reagent
water and dilute to 1 L.

7.1.7 Hydrochloric acid (HCl) (1+4) - Add 200 mL conc. HCl to 400 mL
reagent water and dilute to 1 L.

7.1.8 Ammonium hydroxide - Concentrated (specific gravity 0.902).

7.1.9 Tartaric acid - (CASRN 87-69-4).

7.2 Standards

7.2.1 Introduction

The Contractor must provide all standards to be used with this

contract. These standards may be used only after they have been
certified according to the procedure in Exhibit E, Section 8.0. The
Contractor must be able to verify that the standards are certified.
Manufacturer’s certificates of analysis must be retained by the
Contractor and presented upon request.

7.2.2 Stock Standard Solutions

7.2.2.1 Stock standard solutions may be purchased from a reputable

commercial source or prepared from reagent grade chemicals or
metals (99.99-99.999% pure). All salts should be dried for 1 hour
at 105°C unless otherwise specified. Stock solutions should be
stored in Fluorinated Ethylene Propylene (FEP) fluorocarbon
bottles. Note that some metals, particularly those which form
surface oxides, require cleaning prior to being weighed. This may
be achieved by pickling the surface of the metal in acid. An
amount in excess of the desired weight should be pickled

D-9/ICP-MS ILM05.3
Exhibit D (ICP-MS) -- Section 7
Reagents and Standards (Con’t)

repeatedly, rinsed with water, dried and weighed until the desired
weight is achieved.

7.2.2.2 Aluminum solution, stock [1 mL = 1000 micrograms (µg) Al] - Pickle

aluminum metal in warm (1+1) HCl to an exact weight of 0.100 g.
Dissolve in 10 mL conc. HCl and 2 mL conc. nitric acid, heating to
effect solution. Continue heating until the volume is reduced to
4 mL. Cool and add 4 mLs of reagent water. Heat until volume is
reduced to 2 mL. Cool and dilute to 100 mL with reagent water.

7.2.2.3 Antimony solution, stock (1 mL = 1000 µg Sb) - Dissolve 0.100 g

antimony powder in 2 mL (1+1) nitric acid and 0.5 mL conc. HCl,
heating to effect solution. Cool, add 20 mL reagent water and
0.15 g tartaric acid. Warm the solution to dissolve the white
precipitate. Cool and dilute to 100 mL with reagent water.

7.2.2.4 Arsenic solution, stock (1 mL = 1000 µg As) - Dissolve 0.1320 g

As2O3 in a mixture of 50 mL reagent water and 1 mL conc. ammonium
hydroxide. Heat gently to dissolve. Cool and acidify solution
with 2 mL conc. nitric acid. Dilute to 100 mL with reagent water.

7.2.2.5 Barium solution, stock (1 mL = 1000 µg Ba) - Dissolve 0.1437 g

BaCO3 in a solution mixture of 10 mL reagent water and 2 mL conc.
nitric acid. Heat and stir to effect solution and degassing.
Dilute to 100 mL with reagent water.

7.2.2.6 Beryllium solution, stock (1 mL = 1000 µg Be) - Dissolve 1.965 g

BeSO4 C 4H2O (DO NOT DRY) in 50 mL reagent water. Add 1 mL conc.
nitric acid. Dilute to 100 mL with reagent water.

7.2.2.7 Bismuth solution, stock (1 mL = 1000 µg Bi) - Dissolve 0.1115 g

Bi2O3 in 5 mL conc. nitric acid. Heat to effect solution. Cool
and dilute to 100 mL with reagent water.

7.2.2.8 Cadmium solution, stock (1 mL = 1000 µg Cd) - Pickle cadmium metal

in (1+9) nitric acid to an exact weight of 0.100 g. Dissolve in 5
mL (1+1) nitric acid, heating to effect solution. Cool and dilute
to 100 mL with reagent water.

7.2.2.9 Chromium solution, stock (1 mL = 1000 µg Cr) - Dissolve 0.1923 g

CrO3 in a solution mixture of 10 mL reagent water and 1 mL conc.
nitric acid. Dilute to 100 mL with reagent water.

7.2.2.10 Cobalt solution, stock (1 mL = 1000 µg Co) - Pickle cobalt metal

in (1+9) nitric acid to an exact weight of 0.100 g. Dissolve in 5
mL (1+1) nitric acid, heating to effect solution. Cool and dilute
to 100 mL with reagent water.

7.2.2.11 Copper solution, stock (1 mL = 1000 µg Cu) - Pickle copper metal

in (1+9) nitric acid to an exact weight of 0.100 g. Dissolve in 5
mL (1+1) nitric acid, heating to effect solution. Cool and dilute
to 100 mL with reagent water.

7.2.2.12 Indium solution, stock (1 mL = 1000 µg In) - Pickle indium metal

in (1+1) nitric acid to an exact weight of 0.100 g. Dissolve in
10 mL (1+1) nitric acid, heating to effect solution. Cool and
dilute to 100 mL with reagent water.

7.2.2.13 Lead solution, stock (1 mL = 1000 µg Pb) - Dissolve 0.1599 g PbNO3

in 5 mL (1+1) nitric acid. Dilute to 100 mL with reagent water.

ILM05.3 D-10/ICP-MS
 Exhibit D (ICP-MS) -- Section 7
Reagents and Standards (Con’t)

7.2.2.14 Magnesium solution, stock (1 mL = 1000 µg Mg) - Dissolve 0.1658 g

MgO in 10 mL (1+1) nitric acid, heating to effect solution. Cool
and dilute to 100 mL with reagent water.

7.2.2.15 Manganese solution, stock (1 mL = 1000 µg Mn) - Pickle manganese

flake in (1+9) nitric acid to an exact weight of 0.100 g.
Dissolve in 5 mL (1+1) nitric acid, heating to effect solution.
Cool and dilute to 100 mL with reagent water.

7.2.2.16 Nickel solution, stock (1 mL = 1000 µg Ni) - Dissolve 0.100 g

nickel powder in 5 mL conc. nitric acid, heating to effect
solution. Cool and dilute to 100 mL with reagent water.

7.2.2.17 Scandium solution, stock (1 mL = 1000 µg Sc) - Dissolve 0.1534

Sc2O3 in 5 mL (1+1) nitric acid, heating to effect solution. Cool
and dilute to 100 mL with reagent water.

7.2.2.18 Selenium solution, stock (1 mL = 1000 µg Se) - Dissolve 0.1405 g

SeO2 in 20 mL reagent water and dilute to 100 mL with reagent
water.

7.2.2.19 Silver solution, stock (1 mL = 1000 µg Ag) - Dissolve 0.100 g

silver metal in 5 mL (1+1) nitric acid, heating to effect
solution. Cool and dilute to 100 mL with reagent water. Protect
from the light.

7.2.2.20 Terbium solution, stock (1 mL = 1000 µg Tb) - Dissolve 0.1176 g

Tb4O7 in 5 mL conc. nitric acid, heating to effect solution. Cool
and dilute to 100 mL with reagent water.

7.2.2.21 Thallium solution, stock (1 mL = 1000 µg Tl) - Dissolve 0.1303 g

TlNO3 in a solution mixture of 10 mL reagent water and 1 mL conc.
nitric acid. Dilute to 100 mL with reagent water.

7.2.2.22 Vanadium solution, stock (1 mL = 1000 µg V) - Pickle vanadium

metal in (1+9) nitric acid to an exact weight of 0.100 g.
Dissolve in 5 mL (1+1) nitric acid, heating to effect solution.
Cool and dilute to 100 mL with reagent water.

7.2.2.23 Yttrium solution, stock (1 mL = 1000 µg Y) - Dissolve 0.1270 g

Y2O3 in 5 mL (1+1) nitric acid, heating to effect solution. Cool
and dilute to 100 mL with reagent water.

7.2.2.24 Zinc solution, stock (1 mL = 1000 µg Zn) - Pickle zinc metal in

(1+9) nitric acid to an exact weight of 0.100 g. Dissolve in 5 mL
(1+1) nitric acid, heating to effect solution. Cool and dilute to
100 mL with reagent water.

7.2.3 Secondary Dilution Standards

Prepare mixed secondary dilution standard solutions by diluting the

appropriate volumes of stock standards with acidified reagent water
to obtain the final volume. Originating stock standards should be
checked for the presence of impurities which might influence the
accuracy of the standard. Freshly prepared standards should be
transferred to acid-cleaned, not previously used, FEP fluorocarbon
bottles for storage and monitored periodically for stability. Mixed
secondary dilution standard solutions may be purchased. The
purchased standards shall meet the requirements in Section 7.2.1.

D-11/ICP-MS ILM05.3
Exhibit D (ICP-MS) -- Section 7
Reagents and Standards (Con’t)

7.2.4 Working Standards

7.2.4.1 Mixed Calibration Standard Solutions

Care must be taken in the preparation of mixed calibration

standards to ensure that the elements are compatible and stable.
Fresh calibration standards should be prepared from mixed standard
solutions every two weeks or as needed. Dilute the mixed
standards to levels appropriate to the operating range of the
instrument using reagent water containing 1% (v/v) nitric acid.
The element concentrations in the calibration standards should be
sufficiently high to produce good measurement precision and to
accurately define the slope of the response curve. If the direct
addition procedure is being used, add internal standards.

7.2.4.2 Internal Standard Solution

Prepare mixed standard by diluting 10 mL each of the chosen

element’s stock standards to 100 mL with reagent water. Use this
solution for additions to blanks, calibration standards, and
samples, or dilute by an appropriate amount using 1% (v/v) nitric
acid if the internal standards are being added by a peristaltic
pump.

7.2.4.3 Tuning Solution

This solution is used for instrument tuning and mass calibration

prior to analysis. Prepare mixed standard by diluting beryllium,
magnesium, cobalt, indium, and lead stock standards to 100 µg/L
with 1% (v/v) nitric acid. Do not add internal standard to this
solution.

7.2.4.4 Interference Check Sample (ICS)

The ICS consists of two solutions: Solution A (ICSA) and Solution

AB (ICSAB). ICSA consists of the interferents and ICSAB consists
of the analytes mixed with the interferents. If the direct
addition procedure is being used, add internal standards.

7.2.4.4.1 Solution A - Contains 100 milligrams per Liter (mg/L) of

aluminum, calcium, iron, magnesium, potassium, sodium,
phosphorus (as orthophosphate), sulfur (as sulfate), 200 mg/L
carbon, 1000 mg/L chloride, and 2 mg/L molybdenum and titanium.

7.2.4.4.2 Solution AB - Contains all of the elements in Solution A plus

all target analytes at a concentration of 20 µg/L.

7.2.4.5 Contract Required Quantitation Limit (CRQL) Check Standard (CRI)

The concentrations of the analytes in the CRI shall be at the

CRQL. Information regarding the CRI shall be reported on Form
IIB-IN.

7.2.4.6 Method Detection Limit (MDL) Solution

The MDL solution shall be at a concentration of 3 to 5 times the

expected MDL.

7.3 Blanks

Three types of blanks are required for this method. A calibration blank
is used to establish the analytical calibration curve, the Preparation
Blank (PB) (see Section 12.5.2) is used to assess possible contamination

ILM05.3 D-12/ICP-MS
 Exhibit D (ICP-MS) -- Sections 7 & 8
Sample Collection, Preservation, and Storage

from the sample preparation procedure and to assess spectral background,

and the rinse blank is used to flush the instrument between samples in
order to reduce memory interferences.

7.3.1 Calibration Blank - Consists of 1% (v/v) nitric acid in reagent

water. If the direct addition procedure is being used, add internal
standards.

7.3.2 Preparation Blank - Must contain all the reagents in the same volumes
as used in preparing the samples. The PB must be carried through the
complete procedure and contain the same acid concentration in the
final solution as the sample solution used for analysis.

7.3.3 Rinse Blank - Consists of 2% (v/v) nitric acid in reagent water.

8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE

8.1 Sample Collection and Preservation

All samples must be collected in glass or polyethylene containers.

Water/aqueous samples must be preserved with nitric acid to pH less than
2 immediately after collection. All samples must be iced or
refrigerated at 4°C (±2°C) from the time of collection until digestion.

8.1.1 Dissolved Metals

For the determination of dissolved metals, the sample must be

filtered through a 0.45 micrometer (:m) pore diameter membrane
filter at the time of collection or as soon as possible. Use a
portion of the sample to rinse the filter flask, discard this
portion, and collect the required volume of filtrate. Preserve the
filtrate with nitric acid to pH less than 2 immediately after
filtration.

8.2 Procedures for Sample Storage

The samples must be protected from light and refrigerated at 4°C (±2°C)
from the time of receipt until 60 days after the delivery of a complete,
reconciled data package to USEPA. After 60 days the samples may be
disposed of in a manner that complies with all applicable regulations.

8.3 Procedure for Sample Digestate Storage

Sample digestates must be stored until 365 days after delivery of a

complete, reconciled data package to USEPA.

8.4 Contract Required Holding Time

The maximum holding time for metals is 180 days from Validated Time of
Sample Receipt (VTSR).

D-13/ICP-MS ILM05.3
Exhibit D (ICP-MS) -- Section 9
Calibration and Standardization

9.0 CALIBRATION AND STANDARDIZATION

9.1 Instrument Operating Parameters

Because of the differences between various makes and models of

satisfactory instruments, no detailed operating instructions can be
provided. Instead, the analyst should follow the instructions provided
by the manufacturer of the particular instrument. The Method Detection
Limit (MDL), precision, linear dynamic range, and interference effects
must be investigated and established for each individual element on that
particular instrument. All measurements must be within the operational
range of the instrument where corrections are valid. It is the
responsibility of the analyst to verify that the instrument
configuration and operating conditions used satisfy the analytical
requirements and to maintain Quality Control (QC) data confirming
instrument performance and analytical results.

9.2 Inductively Coupled Plasma - Mass Spectrometry (ICP-MS) Instrument

Calibration Procedure

9.2.1 Precalibration routine - The following precalibration routine must be

completed prior to calibrating the instrument.

Set up the instrument with proper operating parameters established in

Section 9.1. The instrument must be allowed to become stable prior
to calibration. Conduct any necessary mass calibration and
resolution routines to bring peak width within the manufacturer’s
specifications and adjust mass calibration to within 0.1 amu over the
range of 6 to 210 amu.

Demonstrate instrument stability and precision by analyzing the

tuning solution a minimum of five times consecutively. This may be
carried out as five separate analyses or as a single analysis with at
least five integrations. The percent relative standard deviation of
the absolute signals for all analytes in the tuning solution must be
less than 5%.

9.2.2 Internal Standardization

Internal standardization must be used in all analyses (except the

tuning solution) to correct the instrument drift and physical
interferences. A list of acceptable internal standards is provided
in Table 4 - Internal Standards. For full range mass scans, a
minimum of five internal standards shall be used. The masses of the
internal standards shall bracket the masses of the analyte. The
internal standards selected for a run must be consistent throughout
the entire run. Internal standards shall be present in all samples,
standards, and blanks (except the tuning solution) at identical
levels. This may be achieved by directly adding an aliquot of the
internal standards solution to each sample, standard, and blank, or
by mixing with the sample solution prior to nebulization using a
second channel of the peristaltic pump and mixing coil. The
concentration of the internal standard should be sufficiently high
for good precision and to minimize the possibility of correction
errors if the internal standard is naturally present in the sample.
Depending on the sensitivity of the instrument, a concentration range
of 20 µg/L to 200 µg/L of each internal standard is recommended.
Internal standards should be added to samples, standards, and blanks
in a similar manner, in order for dilution effects to be disregarded.

ILM05.3 D-14/ICP-MS
 Exhibit D (ICP-MS) -- Section 9
Calibration and Standardization (Con’t)

9.2.3 Calibration

Instruments shall be calibrated daily, once every 24 hours, or each

time the instrument is set up. The instrument standardization date
and time shall be included in the raw data. Calibration standards
shall be prepared as in Section 7.2.4.1. Calibrate the instrument
with at least two standards, one of which must be a blank standard.
A minimum of three replicate integrations are required for data
acquisition. Use the average of the integrations for instrument
calibration and data reporting.

NOTE: Any changes or corrections to the analytical system shall be

followed by recalibration.

9.3 Initial Calibration Verification (ICV)

9.3.1 Immediately after each instrument has been calibrated, the accuracy
of the initial calibration shall be verified and documented for every
analyte by the analysis of the ICV solution(s) for each mass used to
report final results.

9.3.2 Only if the ICV solution(s) is(are) not available from USEPA, or
where a certified solution of an analyte is not available from any
source, analyses shall be conducted on an independent standard at a
concentration other than that used for instrument calibration, but
within the calibration range. An independent standard is defined as
a standard composed of the analytes from a different source other
than those used in the standards for instrument calibration.

9.3.3 The ICV solution(s) shall be run at each mass used for reporting
final results. The values for the ICV shall be reported on Form IIA-
IN.

9.4 Continuing Calibration Verification (CCV)

9.4.1 To ensure calibration accuracy during each analysis run, one of the
following standards shall be used for the CCV for each mass used for
reporting final results for each element, at a frequency of 10% or
every 2 hours during an analysis run, whichever is more frequent.
The standard shall also be analyzed and reported for each mass used
for reporting final results for each element at the beginning of the
run and after the last analytical sample. The analyte concentrations
in the CCV standard(s) shall be different from the concentrations for
the ICV and shall be one of the following solutions at or near one-
half of the calibration standard:

C USEPA Solutions

C NIST Standards

C A Contractor-prepared standard solution

The same CCV standard shall be used throughout the analysis runs for
a Sample Delivery Group (SDG) of samples received.

9.4.2 Each CCV analyzed shall reflect the conditions of analysis of all
associated analytical samples (the preceding 10 analytical samples or
the preceding analytical samples up to the previous CCV). The
duration of analysis, rinses, and other related operations which may
affect the CCV measured result may not be applied to the CCV to a
greater extent than the extent applied to the associated analytical
samples. For instance, the difference in time between a CCV analysis
and the blank immediately following it, as well as the difference in

D-15/ICP-MS ILM05.3
Exhibit D (ICP-MS) -- Sections 9 & 10
Procedure

time between the CCV and the analytical sample immediately preceding
it, may not exceed the lowest difference in time between any two
consecutive analytical samples associated with the CCV.

9.4.3 Information regarding the CCV shall be reported on Form IIA-IN.

9.5 Initial and Continuing Calibration Blank (ICB/CCB)

A calibration blank shall be analyzed for each mass used for reporting
final results for each element immediately after every ICV and CCV, at a
frequency of 10% or every 2 hours during the run, whichever is more
frequent. The blank shall be analyzed at the beginning of the run and
after the last analytical sample.

NOTE: A CCB shall be analyzed immediately after the last CCV, and the
last CCV shall be analyzed immediately after the last analytical sample
of the run. The results of the calibration blanks shall be reported on
Form III-IN.

10.0 PROCEDURE

10.1 Sample Preparation

10.1.1 If insufficient sample amount (less than 90% of the required amount)
is received to perform the analyses, the Contractor shall contact the
Sample Management Office (SMO) to inform them of the problem. SMO
will contact the Region for instructions. The Region will either
require that no sample analysis be performed or will require that a
reduced volume be used for the sample analysis. No other changes in
the analysis will be permitted. The Contractor shall document the
Region’s decision in the Sample Delivery Group (SDG) Narrative.

10.1.2 If multiphase samples (e.g., two-phase liquid sample, oily

sludge/sandy soil sample) are received by the Contractor, the
Contractor shall contact SMO to apprise them of the type of sample
received. SMO will contact the Region. If all phases of the sample
are amenable to analysis, the Region may require the Contractor to do
any of the following:

C Mix the sample and analyze an aliquot from the homogenized

sample.

C Separate the phases of the sample and analyze one or more of

the phases, separately. SMO will provide EPA sample numbers
for the additional phases, if required.

C Do not analyze the sample.

10.1.2.1 If all of the phases are not amenable to analysis (i.e., outside
scope), the Region may require the Contractor to do any of the
following:

C Separate the phases and analyze the phase(s) that is(are)

amenable to analysis. SMO will provide EPA sample numbers
for the additional phases, if required.

C Do not analyze the sample.

