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Niessner, Schäffer

Organic Trace
Analysis

Reinhard Niessner, Technical University of Munich

Andreas Schäffer, RWTH Aachen University

DOI 10.1515/9783110441154-201
Authors
Prof. Dr. Reinhard Niessner
Institute of Hydrochemistry, Chair of Analytical Chemistry
Technical University of München
Marchioninistr. 17
D-81377 München
[email protected]

Prof. Dr. Andreas Schäffer

RWTH Aachen University
Institute for Environmental Research
Worringerweg 1
D-52074 Aachen
[email protected]

ISBN 978-3-11-044114-7
e-ISBN (PDF) 978-3-11-044115-4
e-ISBN (EPUB) 978-3-11-043293-0

Library of Congress Cataloging-in-Publication Data

A CIP catalog record for this book has been applied for at the Library of Congress.

Bibliographic information published by the Deutsche Nationalbibliothek

The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed
bibliographic data are available on the Internet at http://dnb.dnb.de.

© 2017 Walter de Gruyter GmbH, Berlin/Boston

Typesetting: Integra Software Services Pvt. Ltd.
Printing and binding: CPI books GmbH, Leck
Cover image: Andrew Brookes, National Physical Laboratory/Science Photo Library
@ Printed on acid-free paper
Printed in Germany

www.degruyter.com
Preface
Our book Organic Trace Analysis is dedicated to advanced students of analytical
chemistry as core discipline first. Beyond them, also those learning and practising
food chemistry, pharmaceutical chemistry, life sciences, or environmental sciences in
general, will benefit from this textbook.
Of course, many excellent monographs on chromatography, mass spectrometry
etc. are available, but we had the strong feeling, that they do not cover teaching
the specialties and peculiarities comprising trace analysis of organic compounds:
sampling from the very diverse matrices, sample pre-treatment, analyte enrichment,
critical assessment of chromatography or separation techniques, up to the application
of bioanalytical tools.
Organic trace analysis is full of pitfalls and surprise! The enormous complexity
and molecular diversity of organic molecules asks for sometimes strange methodo-
logies. Compared to inorganic compounds the analytes are often labile, but some of
them biologically extremely effective. Even more diverse are the matrices from where
they have to be isolated covering soil, water, and atmosphere, but also organisms liv-
ing in these compartments. Hence, organic trace analysis is characterized as a refined
craftsmanship, dealing with a multitude of techniques.
Knowledge on spectroscopy, physical chemistry, molecular biotechnology, chem-
ical engineering, and statistics are the basics for it.
We had the intention to provide a balanced mixture of analytical basics, news
from the forefront of (bio)analytical chemistry and separation science, completed by
a bunch of approved methods applied to everlasting trace analytical problems.
The authors like to thank the extremely helpful team of de Gruyter! They made
our manuscript finally readable. Many thanks also to Prof. Totaro Imasaka, Kyushu
University at Fukuoka, who hosted RN for longer periods. There, a considerable part
of this textbook became written. AS is grateful for the patience of his wife and family
tolerating many weekends and vacations when the other half of the manuscript was
developed.
Reinhard Niessner
Munich, April 2017

Andreas Schaeffer
Aachen, April 2017

DOI 10.1515/9783110441154-202
Contents

1 Overview 1
1.1 General Remarks 1
1.2 What Does “Organic Traces” Mean? 1
1.3 Importance of Organic Trace Analysis 2
1.4 Peculiarities with Organic Trace Analysis 4
1.5 Essential Matrices in Organic Trace Analysis 5
1.6 Aims of Organic Trace Analysis 7
Further Reading 8
Bibliography 9

2 Statistical Evaluation 10
2.1 General Remarks 10
2.2 Calibration Function 10
2.3 Sensitivity 11
2.4 Types of Error 11
2.5 Limit of Detection/Limit of Quantification 14
2.6 Precision 15
2.7 Accuracy 15
2.8 Correlation and regression 16
Further Reading 18

