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HANDBOOK OF

WATER
ANALYSIS
SECOND EDITION



HANDBOOK OF

WATER
ANALYSIS
SECOND EDITION

EDITED BY

LEO M. L. NOLLET

Boca Raton London New York

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Library of Congress Cataloging-in-Publication Data
Handbook of water analysis / editor, Leo M.L. Nollet. -- 2nd ed.
p. cm.
Includes bibliographical references and index.
ISBN-13: 978-0-8493-7033-5 (alk. paper)
ISBN-10: 0-8493-7033-7 (alk. paper)
1. Water--Analysis--Handbooks, manuals, etc. I. Nollet, Leo M. L., 1948- II. Title.
QD142.H36 2007
628.1’61--dc22
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2007006719


Table of Contents

Preface ........................................................................................................................................... vii
Author ............................................................................................................................................ ix
Contributors .................................................................................................................................. xi
1.

Sampling Methods in Surface Waters .............................................................................1
Munro Mortimer, Jochen F. Mu¨ller, and Matthias Liess

2.

Methods of Treatment of Data ........................................................................................47
Riccardo Leardi

3.

Radioanalytical Methodology for Water Analysis ......................................................77
Jorge S. Alvarado

4.

Bacteriological Analysis of Water ...................................................................................97
Paulinus Chigbu and Dmitri Sobolev

5.

Marine Toxins Analysis ..................................................................................................135
Luis M. Botana, Amparo Alfonso, M. Carmen Louzao, Mercedes R. Vieytes,
and Marı´a R. Velasco

6.

Halogens .............................................................................................................................157
Geza Nagy and Livia Nagy

7.

Analysis of Sulfur Compounds in Water....................................................................201
Laura Coll and Leo M.L. Nollet

8.

Phosphates..........................................................................................................................219
Philippe Monbet and Ian D. McKelvie

9.

Cyanides .............................................................................................................................253
Meissam Noroozifar

10.

Asbestos in Water .............................................................................................................269
James S. Webber

11.

Heavy Metals, Major Metals, Trace Elements............................................................275
Jorge E. Marcovecchio, Sandra E. Botte´, and Rube´n H. Freije

12.

Determination of Silicon and Silicates ........................................................................313
Salah M. Sultan
v


vi
13.

Main Parameters and Assays Involved with Organic Pollution of Water...........337
Claudia E. Domini, Lorena Vidal, and Antonio Canals

14.

Determination of Organic Nitrogen and Urea ...........................................................367
Stefano Cozzi and Michele Giani

15.

Organic Acids ....................................................................................................................393
Sigrid Peldszus

16.

Determination of Phenolic Compounds in Water.....................................................409

˚ ke Jo¨nsson
Tarekegn Berhanu and Jan A

17.

Characterization of Freshwater Humic Matter ...........................................................435
Juhani Peuravuori and Kalevi Pihlaja

18.

Analysis of Pesticides in Water .....................................................................................449
Evaristo Ballesteros Tribaldo

19.

Fungicide and Herbicide Residues in Water..............................................................491
Sara Bogialli and Antonio Di Corcia

20.

Polychlorobiphenyls ........................................................................................................529
Alessio Ceccarini and Stefania Giannarelli

21.

Determination of PCDDs and PCDFs in Water.........................................................563
Luigi Turrio-Baldassarri, Anna L. Iamiceli, and Silvia Alivernini

22.

Polynuclear Aromatic Hydrocarbons ...........................................................................579
Chimezie Anyakora

23.

Analysis of Volatile Organic Compounds in Water .................................................599
Iva´n P. Roma´n Falco´ and Marta Nogueroles Moya

24.

Analysis of Surfactants in Samples from the Aquatic Environment ....................667
B. Thiele and Leo M.L. Nollet

25.

Analysis of Endocrine Disrupting Chemicals and Pharmaceuticals
and Personal Care Products in Water...........................................................................693
Guang-Guo Ying

26.

Residues of Plastics..........................................................................................................729
Caroline Sablayrolles, Mireille Montre´jaud-Vignoles, Michel Treilhou,
and Leo M.L. Nollet

Index .............................................................................................................................................745