10.1.2.2 No other changes in the analyses will be permitted. The

Contractor shall document the Region’s decision in the SDG
Narrative.

ILM05.3 D-16/ICP-MS
 Exhibit D (ICP-MS) -- Section 10
Procedure (Con’t)

10.1.3 Sample Preparation Procedures

10.1.3.1 Preparation Method/Code (HW2)

Shake and transfer a 100 mL aliquot of the sample to a 250 mL

heating vessel, add 2 mL (1+1) nitric acid and 1 mL of (1+1)
hydrochloric acid (HCl) to the sample. Cover with a ribbed watch
glass and heat on either a hot plate, block digester, or
equivalent heating source which is adjustable and capable of
maintaining a temperature of 92-95°C for 2 hours, or until the
sample volume is reduced to about 20 mL (DO NOT BOIL). Cover with
a watch glass to prevent additional evaporation and reflux for 30
minutes. Cool sample, transfer to a 50 mL volumetric flask, and
adjust sample volume to 50 mL with reagent water. Mix and allow
any solids present to settle by gravity overnight or centrifuge
(if after settling or centrifuging, the sample contains suspended
solids, a portion of the sample may be filtered prior to
analysis).

10.1.3.1.1 Prior to analysis, adjust the chloride concentration by

pipetting 20 mL of the digestate into a 50 mL volumetric flask
and dilute to volume with reagent water and mix. If the direct
addition method is being used, add internal standards and mix.
The sample is now ready for analysis.

10.1.3.2 Preparation Method/Code (HW3)

Shake sample and transfer 50-100 mL of well-mixed sample to an

appropriate polytetrafluoroethylene (PTFE), polypropylene, or
polyethylene heating vessel. Add 2 mL of (1+1) nitric acid and 1
mL of (1+1) hydrochloric acid to the vessel. Cover with a ribbed
watch glass or similar cover and heat on a hot plate, block
digester, or equivalent heating source that is adjustable and
capable of maintaining a temperature of 92-95°C until the sample
volume has been reduced by half. Cover with a watch glass or
similar cover to prevent further evaporation and reflux for an
additional 30 minutes. Cool sample and filter to remove insoluble
material.

NOTE: In place of filtering, the sample, after dilution and

mixing, may be centrifuged or allowed to settle by gravity
overnight to remove insoluble material.

Adjust volume to 50-100 mL with reagent water. The sample is now

ready for analysis. If volumes less than 100 mL are used, all
other reagents shall be reduced appropriately (e.g., if 50 mL is
used, reduce reagent volumes by one-half). The final volume of
the digestate must equal the initial volume of the sample aliquot.

10.2 Sample Analysis

10.2.1 For every new or unusual matrix, it is highly recommended that a

semi-quantitative analysis be carried out to screen for high element
concentrations. Information gained from this may be used to prevent
potential damage to the detector during sample analysis and to
identify elements which may be higher than the linear range. Matrix
screening may be carried out by diluting the sample by a factor of
500 and analyzing in semi-quantitative mode. The sample should also
be screened for background levels of all elements chosen for use as
internal standards in order to prevent bias in the calculation of
analytical data.

D-17/ICP-MS ILM05.3
Exhibit D (ICP-MS) -- Section 10
Procedure (Con’t)

10.2.2 Initiate instrument operating configuration. Tune and calibrate the

instrument for the analytes of interest. Establish instrument
software run procedures for quantitative analysis. For all sample
analyses, a minimum of three replicate integrations are required for
data acquisition. Use the average of the integrations for data
reporting.

10.2.3 The rinse blank should be used to flush the system between samples.
Allow sufficient time to remove traces of the previous sample or a
minimum of one minute. Samples should be aspirated for a sufficient
period of time to obtain a stable response prior to the collection of
data.

10.2.4 Samples having concentrations higher than the established linear

dynamic range should be diluted into range and re-analyzed. The
sample should first be analyzed for the trace elements, protecting
the detector from the high concentration elements, if necessary, by
the selection of appropriate scanning windows. The sample should
then be diluted for the determination of the remaining elements.
Alternatively, the dynamic range may be adjusted by selecting an
alternative isotope of lower natural abundance, provided QC data for
that isotope have been established. The dynamic range must not be
adjusted by altering instrument conditions to an uncharacterized
state.

10.2.5 All masses which might affect data quality must be monitored during
the analytical run. At a minimum, those masses prescribed in Table 2
- Mass Choices for Elements that Must Be Monitored During the
Analytical Run, must be monitored in the same scan that is used for
the collection of the data. This information should be used to
correct the data for identified interferences.

10.2.6 During the analysis of samples, the laboratory must comply with the
required QC described in Section 12. For the determination of
dissolved analytes when the Region has specified that no preparation
is required, the Preparation Blank (PB) and Laboratory Control Sample
(LCS) are not required.

ILM05.3 D-18/ICP-MS
 Exhibit D (ICP-MS) -- Section 11
Data Analysis and Calculations

11.0 DATA ANALYSIS AND CALCULATIONS

11.1 Recommended Elemental Equations

Elemental expressions recommended for sample data calculations are

listed in Table 3 - Recommended Elemental Expressions for Isobaric
Interferences. Do not report element concentrations below the
determined Method Detection Limit (MDL).

11.2 Data Value Corrections

Data values should be corrected for instrument drift or sample matrix

induced interferences by the application of internal standardization.
Corrections for characterized spectral interferences should be applied
to the data. Chloride interference corrections should be made on all
samples, regardless of the addition of hydrochloric acid (HCl), as the
chloride ion is a common constituent of environmental samples.

11.3 Multiple Monitored Isotopes

If an element has more than one monitored isotope, examination of the

concentration calculated for each isotope or the isotope ratios will
provide useful information in detecting a possible spectral
interference. Consideration should therefore be given to both primary
and secondary isotopes in the evaluation of sample concentration. In
some cases, secondary isotopes may be less sensitive or more prone to
interferences than the primary recommended isotopes, therefore
differences between the results do not necessarily indicate a problem
with data calculated for the primary isotopes.

11.4 Prepared Sample Analysis (HW2)

EQ. 1 Prepared Sample Concentration by Method HW2

WHERE, C = Instrument value in µg/L (The average of all

replicate integrations).
Vf = Final digestion volume (50 mL)
Vi = Initial digestion volume (100 mL)
DF = Dilution Factor

D-19/ICP-MS ILM05.3
Exhibit D (ICP-MS) -- Section 11
Data Analysis and Calculations (Con’t)

11.5 Prepared Sample Analysis (HW3)

EQ. 2 Prepared Sample Concentration by Method HW3

Vf
Concentration (g/L) = C x x DF
Vi

WHERE, C = Instrument value in µg/L (The average of all

replicate integrations).
Vf = Final digestion volume (mL)
Vi = Initial digestion volume (mL)
DF = Dilution Factor

11.6 Adjusted Method Detection Limit (MDL)/Adjusted Contract Required

Quantitation Limit (CRQL) Calculation

To calculate the adjusted CRQL or adjusted MDL, multiply the value of

the CRQL (µg/L) or MDL (µg/L) by the sample dilution factor.

ILM05.3 D-20/ICP-MS
 Exhibit D (ICP-MS) -- Section 12
Quality Control
12.0 QUALITY CONTROL (QC)

12.1 Tune Standard

The Tune Standard shall be prepared in the same acid matrix as the
calibration standards and analyzed at least 5 times consecutively.
Analyses may be carried out as five separate analyses or as a single
analysis with at least five integrations. If the mass calibration is
not within 0.1 amu over the range of 6 to 210 amu, or the percent
Relative Standard Deviation (%RSD)of the absolute signals of the
analytes exceeds 5%, the analysis shall be terminated, the problem
corrected, and the instrument re-tuned. All sample results reported
must be associated with an instrument tune that meets these
requirements.

12.2 Initial Calibration Verification (ICV)

The ICV Standard shall be prepared in the same acid matrix as the
calibration standards and in accordance with the instructions provided
by the supplier. If measurements exceed the control limits of 90% (low)
and 110% (high), the analysis shall be terminated, the problem
corrected, the instrument recalibrated, and the calibration reverified.
Information regarding the ICV shall be reported on Form IIA-IN.

12.3 Continuing Calibration Verification (CCV)

The CCV standard shall be prepared by combining compatible elements at a

concentration equivalent to the mid-points of their respective
calibration curves. If the deviation of the CCV is greater than the
specified control limits of 90% (low) and 110% (high), the analysis
shall be stopped, the problem corrected, the instrument recalibrated,
the calibration verified, and re-analysis of the preceding 10 analytical
samples or all analytical samples analyzed since the last compliant
calibration verification shall be performed for the elements affected.
Information regarding the CCV shall be reported on Form IIA-IN.

12.4 Contract Required Quantitation Limit (CRQL) Check Standard (CRI)

12.4.1 To verify linearity near the CRQL, a standard at the CRQL (CRI) shall
be prepared, in the same acid matrix as the calibration standards,
and analyzed at the beginning (immediately following the ICV/ICB and
immediately preceding the Interference Check Sample (ICS) analyses).
In addition, the contractor shall analyze the CRI at the end of each
sample analysis run and at a frequency of not less than once per 20
analytical samples1 per analysis run. These subsequent analyses of
the CRI shall be immediately followed by CCV/CCB analyses.

12.4.2 The CRI shall be run for every required isotope used for the analysis
of all Inductively Coupled Plasma - Mass Spectrometry (ICP-MS)
analytes. Information regarding the CRI shall be reported on Form
IIB-IN.

12.4.3 If the percent recovery of the CRI falls outside the control limits
of 70-130% (50-150% for cobalt, manganese, and zinc) for one or more
analytes, the CRI shall be re-analyzed immediately for those analytes
only. If the results of the re-analysis for those analytes fall
within the control limits, no further corrective action is required.
If the results of the re-analysis for those analytes do not fall
within the control limits, the analysis shall be terminated, the

1
As defined in Exhibit G, CRI is an analytical sample.

D-21/ICP-MS ILM05.3
Exhibit D (ICP-MS) -- Section 12
Quality Control (Con’t)
problem corrected, the instrument recalibrated, the CRI analyzed, and
the samples associated with the CRI re-analyzed.

12.5 Blank Analyses

There are two different types of blanks required by this method. The
calibration blank is used in establishing the analytical curve while the
preparation blank is used to monitor for possible contamination.

12.5.1 Initial and Continuing Calibration Blank (ICB/CCB)

The ICB and CCB are prepared with acid and reagent water. If the
absolute value of the calibration blank (ICB/CCB) result exceeds the
CRQL (see Exhibit C), the analysis shall be terminated, the problem
corrected, the instrument recalibrated, the calibration verified, and
re-analysis of the preceding 10 analytical samples or all analytical
samples analyzed since the last compliant calibration blank shall be
performed for the elements affected.

12.5.2 Preparation Blank (PB)

12.5.2.1 The PB shall contain all the reagents and in the same volumes as
used in processing the samples. The PB shall be carried through
the complete procedure and contain the same acid concentration in
the final solution as the sample solution used for analysis.

12.5.2.2 At least one PB, consisting of reagent water processed through

each sample preparation and analysis procedure (see Section 10),
shall be prepared and analyzed with every Sample Delivery Group
(SDG), or with each batch2 of samples digested, whichever is more
frequent.

12.5.2.3 The first batch of samples in an SDG is to be assigned to

Preparation Blank one, the second batch to Preparation Blank two,
etc. (see Form III-IN). Each Sample Data Package shall contain
the results of all PB analyses associated with the samples in that
SDG.

12.5.2.4 The PB is to be reported for each SDG and used in all analyses to
ascertain whether sample concentrations reflect contamination in
the following manner:

12.5.2.4.1 If the absolute value of the concentration of the blank is less

than or equal to the CRQL (see Exhibit C), no further action is
required.

12.5.2.4.2 If the analyte concentration in the blank is above the CRQL,

the lowest concentration of that analyte in the associated
samples shall be greater than or equal to 10 times the blank
concentration. Otherwise, all samples, associated with the
blank, with the analyte concentration less than 10 times the
blank concentration and above the CRQL, shall be redigested and
re-analyzed with appropriate new Quality Control (QC) for that
analyte. The only exception to this shall be an identified
field blank. The sample concentration is not to be corrected
for the blank value.

12.5.2.4.3 If the concentration of the blank is below the negative CRQL,

then all samples reported below 10 times the CRQL associated

2
A group of samples prepared at the same time.

ILM05.3 D-22/ICP-MS
 Exhibit D (ICP-MS) –- Section 12
Quality Control (Con’t)
with the blank, shall be redigested and re-analyzed with
appropriate new QC.

12.5.2.4.4 The values for the PB shall be reported on Form III-IN.

12.6 Interference Check Sample (ICS)

12.6.1 The ICS is prepared by the analyst or obtained from USEPA, if

available.

12.6.2 To verify corrections for elemental and polyatomic isobaric

interferences, the Contractor shall analyze and report the results
for the ICS for all elements on the Target Analyte List (TAL) and
analyze for all interferents, at the beginning of each analysis run,
but not before the ICV. This analysis of the ICS shall be
immediately followed by analysis of a CCV/CCB pair. The ICS
solutions shall be obtained from USEPA, if available, and analyzed
according to instructions supplied with the ICS. The Contractor
shall not dilute the ICS (for the higher concentration elements) more
than is necessary to meet the linear range values of the instrument.

12.6.3 The ICS consists of two solutions: Solution A and Solution AB.
Solution A consists of the interferents, and Solution AB consists of
the analytes mixed with the interferents. An ICS analysis consists
of analyzing both solutions consecutively, starting with Solution A.

12.6.4 The analytical results of ICS Solution A (ICSA) shall fall within the
control limit of ±3 times the CRQL of the analyte’s true value or
±20% of the analyte’s true value (the true value shall be zero unless
otherwise stated) in the ICSA, whichever is greater. If not, the
analysis shall be terminated, the problem corrected, the instrument
recalibrated, and re-analysis of the analytical samples analyzed
since the last compliant ICSA shall be performed. The ICSA results
for these analytes shall be reported from an undiluted sample
analysis.

12.6.5 Results for the ICS Solution AB (ICSAB) during the analytical runs
shall fall within the control limit of ±3 times the CRQL of the true
value or ±20% of the true value, whichever is greater, for the
analytes included in the ICSAB. If not, the analysis shall be
terminated, the problem corrected, the instrument recalibrated, and
re-analysis of the analytical samples analyzed since the last
compliant ICSAB shall be performed.

NOTE: The control limits and concentrations for the ICSAB are being
monitored. These may be adjusted to provide greater control of
interferences.

12.6.6 If true values for analytes contained in the ICS are not supplied
with the solutions, the mean shall be determined by initially
analyzing the ICS at least five times repetitively for the particular
analytes. This mean determination shall be made during an analytical
run where the results for a previously supplied ICS met all contract
specifications. Additionally, the results of this initial mean
determination shall be used as the true value for the lifetime of
that solution (i.e., until the solution is exhausted). Only if the
ICS solutions are not available from USEPA, independent Check Samples
shall be prepared with interferent and analyte concentrations at the
levels specified in Sections 7.2.4.4.1 and 7.2.4.4.2. The mean value
and standard deviation shall be established by initially analyzing
the Check Samples at least five times repetitively for each analyte
listed on Form IVB-IN. Results shall fall within the control limit
of ±3 times the CRQL of the established mean value or ±20% of the

D-23/ICP-MS ILM05.3
Exhibit D (ICP-MS) -- Section 12
Quality Control (Con’t)
established mean value, whichever is greater. The mean and standard
deviation shall be reported in the raw data. Results from the ICS
analyses shall be reported on Form IVB-IN for all ICP-MS parameters.

12.7 Spike Sample Analysis

12.7.1 The spike sample analysis is designed to provide information about

the effect of sample matrix on the digestion and/or measurement
methodology. The spike is added before the digestion (i.e., prior to
the addition of other reagents). At least one spike sample analysis
(matrix spike) shall be performed for each SDG3.

12.7.2 If the spike analysis is performed on the same sample that is chosen
for the duplicate sample analysis, spike calculations shall be
performed using the results of the sample designated “original
sample” (see Section 12.8). The average of the duplicate results
cannot be used for the purpose of determining percent recovery.
Samples identified as field blanks and Performance Evaluation (PE)
samples shall not be used for spiked sample analysis. USEPA may
require that a specific sample be used for the spike sample analysis.

12.7.3 The analyte spike shall be added in the amount given in Table 5 -
Spiking Levels for Spike Sample Analysis, for each element analyzed.

12.7.4 If the spike recovery is not at or within the limits of 75-125%, the
data for all samples received and associated with that spike sample
and shall be flagged with the letter “N” on Forms IA/IB-IN and VA-IN.
An exception to this rule is granted when the sample concentration
exceeds the Spike Added (SA) concentration by a factor of four or
more. In such an event, the data shall be reported unflagged even if
the percent recovery does not meet the 75-125% recovery criteria.

12.7.5 When the matrix spike recovery falls outside the control limits and
the sample result does not exceed four times the spike added, a post-
digestion spike shall be performed for those elements that do not
meet the specified criteria. Note that if a post-digestion spike
analysis is required for an analyte, the same EPA sample that was
used for the matrix spike shall be used for the post-digestion spike
analysis. Spike an unspiked aliquot of the digestate at two times
the indigenous level or two times the CRQL, whichever is greater.
Results of the post-digestion spike shall be reported on Form VB-IN.

12.7.6 In the instance where there is more than one spike sample per matrix
per SDG, if one spike sample recovery is not within contract
criteria, flag all the samples in the SDG. Individual component
percent recoveries are calculated as follows:

EQ. 3 Spike Percent Recovery

SSR − SR
%Recovery = x 100
SA

WHERE, SSR = Spike Sample Result

SR = Sample Result
SA = Spike Added

3
USEPA may require additional spike sample analyses, upon USEPA Regional
CLP Project Officer (CLP PO) request.

ILM05.3 D-24/ICP-MS
 Exhibit D (ICP-MS) –- Section 12
Quality Control (Con’t)

12.7.7 When sample concentration is less than the Method Detection Limit
(MDL), use SR = 0 only for purposes of calculating percent recovery.
The Spike Sample Results (SSRs), Sample Results (SRs), Spike Added
(SA), and percent recovery (positive or negative) shall be reported
on Form VA-IN.

12.7.8 The units used for reporting SSRs will be identical to those used for
reporting sample results on Form IA-IN.

12.8 Duplicate Sample Analysis

12.8.1 One duplicate sample shall be analyzed for each SDG4. Duplicates
cannot be averaged for reporting on Form IA-IN.

12.8.2 Samples identified as field blanks and PE samples shall not be used
for duplicate sample analysis. USEPA may require that a specific
sample be used for duplicate sample analysis. The Relative Percent
Difference (RPD) for each analyte is calculated as follows:

EQ. 4 Duplicate Sample Relative Percent Difference

S−D
RPD = x 100
(S + D)/2

WHERE, RPD = Relative Percent Difference

S = Sample Result (original)
D = Duplicate Result

12.8.3 The results of the duplicate sample analyses shall be reported on

Form VI-IN. A control limit of 20% for RPD shall be used for
original and duplicate sample values greater than or equal to five
times the CRQL (see Exhibit C). A control limit equal to the CRQL
shall be entered in the “Control Limit” column on Form VI-IN if
either the sample or duplicate value is less than five times the
CRQL. If the sample and duplicate values are greater than or equal
to five times the CRQL, or if the sample and duplicate values are
less than the CRQL, the “Control Limit” field is left empty.

12.8.4 If one result is above five times the CRQL level and the other is
below, use the CRQL criteria to determine if the duplicate analysis
is in control. If both sample and duplicate values are less than the
MDL, the RPD is not calculated on Form VI-IN. If the duplicate
sample results are outside the control limits, flag all the data for
samples received associated with that duplicate sample with an “*” on
Forms IA/IB-IN and VI-IN. In the instance where there is more than
one duplicate sample per SDG, if one duplicate result is not within
contract criteria, flag all samples in the SDG. The percent
difference data will be used by USEPA to evaluate the long-term
precision of the methods for each element. Specific control limits
for each element may be added to Form VI-IN at a later date based on
these precision results.

