Quality of Domestic Water Supplies:

Chemical Analysis Guide

Dr PP Mpungose
Office: 2.20B, D6 Campus
E-mail: [email protected]

1
 WHAT IS THE PURPOSE OF THE ANALYSIS GUIDE?

The purpose of this guide is to provide general information on water

quality analysis specifically on the aspects listed below:

• General overview of analytical methods for the analysis of water for

domestic use

• The suitability and limitations of different methods of analysis

• Characteristics of substances of concern in domestic water and units

in which they are expressed

• The concept of uncertainty associated with water quality analysis

• Quality assurance in water quality analysis.

2
PART 1: FAMILIARISE YOURSELF WITH THE CONCEPT
OF WATER QUALITY ANALYSIS

In order to evaluate the concepts of water quality analysis and water

quality assessment for domestic use it is important to have a clear
understanding of the following aspects:

• Water quality and fitness for domestic use

• Analytical methods: Which methods are available and what their

limitations are

• Expression of analytical results: Different units for different

constituents

• Uncertainty of testing: What the causes are and how uncertainty can
be quantified

3
 WATER QUALITY

What is water quality?

• The term "water quality" is used to describe the microbiological,
physical and chemical properties of water that determine its fitness
for a specific use. These properties are determined by substances
which are either dissolved or suspended in the water.

4
 WATER QUALITY …
Dissolved substances:
• Water has excellent dissolving capability.
• As water moves through its hydrological cycle, it comes into contact with
a vast range of substances which may be dissolved by the water to a
greater or lesser extent.

• The type and amount of these dissolved substances (together with

suspended and colloidal substances) determine the properties
(quality) of the water.

• Substances that can be dissolved by water include gasses such as

oxygen (O2) and carbon dioxide (CO2), inorganic compounds such as
sodium chloride (NaCl) and calcium sulphate (CaSO4), and organic
substances such as humic acids and carbohydrates.

• In order to evaluate the quality of water one has to determine the

concentration of dissolved substances that are relevant to the particular
use of the water, (together with the physical and microbiological

5
properties of the water).
 WATER QUALITY …

Suspended substances
• In addition to the substances that are dissolved in water, some
substances may not dissolve in water but remain in suspension as
very small suspended or colloidal particles.

• These particles also affect the quality of the water and their presence
and concentration in water must also be determined. An example of
this category of substances is micro-organisms.

• They are so small that they cannot be seen individually with the
naked eye, but they may have important effects on water quality.

6
 WHAT IS FITNESS FOR USE?
Fitness for use describes the required water quality for a specific use.

Water use
• Different water uses require different qualities of water. For example,
water of a relatively poor quality may be fit for use as irrigation water
but will not be fit for use as domestic water.
• On the other hand, water which is fit for domestic use may not be fit
for industrial use such as boiler feed water where water of high purity
is required.

In order to evaluate fitness for use, water use is divided into four main
categories:
• Domestic use (e.g. for drinking, food preparation, clothes washing,
bathing, gardening)
• Recreational use (e.g. swimming, fishing, boating)
• Industrial use (e.g. power generation, process water, food
processing)
• Agricultural use (e.g. water for animals, irrigation)

7
 WHY IS IT NECESSARY TO DO A WATER QUALITY
ANALYSIS?
• Water may contain dissolved substances or micro-organisms which
may not necessarily affect the appearance or taste of the water but
which may have serious health or other effects, making the water
unfit for domestic use.

• The fitness for domestic use of a particular water can therefore only
be assessed if an analysis of the water is available which includes the
substances of concern for domestic use.

• Appearance and taste of water may be misleading.

• When water looks clean and tastes good, many people will accept it as a
good quality drinking water.
• This may be dangerous because the water may contain excessive
amounts of harmful substances such as mercury or micro-organisms
which may have both short-term and long-term health effects on
consumers.
• These substances are not apparent by looking at, or tasting the water.
They can only be quantified by a proper analysis of the water.