3 Quality Control Strategies 19

3.1 General Remarks 19
3.2 Artificially Generated Matrix Surrogates 19
3.3 Addition of an Internal Standard 21
3.4 Validation by Applying Independent Analytical Methods 25
3.5 Validation by Reference Material 26
3.6 QC by Applying Good Laboratory Practices 30
Further Reading 31
Bibliography 31

4 Sampling of Organic Trace Contaminants 33

4.1 General Remarks 33
4.2 Sampling from Organisms 35
4.2.1 General Remarks 35
4.2.2 Animal Tissue Samples 36
4.2.3 Human Samples 42
4.2.4 Plant Sampling 44

DOI 10.1515/9783110441154-203
VIII Contents

4.3 Trace Gas Sampling 46

4.3.1 General Remarks 46
4.3.2 Gas Grab Sampling 47
4.4 Rain, Surface Water and Particulate Matter Sampling 48
4.4.1 General Remarks 48
4.4.2 Rain 49
4.4.3 Surface Water, Deep Water, Groundwater 50
4.4.4 Particulate Matter Sampling 52
4.5 Soil and Sediment Sampling 54
4.5.1 General Remarks 54
4.5.2 Soil 55
4.5.3 Sediment 57
4.6 Diffusion Sampling (Passive Sampling) 58
4.7 Sampling of Colloidal Matter (Hydrosol, Aerosol) 62
4.7.1 General Remarks 62
4.7.2 Hydrosol Sampling 63
4.7.3 Aerosol Sampling 67
4.8 Sources for Artifact Formation 69
4.8.1 General Remarks 69
4.8.2 Sources of Artifacts 69
Further Reading 71
Bibliography 71

5 Sample Treatment Before Analysis 76

5.1 General Remarks 76
5.2 Sample Pretreatment (Stabilization and Storage) 76
Bibliography 78

6 Enrichment and Sample Cleanup 79

6.1 General Remarks 79
6.2 Liquid Samples (Water, Body Fluids, Beverages) 79
6.2.1 Liquid–Liquid Extraction 79
6.2.2 Pre-concentration after LLE (Evaporation, Freeze-Drying) 81
6.2.3 Solid-phase Extraction 83
6.2.4 Solid-phase Microextraction 87
6.2.5 Dispersive liquid–liquid microextraction 89
6.2.6 Micellar Extraction 90
6.2.7 Headspace Extraction 92
6.2.8 Purge and Trap Extraction 93
6.3 Solid Samples (Particulate Matter, Soil, Sediment, Plant and Animal
Material) 94
6.3.1 Solid–Liquid Extraction 95
 Contents IX

6.3.2 Assisted Solid–Liquid Extraction (Soxhlet, ASE, Microwave

Extraction, Ultrasonication, Supercritical Fluid Extraction) 97
6.3.3 Enzymatic Digestion 106
6.3.4 Non-extractable Residues 107
6.3.5 Steam Distillation 108
6.3.6 Size Fractionation of Dispersed Solid Matter 110
6.4 Gaseous Samples and Aerosols 113
6.4.1 General Remarks 113
6.4.2 Liquid Absorption of Trace Gases 113
6.4.3 Solid Adsorption of Trace Gases 114
6.4.4 Filtration 115
6.4.5 Diffusion Sampling (Denuder Sampling) 117
6.4.6 Sampling by Condensation 119
6.4.7 Size-Resolved Particle (Aerosol) Sampling 120
Further Reading 123
Bibliography 125