4
USEPA may require additional duplicate sample analyses, upon USEPA
Regional CLP PO request.

D-25/ICP-MS ILM05.3
Exhibit D (ICP-MS) -- Section 12
Quality Control (Con’t)
12.9 Laboratory Control Sample (LCS) Analysis

12.9.1 A water/aqueous LCS (LCSW) shall be analyzed for each analyte using
the same sample preparations, analytical methods, and Quality
Assurance/Quality Control (QA/QC) procedures employed for USEPA
samples received.

12.9.2 The LCSW solution must be obtained from USEPA (if unavailable, the
ICV solution(s) may be used). One aqueous LCS shall be prepared and
analyzed for each group of samples in an SDG, or for each batch of
samples digested, whichever is more frequent.

12.9.3 All LCSW and percent recovery results shall be reported on Form VII-
IN. If the percent recovery for the LCSW falls outside the control
limits of 80-120%, the analyses shall be terminated, the problem
corrected, and the samples associated with that LCSW redigested and
re-analyzed with appropriate new QC.

12.10 ICP-MS Serial Dilution Analysis

12.10.1 Prior to reporting concentration data for the analyte elements, the
Contractor shall analyze and report the results of the ICP-MS serial
dilution analysis. The ICP-MS serial dilution analysis shall be
performed on a sample from each SDG. Samples identified as field
blanks and PE samples shall not be used for serial dilution analysis.

12.10.2 If the analyte concentration is sufficiently high (minimally a factor

of 50 above the MDL in the original sample), the serial dilution (a
five-fold dilution) shall then agree within 10% of the original
determination after correction for dilution. If the dilution
analysis for one or more analytes is not within a control limit of
10%, and the internal standards in the original sample met the
contract criteria, an interference effect must be suspected, and the
data for all affected analytes in the samples received and associated
with that serial dilution must be flagged with an “E” on Forms IA/IB-
IN and VIII-IN.

12.10.3 The percent differences for each component are calculated as follows:

EQ. 5 Serial Dilution Percent Difference

I− S
%Difference = x 100
I

WHERE, I = Initial Sample Result (Instrument Reading)

S = Serial Dilution Result (Instrument Reading x5)

12.10.4 In the instance where there is more than one serial dilution per SDG,
if one serial dilution result is not within the contract criteria,
flag all samples in the SDG. Serial dilution results and “E” flags
shall be reported on Form VIII-IN.

12.10.5 If the internal standard responses for the field sample chosen for
serial dilution analysis are not within the limits and the
appropriate corrective action (two-fold dilution and reanalysis) is
taken, the following shall apply to the serial dilution analysis: if
the internal standard responses of the field sample reanalysis are
within the limits, the serial dilution results are to be reported

ILM05.3 D-26/ICP-MS
 Exhibit D (ICP-MS) –- Section 12
Quality Control (Con’t)
from a five-fold dilution of the reanalyzed sample. If the internal
standard responses of the field sample reanalysis are not within the
limits, the serial dilution results are to be reported from a five-
fold dilution of the original sample.

12.11 Internal Standards

12.11.1 The analyst shall monitor the responses from the internal standards
throughout the sample set being analyzed. Ratios of the internal
standard responses between isotopes should also be routinely
monitored. This information may be used to correct potential
problems caused by mass dependent drift, errors incurred in adding
the internal standards or increases in the concentrations of
individual internal standards caused by background contributions from
the sample. The absolute response of any one internal standard must
not deviate more than 60-125% of the original response in the
calibration blank. If deviations greater than these are observed in
field samples, matrix spikes, or duplicate samples, the original
sample shall be diluted by a factor of two, internal standards added,
and the sample re-analyzed. If the internal standard responses for
the diluted sample analysis are within the limits, report the results
of this analysis on the appropriate Summary Form. If the internal
standard responses for the diluted sample analysis are not within the
limits, note this in the SDG Narrative and report the results of the
undiluted original sample analysis on the appropriate Summary Form.

12.12 Method Detection Limit (MDL) Determination

12.12.1 Before any field samples are analyzed under this contract, the MDLs
shall be determined for each instrument used, prior to the start of
contract analyses, and annually thereafter, and shall meet the levels
specified in Exhibit C.

An MDL study shall be performed after major instrument maintenance,

or changes in instrumentation or instrumental conditions to verify
the current sensitivity of the analysis.

12.12.2 To determine the MDLs, the Contractor shall run MDL studies following
the procedures given in 40 CFR, Part 136. The Contractor shall
prepare the MDL samples by each digestion procedure used and shall
analyze these samples on each instrument used. The Contractor shall
also analyze non-prepared MDL samples on each instrument used.

12.12.3 The determined concentration of the MDL shall be less than half the
concentration of the CRQL listed in Exhibit C.

12.12.4 The direct analysis MDL (Preparation Method/Code “NP1”) shall be used
to determine the appropriate concentration qualifier for the results
of instrument QC.

12.12.5 The results of the MDL determination studies shall be forwarded to

the USEPA Regional CLP PO, Sample Management Office (SMO), and
Quality Assurance Technical Support (QATS).

12.12.6 The MDL results shall be reported on Form IX-IN.

12.13 Linear Dynamic Range (LDR)

12.13.1 Before any field samples are analyzed under this contract, the upper
limit of the linear calibration range shall be established for each
analyte by determining the signal responses from a minimum of three
different concentration standards, one of which is close to the upper
limit of the linear range, prior to the start of contract analyses

D-27/ICP-MS ILM05.3
Exhibit D (ICP-MS) -- Section 12
Quality Control (Con’t)
and at least quarterly thereafter. The linear calibration range used
for the analysis of samples shall be determined from the resulting
data. The upper LDR limit shall be an observed signal no more than
10% below the level extrapolated from lower standards. Determined
sample analyte concentrations that are greater than 90% of the
determined upper LDR limit must be diluted and re-analyzed. The LDRs
must be verified whenever a change in instrument hardware operating
conditions indicate they should be redetermined, or verified
quarterly.

12.14 Example Analytical Sequence for ICP-MS

Tune
S0
S
ICV
ICB
CRI
ICSA
ICSAB
CCV
CCB
10 samples
CCV
CCB
7 samples
CRI
CCV
CCB
10 samples, etc.

ILM05.3 D-28/ICP-MS
 Exhibit D (ICP-MS) -- Sections 13-16
Method Performance
13.0 METHOD PERFORMANCE

Not applicable.

14.0 POLLUTION PREVENTION

See Section 1.15 in Exhibit D - Introduction to Analytical Methods.

15.0 WASTE MANAGEMENT

See Section 1.16 in Exhibit D - Introduction to Analytical Methods.

16.0 REFERENCES

16.1 US Environmental Protection Agency. Determination of Trace Elements in

Waters and Wastes by Inductively Coupled Plasma - Mass Spectrometry.
Method 200.8. Revision 5.4. 1994.

16.2 US Environmental Protection Agency. Test Methods for Evaluating Solid

Waste, Physical/Chemical Methods (SW-846). Method 6020A. Third Edition,
Update IV-A. 1986.

16.3 US Government Printing Office. 40 Code of Federal Regulations, Part 136,

Section 1, Appendix B.

16.4 US Environmental Protection Agency. Determination of Trace Elements in

Waters and Wastes by Inductively Coupled Plasma - Mass Spectrometry.
Method 200.8. Revision 5.4. 1994. Modified for the Contract Laboratory
Program.

D-29/ICP-MS ILM05.3
Exhibit D (ICP-MS) -- Section 17
Tables/Diagrams/Flowcharts
17.0 TABLES/DIAGRAMS/FLOWCHARTS

Table 1. Isobaric Molecular-Ion Interferences

Analyte Oxygen Hydroxyl Nitrogen Chlorine Sulfur Carbon Other

121
Sb PdO AgN AgC
123
Sb AgO AgN SrCl ZrS CdC
75
As CoO NiOH NiN ArCl CaS CuC
138
Ba SnO SbOH
137
Ba SbO SnOH MoCl
136
Ba SnO SnOH SnC
135
Ba SnO SnOH MoCl
134
Ba SnO SnOH SnN MoCl SnC
132
Ba SnO, InOH SnN MoCl MoS SnC
CdO
130
Ba CdO CdOH SnN, CdN MoCl MoS SnC
9
Be
114
Cd MoO MoOH MoN SeCl SeS
112
Cd MoO, MoOH MoN SeCl, AsCl SeS MoC
ZrO
111
Cd MoO MoOH MoN GeCl
110
Cd MoO, MoN, ZrN GeCl, AsCl SeS MoC
ZrO
113
Cd MoO MoOH SeCl, AsCl
116
Cd MoO
106
Cd ZrO MoN, ZrN GeS MoC, ZrC
108
Cd MoO, ZrOH MoN, ZrN GeCl SeS, GeS MoC, ZrC
ZrO
52
Cr ArO ClOH ArC
53
Cr ClO ArOH KN NCl, OCl KC
50
Cr SO ArN SO ArC Mo++
54
Cr ClOH ArN, CaN CaC
59
Co CaO CaOH ScN MgCl AlS TiC Sn++
63
Cu TiO, PO2 TiOH TiN SiCl, MgCl PS VC ArNa
65
Cu TiO TiOH VN SiCl S2, SO2H CrC
208
Pb
206
Pb

ILM05.3 D-30/ICP-MS
 Exhibit D (ICP-MS) -- Section 17
Tables/Diagrams/Flowcharts (Con’t)

Table 1. Isobaric Molecular-Ion Interferences (Con’t)

Analyte Oxygen Hydroxyl Nitrogen Chlorine Sulfur Carbon Other

207
Pb
204
Pb
55
Mn KO ArOH KN NaS CaC Cd++
202
Hg WO
200
Hg WO WOH WN
199
Hg WO WOH
201
Hg WOH
198
Hg WO TaOH WN WC
204
Hg
196
Hg WN WC
58
Ni CaO KOH CaN NaCl MgS TiC Cd++, Sn++
60
Ni CaO CaOH TiN MgCl, NaCl SiS TiC Sn++
62
Ni TiO ScOH TiN AlCl, MgCl SiS TiC, CrC Sn++
61
Ni ScO CaOH TiN MgCl SiS TiC Sn++
64
Ni TiO TiOH TiN, CrN SiCl, AlCl S2 CrC
80
Se ZnO CuOH ZnN ScCl, CaCl TiS ZnC
78
Se NiO NiOH ZnN CaCl, KCl TiS ZnC
82
Se ZnO CuOH ZnN TiCl, ScCl TiS, CrS
76
Se NiO CoOH NiN KCl CaS ZnC
77
Se NiO NiOH CuN CaCl, ArCl ScS CuC
74
Se NiO FeOH NiN Cl2, KCl CaS NiC
107
Ag ZrO ZrOH GeCl AsS MoC
109
Ag MoOH MoN GeCl SeS MoC
205
Tl
203
Tl WOH
51
V ClO SOH ClN ClO, ClN FS KC
50
V SO ArN ArC Mo++
64
Zn TiO TiOH TiN, CrN SiCl, AlCl S2 CrC
66
Zn TiO TiOH CrN PCl, SiCl S2 FeC
68
Zn CrO VOH FeN PCl ArS FeC Ba++

D-31/ICP-MS ILM05.3
Exhibit D (ICP-MS) –- Section 17
Tables/Diagrams/Flowcharts (Con’t)

Table 1. Isobaric Molecular-Ion Interferences (Con’t)

Analyte Oxygen Hydroxyl Nitrogen Chlorine Sulfur Carbon Other

67
Zn VO TiOH CrN SCl ClS MnC Ba++
70
Zn FeO CrOH GeN Cl2 ArS NiC

NOTE: The information provided in this table does not indicate that all of the
described interferences need to be tested. However, this table can be
consulted if unusual samples are encountered.

ILM05.3 D-32/ICP-MS
 Exhibit D (ICP-MS) -- Section 17
Tables/Diagrams/Flowcharts (Con’t)
Table 2. Mass Choices for Elements that Must Be Monitored
During the Analytical Run

Mass Element of Interest

121 Antimony
75 Arsenic
134, 135, 136, 137 Barium
9 Beryllium
111, 114 Cadmium
52, 53 Chromium
59 Cobalt
63, 65 Copper
206, 207, 208 Lead
24, 25, 26 Magnesium
55 Manganese
60, 61, 62 Nickel
77, 78, 80, 82 Selenium
107, 109 Silver
203, 205 Thallium
51 Vanadium
66, 67, 68 Zinc

NOTE: Underlined isotopes are preferred for measurements. Where possible,

alternative isotopes are indicated. Those isotopes not listed shall not be
used as a primary isotope for measurement, although they may be monitored for
interference corrections if necessary.

D-33/ICP-MS ILM05.3
Exhibit D (ICP-MS) – Section 17
Tables/Diagrams/Flowcharts (Con’t)
Table 3. Recommended Elemental Expressions for Isobaric Interferences

Element Isobaric Expression Proportional to Elemental

Correction Concentration
Sb none (1.0000)(121C)
As ArCl, Se (1.0000)(75C) - (3.127)[(77C) - (0.815)(82C)]
Ba none (1.0000)(137C)
Be none (1.0000)(9C)
Cd MoO, Pd (1.000)(111C) - (1.073)[(108C) - (0.712)(106C)]
Cr none (1.0000)(52C)
Co none (1.0000)(59C)
Cu none (1.0000)(63C)
Pb none (1.0000)(206C) + (1.0000)(207C) + (1.0000)(208C)
Mn none (1.0000)(55C)
Ni none (1.0000)(60C)
Se none (1.0000)(82C)
Ag none (1.0000)(107C)
Tl none (1.0000)(205C)
V ClO, Cr (1.0000)(51C) - (3.127)[(53C) - (0.113)(52C)]
Zn none (1.0000)(66C)
Sc none (1.0000)(45C)
Y none (1.0000)(89C)
Rh none (1.0000)(103C)
In Sn (1.0000)(115C) - (0.0140)(118C)
Tb none (1.0000)(159C)
Ho none (1.0000)(165C)
Bi none (1.0000)(209C)

C - Calibration blank subtracted counts at specified mass

The coefficients in correction equations were calculated using natural

isotopic abundances, and assuming zero instrumental fractionation. For each
particular instrument these coefficients must be determined experimentally.

The correction equations shall not be applied if appropriate interference

check sample measurement demonstrates absence of interference above the CRQL.

ILM05.3 D-34/ICP-MS
 Exhibit D (ICP-MS) – Section 17
Tables/Diagrams/Flowcharts (Con’t)
Table 4. Internal Standards (must use at least five)

Internal Standard Mass CAS Number

Lithium 6 7439-93-2
Scandium 45 7440-20-2
Yttrium 89 7440-65-5
Rhodium 103 7440-16-6
Indium 115 7440-74-6
Terbium 159 7440-27-9
Holmium 165 7440-60-0
Lutetium 175 7439-94-3
Bismuth 209 7440-69-9

NOTE: Use of Li6 requires enriched standard.

Table 5. Spiking Levels for Spike Sample Analysis

Analyte Spike (µg/L)

Sb 100
As 40
Ba 2000
Be 50
Cd 50
Cr 200
Co 500
Cu 250
Pb 20
Mn 500
Ni 500
Se 10
Ag 50
Tl 50
V 500
Zn 500

D-35/ICP-MS ILM05.3
 EXHIBIT D - PART C

ANALYTICAL METHODS

FOR

COLD VAPOR MERCURY ANALYSIS

D-1/Mercury ILM05.3
 THIS PAGE INTENTIONALLY LEFT BLANK

ILM05.3 D-2/Mercury
 Exhibit D - Analytical Methods for Cold Vapor Mercury Analysis

Table of Contents

Section Page

1.0 SCOPE AND APPLICATION . . . . . . . . . . . . . . . . . . . . . . . . 5

2.0 SUMMARY OF METHOD . . . . . . . . . . . . . . . . . . . . . . . . . . 5

2.1 Water by Automated and Manual Techniques . . . . . . . . . . . 5

2.2 Soil/Sediment by Manual Technique . . . . . . . . . . . . . . . 5

3.0 DEFINITIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

4.0 INTERFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

4.1 Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

4.2 Soil/Sediment . . . . . . . . . . . . . . . . . . . . . . . . . 6

5.0 SAFETY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

6.0 EQUIPMENT AND SUPPLIES . . . . . . . . . . . . . . . . . . . . . . . 7

6.1 General Information for Water and Soils (Automated and

Manual Techniques) . . . . . . . . . . . . . . . . . . . . . . 7

6.2 Water by Automated Technique . . . . . . . . . . . . . . . . . 7

6.3 Water and Soil/Sediment by Manual Technique . . . . . . . . . . 7

7.0 REAGENTS AND STANDARDS . . . . . . . . . . . . . . . . . . . . . . . 8

7.1 Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

7.2 Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE . . . . . . . . . . . . 10

8.1 Sample Collection and Preservation . . . . . . . . . . . . . . 10

8.2 Procedure for Sample Storage . . . . . . . . . . . . . . . . . 10

8.3 Contract Required Holding Time . . . . . . . . . . . . . . . . 10

9.0 CALIBRATION AND STANDARDIZATION . . . . . . . . . . . . . . . . . . . 11

9.1 Cold Vapor Atomic Absorption (AA) Instrument Calibration

Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

9.2 Initial Calibration Verification (ICV) . . . . . . . . . . . . 11

9.3 Continuing Calibration Verification (CCV) . . . . . . . . . . . 11

9.4 Initial and Continuing Calibration Blank (ICB/CCB) . . . . . . 12

10.0 PROCEDURE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

10.1 Sample Preparation . . . . . . . . . . . . . . . . . . . . . . 13

10.2 Sample Analysis . . . . . . . . . . . . . . . . . . . . . . . . 16

11.0 DATA ANALYSIS AND CALCULATIONS . . . . . . . . . . . . . . . . . . . 17

11.1 Water/Aqueous by Automated Technique . . . . . . . . . . . . . 17

11.2 Water/Aqueous by Manual Technique . . . . . . . . . . . . . . . 17

11.3 Soil by Manual Technique . . . . . . . . . . . . . . . . . . . 17

11.4 Adjusted Method Detection Limit (MDL)/Adjusted Contract

Required Quantitation Limit (CRQL) Calculation . . . . . . . . 17

12.0 QUALITY CONTROL . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

12.1 Initial Calibration Verification (ICV) . . . . . . . . . . . . 19

12.2 Continuing Calibration Verification (CCV) . . . . . . . . . . . 19

12.3 Contract Required Quantitation Limit (CRQL) Check

Standard (CRI) . . . . . . . . . . . . . . . . . . . . . . . . 19

12.4 Blank Analyses . . . . . . . . . . . . . . . . . . . . . . . . 19

12.5 Spike Sample Analysis . . . . . . . . . . . . . . . . . . . . . 20

12.6 Duplicate Sample Analysis . . . . . . . . . . . . . . . . . . . 21

12.7 Laboratory Control Sample (LCS) Analysis . . . . . . . . . . . 22

12.8 Method Detection Limit (MDL) Determination . . . . . . . . . . 23

12.9 Example Analytical Sequence for Mercury . . . . . . . . . . . . 23

D-3/Mercury ILM05.3
 Exhibit D - Analytical Methods for Cold Vapor Mercury Analysis

Table of Contents (Con’t)

Section Page

13.0 METHOD PERFORMANCE . . . . . . . . . . . . . . . . . . . . . . . . . 24

14.0 POLLUTION PREVENTION . . . . . . . . . . . . . . . . . . . . . . . . 24

15.0 WASTE MANAGEMENT . . . . . . . . . . . . . . . . . . . . . . . . . . 24

16.0 REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24

17.0 TABLES/DIAGRAMS/FLOWCHARTS . . . . . . . . . . . . . . . . . . . . . 24

ILM05.3 D-4/Mercury
 Exhibit D (Mercury) -- Sections 1 & 2
Scope and Application

1.0 SCOPE AND APPLICATION

The analytical method that follows is designed to analyze water,

sediment, sludge, and soil samples taken from hazardous waste sites
using a cold vapor technique with Atomic Absorption (AA) for total
mercury.

