Ana M.

Botana
9 Analysis of environmental toxicants

9.1 Introduction

The movement and fate of environmental contaminants are key aspects to deter-
mine their impact in the environment. As a general principle, the transportation
and fate of contaminants is controlled by their physical transport and reactivity.
It involves either chemical or biochemical reactions or other physical interac-
All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under U.S. or applicable copyright law.

tions with other phases, therefore those chemicals released into the environ-
ment rarely remain in the form, or at the location, of release. Figure 9.1 shows
the main ways involved in transport and chemical fate. Most often, those sub-
stances are originated in the anthroposphere and they can pass to the air, earth,
water (either surface or ground waters), sediments, and to the biota (plants and
animals).
The dilution of the toxicant in question as well as transfer among living creatures
can happen and therefore concentration or bioaccumulation takes place, while at the
same time most transport between environmental phases results in wider dissemina-
tion; for instance, lipid-soluble toxicants are readily taken up by organisms following
exposure in air, water, or soil. They can persist in the tissues long enough to be trans-
ferred to the next trophic level, unless they are quickly metabolized. At this moment,
if the organism is more susceptible than those at the previous level, the toxicant can
become deleterious.
In order to study toxicants from the point of view of the analytical methodolo-
gies to identify them, it is convenient to classify them according to their chemical
behavior. However, no single classification method is applicable for the entire
spectrum of toxic agents present in the environment. In this chapter the classi-
fication is based on the analytical behavior of toxicants due to the fact that toxi-
cants can be grouped according to the analytical procedures involved to measure
them. In the Stas-Otto scheme [1], toxicants have been divided into the following
groups:
(a) Volatile toxicants, e. g., hydrocianic acid, alcohols, acetone, phenol, chloral
hydrate.
(b) Extractive toxicants:
(i) Toxicants extractable by ether from acid solution, e. g., organic acids, nitro
compounds.
(ii) Toxicants extractable by ether from alkaline solution, e. g., alkaloids.
(iii) Metals and metalloids, e. g., copper, mercury, zinc, silver, antimony.
Copyright 2018. De Gruyter.

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Account: s1229929.main.eds
 9 Analysis of environmental toxicants 247

Air
(atmosphere)
er
at r
W pou Pa
va O rtic
2,
SO ula
2 te m
at
er
ia
l,

en
yg
Ox

Water Humans
(hydrosphere) Environment (anthroposphere)
Wa cium
cal

,
ass
ter sal

iom
, bi ts
car

fee ewab s,
le b
e
bo

ren ticid
nat

Pes

ds
es ,

Earth Living organisms

(geosphere) (biosphere)
Plant nutrients

Figure 9.1: Interchange of some environmental toxicants delivered between anthroposphere and the
other environmental sections that are involved in chemical fate.

9.2 General guidelines of chemical analysis in the environment

Chemical analysis of toxicants in the environment can be carried out in two dif-
ferent ways, depending on: weather toxicants are in high concentrations or in low
concentrations. The second possibility is worth looking at in much detail, because
the analytical procedures involved will be much more complex. In order to be able to
determine very small amounts (very low concentrations) of chemicals in the environ-
ment, it is necessary to follow a series of operations (Figure 9.2):
1. isolation (extraction and separation) of the chemicals of interest from sample
matrix (air, water, sediment, living beings, etc.)
2. separation and purification of the chemical of interest from other co-extracted
chemicals (sample cleanup)
3. if necessary, sample concentration
4. measurement by highly selective and sensitive analytical equipment.

Occasionally, it is also necessary to derivatize (chemically modify) the chemicals of

interest prior to their analysis.
Within the broad range of instrumental methods used in environmental analysis,
there are three methods which are the most commonly implemented ones, namely:

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 248 Ana M. Botana

Sampling

Measurement

Extraction
(if required)

Clean-up
(if required) Sample concentration

Figure 9.2: General guidelines in chemical analysis of environmental samples.

atomic spectrometry, GC, and LC. The following section describes the series of opera-
tions in more detail, focusing on these three groups of instrumental methods.

9.2.1 Isolation (extraction and separation)

The methods for separation of toxicants depend on the type of sample, and in this
section samples are divided into three types: water samples; sediment, soil, and bio-
logical samples; and air samples. In Figure 9.3 the extraction and separation methods
regarding the type of sample are shown.