7 Chromatography 129
7.1 General Remarks 129
7.2 Chromatographic Separation 130
7.2.1 Adsorption Chromatography 133
7.2.2 Ion-Exchange Chromatography 135
7.2.3 Size-Exclusion Chromatography 137
7.3 Basics and Working Principles 139
7.3.1 Parameters to Achieve Best Resolving Power 140
7.3.2 General Recommendations 144
7.4 High-Performance Liquid Chromatography 145
7.4.1 General Information 145
7.4.2 Mobile Phase (HPLC) 145
7.4.3 Stationary-Phase Materials 151
7.4.4 Columns 156
7.4.5 HPLC Detectors 158
7.4.6 Separation Parameters in HPLC 168
7.4.7 Derivatization Methods (Pre-Column, Post-Column) in HPLC 170
7.4.8 Hyphenated Techniques (HPLC–MS, HPLC-NMR) 173
7.5 Gas chromatography 176
7.5.1 General Remarks 176
7.5.2 Separation Columns and Stationary Phases (GC) 177
7.5.3 Mobile Phase 179
7.5.4 Isothermal versus Temperature-Programmed GC 181
7.5.5 Injection Techniques for GC 182
X Contents

7.5.6 GC Separations at Extreme Temperatures 182

7.5.7 Derivatization Techniques in GC 184
7.5.8 Change of State During GC Separation (Pyrolysis, Carbon Skeleton
Formation) 185
7.5.9 Analyte Detection in GC (Electrical, Electrochemical, Optical) 186
7.5.10 Hyphenated Techniques (GC–MS) 198
7.5.11 Multidimensional GC Separations (GC × GC) 201
Further Reading 204
Bibliography 206

8 Capillary Electrophoresis (CE) 208

8.1 General Remarks 208
8.2 Working Principles 208
8.2.1 Interaction of Charged Analyte Species with an External Electric
Field 208
8.2.2 Electroendosmotic Flow 209
8.2.3 Control of EOF 211
8.2.4 Flow Dynamics, Efficiency and Resolution 212
8.3 Modes of CE Operation 214
8.3.1 CZE 214
8.3.2 Capillary Gel Electrophoresis 215
8.3.3 Micellar Electrokinetic Capillary Chromatography 216
8.3.4 Capillary Isoelectric Focusing 217
8.3.5 Capillary Isotachophoresis 218
8.4 Sample Injection (CE) 219
8.4.1 Hydrodynamic Injection 220
8.4.2 Electrokinetic Injection 221
8.5 Separation Parameters in CE 221
8.5.1 Capillary Properties and Conditioning 221
8.5.2 Temperature Effect in CE 222
8.5.3 Electric Field in CE 223
8.6 Detection of Analytes in CE 223
8.6.1 UV–Vis Detection in CE 224
8.6.2 Fluorescence and Chemiluminescence Detection in CE 224
8.6.3 Amperometric and Conductometric Detection in CE 225
8.6.4 Hyphenated Techniques (CE-MS) 225
8.6.5 Indirect Detection Methods in CE 225
8.6.6 Increasing the Sensitivity of Detection in CE 226
Further Reading 227
Bibliography 227
 Contents XI

9 Mass Spectrometry 229

9.1 Introduction 229
9.2 Basic Equipment 229
9.3 Ionization in MS 230
9.3.1 Hard Ionization by Electron Impact 231
9.3.2 Soft Ionization 232
9.4 Separation of m/z Species 239
9.4.1 One-Dimensional Mass Separation 239
9.4.2 Two-Dimensional Mass Separation 241
9.4.3 Three-Dimensional Mass Separation by Ion Trap MS 244
9.5 Molecular Imaging by MS 247
Further Reading 247
Bibliography 248

10 Receptor-based Bioanalysis for Mass Screening 250

10.1 General Remarks 250
10.2 Natural Receptors (Enzymes and Antibodies) 251
10.3 Working Principle of Enzymes (Enzymatic Catalysis, Enzymatic
Inhibition) 252
10.4 Working Principle of Antibodies (IA, Test Format, Microarray, Dip
Stick) 254
10.5 Principles of Effect-Directed Analysis 262
Further Reading 264
Bibliography 265