8
 WHAT DOES WATER QUALITY ANALYSIS ENTAIL?

Although the actual analytical procedure forms a very important part of

water quality analysis, it is only one action in a series of actions in
water quality analysis, namely:

• Identification of the need for water quality information

• Taking of sample(s) to be analysed
• On-site analysis of samples
• Preservation (if necessary), transport and storage of samples
• Analysis of sample
• Calculation of results
• Reporting of results
• Assessment of water quality
• Information transfer/reporting

9
 THE CHEMICAL ANALYSIS PROCESS

1. Obtain an uncontaminated sample representative of the whole medium

to be analyzed (sampling and sample pretreatment)
• Proper sample preservation is important
2. Sample processing to an analyzable form (laboratory treatment)
• Destructive or nondestructive processing
• Example: Digestion of fish tissue in strong acid for metals analysis
3. Determination of the quantity of analyte (laboratory assay)
• Often with sophisticated instruments
• May be very low levels such as parts per billion (ppb)
4. Calculation of kinds and quantities of analytes
• Generally by computer
• Statistical analysis of reliability of results

10
11
 WHAT ARE THE GENERAL PROPERTIES OF THE
SUBSTANCES IN DOMESTIC WATER AND HOW DO
THEY AFFECT WATER QUALITY?

The general properties of substances of concern in domestic water vary

over a wide spectrum and can be categorised as:
• Chemical
• Physical or
• Microbiological in nature.

The properties of each substance determine how water quality is

affected by that substance.

12
 WHAT ARE THE CHEMICAL PROPERTIES OF
DOMESTIC WATER?
The chemical properties of water are determined by the following groups
of dissolved substances:

• Metallic substances such as arsenic, cadmium, calcium, copper, iron,

magnesium, manganese, potassium, sodium and zinc

• Inorganic non-metallic substances such as chloride, fluoride, nitrate,

sulphate

• Aggregate organic substances measured as total organic carbon

(TOC), chemical oxygen demand (COD) and trihalomethanes (THM)

• Aggregate inorganic substances, such as those measured by total

dissolved solids (TDS), hardness and chemical stability.

13
 WHAT ARE THE PHYSICAL PROPERTIES OF
DOMESTIC WATER

The physical properties of water include properties such as turbidity,

temperature, electrical conductivity, pH as well as colour, taste and
odour.

The physical properties of water largely determine its aesthetic

properties, i.e. appearance, taste and general drinkability of the water.

14
 WHAT ARE THE MICROBIOLOGICAL PROPERTIES OF
WATER?

• The microbiological properties of water are determined by the type

and numbers of micro-organisms present in the water.

• A variety of micro-organisms can be present even in very good quality

domestic waters.

• Most of these micro-organisms are harmless but if the water is

polluted, pathogens may be present.

15
 HOW IS THE CHEMICAL, PHYSICAL AND MICROBIOLOGICAL
QUALITY OF WATER DETERMINED AND EXPRESSED?

• The quantity of dissolved chemical constituents in water is normally

expressed in concentration units, i.e. mass per volume, mostly in
milligram per litre (mg/L).

• The concentration of substances in water may be expressed using

different sets of units. These different sets are used for different
purposes,
• e.g. concentration in milligrams per litre (mg/L) is normally used in
water quality assessment, while molar concentrations (mol/L) are
used when doing calculations of the mass of substances that react
in chemical reactions.

• Different sets of units are also used for expressing hardness or

chemical stability of water.

16
 CONCENTRATION UNITS OF (PHYSICAL) MASS PER
VOLUME
1. Milligram per litre, mg/L – most commonly used concentration unit
for most substances in water.

2. Parts per million, ppm - for dilute solutions ppm is practically

identical to mg/L,

3. Microgram per litre, μg/L - used for very low concentrations. 1000
μg/L = 1 mg/L.

4. Parts per billion, ppb – for dilute solutions ppb is practically identical
to μg/L.

5. Gram per litre, g/L – used for high concentrations. 1000 mg/L = 1 g/L.

6. Percentage, % - used for high concentrations, e.g. for the

concentration of process chemicals. Percentage is similar to parts
per hundred, or pph or g/100g.

17
 WATER HARDNESS UNITS
The hardness of water is determined by the concentration of divalent
cations in the water, mostly calcium and magnesium. Hardness affects
the lather-forming ability of water with soap. The different forms of
hardness are:
• carbonate or temporary hardness, which is caused by calcium and
magnesium associated with bicarbonate in the water,

• non-carbonate or permanent hardness, which is caused by calcium

and magnesium associated with ions other than bicarbonate such as
chloride and sulphate,

• calcium hardness, caused by all the calcium ions in solution,

• magnesium hardness, caused by all the magnesium ions in solution,

and

• total hardness, which is the sum of calcium and magnesium

18
hardness.
 ALKALINITY OF WATER

• Total alkalinity of water is a measure of its acid-neutralising capacity.