In addition to inorganic forms of mercury, organic mercury may also be

present. These organo-mercury compounds will not respond to the cold
vapor AA technique unless they are first broken down and converted to
mercuric ions. Potassium permanganate oxidizes many of these compounds,
but studies have shown that a number of organo-mercury compounds,
including phenyl mercuric acetate and methyl mercuric chloride, are only
partially oxidized by this reagent. Potassium persulfate has been found
to give approximately 100% recovery when used as the oxidant with these
compounds. Therefore, a persulfate oxidation step following the
addition of the permanganate has been included to ensure that organo­
mercury compounds, if present, will be oxidized to the mercuric ion
before measurement. A heat step is required for methyl mercuric
chloride when present in, or spiked to, a natural system.

The range of the method may be varied through instrument and/or recorder
expansion. Using a 100 milliliters (mL) sample, a detection limit of
less than 0.1 micrograms per Liter (µg/L) can be achieved.

The range of the method for soil/sediments is 0.05 milligrams per

kilogram (mg/kg) to 5 mg/kg. The range may be extended above or below
the normal range by increasing or decreasing sample size or through
instrument and recorder control.

2.0 SUMMARY OF METHOD

2.1 Water by Automated and Manual Techniques

This is a physical method based on the absorption of radiation at 253.7

nanometers (nm) by mercury vapor. Free mercury atoms can exist at room
temperature; therefore, mercury can be measured by Atomic Absorption
(AA) without a heated sample cell. Organic compounds are oxidized, and
in the cold vapor mercury technique, mercury is chemically reduced to
the free atomic state by reacting the sample with a strong reducing
agent like stannous chloride or sodium borohydride in a closed reaction
vessel. The volatile free mercury is then driven from the reaction
flask by bubbling air through the solution. Mercury atoms are carried
in the air stream through tubing connected to an absorption cell, which
is placed in the light path of the AA spectrophotometer. Sometimes the
cell is heated slightly to avoid water condensation; otherwise the cell
is completely unheated. As the mercury atoms pass into the sampling
cell, measured absorbance rises indicating the increasing concentration
of mercury atoms in the light path. Some systems allow the mercury
vapor to pass from the absorption tube to waste, in which case the
absorption peaks and then falls as the mercury is depleted. The highest
absorbance observed during the measurement will be taken as the
analytical signal.

2.2 Soil/Sediment by Manual Technique

2.2.1 A weighed portion of the sample is acid digested for 2 minutes at

95°C, followed by oxidation with potassium permanganate and potassium
persulfate. Mercury in the digested sample is then measured by the
conventional cold vapor technique.

2.2.2 An alternate digestion involving the use of an autoclave is described

in Section 10.1.4.2.1.2.

D-5/Mercury ILM05.3
Exhibit D (Mercury) -- Sections 3 & 4
Definitions

3.0 DEFINITIONS

See Exhibit G for a complete list of definitions.

4.0 INTERFERENCES

4.1 Water

4.1.1 Some sea waters and wastewaters high in chlorides have shown a
positive interference, and require additional permanganate [as much
as 25 milliliters (mL)]. During the oxidation step, chlorides are
converted to free chlorine which will also absorb radiation at 253
nanometers (nm). Care must be taken to assure that free chlorine is
absent before the mercury is reduced and swept into the cell. This
may be accomplished by using an excess of hydroxylamine sulfate
reagent (25 mL). Both inorganic and organic mercury spikes have been
quantitatively recovered from the sea water using this technique.

4.1.2 Formation of a heavy precipitate, in some wastewaters and effluents,

has been reported upon addition of concentrated sulfuric acid. If
this is encountered, the problem sample cannot be analyzed by this
method.

4.1.3 Possible interference from sulfide is eliminated by the addition of

potassium permanganate. Concentrations as high as 20 milligram per
Liter (mg/L) of sulfide as sodium sulfide do not interfere with the
recovery of added inorganic mercury from reagent water.

4.1.4 Copper has also been reported to interfere; however, copper

concentrations as high as 10 mg/L have no effect on recovery of
mercury from spiked samples.

4.1.5 Samples containing solids must be blended and then mixed while being
sampled if total mercury values are to be reported.

4.2 Soil/Sediment

4.2.1 The same types of interferences that may occur in water samples are
also possible with sediments (i.e., sulfides, high copper, high
chlorides, etc.).

4.2.2 Samples containing high concentrations of oxidizable organic

materials, as evidenced by high chemical oxygen demand values, may
not be completely oxidized by this procedure. When this occurs, the
recovery of organic mercury will be low. The problem can be
eliminated by reducing the weight of the original sample or by
increasing the amount of potassium persulfate (and consequently
stannous chloride) used in the digestion.

ILM05.3 D-6/Mercury
 Exhibit D (Mercury) -- Sections 5 & 6
Safety

5.0 SAFETY

See Section 1.14 in Exhibit D - Introduction to Analytical Methods.

6.0 EQUIPMENT AND SUPPLIES

Brand names, suppliers, and part numbers are for illustrative purposes
only. No endorsement is implied. Equivalent performance may be
achieved using equipment and supplies other than those specified here,
however, a demonstration of equivalent performance meeting the
requirements of this Statement of Work (SOW) is the responsibility of
the Contractor. The Contractor shall document any use of alternate
equipment or supplies in the Sample Delivery Group (SDG) Narrative.

6.1 General Information for Water and Soils (Automated and Manual
Techniques)

6.1.1 Atomic Absorption (AA) Spectrophotometer - Any AA unit having an open

sample presentation area in which to mount the absorption cell is
suitable. Instrument settings recommended by the particular
manufacturer should be followed.

NOTE: Instruments designed specifically for the measurement of

mercury using the cold vapor technique are commercially available and
may be substituted for the AA spectrophotometer.

NOTE: All cold vapor mercury analyzers shall be equipped with all
manufactured required equipment (i.e., dryers) to ensure that the
specified CRQLs are met.

6.1.2 Mercury Hollow Cathode Lamp

6.1.3 Recorder - Any multi-range variable speed recorder that is compatible

with the UV detection system is suitable.

6.2 Water by Automated Technique

6.2.1 Automated Analyzer instrumentation consisting of:

6.2.1.1 Sampler with provision for sample mixing

6.2.1.2 Manifold

6.2.1.3 Proportioning Pump(s)

6.2.1.4 High temperature heating bath with distillation coil(s)

6.2.1.5 Vapor-liquid separator

6.2.1.6 Absorption cell with quartz windows

6.3 Water and Soil/Sediment by Manual Technique

6.3.1 Absorption Cell - Standard spectrophotometer cells

6.3.2 Air Pump - Any device capable of delivering 1 Liter (L) of air per
minute may be used.

6.3.3 Flowmeter - Capable of measuring an air flow of 1 L per minute.

6.3.4 Aeration Tubing - Tygon tubing is used for transporting the mercury
vapor from the sample bottle to the absorption cell and for its
return.

D-7/Mercury ILM05.3
Exhibit D (Mercury) -- Sections 6 & 7
Reagents and Standards

6.3.4.1 Straight glass tubing terminating in a coarse porous frit is used

for sparging air into the sample.

6.3.5 Drying Tube - 6" X 3/4" diameter tube containing 20 grams (g) of
magnesium perchlorate.

NOTE: In place of the magnesium perchlorate drying tube, a small

reading lamp with a 60-watt bulb may be used to prevent condensation
of moisture inside the cell. The lamp is positioned to shine on the
absorption cell maintaining the air temperature in the cell about
10°C above ambient temperature.

7.0 REAGENTS AND STANDARDS

7.1 Reagents

7.1.1 Water by Automated Technique

7.1.1.1 Reagent Water - The purity of this water must be equivalent to

ASTM Type II water (ASTM D1193-77). Use this preparation for all
reagents, standards, and dilutions of solutions.

7.1.1.2 Sulfuric acid, concentrated - Reagent grade.

7.1.1.2.1 Sulfuric acid, 2N - Dilute 56 milliliters (mL) of concentrated

sulfuric acid to 1 Liter (L) with reagent water.

7.1.1.2.2 Sulfuric acid, 10% - Dilute 100 mL concentrated sulfuric acid

to 1 L with reagent water.

7.1.1.3 Nitric acid, concentrated - Reagent grade of low mercury content.

Nitric acid, 0.5% wash solution - Dilute 5 mL of concentrated

nitric acid to 1 L with reagent water.

7.1.1.4 Stannous sulfate - Add 50 grams (g) stannous sulfate to 500 mL of

2N sulfuric acid (see Section 7.1.1.2.1). This mixture is a
suspension and should be stirred continuously during use.

NOTE: Stannous chloride may be used in place of stannous sulfate.

7.1.1.5 Sodium chloride-hydroxylamine sulfate solution - Dissolve 30 g of

sodium chloride and 30 g of hydroxylamine sulfate in reagent water
to 1 L.

NOTE: Hydroxylamine hydrochloride may be used in place of

hydroxylamine sulfate.

7.1.1.6 Potassium permanganate (KMnO4) - 0.5% solution, w/v. Dissolve 5 g

of potassium permanganate in 1 L of reagent water.

7.1.1.7 Potassium permanganate, 0.1N - Dissolve 3.16 g of potassium

permanganate in reagent water and dilute to 1 L.

7.1.1.8 Potassium persulfate - 0.5% solution, w/v. Dissolve 5 g of

potassium persulfate in 1 L of reagent water.

7.1.1.9 Air scrubber solution - Mix equal volumes of 0.1N potassium

permanganate (see Section 7.1.1.6) and 10% sulfuric acid (see
Section 7.1.1.2.2).

ILM05.3 D-8/Mercury
 Exhibit D (Mercury) -- Section 7
Reagents and Standards (Con’t)

7.1.2 Water and Soil/Sediment by Manual Technique

7.1.2.1 Reagent water - The purity of this water must be equivalent to

ASTM Type II water (ASTM D1193-77). Use this preparation for all
reagents, standards, and dilutions of solutions.

7.1.2.2 Sulfuric acid, concentrated - Reagent grade.

7.1.2.2.1 Sulfuric acid, 0.5N - Dilute 14.0 mL of concentrated sulfuric

acid to 1 L. (Water technique only.)

7.1.2.3 Nitric acid, concentrated - Reagent grade of low mercury content.

If a high Preparation Blank (PB) is obtained, it may be necessary
to distill the nitric acid.

7.1.2.4 Stannous sulfate - Add 25 g stannous sulfate to 250 mL of 0.5N

sulfuric acid. This mixture is a suspension and should be stirred
continuously during use.

NOTE: Stannous chloride may be used in place of stannous sulfate.

7.1.2.5 Sodium chloride-hydroxylamine sulfate solution - Dissolve 12 g of

sodium chloride and 12 g of hydroxylamine sulfate in reagent water
and dilute to 100 mL.

NOTE: Hydroxylamine hydrochloride may be used in place of

hydroxylamine sulfate.

7.1.2.6 Potassium permanganate (KMnO4) - 5% solution, w/v. Dissolve 5 g

of potassium permanganate in 100 mL of reagent water.

7.1.2.7 Potassium persulfate - 5% solution, w/v. Dissolve 5 g of

potassium persulfate in 100 mL of reagent water.

7.2 Standards

7.2.1 Introduction

The Contractor must provide all standards to be used with this

contract. These standards may be used only after they have been
certified according to the procedure in Exhibit E, Section 8.0. The
Contractor must be able to verify that the standards are certified.
Manufacturer’s certificates of analysis must be retained by the
Contractor and presented upon request.

7.2.1.1 Stock standard solutions may be purchased or prepared from reagent

grade chemicals or metals.

7.2.1.2 Stock mercury solution - Dissolve 0.1354 g of mercuric chloride in

75 mL of reagent water. Add 10 mL of concentrated nitric acid and
adjust the volume to 100.0 mL [1.0 mL = 1.0 milligram (mg) Hg].

7.2.1.3 Working mercury solution - Make successive dilutions of the stock

mercury solution (see Section 7.2.1.2) to obtain a working
standard containing 0.1 micrograms (µg) per mL. This working
standard and the dilutions of the stock mercury solution should be
prepared fresh daily. Acidity of the working standard should be
maintained at 0.15% nitric acid. This acid should be added to the
flask as needed before the addition of the aliquot. From this
solution, prepare standards.

D-9/Mercury ILM05.3
Exhibit D (Mercury) -- Sections 7 & 8
Sample Collection, Preservation, and Storage

7.2.2 Working Standards

7.2.2.1 Contract Required Quantitation Limit (CRQL) Check Standard (CRI)

The concentration of the CRI for mercury shall be at the CRQL.

Information regarding the CRI shall be reported on Form IIB-IN.

7.2.2.2 Method Detection Limit (MDL) Solution

The MDL solution shall be at a concentration of 3 to 5 times the

expected MDL.

8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE

8.1 Sample Collection and Preservation

All samples must be collected in glass or polyethylene containers.

Water/aqueous samples must be preserved with nitric acid to pH less than
2 immediately after collection. All samples must be iced or
refrigerated at 4°C (±2°C) from the time of collection until digestion.

8.1.1 Dissolved Metals

For the determination of dissolved metals, the sample must be

filtered through a 0.45 micrometer (µm) pore diameter membrane filter
at the time of collection or as soon as possible. Use a portion of
the sample to rinse the filter flask, discard this portion, and
collect the required volume of filtrate. Preserve the filtrate with
nitric acid to pH less than 2 immediately after filtration.

8.2 Procedure for Sample Storage

The samples must be protected from light and refrigerated at 4°C (±2°C)
from the time of receipt until 60 days after delivery of a complete,
reconciled data package to USEPA. After 60 days the samples may be
disposed of in a manner that complies with all applicable regulations.

8.3 Contract Required Holding Time

The maximum holding time for mercury is 26 days from Validated Time of
Sample Receipt (VTSR).

ILM05.3 D-10/Mercury
 Exhibit D (Mercury) -- Section 9
Calibration and Standardization

9.0 CALIBRATION AND STANDARDIZATION

9.1 Cold Vapor Atomic Absorption (AA) Instrument Calibration Procedure

9.1.1 Instruments shall be calibrated daily or once every 24 hours and each
time the instrument is set up. The instrument standardization date
and time shall be included in the raw data.

9.1.2 The date and time of preparation and analysis shall be given in the
raw data.

9.1.3 Calibration standards shall be prepared fresh with each preparation

batch. Prepare a minimum of five calibration standards (which
includes a blank) in graduated amounts in the appropriate range. One
of the standards must be at the Contract Required Quantitation Limit
(CRQL).

9.1.4 Aspirate the standards and record the readings. Results for these
standards shall be within 5% of the true value. Each standard
concentration and the calculations to show that the 5% criteria has
been met shall be given in the raw data. If the values do not fall
within this range, recalibration is necessary. The 5% criteria does
not apply to the calibration standard at the CRQL. The acceptance
criteria for the initial calibration curve is a correlation
coefficient more than or equal to 0.995.

9.1.5 Baseline correction is acceptable as long as it is performed after

every sample or after the Continuing Calibration Verification (CCV)
and Blank (CCB) check. Resloping is acceptable as long as it is
immediately preceded and immediately followed by a compliant CCV and
CCB.

9.2 Initial Calibration Verification (ICV)

9.2.1 Immediately after the AA system has been calibrated, the accuracy of
the initial calibration shall be verified and documented for mercury
by the analysis of the ICV solution at the wavelength used for
analysis.

9.2.2 Only if the ICV solution is not available from USEPA, or where a
certified solution of the analyte is not available from any source,
analyses shall be conducted on an independent standard at a
concentration other than that used for instrument calibration, but
within the calibration range. An independent standard is defined as
a standard composed of the analyte from a different source than that
used in the standards for the instrument calibration. The value for
the ICV shall be reported on Form IIA-IN.

9.3 Continuing Calibration Verification (CCV)

9.3.1 To ensure calibration accuracy during each analysis run, one of the
following standards is to be used for the CCV and shall be analyzed
and reported at a frequency of 10% or every 2 hours during an
analysis run, whichever is more frequent. The standard shall also be
analyzed and reported at the beginning of the run and after the last
analytical sample. The analyte concentration in the CCV standard
shall be different than the concentration used for the ICV and shall
be one of the following solutions at or near the mid-range level of
the calibration curve:

D-11/Mercury ILM05.3
Exhibit D (Mercury) -- Section 9
Calibration and Standardization (Con’t)

C USEPA Solutions

C NIST Standards

C A Contractor-prepared standard solution

The same CCV standard shall be used throughout the analysis runs for
a Sample Delivery Group (SDG) of samples received.

9.3.2 Each CCV analyzed shall reflect the conditions of analysis of all
associated analytical samples (the preceding 10 analytical samples or
the preceding analytical samples up to the previous CCV). The
duration of analysis, rinses, and other related operations that may
affect the CCV measured result may not be applied to the CCV to a
greater extent than the extent applied to the associated analytical
samples. For instance, the difference in time between a CCV analysis
and the blank immediately following it, as well as the difference in
time between the CCV and the analytical sample immediately preceding
it, may not exceed the lowest difference in time between any two
consecutive analytical samples associated with the CCV.

9.3.3 Information regarding the CCV shall be reported on Form IIA-IN.

9.4 Initial and Continuing Calibration Blank (ICB/CCB)

A calibration blank shall be analyzed at each wavelength used for

analysis immediately after every ICV and CCV, at a frequency of 10% or
every 2 hours during the run, whichever is more frequent. The blank
shall be analyzed at the beginning of the run and after the last
analytical sample.

NOTE: A CCB shall be analyzed immediately after the last CCV, and the
last CCV shall be analyzed immediately after the last analytical sample
of the run. The results for the calibration blanks shall be reported on
Form III-IN.

ILM05.3 D-12/Mercury
 Exhibit D (Mercury) -- Section 10
Procedure

10.0 PROCEDURE

10.1 Sample Preparation

10.1.1 If insufficient sample amount (less than 90% of the required amount)
is received to perform the analyses, the Contractor shall contact the
Sample Management Office (SMO) to inform them of the problem. SMO
will contact the Region for instructions. The Region will either
require that no sample analyses be performed or will require that a
reduced volume be used for the sample analysis. No other changes in
the analyses will be permitted. The Contractor shall document the
Region’s decision in the Sample Delivery Group (SDG) Narrative.

10.1.2 If multiphase samples (e.g., two-phase liquid sample, oily

sludge/sandy soil sample) are received by the Contractor, the
Contractor shall contact SMO to apprise them of the type of sample
received. SMO will contact the Region. If all phases of the sample
are amenable to analysis, the Region may require the Contractor to do
any of the following:

C Mix the sample and analyze an aliquot from the homogenized

sample.

C Separate the phases of the sample, and analyze one or more of

the phases separately. SMO will provide EPA sample numbers for
the additional phases, if required.

C Do not analyze the sample.

10.1.2.1 If all of the phases are not amenable to analysis (i.e., outside
the scope), the Region may require the Contractor to do any of the
following:

C Separate the phases and analyze the phase(s) that is (are)

amenable to analysis. SMO will provide EPA sample numbers
for the additional phases, if required.

C Do not analyze the sample.

10.1.2.2 No other changes in the analyses will be permitted. The

Contractor shall document the Region's decision in the SDG
Narrative.

10.1.3 Water Preparation of Standards and Samples (Manual Technique)

10.1.3.1 Standards Preparation

10.1.3.1.1 Transfer aliquots of the working mercury solution to a series

of 300 milliliters (mL) BOD bottles or other suitable digestion
vessels. Add enough reagent water to each bottle to make a
total volume of 50-100 mL.

10.1.3.1.2 Mix thoroughly and add 5 mL of concentrated sulfuric acid (see

Section 7.1.2.2) and 2.5 mL of concentrated nitric acid (see
Section 7.1.2.3) to each bottle. Add 15 mL of KMnO4 (see
Section 7.1.2.6) solution to each bottle and allow to stand at
least 15 minutes. Add 8 mL of potassium persulfate (see
Section 7.1.2.7) to each bottle and heat for 2 hours in a water
bath or block digester maintained at 95°C. (If an autoclave is
employed, cover the BOD bottles with foil and heat in the
autoclave for 15 minutes at 120°C and 15 PSI instead of heating
for 2 hours in a waterbath at 95°C). Cool and add 6 mL of
sodium chloride-hydroxylamine sulfate solution (see Section

D-13/Mercury ILM05.3
Exhibit D (Mercury) -- Section 10
Procedure (Con’t)

7.1.2.5) to reduce the excess permanganate. When the solution

has been decolorized, wait 30 seconds, add 5 mL of the stannous
sulfate solution (see Section 7.1.2.4) and immediately attach
the bottle to the aeration apparatus to form a closed system.
At this point the sample is allowed to stand quietly without
manual agitation. If volumes less than 100 mL are used, all
other reagents shall be reduced accordingly (e.g., if 50 mL is
used, reduce reagent volumes by one-half).