11 Selected Applications 269

11.1 Trace Analysis of Polycyclic Aromatic Hydrocarbons (PAHs) 269
11.1.1 General Remarks (Occurrence, Physical and Chemical
Properties) 269
11.1.2 Sampling Strategies for PAHs (Water, Air, Soil, Body Fluids) 271
11.1.3 Wet-chemical Analysis (HPLC, Thin-layer Chromatography) 278
11.1.4 GC Analysis of PAH 282
11.1.5 Immunological Bioanalysis of PAHs 284
11.1.6 In situ PAH Analysis by Spectroscopic Techniques (Laser
Fluorescence, Photoelectron Emission) 288
11.2 Polychlorinated Biphenyls, Dibenzodioxins and -Furans 293
11.2.1 General Remarks on Occurrence and Importance 293
11.2.2 Sampling Strategies for Polyhalogenated Aromatic
Hydrocarbons 297
11.2.3 GC Analysis of PCDDs/PCDFs and PCBs 299
11.2.4 Bioanalytical Methods for PCDD/PCDF and PCB Screening 304
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XII Contents

11.3 Organophosphorus Compounds 310

11.3.1 General Remarks on Occurrence and Importance 310
11.3.2 Sampling Strategies for OPs (Water, Soil, Air, Body Fluid, Food
and Nutraceuticals, Living Tissue) 314
11.3.3 GC Analysis of OPs 318
11.3.4 Wet-chemical Analysis of OPs (HPLC–MS, TLC, Capillary
Electrophoresis) 319
11.3.5 Bioanalysis of OPs 324
Further Reading: Polycyclic Aromatic Hydrocarbons 334
Further Reading: Polychlorinated Biphenyls (PCBs), Dibenzodioxins
(PCDDs) and –Furans (PCDFs) 335
Further Reading: Organophosphates 335
Bibliography 335

List of Abbreviations 347

Index 351
1 Overview
1.1 General Remarks
This textbook has the intention to give an introduction and information to those
scientists facing analytical problems connected with organic molecules in very tiny
amounts, and this in different matrices. We call it organic trace analysis. Since dealing
with this is very different from what is practiced in inorganic trace analysis, it seems
justified to present a comprehensive view of how to handle this.

1.2 What Does “Organic Traces” Mean?

Trace analysis is defined as the qualitative and quantitative determination of a very
small amount of substances within any matrix. Organic trace compounds stem from
organic or bioorganic chemistry. We will not consider inorganic carbon-containing
substances like carbonates or different forms of elemental carbon, despite their im-
portance. Of course, a clear separation is impossible, for example, organometallic
compounds of transition elements are often rated as a part of inorganic chemistry.
The same goes for microbial matter, which may partly be seen as biopolymers. In the
following sections, we will show some examples for further understanding.
Trace analysis is relative in terms of concentration. First of all, we should re-
cognize the difference between “trace analysis methods” and those belonging to
“microanalysis” techniques, or nowadays “nanoanalytics.” Trace analysis methods
deal with concentration determination within a given sample, whereas a microana-
lysis technique identifies a compound localized at a selected spot. The latter does not
analyze the total volume.
Frequently, trace concentrations are presented as fractions in a dimensionless
notation. Foremost, one has to decide whether a mass-to-mass fraction (manalyte /
msample ) or a mass-to-volume fraction (manalyte /vsample ) is meant. Fractions given as
manalyte /vsample need additional parameters, as the volume depends on pressure and
temperature. For aqueous samples, the difference between m/v and m/m is negligible.
These ratios are shown in Table 1.1.
Let’s get an impression of these amounts, 1 ppq is equivalent to 1 drop (50 ,L)
of water diluted into a cube of water measuring approximately 3,680 m on one side
(50 billion cubic meters). This is roughly the volume of Lake Constance, the second
largest fresh water lake in Northern Europe. This concentration ratio is currently the
lower limit in organic trace analysis. The US-Environmental Protection Agency (US-
EPA) has set its threshold for safe dioxin exposure at a toxicity equivalence (TEQ) of
0.7 pg/kg of body weight per day. This corresponds to 0.7 ppq. The upcoming threshold
value for endocrine disruptors, substances blocking the function of natural endo-
genic hormones, is discussed to be in the lower ppt–ppq range, too, like the example