• It is principally a function of the carbonate, bicarbonate and

hydroxide content of the water and is determined by titrating the
water to a specific end point.

• Total alkalinity is determined by titrating with a strong acid to a pH

end point of 4,5.

19
PART 2: FAMILIARISE YOURSELF WITH THE GENERAL METHODS
OF ANALYSIS FOR DOMESTIC WATER

What are the general methods used for water quality analysis?

Methods for water quality analysis can be divided into three general
categories:
1. Manual laboratory analytical methods (or so-called "wet" chemical
methods of analysis)

2. Instrumental and automated chemical and physical methods of

analysis

3. Microbiological methods of analysis

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MAJOR CATEGORIES OF CHEMICAL ANALYSIS
Chemical analysis: Determination of the physical properties or
chemical composition of samples of matter.

21
MAJOR CATEGORIES OF CHEMICAL ANALYSIS

22
CHEMICAL ANALYSIS

23
CHEMICAL ANALYSIS

24
MAJOR CATEGORIES OF CHEMICAL ANALYSIS

1. Classical methods involving primarily chemical reactions and

simple measurements of mass and volume
• Classical methods are often wet chemical methods largely
involving analytes and reagents in solution
• Example of titration of acid sample with standard base
solution:
H+ + Na+ + OH- → H2O + Na+

2. Physical methods involve measurements of parameters such

as light intensity and are usually done with instruments
• Instrumental methods using instruments that measure
parameters such as absorption of light

25
 CHEMICAL/PHYSICAL METHODS OF ANALYSIS

What are the manual laboratory methods of analysis?

The manual laboratory methods include:

• Gravimetric methods (analysis by mass)
• Volumetric methods (analysis by volume)
• Colorimetric methods (analysis by colour).

26
 WHAT ARE GRAVIMETRIC METHODS OF ANALYSIS?

• Gravimetric methods of analysis means analysis by mass and include

all determinations where the final results are obtained by means of
precipitation and weighing of a solid, or where solids are filtered from
the water (such as the determination of total suspended solids, TSS),
or where water is evaporated to determine a residue (such as TDS).

• An accurate analytical balance is the key to good gravimetric

analyses.
• The constituent to be determined is usually filtered from the water
(precipitates or suspended solids) or the water is evaporated and the
residue weighed.
• In the case of filtration an appropriate pre-weighed filter paper with
the right pore size must be used and the solids must be transferred
quantitatively to the filter paper.
• Following filtration, the filter paper with filtered material must be
dried at a specified temperature e.g.105 0C until constant mass,
then cooled to room temperature before weighing and calculating
of the final mass.

27
 GRAVIMETRIC ANALYSIS
Gravimetric analysis consists of isolating a product from the analyte in
weighable form and weighing it to determine the amount of analyte in the
sample

Gravimetric analysis describes a set of methods (precipitation, volatilization) used

in analytical chemistry for the quantitative determination of an analyte based on its

28
mass.
 GRAVIMETRIC ANALYSIS

As an example, the chloride content of a weighed, water-soluble sample

can be determined by precipitating the chloride in the dissolved sample
with excess silver nitrate (AgNO3) solution:

Ag+(aq) + Cl-(aq) → AgCl(s)

Where the atomic mass of chloride is 35.45 g/mol and the molar mass of
AgCl is 143.32 g/mol:

29
GRAVIMETRIC ANALYSIS: LEARNING CHECK
Questions 1:
A General Chemistry student performed the “Determination of
Chloride Content in a Water Sample” test. The amount of chloride
ion in a 100.0 mL water sample was determined by adding excess
silver nitrate. As a results, 1.0g of silver chloride was precipitated.

i. Write the balanced chemical equation for the reaction between

the silver nitrate and sodium chloride forming silver chloride and
sodium nitrate.
ii. Calculate the number of moles of chloride ions in the water
sample
iii. Calculate the number of grams of chloride ions in the water
sample.
iv. Calculate the concentration of chloride ions in the water sample
in ppm (mg/L).