10.1.3.1.3 The circulating pump, which has previously been adjusted to a

rate of 1 Liter (L) per minute, is allowed to run continuously
(see Note 1). The absorbance will increase and reach maximum
within 30 seconds. As soon as the response levels off, open
the bypass valve and continue the aeration until the absorbance
returns to its minimum value (see Note 2). Close the bypass
valve, remove the stopper and frit from the BOD bottle and
continue the aeration. Proceed with the standards and
construct a standard curve by plotting instrument response at
253 nanometers (nm) versus micrograms (µg) of mercury.

NOTE 1: An open system where the mercury vapor is passed

through the absorption cell only once may be used instead of
the closed system.

NOTE 2: Because of the toxic nature of mercury vapor,

precaution must be taken to avoid its inhalation. Therefore, a
bypass has been included in the system to either vent the
mercury vapor into an exhaust hood or pass the vapor through
some absorbing media, such as equal volumes of 0.1 M KMnO4, and
10% H2SO4 or 0.25% iodine in a 3% KI solution. A specially
treated charcoal that will adsorb mercury vapor is commercially
available.

10.1.3.2 Sample Preparation

10.1.3.2.1 Preparation Method/Code (CW1)

10.1.3.2.1.1 Transfer 50-100 mL, or an aliquot diluted to 50-100 mL,

containing not more than 1.0 µg of mercury, to a 300 mL BOD
bottle or other suitable digestion vessel, and continue as
described in Section 10.1.3.1.2.

NOTE: The same amount of KMnO4 added to the samples should

be present in standards and blanks.

10.1.3.2.1.2 Cool and add 6 mL of sodium chloride-hydroxylamine sulfate

(see Section 7.1.2.5) to reduce the excess permanganate.
Purge the headspace in the BOD bottle for at least 1 minute
and add 5 mL of stannous sulfate (see Section 7.1.2.4) and
immediately attach the bottle to the aeration apparatus.

NOTE: Add reductant in 6 mL increments until KMnO4 is

completely reduced (until the color is no longer purple).

10.1.4 Soil/Sediment Preparation of Standards and Samples (Manual)

10.1.4.1 Standards Preparation

10.1.4.1.1 Transfer aliquots of the working mercury solutions (see Section

7.2.1.3) to a series of 300 mL BOD bottles or other suitable
digestion vessels. Add enough reagent water to each bottle to
make a total volume of 10 mL.

ILM05.3 D-14/Mercury
 Exhibit D (Mercury) -- Section 10
Procedure (Con’t)

10.1.4.1.2 Add 5 mL of concentrated H2SO4 (see Section 7.1.2.2) and 2.5 mL

of concentrated HNO3 (see Section 7.1.2.3) and heat 2 minutes
in a water bath or block digester at 95°C. Allow the sample to
cool and add 50 mL reagent water, 15 mL of KMnO4 solution (see
Section 7.1.2.6) and 8 mL of potassium persulfate solution (see
Section 7.1.2.7) to each bottle and return to the water bath or
block digester for 30 minutes. Cool and add 6 mL of sodium
chloride-hydroxylamine sulfate solution (see Section 7.1.2.5)
to reduce the excess permanganate. Add 50 mL of reagent water
(final volume of reagent water = 100 mL). Treating each bottle
individually, add 5 mL of stannous sulfate solution (see
Section 7.1.2.4) and immediately attach the bottle to the
aeration apparatus. At this point the sample is allowed to
stand quietly without manual agitation. If an autoclave is
used, the standards shall be prepared in the same way as the
samples (see Section 10.1.4.2.1.2).

10.1.4.1.3 The circulating pump, which has previously been adjusted to a

rate of 1 L per minute, is allowed to run continuously. The
absorbance, as exhibited either on the spectrophotometer or the
recorder, will increase and reach maximum within 30 seconds.
As soon as the response levels off, open the bypass valve and
continue the aeration until the absorbance returns to its
minimum value. Close the bypass valve, remove the fritted
tubing from the BOD bottle and continue the aeration. Proceed
with the standards and construct a standard curve by plotting
peak height versus µg of mercury.

10.1.4.2 Sample Preparation

10.1.4.2.1 Preparation Method/Code (CS1)

10.1.4.2.1.1 Weigh a representative 0.20 g (±0.01 g) portion of wet

sample and place in the bottom of a BOD bottle. Add enough
reagent water to each sample to make a total volume of 10
mL. Continue as described in Section 10.1.4.1.2.

10.1.4.2.1.2 If an autoclave is used, add 5 mL of concentrated H2SO4 and

2 mL of concentrated HNO3 to the 0.20 g (±0.01 g) of
sample. Add 5 mL of saturated KMnO4 solution and 8 mL of
potassium persulfate solution and cover with a piece of
aluminum foil. The sample is autoclaved at 120°C and 15 PSI
for 15 minutes. Cool, make up to a volume of 100 mL with
reagent water, and add 6 mL of sodium chloride-hydroxylamine
sulfate solution (see Section 7.1.2.5) to reduce the excess
permanganate. Purge the headspace of the sample bottle for
at least one minute and continue as described under Section
10.1.4.1.2.

10.1.5 Preparation of Standards for Automated Cold Vapor Analysis Technique

(Analysis Method - AV)

10.1.5.1 Standards Preparation

Make successive dilutions of the stock mercury solution to obtain

a working standard containing 0.1 µg per mL. This working
standard and the dilutions of the stock mercury solution should be
prepared fresh daily. Acidity of the working standard should be
maintained at 0.15% nitric acid. This acid should be added to the
flask as needed before the addition of the aliquot. From this
solution, prepare standards.

D-15/Mercury ILM05.3
Exhibit D (Mercury) -- Section 10
Procedure (Con’t)

10.2 Sample Analysis

10.2.1 Set up instrument with proper operating parameters.

10.2.2 Profile and calibrate instrument according to instrument

manufacturer's recommended procedures, using calibration standard
solutions mentioned in Section 9.1. Samples prepared by a certain
method must be analyzed with calibration and QC standards prepared by
the same method. Therefore, only one Preparation Method/Code can be
associated with each run.

10.2.3 Analyze the Continuing Calibration Verification (CCV) instrument

check standard and the Continuing Calibration Blank (CCB) after every
10 analytical samples.

10.2.4 Analysis of Water/Aqueous Samples by the Automated Cold Vapor

Technique (AV) Preparation Method/Code (CW2)

10.2.4.1 Set up manifold.

10.2.4.2 Feed all the reagents through the system with acid wash solution
(see Section 7.1.1.3) through the sample line, adjusting the
heating bath to 105°C.

10.2.4.3 Turn on the Atomic Absorption (AA) Spectrophotometer, adjust

instrument settings as recommended by the manufacturer, align
absorption cell in light path for maximum transmittance and place
heat lamp directly over absorption cell.

10.2.4.4 Arrange working mercury standards in sampler and start sampling.

Complete loading of sample tray with unknown samples.

10.2.4.5 After the analysis is complete, put all lines except the H2SO4
line in reagent water to wash out system. After flushing, wash
out the H2SO4 line. Also flush the coils in the high temperature
heating bath by pumping stannous sulfate (see Section 7.1.1.4)
through the sample lines followed by reagent water. This will
prevent build-up of oxides of manganese.

ILM05.3 D-16/Mercury
 Exhibit D (Mercury) -- Section 11

Data Analysis and Calculations

11.0 DATA ANALYSIS AND CALCULATIONS

11.1 Water/Aqueous by Automated Technique

11.1.1 Prepare a standard curve by plotting the instrumental response of

processed standards against true concentration values. Use a linear
regression equation to determine the concentration of field and
Quality Control (QC) samples.

11.1.2 If samples were diluted for analysis, multiply the results from the
linear regression by the dilution factor.

11.2 Water/Aqueous by Manual Technique

11.2.1 Determine the instrumental response of the unknown and determine the
mercury value from the standard curve.

11.2.2 Calculate the mercury concentration in the sample by the formula:

EQ. 1 Aqueous Sample Concentration (Manual)

11.3 Soil by Manual Technique

11.3.1 Measure the instrumental response of the unknown and determine the
mercury value from the standard curve.

11.3.2 Calculate the mercury concentration in the sample by the formula:

EQ. 2 Soil Sample Concentration (Manual)

WHERE, C = Concentration from curve (µg/L)

W = Wet sample weight (g)
S = % Solids/100 (see Exhibit D - Introduction to
Analytical Methods, Section 1.6).

11.4 Adjusted Method Detection Limit (MDL)/Adjusted Contract Required

Quantitation Limit (CRQL) Calculation

To calculate the adjusted MDL or adjusted CRQL for water/aqueous

samples, multiply the value of the MDL (µg/L) or CRQL (µg/L) by the
Dilution Factor. Calculate the adjusted MDL or adjusted CRQL for soil
samples as follows:

D-17/Mercury ILM05.3
Exhibit D (Mercury) -- Section 11
Data Analysis and Calculations (Con’t)

EQ. 3 Adjusted Soil MDL/Adjusted Soil CRQL Concentration

WHERE, C = MDL or CRQL concentration (mg/kg)

WM = Method required wet sample weight (g)
WR = Reported wet sample weight (g)
S = % Solids/100 (see Exhibit D - Introduction to
Analytical Methods, Section 1.6).
DF = Dilution Factor

ILM05.3 D-18/Mercury
 Exhibit D (Mercury) -- Section 12
Quality Control

12.0 QUALITY CONTROL

12.1 Initial Calibration Verification (ICV)

The ICV Standard shall be prepared in the same acid matrix as the
samples and carried through the entire preparation and analysis
procedure. If measurements exceed the control limits of 80% (low) and
120% (high), the analysis shall be terminated, the problem corrected,
the instrument recalibrated, and the calibration reverified.
Information regarding the ICV shall be reported on Form IIA-IN.

12.2 Continuing Calibration Verification (CCV)

The CCV Standard shall be prepared by the analyst at a concentration

equivalent to the mid-point of the calibration curve and carried through
the entire preparation and analysis procedure. If the deviation of the
CCV is greater than the control limits of 80% (low) and 120% (high), the
analysis shall be stopped, the problem corrected, the instrument
recalibrated, the calibration verified, and re-analysis of the preceding
10 analytical samples or all analytical samples analyzed since the last
compliant calibration verification shall be performed. Information
regarding the CCV shall be reported on Form IIA-IN.

12.3 Contract Required Quantitation Limit (CRQL) Check Standard (CRI)

12.3.1 To verify linearity near the CRQL, the Contractor shall analyze a CRI
at the beginning and end of each sample analysis run, immediately
following the ICV/ICB. In addition, the Contractor shall analyze and
report the results for the CRI at a frequency of not less than once
per 20 analytical samples1 per analysis run. The CRI analysis shall
be run immediately followed by the CCV and Continuing Calibration
Blank (CCB) analyses. The CRI shall be prepared by spiking an
aliquot of reagent water with mercury at the CRQL. The CRI shall be
taken through the same process used to digest and analyze the
associated samples.

12.3.2 CRI and percent recovery results shall be reported on Form IIB-IN.
If the percent recovery falls outside the control limits of 70-130%,
the CRI shall be re-analyzed immediately. If the result of the re-
analysis falls within the control limits, no further corrective
action is required. If the result of the re-analysis does not fall
within the control limits, the analysis shall be terminated, the
problem corrected, the instrument recalibrated, or the CRI and
associated samples redigested and analyzed.

12.4 Blank Analyses

There are two different types of blanks required by this method. The
calibration blank is used in establishing the analytical curve while the
preparation blank is used to monitor for possible contamination.

12.4.1 Initial and Continuing Calibration Blank (ICB/CCB)

The ICB and CCB are prepared with acids and reagent water and carried
through the entire preparation and analysis procedure. If the
absolute value of the calibration blank (ICB/CCB) result exceeds the
CRQL (see Exhibit C), the analysis shall be terminated, the problem
corrected, the instrument recalibrated, the calibration verified, and
re-analysis of the preceding 10 analytical samples or all analytical

1
As defined in Exhibit G, CRI is an analytical sample.

D-19/Mercury ILM05.3
Exhibit D (Mercury) -- Section 12
Quality Control (Con’t)

samples analyzed since the last compliant calibration blank shall be

performed.

12.4.2 Preparation Blank (PB)

12.4.2.1 The PB shall contain all the reagents and in the same volumes as
used in processing the samples. The PB shall be carried through
the complete procedure and contain the same acid concentration in
the final solution as the sample solution used for analysis.

12.4.2.2 At least one PB, consisting of reagent water processed through

each sample preparation and analysis procedure (see Section 10),
shall be prepared and analyzed with every Sample Delivery Group
(SDG), or with each batch2 of samples digested, whichever is more
frequent.

12.4.2.3 The first batch of samples in an SDG is to be assigned to

Preparation Blank one, the second batch to Preparation Blank two,
etc. (see Form III-IN). Each Sample Data Package shall contain
the results of all PB analyses associated with the samples in that
SDG.

12.4.2.4 The PB is to be reported for each SDG and used in all analyses to
ascertain whether sample concentrations reflect contamination in
the following manner:

12.4.2.4.1 If the absolute value of the concentration of the blank is less

than or equal to the CRQL (see Exhibit C), no further action is
required.

12.4.2.4.2 If the analyte concentration in the blank is above the CRQL,

the lowest concentration of the analyte in the associated
samples shall be greater than or equal to 10 times the blank
concentration. Otherwise, all samples associated with that
blank, with the analyte concentration less than 10 times the
blank concentration and above the CRQL, shall be redigested and
re-analyzed with appropriate new Quality Control (QC). The
only exception to this shall be an identified field blank. The
sample concentration is not to be corrected for the blank
value.

12.4.2.4.3 If the concentration of the blank is below the negative CRQL,

then all samples reported below 10 times the CRQL and
associated with the blank shall be redigested and re-analyzed
with appropriate new QC.

12.4.2.4.4 The values for the PB shall be reported on Form III-IN.

12.5 Spike Sample Analysis

12.5.1 The spike sample analysis is designed to provide information about

the effect of the sample matrix on the digestion and/or measurement
methodology. The spike is added before the digestion (i.e., prior to
the addition of other reagents). At least one spike sample analysis
(matrix spike) shall be performed on each group of samples of a
similar matrix type (i.e., water, soil) or for each SDG.3 The sample

2
A group of samples prepared at the same time.
3
USEPA may require additional spike sample analyses, upon USEPA Regional
CLP Project Officer (CLP PO) request.

ILM05.3 D-20/Mercury
 Exhibit D (Mercury) -- Section 12
Quality Control (Con’t)

and its associated spike sample shall initially be run at the same
dilution.

12.5.2 If the spike analysis is performed on the same sample that is chosen
for the duplicate sample analysis, spike calculations shall be
performed using the results of the sample designated as the “original
sample” (see Section 12.6). The average of the duplicate results
cannot be used for the purpose of determining percent recovery.
Samples identified as field blanks and Performance Evaluation (PE)
samples shall not be used for spiked sample analysis. USEPA may
require that a specific sample be used for the spike sample analysis.

12.5.3 The analyte spike shall be added at 1 µg/L (water) or 0.5 mg/kg
(soil). Adjustment shall be made to maintain these spiking levels
when the weight of sample taken deviates by more than 10% of these
values.

12.5.4 If the spike recovery is not at or within the limits of 75-125%, the
data of all samples received and associated with that spike sample
and determined by the same analytical method shall be flagged with
the letter “N” on Forms IA-IN and VA-IN. An exception to this rule
is granted when the sample concentration exceeds the spike added
concentration by a factor of four or more. In such an event, the
data shall be reported unflagged even if the percent recovery does
not meet the 75-125% recovery criteria.

12.5.5 In the instance where there is more than one spike sample per matrix,
per method, per SDG, and one spike sample recovery is not within
contract criteria, flag all the samples of the same matrix and method
in the SDG. Individual component percent recoveries (%R) are
calculated as follows:

EQ. 4 Spike Percent Recovery

WHERE, SSR = Spiked Sample Result

SR = Sample Result
SA = Spike Added

12.5.6 When sample concentration is less than the Method Detection Limit
(MDL), use SR = 0 only for purposes of calculating percent recovery.
The Spike Sample Results (SSRs), Sample Results (SRs), Spike Added
(SA), and percent recovery (positive or negative) shall be reported
on Form VA-IN.

12.5.7 The units used for reporting SSRs will be identical to those used for
reporting sample results on Form IA-IN.

12.6 Duplicate Sample Analysis

12.6.1 One duplicate sample shall be analyzed from each group of samples of
a similar matrix type (i.e., water, soil) or for each SDG.4
Duplicates cannot be averaged for reporting on Form IA-IN. The

4
USEPA may require additional duplicate sample analyses, upon USEPA
Regional CLP PO request.

D-21/Mercury ILM05.3
Exhibit D (Mercury) -- Section 12
Quality Control (Con’t)

sample and its associated duplicate sample shall initially be run at

the same dilution.

12.6.2 Duplicate sample analyses are required for percent solids. Samples
identified as field blanks and PE samples shall not be used for
duplicate sample analysis. USEPA may require that a specific sample
be used for duplicate sample analysis. The Relative Percent
Difference (RPD) is calculated as follows:

EQ. 5 Duplicate Sample Relative Percent Difference

WHERE, RPD = Relative Percent Difference

S = Sample Result (original)
D = Duplicate Result

12.6.3 The results of the duplicate sample analyses shall be reported on

Form VI-IN. A control limit of 20% for RPD shall be used for
original and duplicate sample values greater than or equal to five
times the CRQL (see Exhibit C). A control limit of the CRQL value
shall be entered in the “Control Limit” column on Form VI-IN if
either the sample or duplicate value is less than five times the
CRQL. If the sample and duplicate values are greater than or equal
to five times the CRQL, or if the sample and duplicate values are
less than the CRQL, the “Control Limit” field is left empty.

12.6.4 If one result is above five times the CRQL level and the other is
below, use the CRQL criteria to determine if the duplicate analysis
is in control. If both sample and duplicate values are less than the
MDL, the RPD is not calculated on Form VI-IN. For solid sample or
solid duplicate results less than five times the CRQL, enter the
value of the CRQL, corrected for sample weight and percent solids
(i.e., original, not duplicate sample weight and percent solids), in
the “Control Limit” column. If the duplicate sample results are
outside the control limits, flag all the data for samples received
associated with that duplicate sample with an “*” on Forms IA-IN and
VI-IN. In the instance where there is more than one duplicate sample
per SDG, if one duplicate result is not within contract criteria,
flag all samples of the same matrix and method in the SDG. The
percent difference data will be used by USEPA to evaluate the long-
term precision of the method. Specific control limits for each
element will be added to Form VI-IN at a later date based on these
precision results.

12.7 Laboratory Control Sample (LCS) Analysis

12.7.1 A solid LCS (LCSS) shall be analyzed using the same sample
preparations, analytical methods, and Quality Assurance (QA)/QC
procedures employed for the EPA samples received.

12.7.2 The USEPA provided LCSS shall be prepared and analyzed using the
procedures applied to the solid samples received (exception: percent
solids determination not required). If the USEPA LCSS is
unavailable, other USEPA QC Check samples or other certified
materials may be used. In such a case, control limits for the LCSS
must be documented and provided. One LCSS shall be prepared and

ILM05.3 D-22/Mercury
 Exhibit D (Mercury) -- Section 12
Quality Control (Con’t)

analyzed for every group of solid samples in a SDG, or for each batch
of samples digested, whichever is more frequent.

12.7.3 All LCSS and percent recovery results will be reported on Form VII­
IN. If the results for the LCSS fall outside the control limits
established by USEPA, the analyses shall be terminated, the problem
corrected, and the samples associated with that LCSS redigested and
re-analyzed with appropriate new QC.