9.2.2 Separation and purification

Extracts from environmental samples can be complicated mixtures. Components of

these mixtures can interfere with the analytical methods to be used, especially in
the case of GC and LC analyses by giving poor separation because of over separation

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 9 Analysis of environmental toxicants 249

Extraction / Separation Methods

Type of sample Method

Selection of extraction method: based on molecular weight, boiling point and polarity

Purge & trap method

Volatile organic compounds
Headspace method

Water
Liquid-liquid extraction
Semi-volatile chemicals Solid-phase extraction (SPE)
Solid-phase microextraction (SPME)

Purge & trap method

Sediment, soil and
Soxhlet extraction
biological samples
Organic solvent extraction method Extraction after mechanical mixing
Ultrasonic extraction
Steam distillation

Supercritical fluid extraction (SFE)

Solvent extraction from filter papers or adsorbents

Air samples
Thermal desorption

Figure 9.3: Extraction and separation methods regarding the type of sample.

capacity of a column or by containing compounds that elute at the same time as the
peaks of the compounds of interest. It is, therefore, necessary to clean up, or remove,
those co-extracted compounds as much as possible. Cleanup methods include
acid-alkaline partition, acetonitrile-hexane partition, and column chromatography.
Column chromatography separation can involve adsorption, partition, gel permea-
tion, ion exchange, etc. Figure 9.4 summarizes all the possibilities.

9.2.3 Sample concentration

When sample needs to be concentrated, either a concentrator (like a Kuderna-Danish

concentrator) or rotary evaporator can be used: it depends on the boiling point of the
compounds of interest, their sublimation character, timeframe for analysis, etc.
The concentration setup takes longer than the evaporation setup, and is appli-
cable to low-boiling point compounds as well as to high-boiling point compounds.
The rotary evaporation can concentrate large volumes of samples in a relatively
short period of time, although it causes big evaporative losses and is not suitable for
low-boiling point compounds. However, for further concentration one must use a
micro-column or evaporate under a stream of nitrogen.

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 Acid-alkaline partition
250

Silica gel
Acetonitrile-hexane partition

Adsorption chromatogrphy
(relatively non-polar compounds) Florisil
Sulfur-cleanup
Ana M. Botana

Alkaline decomposition Alumina

Partition chromatogrphy
(high polarity compounds)

Column chromatography

Gel permeation chromatography

(semi-volatile compounds)

Ion-exchange chromatography
(fully ionisable function groups)

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Figure 9.4: Clean-up methods to be used after extraction in environmental samples.
 9 Analysis of environmental toxicants 251

9.2.4 Measurement: Instrumental analytical methods

Modern instrumental techniques of analysis are essential for determining envi-

ronmental toxicants. We are in a very exciting period in the evolution of analytical
chemistry, where the development and optimization of new and improved analyti-
cal techniques are taking place. They allow the detection of much lower amounts of
chemical compounds and so it is possible to determine contaminants that would not
have been possible to detect otherwise. Although it is quite common in literature to
find the instrumental method of analysis related to some specific type of samples,
in this chapter the analytical techniques are described as well as their properties: in
each case the nature of samples that may be analyzed is mentioned.
There are three important groups of analytical techniques to take into consideration:
atomic spectrometry, GC, and LC. A better sensitivity is acquired in many cases with the
use of hyphenated techniques, therefore they will also be mentioned in each group.

9.3 Atomic spectrometry

Atomic spectrometry studies those elements that can be analyzed as atoms. Out of
118 identified elements, about 91 of them are called metals. These metallic elements
are traditionally analyzed with this group of techniques and can be divided into two
classes: those that are essential for survival, such as iron and calcium, and those
that are nonessential or toxic, such as cadmium and lead. These toxic metals, unlike
some organic substances, are not metabolically degradable and their accumulation
in living tissues can cause death or serious health threats. Furthermore, these metals,
dissolved in wastewaters and discharged into surface waters, will be concentrated as
they travel up the food chain. Eventually, extremely poisonous levels of toxins can
migrate to the immediate environment of the public. Metals that seep into ground-
waters will contaminate drinking water wells and harm the consumers of that water.
Pollution from manmade sources can easily create local conditions of elevated pres-
ence, which could lead to disastrous effects on animals and humans. Actually, man’s
exploitation of the world’s mineral resources and the technological activities tend
to unearth, dislodge, and disperse chemicals, particularly metallic elements, which
have recently been brought into the environment in unprecedented quantities and
concentrations and at extreme rates.
Heavy metals can be defined in several ways. One possible definition is the fol-
lowing: heavy metals form positive ions in solution and they have a density five times
greater than that of water. They are of particular toxicological importance. Many
metallic elements play an essential role in the function of living organisms. Humans
receive their allocation of trace elements from food and water, an indispensable link
in the food chain being plant life, which also supports animal life. It is well estab-
lished that assimilation of metals takes place in the microbial world as well as in