DOI 10.1515/9783110441154-001
2 1 Overview

Table 1.1: Abbreviations for relative quantity measures as fractions in parts per
notation.

ppm = parts per million 10–6 = mg/kg = ,g/g = g/t = 10–4 %

ppb = parts per billion 10–9 = ,g/kg = ng/g = mg/t = 10–7 %
ppt = parts per trillion 10–12 = ng/kg = pg/g = ,g/t = 10–10 %
ppq = parts per quadrillion 10–15 = pg/kg = fg/g = ng/t = 10–13 %

mg, ,g, ng, pg and fg are abbreviations for milli-, micro-, nano-, pico- and
femtogram, respectively.

of ethinylestradiol (5–6 ng/L) in a Canadian lake leading to the impairment of fish

populations after chronic exposure [1].

1.3 Importance of Organic Trace Analysis

An easy way to reveal the importance of trace analysis of organic compounds is a
look into the databank SciFinder (see Table 1.2). The frequency of citations reflects
the importance of xenobiotic organic trace compounds quite well.
This is a direct consequence of the physiological or toxic impact of many organic
compounds even in smallest concentrations. Additionally, the ongoing search for bio-
markers in clinical chemistry or continuing clarification of metabolic pathways will
enlarge the need for analyzing minute amounts of chemicals considerably. We also
observe a trend to a first so-called nontarget screening for (almost) everything present
in an environmental matrix. This first became established in water and air analysis
some years ago, when multidimensional chromatography came into operation, and
by the hyphenation of strong separation schemes with high-resolution mass spectro-
metry. By such nontarget analysis, one likes to detect any possible contamination, for
example, within water effluent from a sewage treatment plant which often still con-
tains trace amounts of synthetic chemicals. It is clear that with increasing resolution
and/or detection power of the analytical technique, the number of so far unknown
contaminants will also rise in parallel.

Table 1.2: Citation frequency of analyses of important analytes in SciFinder databank (year 2015).

Trace analysis of References found Analytical conc. range

Pesticides 50,786 ppt

Polycyclic aromatic hydrocarbons 25,884 ppt–ppb
Dioxins 5,939 ppq
Explosives 20,315 ppt–ppb–ppm
Mycotoxins 4,638 ppt
Endocrine disruptors 2,320 ppq–ppt
Benzene, toluene, xylene 14,627 ppt–ppb–ppm
 1.3 Importance of Organic Trace Analysis 3

Table 1.3: List of selected environmental regulations and monitoring programs.

Regulation Location Substances

Decision 2455/2001/EC on a first list EU 33 substances or group of substances

of priority substances shown to be of major concern for
European Waters
Regulation (EC) No 1107/2009 EU Regulation of the European
Parliament and of the Council
concerning the placing of plant
protection products on the market
National primary/secondary drinking US-EPA Disinfectant, disinfectant by-product,
water regulations organic chemicals, foaming agents
Soil Remediation Circular 2009 The Netherlands Aromatic compounds, PAHs,
chlorinated hydrocarbons, pesticides
Atlantic RBCA for Petroleum-Impacted Canada BTEX, aromatic fractions, heavy (>C32 )
Sites in Atlantic Canada Version 3 hydrocarbon fraction
Directive 2013/39/EU watch list for EU Ten substances, which include three
water pharmaceutical substances
(Diclofenac, 17-beta-estradiol (E2) and
17-alpha-ethinylestradiol (EE2)
MAK values (maximum workplace Germany Collection for Occupational Health
concentration) and of BAT values and Safety; numerous accepted
(biological workplace tolerance and suspected carcinogenic
values) substances
CADAMP California, USA Dioxins, furans, PCB congeners,
brominated diphenyl ethers

PAH, polycyclic aromatic hydrocarbon; RBCA, risk-based corrective action; CADAMP, California Ambi-
ent Dioxin Air Monitoring Program; EU, European Union; US-EPA, US-Environmental Protection Agency;
PCBs, polychlorinated biphenyls.