12.8 Method Detection Limit (MDL) Determination

12.8.1 Before any field samples are analyzed under this contract, the MDLs
shall be determined for each digestion procedure and instrument used,
prior to the start of contract analyses, and annually thereafter, and
shall meet the levels specified in Exhibit C.

An MDL study shall be performed after major instrument maintenance,

or changes in instrumentation or instrumental conditions, to verify
the current sensitivity of the analysis.

12.8.2 To determine the MDLs, the Contractor shall run MDL studies following
the procedures given in 40 CFR, Part 136. The Contractor shall
prepare the MDL samples by each digestion procedure used and shall
analyze these samples on each instrument used.

12.8.3 The determined concentration of the MDL shall be less than half the
concentration of the CRQL listed in Exhibit C.

12.8.4 The results of the MDL determination studies shall be forwarded to

the USEPA Regional CLP PO, Sample Management Office (SMO), and
Quality Assurance Technical Support (QATS).

12.8.5 The MDL results shall be reported on Form IX-IN.

12.9 Example Analytical Sequence for Mercury

S0

S0.2

S0.5

S1.0

S2.0

S5.0

S10.0

ICV

ICB

CRI

CCV

CCB

10 samples

CCV

CCB

9 samples

CRI

CCV

CCB

10 samples, etc.

D-23/Mercury ILM05.3
Exhibit D (Mercury) -- Sections 13-17
Method Performance

13.0 METHOD PERFORMANCE

Not applicable.

14.0 POLLUTION PREVENTION

See Section 1.15 in Exhibit D - Introduction to Analytical Methods.

15.0 WASTE MANAGEMENT

See Section 1.16 in Exhibit D - Introduction to Analytical Methods.

16.0 REFERENCES

16.1 US Environmental Protection Agency. Methods for Chemical Analysis of

Water and Wastes. Method 245.1. 1974.

16.2 US Environmental Protection Agency. Methods for Chemical Analysis of

Water and Wastes. Method 245.2. 1974.

16.3 US Environmental Protection Agency. Methods for Chemical Analysis of

Water and Wastes. Method 245.5. 1974.

16.4 US Government Printing Office. 40 Code of Federal Regulations, Part 136,

Section 1, Appendix B.

17.0 TABLES/DIAGRAMS/FLOWCHARTS

Not applicable.

ILM05.3 D-24/Mercury
 EXHIBIT D - PART D

ANALYTICAL METHODS
FOR
TOTAL CYANIDE ANALYSIS

D-1/Cyanide ILM05.3
 THIS PAGE INTENTIONALLY LEFT BLANK

ILM05.3 D-2/Cyanide
 Exhibit D - Analytical Methods for Total Cyanide Analysis

Table of Contents

Section Page

1.0 SCOPE AND APPLICATION . . . . . . . . . . . . . . . . . . . . . . . . 5

2.0 SUMMARY OF METHOD . . . . . . . . . . . . . . . . . . . . . . . . . . 5

2.1 Waters and Soils . . . . . . . . . . . . . . . . . . . . . . . 5

3.0 DEFINITIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

4.0 INTERFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4.1 Sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4.2 Surfactants . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4.3 Oxidizing Agents . . . . . . . . . . . . . . . . . . . . . . . 6

5.0 SAFETY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

6.0 EQUIPMENT AND SUPPLIES . . . . . . . . . . . . . . . . . . . . . . . 7

6.1 Conventional Distillation of Water and Soils . . . . . . . . . 7
6.2 Midi Distillation of Water and Soils . . . . . . . . . . . . . 7

7.0 REAGENTS AND STANDARDS . . . . . . . . . . . . . . . . . . . . . . . 8

7.1 Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
7.2 Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE . . . . . . . . . . . . 11

8.1 Sample Collection and Preservation . . . . . . . . . . . . . . 11
8.2 Procedure for Sample Storage . . . . . . . . . . . . . . . . . 11
8.3 Contract Required Holding Time . . . . . . . . . . . . . . . . 11

9.0 CALIBRATION AND STANDARDIZATION . . . . . . . . . . . . . . . . . . . 12

9.1 Instrument Operating Parameters . . . . . . . . . . . . . . . . 12
9.2 General Procedure . . . . . . . . . . . . . . . . . . . . . . . 12
9.3 Spectrophotometric Instrument Calibration Procedure . . . . . . 12
9.4 Initial Calibration Verification (ICV) . . . . . . . . . . . . 12
9.5 Continuing Calibration Verification (CCV) . . . . . . . . . . . 13
9.6 Initial and Continuing Calibration Blank (ICB/CCB) . . . . . . 13

10.0 PROCEDURE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
10.1 Sample Preparation . . . . . . . . . . . . . . . . . . . . . . 14
10.2 Water and Soil Preparation of Standards and Samples . . . . . . 15
10.3 Sample Analysis . . . . . . . . . . . . . . . . . . . . . . . . 19

11.0 DATA ANALYSIS AND CALCULATIONS . . . . . . . . . . . . . . . . . . . 20

11.1 Water/Aqueous Sample Calculation . . . . . . . . . . . . . . . 20
11.2 Soil Sample Calculation . . . . . . . . . . . . . . . . . . . . 20
11.3 Calculations for Midi Distillation of Waters and Soils . . . . 21
11.4 Adjusted Method Detection Limit (MDL)/Adjusted Contract
Required Quantitation Limit (CRQL) Calculation . . . . . . . . 22

12.0 QUALITY CONTROL (QC) . . . . . . . . . . . . . . . . . . . . . . . . 24

12.1 Initial Calibration Verification (ICV) . . . . . . . . . . . . 24
12.2 Continuing Calibration Verification (CCV) . . . . . . . . . . . 24
12.3 Contract Required Quantitation Limit (CRQL) Check Standard
(CRI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
12.4 Blank Analyses . . . . . . . . . . . . . . . . . . . . . . . . 24
12.5 Spike Sample Analysis . . . . . . . . . . . . . . . . . . . . . 25
12.6 Duplicate Sample Analysis . . . . . . . . . . . . . . . . . . . 27
12.7 Laboratory Control Sample (LCS) Analysis . . . . . . . . . . . 28
12.8 Method Detection Limit (MDL) Determination . . . . . . . . . . 28
12.9 Example Analytical Sequence for Cyanide . . . . . . . . . . . . 29

D-3/Cyanide ILM05.3
 Exhibit D - Analytical Methods for Total Cyanide Analysis

Table of Contents (Con’t)

Section Page

13.0 METHOD PERFORMANCE . . . . . . . . . . . . . . . . . . . . . . . . . 30

14.0 POLLUTION PREVENTION . . . . . . . . . . . . . . . . . . . . . . . . 30

15.0 WASTE MANAGEMENT . . . . . . . . . . . . . . . . . . . . . . . . . . 30

16.0 REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

17.0 TABLES/DIAGRAMS/FLOWCHARTS . . . . . . . . . . . . . . . . . . . . . 30

ILM05.3 D-4/Cyanide
 Exhibit D (Cyanide) –- Sections 1-3
Scope and Application

1.0 SCOPE AND APPLICATION

The analytical method that follows is designed to analyze various water

types, sediment, sludge, and soil samples taken from hazardous waste
sites, for total cyanide.

This analytical method includes the use of acid and heat to remove
cyanide from the sample.

2.0 SUMMARY OF METHOD

2.1 Waters and Soils

2.1.1 The cyanide as hydrocyanic acid (HCN) is released from cyanide

complexes by means of a reflux-distillation and absorbed in a
scrubber containing sodium hydroxide solution. The cyanide ion in
the absorbing solution is then determined colorimetrically.

2.1.2 In the colorimetric measurement, the cyanide is converted to cyanogen

chloride (CNCl), by reaction with chloramine-T at a pH less than 8
without hydrolyzing to the cyanate. After the reaction is complete,
color is formed on the addition of pyridine-barbituric acid reagent.
The absorbance is read between 570 and 580 nanometers (nm). To
obtain colors of comparable intensity, it is essential to have the
same salt content in both the sample and the standards.

3.0 DEFINITIONS

See Exhibit G for a complete list of definitions.

D-5/Cyanide ILM05.3
Exhibit D (Cyanide) -- Sections 4 & 5
Interferences

4.0 INTERFERENCES

Interferences are eliminated or reduced by using the distillation

procedure.

4.1 Sulfides

Sulfides adversely affect the colorimetric procedure. The sample should

be tested in the field for the presence of sulfides as described in
Section 8.1.1.

4.2 Surfactants

The presence of surfactants may cause the sample to foam during

refluxing. If this occurs, the addition of an agent such as Dow Corning
544 antifoam agent will prevent the foam from collecting in the
condenser.

4.3 Oxidizing Agents

Oxidizing agents such as chlorine decompose most of the cyanides. The

sample should be tested in the field for the presence of oxidizing
agents as described in Section 8.1.1.

5.0 SAFETY

See Section 1.14 in Exhibit D - Introduction to Analytical Methods.

ILM05.3 D-6/Cyanide
 Exhibit D (Cyanide) -- Section 6
Equipment and Supplies

6.0 EQUIPMENT AND SUPPLIES

Brand names, suppliers, and part numbers are for illustrative purposes

only. No endorsement is implied. Equivalent performance may be

achieved using equipment and supplies other than those specified here,

however, a demonstration of equivalent performance meeting the

requirements of this Statement of Work (SOW) is the responsibility of

the Contractor. The Contractor shall document any use of alternate

equipment or supplies in the Sample Delivery Group (SDG) Narrative.

6.1 Conventional Distillation of Water and Soils

6.1.1 Reflux distillation apparatus. The boiling flask should be of 1

Liter (L) size with an inlet tube and provision for condenser.
The

gas absorber may be a Fisher-Milligan scrubber.

6.1.2 Spectrophotometer suitable for measurements between 570 and 580

nanometers (nm) with a 1.0 centimeter (cm) cell or larger (for manual

spectrophotometric method).

6.1.3 Automated analyzer instrumentation (for automated spectrophotometric

method) including:

6.1.3.1 Sampler

6.1.3.2 Pump

6.1.3.3 Cyanide manifold

6.1.3.4 Colorimeter with 15 millimeters (mm) flow cells and 580 nm filters

6.1.3.5 Recorder

6.1.3.6 Data system (optional)

6.1.3.7 Glass or plastic tubes for the sampler

6.2 Midi Distillation of Water and Soils

6.2.1 Midi reflux distillation apparatus

6.2.2 Heating block - Capable of maintaining 125°C (±5°C).

6.2.3 Auto analyzer system with accessories:

6.2.3.1 Sampler

6.2.3.2 Pump

6.2.3.3 Cyanide cartridge

6.2.3.4 Colorimeter with 50 mm flow cells and 580 nm filter

6.2.3.5 Chart recorder or data system

6.2.4 Assorted volumetric glassware, pipets, and micropipets

D-7/Cyanide ILM05.3
Exhibit D (Cyanide) – Section 7
Reagents and Standards

7.0 REAGENTS AND STANDARDS

7.1 Reagents

7.1.1 Reagent water - The purity of this water must be equivalent to ASTM
Type II water (ASTM D1193-77). Use this preparation for all
reagents, standards, and dilutions of solutions.

7.1.2 Conventional Distillation and Preparation Reagents of Water and Soils

7.1.2.1 Sodium hydroxide solution, 1.25N - Dissolve 50 grams (g) of NaOH

in reagent water, and dilute to 1 Liter (L) with reagent water.
(Same Distillation and Preparation Reagent for Midi Distillation
of Water and Soils.)

7.1.2.2 Cadmium carbonate - Powdered

7.1.2.3 Ascorbic acid - Crystals

7.1.2.4 Sulfuric acid - Concentrated

7.1.2.5 Hydrochloric acid (HCl) - Concentrated (specific gravity 1.19).

7.1.2.6 Magnesium chloride solution - Weigh 510 g of MgCl2 • 6H2O into a

1000 milliliter (mL) flask, dissolve, and dilute to 1 L with
reagent water. (Same Distillation and Preparation Reagent for
Midi Distillation of Water and Soils.)

7.1.3 Midi Distillation and Preparation Reagents of Water and Soils

7.1.3.1 Sodium hydroxide absorbing solution and sample wash solution,

0.25N - Dissolve 10.0 g NaOH in reagent water and dilute to 1 L.

7.1.3.2 Sulfuric acid, 50% (v/v) - Carefully add a portion of concentrated

H2SO4 to an equal portion of reagent water.

7.1.4 Manual Spectrophotometric Reagents for Water and Soils

7.1.4.1 Acetate Buffer - Dissolve 410 g of NaC2H3O2 • 3H2O in 500 mL of

reagent water. Add sufficient glacial acetic acid to adjust pH to
4.5 (approximately 500 mL).

7.1.4.2 Chloramine-T solution - Dissolve 1.0 g of white, water soluble

chloramine-T in 100 mL of reagent water and refrigerate until
ready to use. Prepare fresh weekly.

7.1.4.3 Color Reagent

7.1.4.3.1 Pyridine-barbituric acid reagent - Place 15 g of barbituric

acid in a 250 mL volumetric flask and add just enough reagent
water to wash the sides of the flask and wet the barbituric
acid. Add 75 mL of pyridine and mix. Add 15 mL of HCl
(specific gravity 1.19), mix, and cool to room temperature.
Dilute to 250 mL with reagent water and mix. This reagent is
stable for approximately six months if stored in a cool, dark
place.

7.1.5 Semi-Automated Spectrophotometric Reagents for Conventional and Midi

Distillation of Water and Soils

7.1.5.1 Chloramine-T solution - Dissolve 0.40 g of chloramine-T in reagent

water and dilute to 100 mL. Prepare fresh daily.

ILM05.3 D-8/Cyanide
 Exhibit D (Cyanide) – Section 7
Reagents and Standards (Con’t)

7.1.5.2 Acetate Buffer - Dissolve 410 g of NaC2H3O2 • 3H2O in 500 mL of

reagent water. Add sufficient glacial acetic acid to adjust pH to
4.5 (approximately 500 mL).

7.1.5.3 Pyridine-barbituric acid solution - Transfer 15 g of barbituric

acid into a 1 liter volumetric flask. Add about 100 mL of reagent
water and swirl the flask. Add 75 mL of pyridine and mix. Add 15
mL of concentrated HCl and mix. Dilute to about 900 mL with
reagent water and mix until the barbituric acid is dissolved.
Dilute to 1 L with reagent water. Store at 4°C (±2°C).

7.1.5.4 Sampler wash - Dissolve 10 g of NaOH in reagent water and dilute

to 1 L. (For conventional distillation of water and soils only.)

7.2 Standards

7.2.1 Introduction

The Contractor must provide all standards to be used with this

contract. These standards may be used only after they have been
certified according to the procedure in Exhibit E, Section 8.0. The
Contractor must be able to verify that the standards are certified.
Manufacturer’s certificates of analysis must be retained by the
Contractor and presented upon request.

7.2.2 Stock Standard Solutions

7.2.2.1 Stock Standard Reagents for Water and Soils

7.2.2.1.1 Stock cyanide solution - Dissolve 2.51 g of KCN and 2 g KOH in

1 L of reagent water. Standardize with 0.0192N AgNO3.

7.2.2.1.2 Standard cyanide solution, intermediate - Dilute 50.0 mL of

stock (1 mL = 1 milligram (mg) CN) to 1000 mL with reagent
water.

7.2.2.1.3 Standard cyanide solution - Prepare fresh daily by diluting 100

mL of intermediate cyanide solution to 1000 mL with reagent
water and store in a glass stoppered bottle. 1 mL = 5.0
micrograms (µg) CN [5.0 milligrams per Liter (mg/L)].

7.2.2.1.4 Sodium hydroxide solution, 0.25N - Dissolve 10 g of NaOH in

reagent water and dilute to 1 L.

7.2.2.2 Stock Standard Reagents for Midi Distillation of Water and Soils

7.2.2.2.1 Stock cyanide solution, 1000 mg/L CN - Dissolve 2.51 g of KCN

and 2.0 g KOH in reagent water and dilute 1 L. Standardize
with 0.0192N AgNO3.

7.2.2.2.2 Intermediate cyanide standard solution, 10 mg/L CN - Dilute 1.0

mL of stock cyanide solution (see Section 7.2.2.2.1) plus 20 mL
of 1.25N NaOH solution (see Section 7.1.2.1) to 100 mL with
reagent water. Prepare this solution at time of analysis.

7.2.2.2.3 Sodium hydroxide solution, 0.1N - Dissolve 4 g of NaOH in

reagent water and dilute to 1 L.

D-9/Cyanide ILM05.3
Exhibit D (Cyanide) – Section 7
Reagents and Standards (Con’t)

7.2.3 Secondary Dilution Standards

7.2.3.1 Secondary Dilution Standards

Prepare secondary dilution standard solutions by diluting the

appropriate volumes of stock standards with 0.25N NaOH. The final
concentration of NaOH in all standards should be 0.25N.

7.2.4 Working Standards

7.2.4.1 Method Detection Limit (MDL) Solution

7.2.4.1.1 The MDL solution shall be at a concentration of 3 to 5 times

the expected MDL.

7.2.4.2 Contract Required Quantitation Limit (CRQL) Check Standard (CRI)

7.2.4.2.1 The concentration of the CRI for cyanide shall be at the CRQL.
Information regarding the CRI shall be reported on Form IIB-IN.

ILM05.3 D-10/Cyanide
 Exhibit D (Cyanide) -- Section 8
Sample Collection, Preservation, and Storage

8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE

8.1 Sample Collection and Preservation

8.1.1 Water Sample Preservation

Collection of total cyanide must be in polyethylene or glass

containers. The sample must be tested for sulfides and oxidizing
agents, and preserved by the sampler immediately upon sample
collection. Place a drop of the sample on lead acetate test paper
(which has been pre-moistened with pH 4 acetate buffer solution) to
detect the presence of sulfides. If sulfides are present (test strip
turns black), the sample volume required for the cyanide
determination should be increased by 25 milliliters (mL). The total
volume of sample should then be treated with powdered cadmium
carbonate or lead carbonate. Yellow cadmium sulfide precipitates if
the sample contains sulfide. Repeat this operation until a drop of
the treated sample solution does not darken the lead acetate test
paper. Filter the solution through a dry filter paper into a dry
beaker, and from the filtrate measure the sample to be used for
analysis. Avoid a large excess of cadmium carbonate and a long
contact time in order to minimize a loss by complexation or occlusion
of cyanide on the precipitated material. If no sulfides are present,
test for the presence of oxidizing agents by placing a drop of the
sample on a strip of potassium iodide - starch test paper (KI -
starch paper); a blue color indicates the need for treatment. Add
ascorbic acid, a few crystals at a time, until a drop of sample
produces no color on the indicator paper. Then add an additional 0.6
gram (g) of ascorbic acid for each liter of sample volume. Preserve
the sample with NaOH to pH greater than 12 and maintain at 4°C (±2°C)
until distillation.

8.1.2 Soil/Sediment Sample Preservation

Samples shall be kept at 4°C (±2°C) from the time of collection until
distillation.

8.2 Procedure for Sample Storage

8.2.1 The samples must be protected from light and refrigerated at 4°C
(±2°C) from the time of receipt until 60 days after delivery of a
complete, reconciled data package to the USEPA. After 60 days the
samples may be disposed of in a manner that complies with all
applicable regulations.

8.2.2 The samples must be stored in an atmosphere demonstrated to be free

of all potential contaminants.

8.2.3 Samples, sample distillates, and standards must be stored separately.

8.3 Contract Required Holding Time

The maximum sample holding time for cyanide is 12 days from Validated
Time of Sample Receipt (VTSR).

D-11/Cyanide ILM05.3
Exhibit D (Cyanide) -- Section 9
Calibration and Standardization

9.0 CALIBRATION AND STANDARDIZATION

9.1 Instrument Operating Parameters

Because of the difference between various makes and models of

satisfactory instruments, no detailed operating instructions can be
provided. The analyst should follow the instructions provided by the
manufacturer of the particular instrument. It is the responsibility of
the analyst to verify that the instrument configuration and operating
conditions used satisfy the analytical requirements and to maintain
Quality Control (QC) data confirming instrument performance and
analytical results.