Preface

The Handbook of Water Analysis, Second Edition, discusses as in the first edition, all types of
water: freshwater from rivers, lakes, canals, and seawater, as well as groundwater from
springs, ditches, drains, and brooks.
Most of the chapters describe the physical, chemical, and other relevant properties of
water components, and covers sampling, cleanup, extraction, and derivatization procedures. Older techniques that are still frequently used are compared to recently developed
techniques. The reader is also directed to future trends. A similar strategy is followed for
discussion of detection methods. In addition, some applications of analysis of water types
(potable water, tap water, wastewater, seawater) are reviewed. Information is summarized
in graphs, tables, examples, and references.
Because water is an excellent solvent, it dissolves many substances. To get correct
results and values, analysts have to follow sample strategies. Sampling has become a
quality-determining step (Chapter 1).
Statistical treatment of data ensures the reliability of the results. Statistical and chemometrical methods are discussed in Chapter 2.
Chapter 3 discusses new technologies on radionuclides and their possible health
hazards in water and the whole environment.
Water is a living element, housing many organisms—wanted or unwanted, harmful or
harmless. Some of these organisms produce toxic substances. Chapter 4 and Chapter 5
discuss bacteriological and algal analysis.
Humans consume and pollute large quantities of water. Chapter 6 through Chapter 26
cover injurious or toxic substances of domestic, agricultural, and industrial sources: halogens, sulphur compounds, phosphates, cyanides, asbestos, heavy and other metals, silicon
compounds, nitrogen compounds, organic acids, phenolic substances, humic matter, pesticides, insecticides, herbicides, fungicides, PCBs, PCDFs, PCDDs, PAHs, VOCs, surfactants,
EDCs, and plastics residues.
Chapter 23, Chapter 25, and Chapter 26 discuss in detail the separation and analysis of
volatile organic compounds (VOCs), endocrine disrupting compounds (EDCs) and pharmaceutical and personal care products (PPCPs), and plastics residues, respectively. Many of
these compounds are widely distributed in the environment but in very small quantities.
This book may be used as a primary textbook for undergraduate students learning
techniques of water analysis. Furthermore, it is intended for the use of graduate students
involved in the analysis of water.
All contributors are international experts in their field of water analysis. I would like to
thank them cordially for all their efforts.

This work is dedicated to my three granddaughters: Fara, Fleur, and Kato. I hope they
will live on a blue planet, the blue being the color of healthy water.
Leo M.L. Nollet

vii



Author

Leo M.L. Nollet is a professor of biochemistry, aquatic ecology, and ecotoxicology in
the department of applied engineering sciences, University College Ghent, member of
Ghent University Association, Ghent, Belgium. His main research interests are in the
areas of food analysis, chromatography, and analysis of environmental parameters. He is
author or coauthor of numerous articles, abstracts, and presentations, and is the editor
of Handbook of Food Analysis, 2nd ed. (three volumes), Food Analysis by HPLC, 2nd ed.,
Handbook of Water Analysis (all titles, Marcel Dekker, Inc.), Chromatographic Analysis of the
Environment, 3d ed., Advanced Technologies of Meat Processing, and Radionuclide Concentrations in Food and the Environment (all titles, CRC Press, Taylor & Francis). He received his
MS (1973) and PhD (1978) in biology from the Katholieke Universiteit Leuven, Leuven,
Belgium.

ix



Contributors

Amparo Alfonso Departamento de Farmacologı´a, Universidad de Santiago
de Compostela, Lugo, Spain
Silvia Alivernini Dipartimento di Sanita` Alimentare ed Animale, Istituto Superiore

di Sanita`, Rome, Italy
Jorge S. Alvarado Environmental Science Division, Argonne National Laboratory,
Argonne, Illinois
Chimezie Anyakora Department of Pharmaceutical Chemistry, University of
Lagos, Lagos, Nigeria
Tarekegn Berhanu Department of Chemistry, University of Addis Ababa, Addis
Ababa, Ethiopia
Sara Bogialli Dipartimento di Chimica, Universita ‘‘La Sapienza’’, Rome, Italy
Luis M. Botana Departamento de Farmacologı´a, Universidad de Santiago de Compostela, Lugo, Spain
Sandra E. Botte´ Area de Oceanografı´a Quı´mica, Instituto Argentino de Oceanografı´a – CONICET, Bahı´a Blanca, Argentina
Antonio Canals Departamento Quı´mica Analı´tica, Nutricio´n y Bromatologia, Universidad de Alicante, Alicante, Spain
Alessio Ceccarini Department of Chemistry and Industrial Chemistry, Universita
degli Studi di Pisa, Pisa, Italy
Paulinus Chigbu Department of Natural Sciences, University of Maryland Eastern
Shore, Princess Anne, Maryland
Laura Coll Departamento de Ingenierı´a Quı´mica, University of Valencia, Burjassot,
Spain
Antonio Di Corcia Dipartimento di Chimica, Universita degli Studi di Roma
‘‘La Sapienza’’ Piazzale Aldo Moro, Rome, Italy
Stefano Cozzi Consiglio Nazionale delle Ricerche, Istituto di Scienze Marine,
Sede di Trieste, Trieste, Italy

xi


xii

Claudia E. Domini Departamento de Quı´mica, Universidad Nacional del Sur,
Bahı´a Blanca, Argentina
Iva´n P. Roma´n Falco´ Departamento de Quı´mica Analı´tica Nutricio´n y Bromatologia, Universidad de Alicante, Alicante, Spain