30
GRAVIMETRIC ANALYSIS

31
 WHAT ARE VOLUMETRIC METHODS OF ANALYSIS?

Volumetric methods of analysis means analysis by volume and includes

all those determinations where the volume of a standard solution is
determined to reach the end point of a reaction, also known as titrimetry.

The equipment required for volumetric analysis include:

• a standard solution for the titration
• an indicator to show when the end-point of the reaction is reached
• volumetric glassware, i.e. pipettes and burettes.

32
 VOLUMETRIC ANALYSIS BY TITRATION

1. A measured quantity of sample is placed in solution

2. A standard solution of known concentration of a titrant that

reacts quantitatively with the analyte is accurately measured
• Usually with a graduated buret

3. Some means such as an indicator consisting of a dye that

changes color when a reaction is complete is used to show
the end point corresponding to the equivalence point at
which the stoichiometric amount of analyte has reacted with
the measured amount of titrant

4. The quantity or concentration of analyte is calculated from

the stoichiometry of the titration reaction

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VOLUMETRIC ANALYSIS BY TITRATION

34
 VOLUMETRIC ANALYSIS BY TITRATION

Titration Curve as a Plot of pH Versus Volume of Titrant for

the Titration of HCl with NaOH

35
 VOLUMETRIC ANALYSIS BY TITRATION

Molar Concentration of HCl by Titration with Standard NaOH

At the equivalence point

moles HCl = moles NaOH
MHCl x (litres HCl) = MNaOH x (litres NaOH)
C1V1 = C2V2

Example: Calculate the concentration of HCl if a 50.0 mL (0.050 L)

sample of HCl required 42.53 mL of 0.1005 M NaOH for titration

36
VOLUMETRIC ANALYSIS: LEARNING CHECK
Dr N Mathebula obtained a water sample from uMgeni river, and she wanted to determine its total
hardness. She conducted an experiment by pipetting 1.00 mL of the water sample into a conical
flask, diluted it with approximately 50 mL of deionised water, and then added 1 mL of an
ammonia/ammonium chloride buffer. She then proceeded to titrate this solution with standard
0.01142 mol/L EDTA solution, using eriochrome black T as an indicator. Table 1 below shows her
experimental results.

Table 1: Determination of total hardness

Experiment 1 2 3

Initial burette reading / mL 1,20 0.02 0,18

Final burette reading / mL 26,24 25.12 25,26

Volume delivered (EDTA)/ mL 25.04 25,10 25,08

Questions:
1. Calculate the average volume delivered of EDTA solution.
2. Write a balanced chemical reaction for the titration reaction
3. Calculate the concentration of [Ca2+] in the water sample.
4. Express the total hardness in the water sample as ppm CaCO3
• Total hardness as ppm CaCO3 = Molarity [Ca2+] ´ Molar mass CaCO3 ´ 1000
5. Based on your calculated total hardness in the water sample , is it safe to drink this water?

37
Give a reason for your answer.
VOLUMETRIC ANALYSIS BY TITRATION

38
WHAT ARE COLORIMETRIC METHODS OF ANALYSIS?

• Colorimetric methods of analysis are methods where the colour of a

solution to which a reagent has been added is directly proportional
to the concentration of the solute of interest.

• The concentration can then be determined by comparing the colour

intensity of the solution with the colour intensity of a reference
standard.

• Colorimetric methods are convenient, fast and economical for

determining the concentration of a variety of compounds of interest
in water for domestic use.

39
WHAT ARE COLORIMETRIC METHODS OF ANALYSIS?

• These measurements may be made with different types of

equipment ranging from colour-comparison tubes, photo-electric
colorimeters to spectrophotometers.

• Photo-electric and spectrophotometric methods are more

convenient and accurate.

40
INSTRUMENTAL METHODS OF ANALYSIS
WHAT ARE INSTRUMENTAL METHODS OF ANALYSIS?
The instrumental methods of chemical analysis are divided
into categories according to the property of the analyte that
is to be measured. Many of the methods can be used for
both qualitative and quantitative analysis.