9.2 General Procedure

The following general procedure applies to most semi-automated

colorimeters. Set up the manifold and complete system per
manufacturer's instructions. Allow the colorimeter and recorder to warm
up for at least 30 minutes prior to use. Establish a steady reagent
baseline, feeding reagent water through the sample line and appropriate
reagents (see Section 7.1.5) through reagent lines. Adjust the baseline
using the appropriate control on the colorimeter. Prepare a standard
curve by plotting absorbance of standard vs. cyanide concentrations [per
250 milliliter (mL)].

9.3 Spectrophotometric Instrument Calibration Procedure

9.3.1 Instruments shall be calibrated daily or once every 24 hours, and

each time the instrument is set up. The instrument standardization
date and time shall be included in the raw data.

9.3.2 The date and time of preparation and analysis shall be given in the
raw data.

9.3.3 Calibration standards shall be prepared fresh daily or each time an

analysis is to be made and discarded after use. Prepare a blank and
at least three calibration standards in graduated amounts in the
appropriate range. One of the calibration standards shall be at the
Contract Required Quantitation Limit (CRQL). The acceptance criteria
for the initial calibration curve is a correlation coefficient
greater than or equal to 0.995.

9.3.4 Any changes or corrections to the analytical system shall be followed

by recalibration.

9.3.5 Baseline correction is acceptable as long as it is performed after

every sample or after the Continuing Calibration Verification (CCV)
and Blank (CCB) check. Resloping is acceptable as long as it is
immediately preceded and immediately followed by a compliant CCV and
CCB.

9.4 Initial Calibration Verification (ICV)

9.4.1 Immediately after each cyanide system has been calibrated, the
accuracy of the initial calibration shall be verified and documented
for cyanide by the analysis of the ICV Solution at the wavelength
used for analysis.

9.4.2 Only if the ICV Solution is not available from USEPA, or where a
certified solution of the analyte is not available from any source,
analyses shall be conducted on an independent standard at a
concentration other than that used for instrument calibration, but

ILM05.3 D-12/Cyanide
 Exhibit D (Cyanide) -- Section 9
Calibration and Standardization (Con’t)

within the calibration range. An independent standard is defined as

a standard composed of the analytes from a different source than
those used in the standards for the instrument calibration.

9.4.3 The ICV shall be distilled. This means that an ICV must be distilled
with each batch of samples analyzed and that the samples distilled
with an ICV must be analyzed with that particular ICV.

9.4.4 The value for the ICV shall be reported on Form IIA-IN.

9.5 Continuing Calibration Verification (CCV)

9.5.1 To ensure calibration accuracy during each analysis run, one of the
following standards is to be used for the CCV and shall be analyzed
and reported at a frequency of 10% or every 2 hours during an
analysis run, whichever is more frequent. The standard shall also be
analyzed and reported at the beginning of the run and after the last
analytical sample. The analyte concentration in the CCV standard
shall be different than the concentration used for the ICV and shall
be one of the following solutions at or near the mid-range level of
the calibration curve:

C USEPA Solutions

C NIST Standards

C A Contractor-prepared standard solution

The same CCV standard shall be used throughout the analysis runs for
a Sample Delivery Group (SDG) of samples received.

9.5.2 Each CCV analyzed shall reflect the conditions of analysis of all
associated analytical samples (the preceding 10 analytical samples or
the preceding analytical samples up to the previous CCV). The
duration of analysis, rinses, and other related operations that may
affect the CCV measured result may not be applied to the CCV to a
greater extent than the extent applied to the associated analytical
samples. For instance, the difference in time between a CCV analysis
and the blank immediately following it, as well as the difference in
time between the CCV and the analytical sample immediately preceding
it, may not exceed the lowest difference in time between any two
consecutive analytical samples associated with the CCV.

9.5.3 Information regarding the CCV shall be reported on Form IIA-IN.

9.6 Initial and Continuing Calibration Blank (ICB/CCB)

A calibration blank shall be analyzed at the wavelength used for

analysis immediately after every ICV and CCV, at a frequency of 10% or
every 2 hours during the run, whichever is more frequent. The blank
shall be analyzed at the beginning of the run and after the last
analytical sample.

NOTE: A CCB shall be analyzed immediately after the last CCV, and the
last CCV shall be analyzed immediately after the last analytical sample
of the run. The results for the calibration blanks shall be reported on
Form III-IN.

D-13/Cyanide ILM05.3
Exhibit D (Cyanide) -- Section 10
Procedure

10.0 PROCEDURE

10.1 Sample Preparation

10.1.1 If insufficient sample amount (less than 90%, of the required amount)
is received to perform the analyses, the Contractor shall contact
Sample Management Office (SMO) to inform them of the problem. SMO
will contact the Region for instructions. The Region will either
require that no sample analyses be performed or will require that a
reduced volume be used for the sample analysis. No other changes in
the analyses will be permitted. The Contractor shall document the
Region’s decision in the Sample Delivery Group (SDG) Narrative.

10.1.2 If multi-phase samples (e.g., two-phase liquid sample, oily

sludge/sandy soil sample) are received by the Contractor, the
Contractor shall contact SMO to apprize them of the type of sample
received. SMO will contact the Region. If all phases of the sample
are amenable to analysis, the Region may require the Contractor to do
any of the following:

C Mix the sample and analyze an aliquot from the homogenized

sample.

C Separate the phases of the sample, and analyze one or more of

the phases separately. SMO will provide EPA sample numbers for
the additional phases, if required.

C Do not analyze the sample.

10.1.2.1 If all of the phases are not amenable to analysis (i.e., outside
scope), the Region may require the Contractor to do any of the
following:

C Separate the phases and analyze the phase(s) that is (are)

amenable to analysis. SMO will provide EPA sample numbers
for the additional phases, if required.

C Do not analyze the sample.

10.1.2.2 No other changes in the analyses will be permitted. The

Contractor shall document the Region's decision in the SDG
Narrative.

10.1.3 Soil samples are not dried prior to analysis. A separate percent
solids determination must be made in accordance with the procedure in
Exhibit D - Introduction to Analytical Methods, Section 1.6.

10.1.4 Before preparation is initiated for an aqueous sample, the Contractor

shall test for the presence of sulfides and oxidizing agents (e.g.,
residual chlorine). The test for sulfides shall be performed by
placing a drop of the sample on a strip of lead acetate paper (which
has been pre-moistened with pH 4 acetate buffer solution). If the
test strip turns black, the Contractor shall treat the total volume
of sample with powdered cadmium carbonate or lead carbonate. Yellow
cadmium sulfide precipitates when the sample contains sulfide. This
operation shall be repeated until a drop of the treated sample
solution does not darken the lead acetate test paper. The solution
shall be filtered through a dry filter paper into a dry beaker, and
the volume of sample to be used for analysis shall be measured from
the filtrate. It is recommended that the Contractor avoid a large
excess of cadmium carbonate and a long contact time in order to
minimize a loss by complexation or occlusion of cyanide on the

ILM05.3 D-14/Cyanide
 Exhibit D (Cyanide) -- Section 10
Procedure (Con’t)

precipitated material. The test for oxidizing agents shall be

performed by placing a drop of the sample on a strip of potassium
iodide - starch test paper (KI - starch paper). If the test strip
turns blue, the Contractor shall contact SMO for further instructions
from the Region before proceeding with sample preparation and
analysis. The Contractor shall document the presence of sulfides or
oxidizing agents in the SDG Narrative.

10.2 Water and Soil Preparation of Standards and Samples

10.2.1 Standards Preparation

10.2.1.1 It is not imperative that all standards be distilled in the same

manner as the samples. At least one standard (mid-range) must be
distilled and compared to similar values on the curve to ensure
that the distillation technique is reliable. The mid-range
standard must be analyzed immediately after the first CCV/CCB. If
the distilled standard does not agree within ±15% of the
undistilled standards, the operator shall find and correct the
cause of the apparent error before proceeding.

10.2.1.2 Standards for Manual Spectrophotometric Analysis of Water and Soil

Samples

Prepare a minimum of three standards and a blank by pipetting

suitable volumes of standard solution into 250 milliliter (mL)
volumetric flasks.

NOTE: The concentration of one of the calibration standards shall

be at the Contract Required Quantitation Limit (CRQL).

To each standard, add 50 mL of 1.25N NaOH and dilute to 250 mL

with reagent water. The same method for color development (i.e.,
pyridine-barbituric acid or pyridine-pyrazolone) must be used for
both the samples and standards. Standards must bracket the
concentration of the samples. If dilution is required, use the
blank solution.

10.2.1.3 Standards for Semi-Automated Spectrophotometric Analysis of Water

and Soil Samples

Calibration standards - Prepare a blank and at least three

calibration standards over the range of the analysis by pipetting
suitable volumes of standard solution into volumetric flasks. One
calibration standard must be at the CRQL. Add NaOH to each
standard to bring the concentration of NaOH to 10 grams per Liter
(g/L). Store at 4°C (±2°C).

10.2.1.4 Standards for Midi Distillation Preparation and Semi-Automated

Spectrophotometric Analysis of Water and Soil Samples

Prepare a minimum of three standards and a blank by pipetting

suitable volumes of standard solution into 50 mL volumetric
flasks. Dilute standards to 50 mL with 0.25N NaOH.

NOTE: One calibration standard must be at the CRQL.

D-15/Cyanide ILM05.3
Exhibit D (Cyanide) -- Section 10
Procedure (Con’t)

10.2.2 Water Samples Preparation (Distillation)

10.2.2.1 Preparation Method/Code (DW1)

10.2.2.1.1 Place 500 mL of sample in the 1 liter boiling flask. Add 50 mL

of NaOH solution (see Section 7.1.2.1) to the absorbing tube
and dilute if necessary with reagent water to obtain an
adequate depth of liquid in the absorber. Connect the boiling
flask, condenser, absorber and trap in the train.

10.2.2.1.2 Start a slow stream of air entering the boiling flask by

adjusting the vacuum source. Adjust the vacuum so that
approximately one bubble of air per second enters the boiling
flask through the air inlet tube.

NOTE: The bubble rate will not remain constant after the
reagents have been added and while heat is being applied to the
flask. It will be necessary to re-adjust the air rate
occasionally to prevent the solution in the boiling flask from
backing up into the air inlet tube.

10.2.2.1.3 Slowly add 25 mL concentrated sulfuric acid (H2SO4) (see

Section 7.1.2.4) through the air inlet tube. Rinse the tube
with reagent water and allow the airflow to mix the flask
contents for three minutes. Pour 20 mL of magnesium chloride
solution (see Section 7.1.2.6) into the air inlet and wash down
with a stream of water.

10.2.2.1.4 Heat the solution to boiling, taking care to prevent the

solution from backing up into and overflowing from the air
inlet tube. Reflux for one hour. Turn off heat and continue
the airflow for at least 15 minutes. After cooling the boiling
flask, disconnect absorber and close off the vacuum source.

10.2.2.1.5 Drain the solution from the absorber into a 250 mL volumetric
flask and bring up to volume with reagent water washings from
the absorber tube.

NOTE: The distillation procedure results in a two-fold

concentration of the sample.

10.2.3 Water Samples Preparation (Midi-Distillation)

10.2.3.1 Preparation Method/Code (DW2)

10.2.3.1.1 The procedure described here utilizes a midi distillation

apparatus and requires a sample aliquot of 50 mL or less for
aqueous samples.

10.2.3.1.2 Pipet 50 mL of sample, or an aliquot diluted to 50 mL, into the

distillation flask along with 2 or 3 boiling chips.

10.2.3.1.3 Add 50 mL of 0.25N NaOH (see Section 7.1.3.1) to the gas

absorbing impinger.

10.2.3.1.4 Connect the boiling flask, condenser, and absorber in the

train. The excess cyanide trap contains 0.5N NaOH.

10.2.3.1.5 Turn on the vacuum and adjust the gang (Whitney) valves to give
a flow of three bubbles per second from the impingers in each
reaction vessel.

ILM05.3 D-16/Cyanide
 Exhibit D (Cyanide) -- Section 10
Procedure (Con’t)

10.2.3.1.6 After five minutes of vacuum flow, inject 5 mL of 50% (v/v)

H2SO4 (see Section 7.1.3.2) through the top air inlet tube of
the distillation head into the reaction vessel. Allow to mix
for 5 minutes.

NOTE: The acid volume must be sufficient to bring the

sample/solution pH to below 2.0.

10.2.3.1.7 Add 2 mL of magnesium chloride solution (see Section 7.1.2.6)

through the top air inlet tube of the distillation head into
the reaction flask. Excessive foaming from samples containing
surfactants may be quelled by the addition of either another 2
mL of magnesium chloride solution or a few drops of a
commercially available anti-foam agent. The Contractor shall
document the addition of magnesium chloride solution or anti-
foam agent in the SDG Narrative.

10.2.3.1.8 Turn on the heating block and set for 123-125°C. Heat the
solution to boiling, taking care to prevent solution backup by
periodic adjustment of the vacuum flow.

10.2.3.1.9 After one and a half hours of refluxing, turn off the heat and
continue the vacuum for an additional 15 minutes. The flasks
should be cool at this time.

10.2.3.1.10 After cooling, close off the vacuum at the gang valve and
remove the absorber. Seal the receiving solutions and store
them at 4°C until analyzed. The solutions must be analyzed for
cyanide within the 12 day holding time specified in Section
8.3.

10.2.4 Soil Samples Preparation

10.2.4.1 Preparation Method/Code (DS1) (Distillation)

10.2.4.1.1 Accurately weigh a representative 1-5 gram (g) portion of wet

sample and transfer it to a boiling flask. Add 500 mL of
reagent water. Shake or stir the sample so that it is
dispersed.

10.2.4.1.2 Add 50 mL of NaOH solution (see Section 7.1.2.1) to the

absorbing tube and dilute if necessary with reagent water to
obtain an adequate depth of liquid in the absorber. Connect
the boiling flask, condenser, absorber, and trap in the train.

10.2.4.1.3 Start a slow stream of air entering the boiling flask by

adjusting the vacuum source. Adjust the vacuum so that
approximately one bubble of air per second enters the boiling
flask through the air inlet tube.

NOTE: The bubble rate will not remain constant after the
reagents have been added and while heat is being applied to the
flask. It will be necessary to re-adjust the air rate
occasionally to prevent the solution in the boiling flask from
backing up into the air inlet tube.

10.2.4.1.4 Slowly add 25 mL of concentrated H2SO4 (see Section 7.1.2.4)

through the air inlet tube. Rinse the tube with reagent water
and allow the airflow to mix the flask contents for 3 minutes.
Pour 20 mL of magnesium chloride solution (see Section 7.1.2.6)
into the air inlet and wash down with a stream of water.

D-17/Cyanide ILM05.3
Exhibit D (Cyanide) -- Section 10
Procedure (Con’t)

10.2.4.1.5 Heat the solution to boiling, taking care to prevent the

solution from backing up and overflowing into the air inlet
tube. Reflux for one hour. Turn off heat and continue the
airflow for at least 15 minutes. After cooling the boiling
flask, disconnect absorber and close off the vacuum source.

10.2.4.1.6 Drain the solution from the absorber into a 250 mL volumetric
flask and bring up to volume with reagent water washings from
the absorber tube.

10.2.4.2 Preparation Method/Code (DS2) (Midi-Distillation)

10.2.4.2.1 The procedure described here utilizes a midi distillation

apparatus and requires a sample aliquot of 1 gram for solid
materials.

10.2.4.2.2 Weigh 1.0 g of sample (to the nearest 0.01 g) into the
distillation flask and dilute to 50 mL with reagent water. Add
2 or 3 boiling chips.

10.2.4.2.3 Add 50 mL of 0.25N NaOH (see Section 7.1.3.1) to the gas

absorbing impinger.

10.2.4.2.4 Connect the boiling flask, condenser, and absorber in the

train. The excess cyanide trap contains 0.5N NaOH.

10.2.4.2.5 Turn on the vacuum and adjust the gang (Whitney) valves to give
a flow of three bubbles per second from the impingers in each
reaction vessel.

10.2.4.2.6 After five minutes of vacuum flow, inject 5 mL of 50% (v/v)

H2SO4 (see Section 7.1.3.2) through the top air inlet tube of
the distillation head into the reaction vessel. Allow to mix
for 5 minutes.

NOTE: The acid volume must be sufficient to bring the

sample/solution pH to below 2.0.

10.2.4.2.7 Add 2 mL of magnesium chloride solution (see Section 7.1.2.6)

through the top air inlet tube of the distillation head into
the reaction flask. Excessive foaming from samples containing
surfactants may be quelled by the addition of either another 2
mL of magnesium chloride solution or a few drops of a
commercially available anti-foam agent. The Contractor shall
document the addition of magnesium chloride solution or anti-
foam agent in the SDG Narrative.

10.2.4.2.8 Turn on the heating block and set for 123-125°C. Heat the
solution to boiling, taking care to prevent solution backup by
periodic adjustment of the vacuum flow.

10.2.4.2.9 After one and a half hours of refluxing, turn off the heat and
continue the vacuum for an additional 15 minutes. The flasks
should be cool at this time.

10.2.4.2.10 After cooling, close off the vacuum at the gang valve and
remove the absorber. Seal the receiving solutions and store
them at 4°C until analyzed. The solutions must be analyzed for
cyanide within the 12 day holding time specified in
Section 8.3.

ILM05.3 D-18/Cyanide
 Exhibit D (Cyanide) -- Section 10
Procedure (Con’t)

10.2.5 Non-Distilled Analyses

10.2.5.1 Preparation Method/Code (NP1)

10.2.5.1.1 This code shall be used to report samples that are not
distilled prior to analysis.

10.2.5.1.2 This Preparation Method/Code shall also be used to report the

non-distilled Method Detection Limit (MDL). The concentration
of this MDL shall be used to determine the appropriate
concentration qualifier for the results of instrument QC
analyses [except the distilled Initial Calibration Verification
(ICV)].

10.3 Sample Analysis

10.3.1 Manual Spectrophotometric Determination

10.3.1.1 Allow all standards and samples to come to ambient room

temperature prior to analysis. Withdraw 50 mL or less of the
solution from the flask and transfer to a 100 mL volumetric flask.
If less than 50 mL is taken, dilute to 50 mL with 0.25N sodium
hydroxide solution (see Section 7.1.3.1). Add 1.0 mL of acetate
buffer (see Section 7.1.4.1) and mix. The dilution factor must be
reported on Form XIII-IN.

10.3.1.2 Add 2 mL of chloramine-T (see Section 7.1.4.2) and mix. After 1

to 2 minutes, add 5 mL of pyridine-barbituric acid solution (see
Section 7.1.4.3.1) and mix. Dilute to mark with reagent water and
mix again. Allow 8 minutes for color development then read
absorbance between 570 and 580 nanometers (nm) in a 1 centimeter
(cm) cell within 15 minutes.

10.3.2 Semi-Automated Spectrophotometric Determination of Distillates

10.3.2.1 Set up the manifold. Pump the reagents through the system until a
steady baseline is obtained.

10.3.2.2 Place calibration standards, blanks, and control standards in the

sampler tray, followed by distilled samples, distilled duplicates,
distilled standards, distilled spikes, and distilled blanks.
Allow all standards and samples to come to ambient room
temperature prior to analysis.

10.3.2.3 When a steady reagent baseline is obtained and before starting the
sampler, adjust the baseline using the appropriate knob on the
colorimeter. Aspirate a calibration standard and adjust the
colorimeter until the desired signal is obtained. Establish the
baseline and proceed to analyze calibration standards, blanks,
control standards, distilled samples, and distilled Quality
Control (QC) samples.

D-19/Cyanide ILM05.3
Exhibit D (Cyanide) -- Section 11
Data Analysis and Calculations

11.0 DATA ANALYSIS AND CALCULATIONS

11.1 Water/Aqueous Sample Calculation

11.1.1 For semi-automated colorimetric determination (Non-Midi-

Distillation), measure the instrument response of the calibration
standards and calculate a linear regression equation. Apply the
equation to the samples and Quality Control (QC) samples to determine
the cyanide concentration in the distillates. To determine the
concentration of cyanide in the original sample, MULTIPLY THE RESULTS
BY ONE-HALF (since the original volume was 500 milliliter (mL) and
the distillate volume was 250 mL). Also correct for, and report on
Form XIII-IN, any dilutions which were made before or after
distillation.