Rube´n H. Freije Departamento de Quı´mica, Universidad Nacional del Sur, Bahı´a
Blanca, Argentina
Michele Giani Laboratory of Marine Biogeochemistry and Chemical Oceanography, Istituto Centrale per la Ricerca scientifica e tecnologica Applicata al Mare,
Chioggia (Venice), Italy
Stefania Giannarelli Department of Chemistry and Industrial Chemistry, Universita degli Studi di Pisa, Pisa, Italy
Anna L. Iamiceli Dipartimento di Sanita` Alimentare ed Animale, Istituto Superiore
di Sanita`, Rome, Italy
˚ ke Jo¨nsson
Jan A
Sweden

Department of Analytical Chemistry, Lund University, Lund,

Riccardo Leardi Department of Chemistry and Food and Pharmaceutical Technologies, University of Genoa, Genoa, Italy
Matthias Liess Department of System Ecotoxicology, VFZ-Helmholtz Centre for
Environmental Research Permoserstrasse 15, D-04318 Leipzig, Germany
M. Carmen Louzao Departamento de Farmacologı´a, Universidad de Santiago de
Compostela, Lugo, Spain
Jorge E. Marcovecchio Area de Oceanografı´a Quı´mica, Instituto Argentino de
Oceanografı´a – CONICET, Bahı´a Blanca, Argentina
Ian D. McKelvie Water Studies Centre, School of Chemistry, Monash University,
Victoria, Australia
Philippe Monbet Water Studies Centre, School of Chemistry, Monash University,
Victoria, Australia
Mireille Montre´jaud-Vignoles Laboratoire Chimie Agro-Industrielle, UMR 1010
INRA/INP-ENSIACET, TOULOUSE, France
Munro Mortimer Environmental Protection Agency, Brisbane, Australia
Marta Nogueroles Moya Departamento de Quı´mica Analı´tica Nutricio´n y Bromatologia, Universidad de Alicante, Alicante, Spain

xiii

Jochen F. Mu¨ller National Research Centre for Environmental Toxicology,
The University of Queensland, Brisbane, Australia
Geza Nagy Department of General and Physical Chemistry, University of Pecs,
Pecs, Hungary
Livia Nagy Department of General and Physical Chemistry, University of Pecs,
Pecs, Hungary
Leo M.L. Nollet Department of Engineering Sciences, Hogeschool Gent, Ghent,
Belgium
Meissam Noroozifar Analytical Research Laboratory, Department of Chemistry,
Faculty of Science, University of Sistan and Baluchestan (USB), Zahedan, Iran
Sigrid Peldszus Department of Civil and Environmental Engineering, University of
Waterloo, Waterloo, Ontario, Canada
Juhani Peuravuori Department of Chemistry, Laboratory of Organic Chemistry and
Chemical Biology, University of Turku, Turku, Finland
Kalevi Pihlaja Department of Chemistry, Laboratory of Organic Chemistry and
Chemical Biology, University of Turku, Turku, Finland
Caroline Sablayrolles Laboratoire Chimie Agro-Industrielle, UMR 1010 INRA/
INP-ENSIACET, TOULOUSE, France
Dmitri Sobolev Department of Biology, Jackson State University, Jackson,
Mississippi
Salah M. Sultan Department of Chemistry, King Fahd University, Dhahran,
Saudi Arabia
B. Thiele Institute for Chemistry and Dynamics of the Geosphere, Institute III:
Phytosphere, Research Centre Ju¨lich, Ju¨lich, Germany
Michel Treilhou Laboratoire de Chimie et Biochimie des Interactions, Centre
Universitaire Jean-Franc¸ois Champollion, Albi, France
Evaristo Ballesteros Tribaldo Department of Physical and Analytical Chemistry,
E.P.S. of Linares, University of Jae´n, Jae´n, Spain

Luigi Turrio-Baldassarri Dipartimento di Sanita` Alimentare ed Animale, Istituto
Superiore di Sanita`, Rome, Italy


xiv

Marı´a R. Velasco, EU-Community Reference Laboratory on Marine Biotoxins,
Agencia Espan˜ola de Seguridad Alimentaria, Vigo, Spain
Lorena Vidal Departamento Quı´mica Analı´tica Nutricio´n y Bromatologia, Universidad de Alicante, Alicante, Spain
Mercedes R. Vieytes Departamento de Farmacologı´a, Universidad de Santiago de
Compostela, Lugo, Spain
James S. Webber Wadsworth Center, New York State Department of Health,
Albany, New York
Guang-Guo Ying CSIRO Land and Water, Adelaide Laboratory PMB 2, Glen
Osmond, Australia and, Guangzhou Institute of Geochemistry, Chinese Academy
of Sciences, Guangzhou, China