The importance of organic trace compounds and their analysis is seen best in the nu-
merous regulations published by national or supranational organizations. A set of the
most important environmental regulations and monitoring programs is depicted in
Table 1.3.
But not only for monitoring the environmental trace analysis of organic sub-
stances is essential. Rigorous quality regulations also exist for the pharmaceutical
drug production or food production. The direct impact of unwanted contaminations
has led to strict monitoring of pesticides, toxins and so on in raw products.
Nowadays, possible bioterroristic attacks ask for rapid development and applic-
ation of extremely sensitive and rapid detection methods for microbial pollution and
derived toxins such as ricin, Botulinus toxins or aflatoxins. The rapid distribution of
freshly produced dairy products (milk, yoghurt, etc.) serves as a template for such
attack. The response time for any countermeasure is only hours.
4 1 Overview

1.4 Peculiarities with Organic Trace Analysis

One has to recognize the many difficulties faced in organic trace analysis:
– Per year, more than 106 new substances become synthesized by organic chem-
ists; so, there is simply no analytical capacity to follow up. The characterization
techniques used by the organic chemists in most cases do not allow a trace
analysis.
– There is no opportunity to apply a simple separation scheme as it was possible
with inorganic substances, for example, separation by precipitation of insol-
uble sulfides. In the last century, food analysts have started to create separation
schemes for organic food ingredients, but the performance was insufficient due to
higher solubility of organic compounds and this was stopped.
– Development of trace analytical determination protocols never happened for reas-
ons of precaution but instead always afterward, i.e. event driven. Once a new
intoxication caused by a harmful organic substance becomes known, the devel-
opment of a trace analytical technique starts. An example for this is the recent
acrylamide contamination of fried food. The substance and its chemical charac-
terization have been published decades ago, but no trace analytical technique was
at hand when needed.
– A special challenge is the chemical analysis of trace contaminants in “diffi-
cult” matrices, such as pesticide residues in plants forming strongly bound or
entrapped residues or in insects; an example for the latter is the assumed intoxica-
tion of bees with neonicotinoids: sub-ng/bee quantities have to be analyzed [2, 3].
– Many compounds possess nearly identical physicochemical properties (vapor
pressure, solubility, mass, spectral features, chirality, etc.), but nevertheless
exhibit completely different physiological effects.
– The matrices containing organic trace compounds may change a lot and this is
often unexpected. Polycyclic aromatic hydrocarbons (PAHs) can be dissolved in
a liquid, but in the presence of dispersed particles they may become attached to
their surfaces, exhibiting now very different partition behavior in separation. PAH
sorbed to resuspended sediment particles may still lead to toxicity symptoms in
exposed fish [4].
– In organic trace analyses, the unambiguous identification of individual molecules
is requested, whereas inorganic trace analysis is often only restricted to determin-
ing the elemental composition. In some cases, the individual isomers, for example
enantiomers, have to be measured. A prominent example for this was the Conter-
gan scandal: the leprosy drug thalidomide exists as two optical isomeric, (R) and
(S), forms. Thalidomide is racemic; the individual enantiomers can racemize. So
administering the pure optical isomer does not help, since racemization happens
in the vein already. It is assumed later, that it is responsible for terrible terato-
genic malformations of the fetus after treatment of pregnant women. At this time,
the possibility of enantiomeric analysis of small quantities was not as developed
today.
 1.5 Essential Matrices in Organic Trace Analysis 5

– The instability of many organic substances is a tremendous challenge. Not only

does this hamper sample treatment and storage but also asks for special caution
in usage of standard dilutions for calibration. Known examples are the oxidation-
sensitive vitamins or certain PAH molecules (e.g., pyrene). Aside from thermal
instability, illumination by sunlight can trigger a change of isomeric forms or
may start degradation by photooxidation. Photo-dimerization of unsaturated
compounds has been observed too.