11.1.2 For manual colorimetric determination, calculate the cyanide, in

micrograms per Liter (µg/L), in the original sample as follows:

EQ. 1 Aqueous Sample Concentration (Manual)

WHERE,
A = µg CN read from standard curve (per 250 mL)
B = mL of original sample for distillation (see Section
10.2.2.1.1)
C = mL taken for colorimetric analysis (see Section
10.3.1.1)
50 mL = volume of original sample aliquot (see Section
10.3.1.1)
1000 mL/L = conversion mL to L

The minimum value that can be substituted for A is the Method

Detection Limit (MDL) value adjusted for volume.

11.2 Soil Sample Calculation

11.2.1 A separate determination of percent solids must be performed (see

Exhibit D - Introduction to Analytical Methods, Section 1.6).

11.2.2 The concentration of cyanide in the sample is determined as follows:

11.2.2.1 Manual Spectrophotometric

EQ. 2 Soil Sample Concentration (Manual)

ILM05.3 D-20/Cyanide
 Exhibit D (Cyanide) -- Section 11

Data Analysis and Calculations (Con’t)

WHERE,
A = µg CN read from standard curve (per 250 mL).
B = mL of distillate taken for colorimetric
determination (see Section 10.3.1.1).
C = wet weight of original sample in g (see Section
10.2.4.1.1).
50 mL = standard volume taken for colorimetric
determination (see Section 10.3.1.1)
% solids = percent solids (see Exhibit D - Introduction to
Analytical Methods, Section 1.6).

11.2.2.2 Semi-Automated Spectrophotometric for Non-Midi-Distillates

If the semi-automated method is used, measure the peak heights of

the calibration standards (visually or using a data system) and
calculate a linear regression equation. Apply the equation to the
samples and QC audits to determine the cyanide concentration in
the distillates.

EQ. 3 Soil Sample Concentration (Semi-automated)

WHERE,
A = µg/L determined from standard curve.
C = wet weight of original sample in g (see Section
10.2.4.1.1).
.25 = conversion factor for distillate final volume
(see Section 10.2.4.1.6).
% solids = percent solids (see Exhibit D - Introduction to
Analytical Methods, Section 1.6).

The minimum value that can be substituted for A is the MDL value.

11.3 Calculations for Midi Distillation of Waters and Soils

11.3.1 Calculations for Semi-automated Colorimetric Determination

11.3.1.1 Prepare a standard curve by plotting absorbance (peak heights,

determined visually or using a data system) of standards (y)
versus cyanide concentration values (total µg CN/L) (x). Perform
a linear regression analysis.

11.3.1.2 Multiply all distilled values by the standardization value to

correct for the stock cyanide solution not being exactly 1000
milligrams per Liter (mg/L) (see Section 7.2.2.2.1).

11.3.1.3 Using the regression analysis equation, calculate sample receiving

solution concentrations from the calibration curve.

D-21/Cyanide ILM05.3
Exhibit D (Cyanide) -- Section 11
Data Analysis and Calculations (Con’t)

11.3.1.4 Calculate the cyanide of aqueous samples in µg/L of original

sample, as follows:

EQ. 4 Aqueous Sample Concentration (Midi)

WHERE,
A = µg/L CN of sample from regression analysis
B = volume of original sample for distillation (0.050 L)
(see Section 10.2.3.1.2)
D = any dilution factor necessary to bracket sample value
within standard values
F = sample receiving solution volume (0.050 L)

The minimum value that can be substituted for A is the MDL value.

11.3.1.5 Calculate the cyanide of solid samples in mg/kg of original

sample, as follows:

11.3.1.5.1 A separate determination of percent solids must be performed

(see Exhibit D - Introduction to Analytical Methods, Section
1.6).

11.3.1.5.2 The concentration of cyanide in the sample is determined as

follows:

EQ. 5 Soil Sample Concentration (Midi)

WHERE,
A = µg/L CN of sample from regression analysis curve
B = wet weight of original sample (see Section
10.2.4.2.2)
D = any dilution factor necessary to bracket sample
value within standard values
E = % solids/100 (see Exhibit D - Introduction to
Analytical Methods, Section 1.6)
F = sample receiving solution volume (0.050 L)

The minimum value that can be substituted for A is the MDL

value.

11.4 Adjusted Method Detection Limit (MDL)/Adjusted Contract Required

Quantitation Limit (CRQL) Calculation

To calculate the adjusted aqueous MDL or adjusted aqueous CRQL for the
manual colorimetric method, multiply the MDL (µg/L) or CRQL (µg/L) by

ILM05.3 D-22/Cyanide
 Exhibit D (Cyanide) -- Section 11

Data Analysis and Calculations (Con’t)

0.25 and substitute the result for the “A” term in Equation 1. To
calculate the adjusted aqueous MDL or adjusted aqueous CRQL for all
other methods, follow the instructions in Section 11.1.1 or substitute
the MDL (µg/L) or CRQL (µg/L) for the “A” term in Equation 4, as
appropriate.

The adjusted soil MDL or adjusted soil CRQL for all methods shall be
calculated as follows:

EQ. 6 Adjusted Soil MDL/Adjusted Soil CRQL Concentration

WHERE, C = MDL or CRQL concentration (mg/kg)

WM = minimum method required wet sample weight (g)
WR = reported wet sample weight (g)
S = % Solids/100 (see Exhibit D - Introduction to
Analytical Methods, Section 1.6).

For the midi-distillation, multiply the adjusted concentration value

(mg/kg) obtained in Equation 6 by any applicable dilution factor.

D-23/Cyanide ILM05.3
Exhibit D (Cyanide) -- Section 12
Quality Control

12.0 QUALITY CONTROL (QC)

12.1 Initial Calibration Verification (ICV)

The ICV standard shall be prepared in the same matrix as the calibration
standards and in accordance with the instructions provided by the
supplier. The ICV standard shall be distilled. If measurements exceed
the control limits of 85% (low) and 115% (high), the analysis shall be
terminated, the problem corrected, the instrument recalibrated, and the
calibration reverified. Information regarding the ICV shall be reported
on Form IIA-IN.

12.2 Continuing Calibration Verification (CCV)

The CCV standard shall be prepared by the analyst at a concentration

equivalent to the mid-point of the calibration curve. If the deviation
of the CCV is greater than the control limits of 85% (low) and 115%
(high), the analysis shall be stopped, the problem corrected, the
instrument recalibrated, the calibration verified, and re-analysis of
the preceding 10 analytical samples or all analytical samples analyzed
since the last compliant calibration verification shall be performed.
Information regarding the CCV shall be reported on Form IIA-IN.

12.3 Contract Required Quantitation Limit (CRQL) Check Standard (CRI)

12.3.1 To verify linearity near the CRQL, a standard at the CRQL (CRI) shall
be prepared, in the same matrix as the calibration standards, and
analyzed at the beginning and at the end of each sample analysis run,
immediately following the ICV/ICB. In addition, the Contractor shall
analyze the CRI at a frequency of not less than once per 20
analytical samples1 per analysis run. The CRI analysis shall be run
immediately followed by the CCV and Continuing Calibration Blank
(CCB) analyses. The CRI shall be prepared by spiking an aliquot of
reagent water with cyanide to yield a concentration in the final
solution equal to the CRQL.

12.3.2 CRI and percent recovery results shall be reported on Form IIB-IN.
If the percent recovery falls outside the control limits of 70-130%,
the CRI shall be re-analyzed immediately. If the result of the re-
analysis falls within the control limits, no further corrective
action is required. If the result of the re-analysis does not fall
within the control limits, the analysis shall be terminated, the
problem corrected, the instrument recalibrated, the CRI analyzed, and
the samples associated with the CRI re-analyzed.

12.4 Blank Analyses

There are two different types of blanks required by this method. The
calibration blank is used in establishing the analytical curve while the
preparation blank is used to monitor for possible contamination.

12.4.1 Initial and Continuing Calibration Blank (ICB/CCB)

The ICB and CCB are prepared with reagents and reagent water. If the
absolute value of the calibration blank (ICB/CCB) result exceeds the
CRQL (see Exhibit C), the analysis shall be terminated, the problem
corrected, the instrument recalibrated, the calibration verified, and
re-analysis of the preceding 10 analytical samples or all analytical

1
As defined in Exhibit G, CRI is an analytical sample.

ILM05.3 D-24/Cyanide
 Exhibit D (Cyanide) -- Section 12
Quality Control (Con’t)

samples analyzed since the last compliant calibration blank shall be

performed.

12.4.2 Preparation Blank (PB)

12.4.2.1 The PB shall contain all the reagents and in the same volumes as
used in processing the samples. The PB shall be carried through
the complete procedure and contain the same concentration in the
final solution as the sample solution used for analysis.

12.4.2.2 At least one PB, consisting of reagent water processed through

each sample preparation and analysis procedure (see Section 10),
shall be prepared and analyzed with every Sample Delivery Group
(SDG), or with each batch2 of samples distilled, whichever is more
frequent.

12.4.2.3 The first batch of samples in an SDG is to be assigned to

Preparation Blank one, the second batch of samples to Preparation
Blank two, etc. (see Form III-IN). Each Sample Data Package shall
contain the results of all the PB analyses associated with the
samples in that SDG.

12.4.2.4 The PB is to be reported for each SDG and used in all analyses to
ascertain whether sample concentrations reflect contamination in
the following manner:

12.4.2.4.1 If the absolute value of the concentration of the blank is less

than or equal to the CRQL (see Exhibit C), no further action is
required.

12.4.2.4.2 If the analyte concentration in the blank is above the CRQL,

the lowest concentration of the analyte in the associated
samples shall be greater than or equal to 10 times the blank
concentration. Otherwise, all samples associated with the
blank, with the analyte concentration less than 10 times the
blank concentration and above the CRQL, shall be redistilled
and re-analyzed with appropriate new QC. The only exception to
this shall be an identified field blank. The sample
concentration is not to be corrected for the blank value.

12.4.2.4.3 If the concentration of the blank is below the negative CRQL,

then all samples associated with the blank and reported below
10 times CRQL shall be reprepared and re-analyzed with
appropriate new QC.

The values for the preparation blank shall be reported on Form

III-IN.

12.5 Spike Sample Analysis

12.5.1 The spike sample analysis is designed to provide information about

the effect of the sample matrix on the distillation and/or
measurement methodology. The spike is added prior to any
distillation steps. At least one spike sample analysis (matrix
spike) shall be performed on each group of samples of a similar

2
A group of samples prepared at the same time.

D-25/Cyanide ILM05.3
Exhibit D (Cyanide) -- Section 12
Quality Control (Con’t)

matrix type (i.e., water, soil) or for each SDG.3 The sample and its
associated spike sample shall initially be run at the same dilution.

12.5.2 If the spike analysis is performed on the same sample that is chosen
for the duplicate sample analysis, spike calculations shall be
performed using the results of the sample designated as the “original
sample” (see Section 12.6). The average of the duplicate results
cannot be used for the purpose of determining percent recovery.
Samples identified as field blanks and Performance Evaluation (PE)
samples shall not be used for spiked sample analysis. USEPA may
require that a specific sample be used for the spike sample analysis.

12.5.3 The analyte spiking solution shall be added to yield a final

concentration of 100 µg/L in the final sample solution prepared for
analysis (i.e., post-distillation). The final volume of the sample
after distillation shall be the basis for the amount of cyanide to be
added as the spike. For instance, the full volume distillation
procedure will require addition of 25 µg cyanide to the sample prior
to distillation [based on the final distillate volume of 250
milliliter (mL)] to meet the specified spiking level; and the midi
distillation procedure requires the addition of 5 µg of cyanide to
the sample prior to distillation (based on the final distillate
volume of 50 mL).

12.5.3.1 For soil samples, the final sample solution prepared for analysis
(i.e., the distillate) shall contain cyanide spiked at a
concentration of 100 µg/L regardless of the distillation procedure
employed, or the amount of sample used for distillation. The
final sample volume after distillation shall be used as the basis
for the amount of cyanide to add as the spike. The units for
reporting soil sample cyanide results shall be mg/kg. To convert
from µg/L to mg/kg, the equation below shall be used:

EQ. 7 Conversion to mg/kg

12.5.4 If the spike recovery is not at or within the limits of 75-125%, the
data of all samples received and associated with that spike sample
and determined by the same analytical method shall be flagged with
the letter “N” on Forms IA-IN and VA-IN. An exception to this rule
is granted when the sample concentration exceeds the spike added
concentration by a factor of four or more. In such an event, the
data shall be reported unflagged even if the percent recovery does
not meet the 75-125% recovery criteria.

12.5.5 When the matrix spike recovery falls outside the control limits and
the sample result does not exceed 4 times the spike added, a post-
distillation spike shall be performed. Note that if a post-
distillation spike analysis is required, the same USEPA sample that
was used for the matrix spike analysis shall be used for the post
digestion spike analysis. Spike the unspiked aliquot of the sample
at 2 times the indigenous level or 2 times CRQL, whichever is
greater. Results of the post-distillation spike shall be reported on
Form VB-IN.

3
USEPA may require additional spike sample analyses, upon USEPA Regional
CLP Project Officer (CLP PO) request.

ILM05.3 D-26/Cyanide
 Exhibit D (Cyanide) -- Section 12
Quality Control (Con’t)

12.5.6 In the instance where there is more than one spike sample per matrix,
per method, per SDG, if one spike sample recovery is not within
contract criteria, flag all the samples of the same matrix and method
in the SDG. Individual component percent recoveries are calculated
as follows:

EQ. 8 Spike Percent Recovery

WHERE,
SSR = Spiked Sample Result
SR = Sample Result
SA = Spike Added

12.5.7 When the sample concentration is less than the Method Detection Limit
(MDL), use SR = 0 only for purposes of calculating percent recovery.
The Spike Sample Results (SSRs), Sample Results (SRs), Spike Added
(SA), and percent recovery (positive or negative) shall be reported
on Form VA-IN.

12.5.8 The units used for reporting spike sample results will be identical
to those used for reporting sample results on Form IA-IN.

12.6 Duplicate Sample Analysis

12.6.1 One duplicate sample shall be analyzed from each group of samples of
a similar matrix type (i.e., water, soil) or for each SDG.4
Duplicates cannot be averaged for reporting on Form IA-IN. The
sample and its associated duplicate sample shall initially be run at
the same dilution.

12.6.2 Duplicate sample analyses are required for percent solids. Samples
identified as field blanks and PE samples shall not be used for
duplicate sample analysis. USEPA may require that a specific sample
be used for duplicate sample analysis. The Relative Percent
Difference (RPD) is calculated as follows:

EQ. 9 Duplicate Sample Relative Percent Difference

WHERE,
RPD = Relative Percent Difference

S = Sample Result (original)

D = Duplicate Result

12.6.3 The results of the duplicate sample analyses shall be reported on

Form VI-IN. A control limit of 20% for RPD shall be used for

4
USEPA may require additional duplicate sample analyses, upon USEPA
Regional CLP PO request.

D-27/Cyanide ILM05.3
Exhibit D (Cyanide) -- Section 12
Quality Control (Con’t)

original and duplicate sample values greater than or equal to five

times the CRQL (see Exhibit C). A control limit of the CRQL value
shall be entered in the “Control Limit” column on Form VI-IN if
either the sample or duplicate value is less than five times the
CRQL. If the sample and duplicate values are greater than or equal
to five times the CRQL, or if the sample and duplicate values are
less than the CRQL, the “Control Limit” field is left empty.

12.6.4 If one result is above five times the CRQL level and the other is
below, use the CRQL criteria to determine if the duplicate analysis
is in control. If both sample and duplicate values are less than the
MDL, the RPD is not calculated on Form VI-IN. For solid sample or
solid duplicate results less than five times the CRQL, enter the
value of the CRQL, corrected for sample weight and percent solids,
(i.e., original, not duplicate sample weight and percent solids), in
the “Control Limit” column. If the duplicate sample results are
outside the control limits, flag all the data for samples received
and associated with that duplicate sample with an “*” on Forms IA-IN
and VI-IN. In the instance where there is more than one duplicate
sample per SDG, if one duplicate result is not within contract
criteria, flag all samples of the same matrix and method in the SDG.
The percent difference data will be used by USEPA to evaluate the
long-term precision of the method. Specific control limits for each
element will be added to Form VI-IN at a later date based on the
precision results.

12.7 Laboratory Control Sample (LCS) Analysis

12.7.1 A solid LCS (LCSS) shall be analyzed using the same sample
preparations, analytical methods, and Quality Assurance (QA)/QC
procedures employed for the EPA samples received. For cyanide, a
distilled ICV shall be used as the aqueous LCS (LCSW).

12.7.2 The USEPA provided LCSS shall be prepared and analyzed using each of
the procedures applied to the solid samples received (exception:
percent solids determination not required). If the USEPA LCSS is
unavailable, other USEPA QC Check samples or other certified
materials may be used. In such a case, the control limits for LCSS
must be documented and provided. One LCSS shall be prepared and
analyzed for every group of solid samples in a SDG, or for each batch
of samples distilled, whichever is more frequent.

12.7.3 All LCSS and percent recovery results will be reported on Form VII­
IN. If the results for the LCSS fall outside the control limits
established by USEPA, the analyses shall be terminated, the problem
corrected, and the samples associated with that LCSS reprepared and
re-analyzed with appropriate new QC.

12.8 Method Detection Limit (MDL) Determination

12.8.1 Before any field samples are analyzed under this contract, the MDLs
shall be determined for non-distilled analyses (Preparation
Method/Code “NP1”) and for each distillation procedure and instrument
used, prior to the start of the contract analyses, and annually
thereafter, and shall meet the levels specified in Exhibit C.

An MDL study shall be performed after major instrument maintenance,

or changes in instrumentation or instrumental conditions to verify
the current sensitivity of the analysis.

12.8.2 To determine the MDLs, the Contractor shall run MDL studies following
the procedures given in 40 CFR, Part 136. The Contractor shall

ILM05.3 D-28/Cyanide
 Exhibit D (Cyanide) -- Section 12
Quality Control (Con’t)

prepare the MDL samples by each distillation procedure used and shall
analyze these samples on each instrument used. The Contractor shall
also analyze the non-distilled MDL samples on each instrument used.

12.8.3 The determined concentration of the MDL shall be less than half the
concentration of the CRQL listed in Exhibit C.

12.8.4 The non-distilled MDL (Preparation Method/Code “NP1”) shall be used

to determine the appropriate concentration qualifier for the results
of instrument QC analyses (except the distilled ICV).

12.8.5 The results of the MDL determination study shall be forwarded to the
USEPA Regional CLP PO, Sample Management Office (SMO), and Quality
Assurance Technical Support (QATS).

12.8.6 The MDL results shall be reported on Form IX-IN.

12.9 Example Analytical Sequence for Cyanide

S0

S10.0

S50.0

S100.0

S200.0

S400.0

ICV (distilled)

ICB

CRI

CCV

CCB

MIDRANGE

9 samples

CCV

CCB

9 samples

CRI

CCV

CCB

10 samples, etc.

D-29/Cyanide ILM05.3
Exhibit D (Cyanide) – Sections 13-17
Method Performance

13.0 METHOD PERFORMANCE

Not applicable.

14.0 POLLUTION PREVENTION

See Section 1.15 in Exhibit D - Introduction to Analytical Methods.

15.0 WASTE MANAGEMENT

See Section 1.16 in Exhibit D - Introduction to Analytical Methods.

16.0 REFERENCES

16.1 US Environmental Protection Agency. Methods for Chemical Analysis of

Water and Wastes. Method 335.2. 1980.

16.2 American Water Works Association/American Public Health

Association/Water Environment Federation. Standard Methods for the
Examination of Water and Wastewater. Method 4500. 18th Edition.

16.3 US Government Printing Office. 40 Code of Federal Regulations, Part 136,

Section 1, Appendix B.

17.0 TABLES/DIAGRAMS/FLOWCHARTS

Not applicable.

ILM05.3 D-30/Cyanide