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1
Sampling Methods in Surface Waters
Munro Mortimer, Jochen F. Mu¨ller, and Matthias Liess

CONTENTS
1.1 Introduction ........................................................................................................................... 2
1.2 General Aspects of Sampling and Sample Handling ..................................................... 3
1.2.1
Initial Considerations ............................................................................................. 3
1.2.2

Spatial Aspects ........................................................................................................ 3
1.2.3
Temporal Aspects ................................................................................................... 3
1.2.4
Number of Samples................................................................................................ 5
1.2.5
Sample Volume ....................................................................................................... 5
1.2.6
Storage and Conservation ..................................................................................... 6
1.2.6.1 Contamination.......................................................................................... 6
1.2.6.2 Loss ............................................................................................................ 6
1.2.6.3 Sorption ..................................................................................................... 7
1.2.6.4 Recommended Storage ........................................................................... 8
1.2.6.5 Quality Control in Water Sampling...................................................... 8
1.3 Sampling Strategies for Different Ecosystems ................................................................. 8
1.3.1
Lakes and Reservoirs ........................................................................................... 13
1.3.2
Streams and Rivers ............................................................................................... 15
1.3.2.1 Location of Sampling within the Stream ........................................... 15
1.3.2.2 Description of the Longitudinal Gradient ......................................... 15
1.3.2.3 Temporal Changes of Water Quality ................................................. 16
1.3.2.4 Using Sediments to Integrate over Time ........................................... 17
1.3.3
Estuarine and Marine Environments ................................................................ 17
1.3.4
Urban Areas........................................................................................................... 18
1.4 Sampling Equipment.......................................................................................................... 20
1.4.1
General Comments ............................................................................................... 20

1.4.2
Manual Sampling Systems .................................................................................. 20
1.4.2.1 Simple Sampler for Shallow Water..................................................... 20
1.4.2.2 Sampler for Large Quantities in Shallow Water .............................. 20
1.4.2.3 Simple Sampler for Deepwater ........................................................... 20
1.4.2.4 Deepwater Sampler (Not Adding Air to the Sample)..................... 21
1.4.2.5 Deepwater Sampler for Trace Elements (Allowing Air
to Mix with the Sample) ....................................................................... 21
1.4.3
Systems for Sampling the Benthic Boundary Layer
at Different Depths................................................................................................ 23
1.4.3.1 Deepwater (>50 m) ............................................................................... 23
1.4.3.2 Shallow Water (<50 m)......................................................................... 23
1


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1.4.4

Automatic Sampling Systems ............................................................................... 23
1.4.4.1 Sampling Average Concentrations ....................................................... 24
1.4.4.2 Sampling Average Concentrations—Sampling Buoy ........................ 24
1.4.4.3 Event-Controlled Sampling of Industrial Short-Term
Contamination.......................................................................................... 24
1.4.4.4 Rapid Underway Monitoring ................................................................ 25
1.4.4.5 Event-Controlled Sampling: Surface Water Runoff from

Agricultural Land .................................................................................... 27
1.4.4.6 Other Considerations Regarding Automatic
Sampling Equipment............................................................................... 27
1.4.5 Extraction Techniques............................................................................................ 29
1.4.5.1 Liquid–Liquid Extraction of Large Volumes ...................................... 30
1.4.5.2 Solid-Phase Extraction Techniques ....................................................... 30
1.4.5.3 Passive Sampler Devices ........................................................................ 34
1.4.6 Concentration of Contaminants in Suspensions and Sediment...................... 38
1.4.6.1 Suspended Particle Sampler for Small Streams.................................. 39
Acknowledgment......................................................................................................................... 41
References ..................................................................................................................................... 42

1.1

Introduction

The quality of output from an environmental sampling project is limited by whichever is
the weakest component—sampling or analysis. Progress in analytical protocols, including
the development of new and more sophisticated techniques described elsewhere in this
handbook, results in the taking of samples increasingly becoming the quality-determining
step in water quality assessment [1,2]. Conclusions based on laboratory results from the
most careful analysis of water samples may be invalidated because the original collection
of the samples was inadequate or invalid. Poor sampling design or mistakes in sampling
technique or sample handling during the sampling process inevitably lead to erroneous
results, which cannot be corrected afterward [3–7].
The objective of this chapter is to describe and discuss methods for environmental
sampling in surface waters (lakes, rivers, and the marine environment). This aspect
of sampling is of major importance in view of the increasing concern about environmental
contamination and its correct description and monitoring. Conventional methods used
for sampling solid material differ considerably and are not covered in this chapter.