1.5 Essential Matrices in Organic Trace Analysis

Organic substances may occur in all matrices and derived compartments as well. As
an example, we can take the path of environmental compounds within the water cycle
(see Figure 1.1).
At the beginning of the water cycle, water vapor becomes condensed to ultrafine
dispersed matter in ambient air (=aerosol) forming a cloud. Without such aerosol
particles, no cloud or fog formation can happen. Depending on the origin of such
particles, the freshly condensed water is already contaminated at its initial state of
existence. During the ongoing water condensation, the water droplets start to rain
out. When falling down, there are plenty of opportunities to pick up other air con-
stituents (gases, small particles, etc.). Also photooxidation starts, hence changing the
composition of an individual droplet. The pollutant may undergo transformation and
translocation processes.
With the advent of rain droplets at ground surface, the dissolved and dispersed
micropollutants follow the way of seeping water. Already the first contact with solid
matter (plant leaves, soil, rock material) offers again many opportunities for the
pollutant. Either it is simply attached by adsorption, or it is fixed by ion exchange, de-
pending on the pH within the aqueous phase, polarity and presence of exchangeable
functional groups. In contact with humic substances or clay particles, the pollutant
may intercalate into their inner spacings, again fixed by ion exchange or with time
by covalent bonding [5]. Since soil microorganisms need organic compounds to gain
energy through assimilation, microbial organisms are happy to incorporate pollut-
ants for further enzymatic digestion. In the course of this, the organic compound
becomes at last metabolized. The often more polar metabolites may behave completely
differently in their transport potentials. When fixed at a surface, air and light may
also start similar decomposition reactions. The original micropollutant might become
enriched within such cells. Other routes go via the roots of plants. Within the rhizo-
sphere, the pollutant can be solubilized by natural surfactants and through this enters
the water-conducting capillaries, xylem and phloem, of a growing plant. Thus, the
pollutants become dumped with time in the plant material.
The partly transformed pollutants dissolved in water or attached to nanoparticles
will follow the water flow through unsaturated and saturated soil layers until they
reach an impermeable layer, forming groundwater. Groundwater serves in many
 6
1 Overview

Cloud formation

Condensing water vapor

Snow Precipitation

Surface runoff

Evaporation
Ocean contributes
about 80 % of total
Lakes water vapor in air

Groundwater

Ocean
Saltwater
Impervious layer Intrusion

Figure 1.1: Water cycle as host and reactor for contaminants within different compartments.
 1.6 Aims of Organic Trace Analysis 7

countries as drinking water reservoirs. When pumped out, it is used for irrigation pur-
poses or production of drinking water. For drinking water pollutants, there exists a
nonzero probability to become bound after ingestion to human receptors with corres-
ponding physiological consequences, or the contaminant becomes translocated again
through excrements reaching soils [6].
In essence, a micropollutant will have many options to make its way through the
different compartments. As a consequence, each of them poses analytically very dif-
ferent challenges for sampling, sample storage, pre-enrichment of the wanted analyte
and selection of the appropriate and tolerant analytical instrumentation.

1.6 Aims of Organic Trace Analysis

The questions to be answered by organic trace analysis may be grouped as follows:

Which substance? How much of it?