The major categories of instrumental methods are:

1. Electroanalytical Methods
• The electroanalytical methods use electrically conductive probes, called electrodes, to make electrical contact
with the analyte solution. The electrodes are used in conjunction with electric or electronic devices to which
they are attached to measure an electrical parameter of the solution. The measured parameter is related to the
identity of the analyte or to the quantity of the analyte in the solution. The major electroanalytical methods
include potentiometry, amperometry, conductometry, electrogravimetry, voltammetry, and coulometry.

2. Spectral (Optical) Methods

• Spectral methods measure the electromagnetic radiation that is absorbed, scattered, or emitted by the analyte.

3. Separation (Chromatographic ) Methods

• Chromatography consists of a large group of separatory methods in which the components of a mixture are
separated by the relative attraction of the components for a stationary phase (a solid or liquid) as a mobile
phase (a liquid or gas) passes over the stationary phase. Chromatography usually is divided into two
categories depending on the type of mobile phase that is used. If the mobile phase is a liquid, the technique
is liquid chromatography; if it is a gas, the technique is gas chromatography.
BASIC COMPONENTS OF AN INSTRUMENT

43
 SIGNAL AND CONCENTRATION

• The instrument measures the change of a physical property of a

solution.

• This change must be related back to the analyte concentration for

quantitative analysis.

• Instrument response to the analyte should be proportional to the

concentration of that analyte

• Increasing concentrations of analyte should result in increasing

signals from the instrument.

Response ∝ Concentration
•Instrument response = constant x concentration

44
 SIGNAL AND CONCENTRATION

To determine the constant we calibrate the instrument.

Calibration:
• process of measuring the instrument response to solutions with
known concentrations.
• These solutions are called standards.
• Standards are made using known amounts of analyte in a known
volume (concentrations).

Plot the instrument response to each standard on a graph to obtain a

calibration curve.

45
 CALIBRATION

Plot the instrument response to each standard on a graph to obtain a calibration

curve.

46
1. WHAT ARE ELECTROANALYTICAL METHODS OF
INSTRUMENTAL ANALYSIS?

47
 1. WHAT ARE ELECTROANALYTICAL METHODS OF
INSTRUMENTAL ANALYSIS?
The most widely-used electrical methods of analysis for water include pH
and electrical conductivity measurements as well as the use of ion-
selective electrodes.
• The pH meter uses a glass electrode and a reference
electrode which are immersed in the test solution and
the electrical potential difference or voltage across
these electrodes is a measure of the hydrogen ions
concentration in solution and therefore of the pH of
the solution.
• pH is defined as the negative logarithm of the hydrogen
ion concentration expressed in moles per litre.

pH = -log [H+]

48
 1. WHAT ARE ELECTROANALYTICAL METHODS OF
INSTRUMENTAL ANALYSIS?
Electrical conductivity measurement is another widely- used electrical
method of analysis.

• The conductivity of a solution is a measure of its ability to carry an

electrical current. This ability varies with the number and type of ions
in solution.

• Conductivity therefore gives an indication of the concentration of

ions and therefore of the dissociated dissolved salts concentration in
solution.

Ion-selective electrodes are selectively

sensitive to a variety of ions such as
potassium, sodium, fluoride, nitrate,
ammonium and others.

49
2. WHAT ARE SPECTRAL METHODS OF
INSTRUMENTAL ANALYSIS?

50
 2. WHAT ARE SPECTRAL METHODS OF INSTRUMENTAL
ANALYSIS?
• Optical methods of analysis measure interactions between radiant
energy (such as visible light or ultraviolet radiation) and substances
dissolved in water (solutes).

• The basis of these methods of analysis is that when a beam of

radiant energy such as white light is passed through a solution, the
emergent beam will be lower in intensity than the entering beam.

51
 2. WHAT ARE SPECTRAL METHODS OF INSTRUMENTAL
ANALYSIS?...

• If the solution does not contain suspended material which scatter

the entering beam, the reduction in intensity is due primarily to
absorption of the light by the solution

• If the degree of absorption is directly proportional to the solute

concentration, then absorption measurement can be used as a
method of analysis.

• The intensity of the emerging beam and therefore the degree of

absorption is usually measured using a spectrophotometer.

• Spectrophotometers may vary from simple and relatively

inexpensive colorimeters to very sophisticated and expensive
instruments that automatically scan the ability of a solution to
absorb radiation over a wide range of wavelengths and
automatically record the results of such measurements.