However, where appropriate, a short discussion of sampling of suspended particulates
(mineral or organic sediments) is included. These water-associated solids are of great
importance for the less water-soluble chemicals (like many insecticides) since such
chemicals are dynamically distributed between the small suspended particles and the
water phase.
One of the basic problems of environmental water analysis is that generally it must be
carried out with selected portions (i.e., samples) of the water of interest, and the quality of
this water must then be inferred from that of the samples. If the quality is essentially
constant in time and space, this inference would present no problem. However, such
constancy is rare if ever observed in the real world; in most circumstances virtually all
waters show both spatial and temporal variations in quality. It follows that the timing and
choice of location for taking water samples must be chosen with great care. Also, since an
increase in the number of sampling locations and sampling occasions increases the cost of


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Sampling Methods in Surface Waters

3

the measurement program, it is important to attempt to define the minimal number of
sampling positions and occasions needed to provide the desired information.
The whole process of analyzing a material consists of several steps: sampling, sample
storage, sample preparation, measurement, evaluation of results, comparison with standards or threshold values, and assessment of results. This chapter is concerned with
sampling strategy, storage of samples, and sampling equipment. Further steps will be
described and discussed in the following chapters on specific chemical groups.
Section 1.2 focuses on some general aspects of sampling design and some characteristics of the substances to be sampled and analyzed, since properties such as degradation
or sorption that may occur after sample collection can substantially affect the results.
Section 1.3 gives an overview of sampling strategies in different ecosystems. The temporal

and spatial scaling of sampling depends to a great extent on the ecosystem under study
and on the question being addressed by the study. Finally, Section 1.4 describes some
types of sampling equipment and their specific properties. This part covers general
methods as well as specific methods like deepwater sampling, event-controlled sampling,
large volume sampling, and time-integrated (passive sampling) methods.

1.2
1.2.1

General Aspects of Sampling and Sample Handling
Initial Considerations

It can be said that there are as many approaches to sampling as there are possible moves
in a chess game. Firstly, the situation to be assessed must be accurately defined. Then an
appropriate sampling design should be chosen on the basis of temporal and spatial
processes of the part of the ecosystem under investigation. Handling, preservation, and
storage of the samples should be adapted to the properties of the chemicals of interest
and the effort invested should be optimized in order to obtain the necessary information
with such resources as are available. In order to achieve these objectives, the following
considerations are useful (Figure 1.1).
1.2.2

Spatial Aspects

Sampling for quality control of material in the metal or food industry normally follows
statistical approaches to ensure that relatively small subsamples will be representative of
the material as a whole. Although similar requirements exist for environmental sampling,
the principal difference is that spatial variation is generally very much greater in the case
of environmental contamination. Currents in flowing water and marine ecosystems must
be considered. Very often stratification crucially affects the distribution of substances of

interest, especially in lakes (see Section 1.3.1). The chosen locations for environmental
sampling must be related to the expected sources of contamination, e.g., different
distances downstream of a sewage effluent discharge point. A detailed description and
understanding of the exact sampling site (locational coordinates, longitudinal gradient,
lateral gradient, depth, water level, and distance to possible sources of contamination) is a
basic requirement of designing an adequate sampling program.
1.2.3

Temporal Aspects

The temporal pattern of sampling is of great importance if the environment to be sampled
shows changes over time, e.g., river systems within minutes or hours, or lakes within days


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Define objectives
and accuracy required

Define locations
of sampling

Define time and frequency
of sampling

Choose analytical methods,

sampling volume

Choose sampling methods

Define sample stabilization
and transport

Define analytical procedures

FIGURE 1.1
Initial considerations for planning and
carrying out sampling procedures.