From the presented characteristics and peculiarities of organic trace analysis, it can be
concluded that the foremost aim will be the unambiguous identification of one single
compound in its unique structure within its surrounding matrix.
This is currently unfeasible, since it also would mean availability of standard com-
pounds in measurable quantity and of highest purity. Otherwise, calibration of the
analytical process would be impossible. Sometimes, synthesis of even tiny amounts
of such standards, especially if isotope labeling is required, becomes extremely cum-
bersome and expensive. Very often toxicity prohibits handling of such compounds. We
also do not always have the analytical instrumentation with the needed performance
to meet the requirements for this. Nevertheless, toxicological considerations ask for in-
dividual identification and quantification, when within a whole group of isomers only
a few are relevant. Examples are polychlorinated biphenyls (PCBs) or polyhalogenated
compounds in general (see Chapter 11).

Bioavailability of pollutants

In order to estimate the uptake of pollutants in exposed organisms, for example earth-
worms or plants in soil, the question arises how much of the pollutant is present in a
bioavailable form rather than to analyze its total concentration. This can be addressed
by extraction with aqueous solutions like 0.1 M CaCl2 or using solid phase extraction
disks/fibers. Obviously, the resulting concentrations are often well below the total con-
centrations, which can be determined by thorough extraction using organic solvents
under drastic conditions (Soxhlet or accelerated pressurized extraction).
More realistic in many cases is to find an answer to:

Which substance group or pattern of individual molecules is present? What is their total amount?
8 1 Overview

This is sometimes simplifying the analytical task. As an example, as the 209 congen-
ers of the PCB family aren’t analytically feasible, and also only some of them are of
toxicological relevance, one can either measure the sum of chlorine bound to the bi-
phenyl structure as a substitute, or the presence and amount of selected PCB patterns.
Alternatively, often only lead substances are analyzed, for example, benzo[a]pyrene
(BaP) serves as the lead substance in water and air pollution monitoring, represent-
ing a class of PAHs (see Chapter 11). BaP is also toxicologically the most important
representative of this class. The same is found for toxins, furans and dioxins.
Once we have this information, we can answer the questions

Does the found concentration exceed a maximum tolerable threshold? Is the found analytical signal
differentiable in a unique manner from a background?

Both questions have severe economic and public relevance. Based on the toxicolo-
gical risk management, the findings will directly influence human society. Dangerous
occupational hygiene and environmental pollution will directly and indirectly impact
living and working conditions. Production lines will become closed when emissions
permanently exceed a standard value. Food has to be destroyed when a tolerable
pesticide contamination level is exceeded. Pesticide application conditions have to
be changed or its usage restricted if groundwater monitoring reveals concentrations
above the (European) threshold of 0.1 ,g/L. Maintenance of hazardous production
facilities may be stopped. In an area where already high contamination levels are
present, new industrial locations may be forbidden. Contaminated ground may pre-
vent construction of new homes. Sewage sludge is no longer applicable as fertilizer in
agriculture. These are just a few examples to show that trace-level contaminants may
lead to various personal, professional and legal consequences.

Further Reading
Barcelo D. Environmental analysis: techniques, applications and quality assurance. In Techniques
and instrumentation in analytical chemistry. Amsterdam, The Netherlands: Elsevier, 1993.
Haghi AK, Carvajal-Millan E. Food composition and analysis: methods and strategies. Oakville, ON:
Apple Academic Press Inc., 2014.
Marsili R. Flavor, fragrance, and odor analysis, 2nd ed. Boca Raton: CRC Press, 2012.
Namiesnik J, Szefer P. Airborne measurements for environmental research: methods and
instruments. Weinheim, Germany: Wiley-VCH Verlag GmbH & Co. KGaA, 2013.
Pico Y. Chemical analysis of food: techniques and applications publisher. Waltham, MA: Elsevier Inc.,
2012.
Quevauviller P, Maier EA, Griepink B. Quality assurance for environmental analysis. Method
evaluation within the measurements and testing program (BCR). In Techniques and
instrumentation in analytical chemistry. Amsterdam, The Netherlands: Elsevier, 1995.
Seifert B, van de Wiel HJ, Dodet B, O’Neill IK. Environmental carcinogens, methods of analysis, and
exposure measurement. Int Agency Res Cancer, Lyon, France 1993;12:109.
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