52
 2. WHAT ARE SPECTRAL METHODS OF
INSTRUMENTAL ANALYSIS?
1. High-temperature absorption methods.
• Atomic absorption spectrometry (AAS) is a very useful method of
analysis for a wide variety of elements at very low concentrations in
water (trace elements). Elements such as iron, copper, nickel, zinc,
calcium etc. can be determined fairly accurately to a fraction of a
mg/l.

• Each element has a characteristic wavelength that its atoms will

absorb in a flame. A light source with wavelength readily absorbed by
the element to be determined is directed through a flame into which
the sample has been aspirated. The decrease in intensity of the light
beam is a measure of the concentration of the element.

• A disadvantage of AAS is that a different light source must be used

for each element. Because of the cost, the use of AAS is only viable
where large numbers of samples have to be analysed.

53
 2. WHAT ARE SPECTRAL METHODS OF
INSTRUMENTAL ANALYSIS?

2. High-temperature emission methods

• High-temperature emission methods of analysis rely on the fact that
many elements, when subjected to suitable excitation (by means of
heating or exposure to other high energy sources) will emit radiation
of characteristic wavelength.

• The intensity of the emitted radiation at a particular wavelength can

be correlated with the quantity of the element present.

• Emission methods include older methods such as flame photometry

(for detection of metals such as sodium, potassium and calcium) to
emission spectrometry methods such as inductively coupled plasma
(ICP) methods.

• ICP is now used as a standard for determination of many metals in

water.

54
 2. WHAT ARE SPECTRAL METHODS OF
INSTRUMENTAL ANALYSIS?
3. Dispersion and scattering methods
• Dispersion and scattering methods of analysis are mainly used for
the determination of turbidity in water.

• Turbidity is measured either by its effect on the transmission of light

(turbidimetry) or by its effect on the scattering of light (nephelometry).

55
3. WHAT ARE CHROMATOGRAPHIC INSTRUMENTAL
METHODS OF ANALYSIS?

56
 3. WHAT ARE CHROMATOGRAPHIC INSTRUMENTAL
METHODS OF ANALYSIS?
• Gas chromatography (GC) entails the vaporisation of a liquid sample
into a mobile gas phase followed by the separation of the different
components so that they can be individually identified and quantified.
The vapourised components are continuously swept through the
packed column by a mobile phase (carrier gas). The components
travel through the column at different rates so that they emerge from
the column at different times. Their presence in the emerging gas is
detected by chemical or physical means and the response recorded.

Gas chromatography has played an

essential role in the analysis of
organic pollutants in water, air, and
wastes.

Gas chromatography with mass

spectrometric detection is a
powerful, sensitive, selective means
of measuring volatile environmental
analytes

57
 3. WHAT ARE CHROMATOGRAPHIC INSTRUMENTAL
METHODS OF ANALYSIS?
• Chromatographic analysis entails the separation of the components
of a solution based on their relative affinity for partitioning between
two phases.

• For example, different compounds may travel at different velocities in

a mobile medium through a column packed with a certain medium (as
a function of their affinity for the two mediums) and this allows
separation of the different compounds.

• Two different phases are commonly used in chromatography.

• The stationary phase may be either a solid or a liquid and
• The moving phase may be either a gas or a liquid.

• When the moving phase is a gas and the stationary phase a liquid, the
method is called gas chromatography and when the moving phase is
a liquid and the stationary phase a solid, it is called liquid
chromatography.

58
 3. WHAT ARE CHROMATOGRAPHIC INSTRUMENTAL
METHODS OF ANALYSIS?
• High performance liquid chromatography (HPLC) has the same basic
components as gas chromatography except that the analyte mixture
is carried by a liquid under very high pressures over very small
particles in a column

• HPLC is especially useful for separating non-volatile species and those that
are not thermally stable such as pesticides, proteins and many water
pollutants, thus extending the range of separations possible with
chromatography.