Interpretation on the basis of
–assessed accuracy
–sampling design (arrows)

or weeks. The schedule of the sampling program depends mainly on the expected
temporal resolution of changes in the environment. In governmental programs for
monitoring wastewater-treatment effluents, sampling around the clock may be required
to determine whether control variables have been met or exceeded.
A single sample gives only a snapshot of the situation, and the power and reliability of
the results are normally low and depend strongly on the background data and additional
information available. However, the advantage is that often the equipment necessary for
this type of sampling is very simple and inexpensive.
If many samples are taken over a period of time, it is often appropriate to match the
sampling rate to the expected pattern of variation in the environment. For example, to
detect peak concentrations during short-term changes of water quality, event-controlled
samplers are useful. When it is necessary to quantify a contaminant load, discontinuous
sampling systems may be needed. Various types of discontinuous sampling that are of

special importance for quality control purposes and for automatic wastewater sampling
in accordance with international standards (ISO 5667-10) are illustrated in Figure 1.2. If
sampling is time proportional, then samples containing identical volumes are taken at
constant time intervals. In discharge-proportional sampling the time intervals are constant
but the volume of each sample is proportional to the volume of discharge during the
specific time interval. In quantity-proportional sampling (or flow-weighted sampling) the
volume of each sample is constant but the temporal resolution of sampling is proportional
to the discharge. The last type is event-controlled sampling, which depends on a trigger
signal (e.g., discharge threshold), which is discussed in Section 1.4.5.
In addition to single and discontinuous sampling, continuous sampling and determination of analytical values is desirable in some cases. An example is the quality control for a


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Q

t
Q

Time proportional

t

Discharge proportional

t

Quantity proportional

t

Q

Q
FIGURE 1.2
Different types of discontinuous sampling.

very complex effluent with unpredictable temporal changes in composition that are not
linked to possible trigger variables like discharge or temperature. For this purpose
automatic sampling and in some cases automatic analyzing units are useful. The expenditure of time and money is in general considerably higher for this type of sampling and
cannot always be justified.
Another important type of sample is a composite sample generated by mixing several
single samples, or a composite of samples accumulated during an automatic sampling
program. Composite samples can also be generated by mixing discontinuous samples
collected according to any of the types discussed previously and depicted in Figure 1.2.
1.2.4

Number of Samples

The number of samples required depends on the problem to be addressed. If an average
concentration is to be obtained from several samples, a general calculation of the necessary number of samples N can be done using the following equation:
 2
S
N¼4
"xd
where S is the estimate of standard deviation of the arithmetic mean of all single samples,

"
x is the estimate of arithmetic mean of all single samples, and d is the tolerable uncertainty
of the result, e.g., 20% (d ¼ 0.2).
If peak concentrations are to be quantified, the number of samples depends on the
specific problem. Some examples are given in Chapter 4.
1.2.5

Sample Volume

The appropriate sample volume depends on the elements or substances required to be
analyzed on their expected concentration in the sample and on the required quantification
limits. For trace metal analyses sample volumes of about 100 mL are sufficient in most
cases. For the analysis of organic chemicals (e.g., pesticides) 1 L samples are commonly
used. A 3 L sample volume has been suggested for both first-flush and flow-weighted


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composite samples in the monitoring of storm water runoff from industries and municipalities [8]. Fox [9] described an apparatus and procedure for the collection, filtration, and
subsequent extraction of 20 L water and suspended-solid samples using readily available,
inexpensive, and sturdy equipment. With this equipment he obtained quantification limits
for several organochlorine (OC) substances at nanogram per liter levels.
1.2.6

Storage and Conservation

Samples that are not analyzed immediately must be protected from addition of contaminants, loss of determinants by sorption or other means, and any other unintended changes
that affect the concentrations of determinants of interest. For this purpose sample bottles
should be chosen for long-term storage with no or as few changes to sample composition
as possible.
1.2.6.1 Contamination
An unintended contamination of samples can occur during the sampling process, either
from external sources or from contaminated sampling or storage equipment. Normally,
polyethylene or Teflon bottles are used in inorganic, and glass or quartz bottles in organic
trace analysis. Organic compounds have been known to leach from the bottle material into
the sample, react with the trace elements under study, and cause systematic mistakes. Such
problems become very important at detection limits below the microgram per gram level.
Some publications recommend that each sample container should be rinsed two or
three times with sample before finally being filled. However, this may lead to errors
when undissolved materials, and perhaps also readily adsorbed substances, are of interest.
It is suggested not to rinse containers with the sample when trace organic compounds
are of interest [3], and in particular when sampling for determinants that adsorb to
container surfaces.
Empirical studies have shown that poly(tetrafluoroethylene) (PTFE) and poly(vinylidene diflouride) (PVDF) can be of varying purity, often resulting in unexpected contamination problems in ultratrace analysis, whereas perfluoroalkoxy (PFA) fluorocarbon
proved to be cleaner by origin, and consequently, acidic washing processes could be
successfully applied. These different fluorinated polymers have been compared regarding
their suitability for container or sampler material [10]. It has been found that PFA exhibits
the lowest nanoroughness and hence seems best suited as container material.
1.2.6.2 Loss
Loss during storage can result from biological processes, hydrolysis, or evaporation.
Available procedures to reduce or prevent these loss processes include:

.

acidification to pH between 1 and 2: prevention of metabolism by microorganisms
and of hydrolysis and precipitation;

cooling and freezing: reduction of bacterial activity;

.

addition of complexing substances: reduction of evaporation; and

.

UV irradiation (together with addition of H2 O2 ): destruction of biological and
organic compounds to prevent complexation reactions.

.

Loss of target elements can also occur due to volatilization. When contact of the sample
with air is to be avoided (because it contains dissolved gases or volatile substances),
sample containers or sample bottles should be completely filled. Evaporation is a problem


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during storage of mercury under reducing conditions; other elements evaporate as
oxides (e.g., As, Sb), halogenides (e.g., Ti, Cr, Mo), or hydrides (e.g., As, Sb, Se), or they
are able to diffuse through the walls of plastic bottles. Volatilization is a special problem
in the case of organic compounds like hydrocarbons or halogenated hydrocarbons.
1.2.6.3 Sorption
Sorption to the walls of sample bottles can reduce the concentration in the water phase

considerably. Depending on the target substances, plastic or quartz bottles show the
lowest adsorption and can, therefore, be used for the storage of samples in aqueous
solution. In general, the wall material of storage bottles can change over time and the
potential for adsorption of target substances can increase considerably. In the case of
many metals, this problem can be reduced by acidifying the sample.
The affinity to glass and PTFE of selected OC, pyrethroid, and triazine pesticides at
concentrations 0:25 mg LÀ1 has been described [11]. For the OC pesticides, the adsorption
behavior correlates well with octanol–water partition coefficients. For triazines, sorption
to glass or PTFE is negligible, whereas a-BHC, lindane, dieldrin, and endrin are weakly
adsorbed relative to DDT, DDE, TDE, permethrin, cypermethrin, and fenvalerate.
Adsorption constants Ka (¼amount of adsorbed pesticide per unit area of surface) have
been calculated (Table 1.1) by this author to quantify the sorption affinity of the compounds
on glass and PTFE:
Ka ¼

Amount of sorbed pesticide per unit area of surface, ng cmÀ2
Concentration in aqueous solution, ng cmÀ3

As an example, the adsorption of fenvalerate on a Duran glass surface is calculated using
the above equation: A bottle with a surface area of 325 cm2 contains 500 mL of an aqueous
solution of fenvalerate. After 48 h under these circumstances, approximately 84% of the
fenvalerate is adsorbed to the glass surface and only about 16% remains in solution, with
the concentration in water reduced accordingly (e.g., from an initial concentration of
10 ng mLÀ1 in a 500 mL bottle, 4.2 ng are adsorbed and 0.8 ng stays in solution, a

TABLE 1.1
Mean Values of the Distribution Coefficient Ka Calculated for Duran Glass and PTFE
Containers (48 h at 258C) with the Associated Deviations (in brackets) Appropriate to the
Range of Concentrations Determined in the Solution
Duran Glass Surface

Pesticide
a-BHC
Lindane
Dieldrin
Endrin
DDD
DDE
DDT
Permethrin
Cypermethrin
Fenvalerate

PTFE Surface

Ka (cm)

Concentration Range
(ng mLÀ1)

Ka (cm)

Concentration
Range (ng mLÀ1)

0.014 (0.007)
0.005
0.027 (0.009)
0.019 (0.006)
0.226 (0.053)
1.35 (0.38)

0.87 (0.25)
1.44 (0.30)
43.3 (16.8)
8.15 (2.48)

0.05
0.04–0.12
0.17–0.19
0.19–0.21
0.09–0.11
0.03–0.05
0.04–0.07
0.01–0.07
0.002–0.007
0.002–0.03

0.036 (0.011)
0.048
0.093 (0.009)
0.059 (0.005)
0.887 (0.087)
5.94 (1.35)
2.028 (0.116)
3.32 (1.68)
11.61 (5.97)
11.8 (3.99)

0.01–0.04
0.04–0.07
0.11–0.15

0.12–0.18
0.01–0.07
0.005–0.02
0.008–0.04
0.001–0.01
0.002–0.007
0.002–0.01

Source: From House, W.A. and Ou, Z., Chemosphere, 24, 819, 1992. With permission.