Figure: Hypothetical HPLC

chromatogram of water pollutants

59
 3. WHAT ARE CHROMATOGRAPHIC INSTRUMENTAL
METHODS OF ANALYSIS?
• Each peak represents a specific chemical compound. The time taken
for each compound to emerge from the column is a characteristic of
that compound and is used to identify the compound. The area under
the peak is proportional to the concentration of the compound in the
sample.
HPLC chromatogram

• Mass spectroscopy is often used in conjunction with gas

chromatography (GC/MS) to give positive identification and
quantification for a large number of individual organic compounds
present in water. Basically, a mass spectrophotometer is an
instrument that sorts out charged gas molecules or ions according to

60
the mass of the species.
 ION CHROMATOGRAPHY
• Ion chromatography, a form of liquid chromatography, measures
concentrations of ionic species by separating them based on their
interaction with a resin.

• Ionic species separate differently depending on species type and

size.

• Ion chromatographs are able to measure concentrations of major

anions, such as fluoride, chloride, nitrate, nitrite, and sulfate, as well
as major cations such as lithium, sodium, ammonium, potassium,
calcium, and magnesium in the parts-per-billion (ppb) range.

• Concentrations of organic acids can also be measured through ion

chromatography.

• Especially useful for anions commonly occurring in water

• Cl- • Br- • SO4- • CN- • CO32-
 MASS SPECTROMETRY
Mass spectrometry involves production of ions followed by
separation by mass/to/charge ratio
• Especially useful for compound identification
100
O CH2CO2H
80 Cl
Relative intensity

60
Cl
40

20

0
160 170 180 190 200 210 220 230
m/e

62
Partial mass spectrum of 2,4-D herbicide
 MICROBIOLOGICAL METHODS OF ANALYSIS

What are microbiological methods of analysis?

• There are different microbiological methods of analysis available
including methods such as the membrane filter technique and the
multiple tube fermentation technique which give quantitative
information on specific groups of organisms.

• There are also qualitative methods available which give qualitative

information on the presence or absence of organisms as well as
advanced methods such as molecular methods of analysis.

63
 FIELD TEST METHODS

For which analyses can field tests and test kits be used?

• There are different field test methods and test kits available for a
range of constituents.

• These methods are useful for determinations such as pH, electrical

conductivity and residual chlorine.

• Test kits can also be used for screening samples and to get an
indication of water quality.

64
 PLANNING FOR THE ANALYSIS

What does planning for an analysis involve?

Proper planning of the following aspects is essential to ensure a

successful analysis:

• Which substances and characteristics to analyse for

• The number and frequency of samples to analyse

• The form in which results must be reported and accuracy required

• The analytical methods to be used

• The required reporting format.

65
 PLANNING FOR THE ANALYSIS

The sampler must communicate in the sampling report any relevant

factors observed during sampling which could affect the analysis. This
could include:
• Unusual physical appearance of the water body such as prolific algal
growth
• Unusually high rate of inflow caused by heavy rains
• Unusual high or low water levels of the water body
• Possible sources of contamination such as animals in and around
the water body, inflow of contaminated streams, etc.

Any unusual factors or problems encountered such as possible

contamination during sampling or possible problems with preservation
or transport, etc.

66
 PLANNING FOR THE ANALYSIS

On what basis are the substances to be determined selected?

• The substances are selected on the basis that the use of the water
dictates the substances that are to be determined.

• Water use: Group A to D, list all the different groups of substances

that are relevant to the domestic use of water. When planning for an
analysis the selection of substances from these groups must be
carefully considered and all relevant factors should be taken into
consideration.

• For example, if the purpose is to assess the quality of domestic

water at the point of use, the list of substances and the criteria will
be different to that if the purpose is to evaluate water from a stream
or a borehole as a possible raw water source for domestic use;
• or if the purpose is to investigate possible pollution of a reservoir or
distribution system, or if the purpose is to monitor the performance
of a treatment plant.

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WHAT ARE THE MAIN PURPOSES FOR WHICH WATER
FOR DOMESTIC USE ARE TO BE ANALYSED?

The main purposes for which water for domestic use are analysed are:
• domestic water at the point of use
• domestic water in a distribution system
• a water source that is used for domestic water
• domestic water during and after treatment.

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 REPORTING OF RESULTS

How is an analysis report prepared?

• The analysis report normally consists of a table of values for each
substance and property determined with the units in which the results
are reported together with an indication of the confidence limits of the
result

• The report should also contain comments on any aspect which the
analyst wishes to bring to the attention of the client, for example if the
sample appears to have been contaminated or if it contained
sediment, etc.

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PART 3: FAMILIARISE YOURSELF WITH THE CONCEPT
OF MEASUREMENT AND ASSOCIATED UNCERTAINTY

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PART 3: FAMILIARISE YOURSELF WITH THE CONCEPT
OF MEASUREMENT AND ASSOCIATED UNCERTAINTY

How can one tell if a test result is exactly right?

• It is not possible to tell if a test result is exactly right.
• The reason is that the result of a measurement (test) is only a best-
estimate or approximation of the true value of the determinant being
measured (e.g. the concentration of a dissolved substance in water).

Why is a test result only a best-estimate?

• When an analysis is repeated many times on the same sample of
water, it will only very rarely happen that the analyst gets exactly the
same result for each analysis.
• This is due to the inherent variability associated with all analytical
techniques.
• It is therefore, not possible to tell which of the different results is
exactly right. The final measurement result is, therefore, not an exact
truth, but a best-estimate of the true value of the test with an
associated measurement uncertainty.

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 SOURCES OF ERRORS / VARIABILITY IN ANALYSIS

Each measurement we make has its own associated error (uncertainty).

There are three types of errors which commonly contribute to

measurement uncertainty.
These are:
1. random errors,
2. systematic errors and
3. gross errors.

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 SOURCES OF ERRORS / VARIABILITY IN ANALYSIS

Random errors result from many different non-measurable contributing

sources of error, e.g:
• non-detectable variance in individual measurements used in the
overall measurement, e.g. volume, mass, titration values, end-point
distinction, etc;
• fluctuations in light intensity, temperature, humidity, power supply,
electromagnetic effects; instrumental background noise and drift;
• human variance;
• standard reference variances; and
• non-detectable deterioration in resources - human
(alertness/fatigue), equipment (calibration/ standardisation) and
chemicals (quality).

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 SOURCES OF ERRORS / VARIABILITY IN ANALYSIS
• Systematic errors result from a variety of distinct, measurable
sources which can be determined, reduced and in some cases
eliminated.
• Systematic errors usually produce a bias (shift) of the result from
the true value.
• Systematic errors are usually due to instrument, method and
personal error

• The sources of such error can be associated with the measurement

technique (e.g. the technique only results in 83% recovery of an
analyte due to incomplete extraction/digestion/fusion, etc.), and/or
the resources used to implement the measurement technique (e.g.
poor training of the analysts, poor calibration of equipment, etc.).

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SOURCES OF ERRORS / VARIABILITY IN ANALYSIS

Gross errors:
• Gross errors occur when a mistake is made while
recording data results, using a measurement
instrument, or calculating measurement.

• Gross errors are mistakes that make the measurement

very far off of the known/accepted value.

• They are neither systematic or random errors.

• For example, writing down 200 when the reading was

2.00

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 ERROR AND TREATMENT OF DATA
All analyses have some error. Important to know degree of error.
Precision and accuracy in chemical analysis

The extent to which the data or the average value of a set of data agree
with the true value being determined is the accuracy of the data

The degree to which numbers in a group of analytical results are in

agreement with each other is the precision of the group of numbers.

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 ERROR AND TREATMENT OF DATA

Precision: Is the closeness o f data to other data which

have been obtained in exactly the same.
• measure of consistency,
• evaluated in terms of the range or spread of results.
• affected by random error but not by systematic error.

Accuracy: is the closeness of a result to the true or

accepted value
• affected by systematic errors but may not be affected
by random error
• mean value is generally evaluated in terms of
accuracy when the true value is known

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ABSOLUTE AND RELATIVE ERROR

78
BASIC STATS

79
STANDARD DEVIATION

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 STANDARD DEVIATION

A series of measurements can be precise (i.e. the results

are grouped closely together) without actually being
accurate (i.e. close to the true value).

Both precision and accuracy are important, and the

concept of uncertainty is an attempt to combine them into
a single, convenient value. The uncertainty is
conventionally reported in the form

• Result = X ± U (units)
• For example:
• [Ca] = 247 mg/L ± 5 mg/L

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 %RSD

The relative standard deviation (RSD) is useful for comparing

the uncertainty between different measurements of varying
absolute magnitude.

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 CLASS EXERCISE
Determine the degree of accuracy and precision in the figures below.

A B

C D

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THANK YOU…

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