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concentration of only 1:6 ng mLÀ1 ). For lindane and permethrin 0.32% and 96%, respectively, of the chemical are absorbed to the glass surface after 48 h.
The role of filtration of water samples at the time of collection and in relation to storage
and preservation of the sample is often an important consideration. Many substances
of interest may be present in a water sample in particulate as well as soluble form. Filtration
removes particulate matter, so that a decision on whether to filter at the point of collection
will depend on the objectives of the study. Another consideration relevant to filtration and
the possible presence of particulate matter are the effects on such matter of adding a sample
preservative such as acid. Generally, it is sound practice to filter before adding a preservative that may solubilize particulate matter or leach contaminants from it.
In the case of water samples that contain microscopic cellular matter such as algae,
the potential effects of filtration, added preservatives, and freezing as a means of preservation, each need to be considered. Filtration will remove microscopic cellular matter, and
along with it determinants that may be relevant to the study. On the other hand, some
preservatives, and certainly freezing, can cause cells to rupture and release materials that
may be of relevance. Guidance to appropriate courses of action is provided in the section

that follows.
1.2.6.4

Recommended Storage

For quality control and for the use of analytical results in forensic chemistry, national and
international standardizations are necessary. Several international standards (ISO) have
been defined for water quality sampling. These cover, among other topics, guidance on
the design of sampling programs [12], sampling techniques [13], and the preservation and
handling of water samples [14]. An alternative source of advice is a compilation of the US
Environmental Protection Agency’s (USEPA) recommended sampling and analysis
methods, which also covers sample preservation, sample preparation, quality control,
and analytical instrumentation [15–17].
Even if the above-mentioned conservation methods are used, the storage period for
water samples is limited. Table 1.2, derived from the current (2003 edition) international
ISO standard [14], gives an overview of recommended sampling and storage bottles as
well as conservation methods and maximum storage periods for different determinants in
the sample.
1.2.6.5 Quality Control in Water Sampling
Each of the sample collection, sample handling, sample storage, and sample preservation
steps should be validated to ensure positive or negative interferences with the determinants of interest are eliminated or at least reduced and quantified. This involves the use of
blanks (to determine possible additions) and reference samples containing known levels
of the relevant analytes (to determine losses and/or changes). In general, such blanks
should accompany each batch of sample containers to a field sampling site, and be
subjected to the same handling regime (e.g., opening, closure, preservation) as actual
sample containers.

1.3

Sampling Strategies for Different Ecosystems

The strategy to be used in environmental sampling differs considerably depending on
the details of the investigated ecosystem and the problems at issue. Hence strategies


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TABLE 1.2
Recommended Storage Containers for Water Samples, with Preservation Options and Maximum
Recommended Periods for Storage Prior to Analysis. Consistent with Ref. [14]

(continued)


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TABLE 1.2 (continued)

Recommended Storage Containers for Water Samples, with Preservation Options and Maximum

Recommended Periods for Storage Prior to Analysis. Consistent with Ref. [14]

,
Chemical oxygen
demand

P or G 100
P

100

Chloramine

P

or G

500

Chlorate

P

or G

500

Chloride

P

or G

100

Chlorinated
solvents

G

250 + head
space vial with
PTFE cap

H2SO4

1 month

Feasible to store 6 months

F

1 month

Feasible to store 6 months

5 min

Analyse on-site within
5 min. of collection

C

7 days
1 month

C
Chlorine
dioxide/residual

P

or G

500

Chlorite

P

or G

500

Chlorophyll

P

or G 1000

24 h

HCl
air

24 h
5 min

C

5 min

C

P 1000

F

P 1000

F*

24 h
filter, and extract
with hot ethanol
filter

1 month

Chromium

HNO3

1 month

Chromium
(VI)
Cobalt

PA or GA 100

C

24 h

PA or BGA 100

HNO3

1 month
5 days

Colour
Conductivity
Copper

P

500

C

P

or BG 100

C

PA or GA 100

air

HNO3

Analyse on-site within
5 min. of collection
Analyse on-site within
5 min. of collection

1 month

PA or GA 100

or G

For purge and trap, HCl
interferes. If chlorinated, see
Note (1)

Feasible to store 6 months

Feasible to store 6 months

24 h

Analysis on-site preferable

1 month

Feasible to store 6 months

Cyanide by
diffusion at pH6

P

500

C

NaOH

24 h

Cyanide easily
liberated

P

500

C

NaOH

7 days

Cyanide, total

P

500

C

NaOH

7 days

Cyanochloride

P

500

C

Fluorides

P

200 not PTFE

Hydrazine

G

500

Hydrocarbons
and petroleum

GS 1000

Iodide

G

500

C

1 month

Iodine

G

500

C

24 h

Preservation only 24 h
if sulphide present
Feasible to store 6 months. Preservation only 24 h if sulphide present

24 h
1 month

HCl

24 h

HCl or H2SO4

1 month

Bottle rinse solvent same as
used for extraction. Do not prerinse
bottle with sample (analytes absorb
to glass).