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 252 Ana M. Botana

Atomic Spectrometry

Atomic
absorption
X-ray
spectrometry

Atomic
emission
Air Water

Inductively
coupled plasma
mass spectrometry
Soils, plants
Geological and related
Vapour materials
generation materials
methods
Mass
spectrometry

Laser-induced
Atomic breakdown
fluorescence spectroscopy

Figure 9.5: Different techniques that are in use nowadays for environmental samples.

plants, and these elements tend to get concentrated as they progress through the food
chain. Imbalances or excessive amounts of a metal species along this route lead to
toxicity symptoms, disorders in the cellular functions, long-term debilitating disabil-
ities in humans, and eventually death.
Due to the different routes of metals in the environment, the samples to be ana-
lyzed are also very different and so are the methods of analysis. Figure 9.5 gives a
coarse idea of the different techniques in use nowadays depending on the type of
sample and Table 9.1 summarizes the samples related to specific techniques.

9.4 Gas chromatography

There are many research works on GC in different analytical and toxicological fields
and the methods are increasing in sophistication to identify and quantify environmen-
tal pollutants adequately. They can be distributed and dispersed by different means
as we already know: it can be via water, soils, food, industrial activities, air, etc. Due
to environmental persistence they remain in nature and are subject to bioaccumu-
lation, which make them very hazardous compounds. This is more difficult because
these compounds are present at trace concentrations [2]. Thus, the accurate determi-
nation of trace level toxicants is a demanding analytical task. GC is one of the most

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 9 Analysis of environmental toxicants 253

Table 9.1: Summary of the techniques in use nowadays regarding the type of sample.

Technique Sample

Atomic absorption spectrometry Air; water; soils, plants and related materials; geological
materials
Atomic emission spectrometry Air; soils, plants and related materials; geological
materials
Vapour generation methods Water
Atomic fluorescence spectrometry Air; soils, plants and related materials
Laser based spectroscopy Water
Laser-induced breakdown spectroscopy Soils, plants and related material
Mass spectrometry Air
Inductively coupled plasma mass Water; soils, plants and related materials; geological
spectrometry materials
Other mass spectrometric techniques Geological materials
X-ray spectrometry Air; water; soils, plants and related materials; geological
materials

frequently used techniques to analyze volatile and semivolatile organic compounds.

In this sense, some major environmental pollutants are: polychlorinated dioxins and
dibenzofurans, polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons,
polybrominated diphenyl ethers, toxaphenes, organochlorines, pesticides and their
major metabolites.
The toxicants have to be separated from co-extracted materials, which is difficult
in case of complex matrices as is the case with most environmental samples: there
are many closely related anthropogenic compounds present at orders of magnitude
of higher concentrations. Therefore, the analytical methods have to be very sensitive
and selective and this is what chromatographic methods have been developed for.
Figure 9.6 shows a selection of different GC techniques that have been applied in envi-
ronmental toxicant analysis.
One-dimensional GC (1-D GC) was the main method for the determination of envi-
ronmental toxicants and in many laboratories, this is still the preferred or available
method. However, for analyzing complex pollutant mixtures this single-column GC
technique has remarkable drawbacks such as: lack of resolution, lack of robustness,
and uncertainty in the identification. It is almost impossible to separate all compo-
nents in a single chromatographic run, because the peak capacity of the column in
the region where the components must be eluted is exceeded; so, to improve res-
olution several solutions need to be applied, like the use of a longer or narrower
column, or a combination of both. To analyze dioxins a very long column would be
required in order to separate quite a big number of compounds, although several
critical pairs still exist within this group [3, 4]. On the other hand, the determination,
for instance, of individual congeners and atropisomers in PCBs is perhaps one of the

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 254 Ana M. Botana

Single column GC-MS

Multidimensional Analysis

One-dimensional GC: Comprehensive two-dimensional

GC-FID (Flame Ionization Detector) gas chromatography
-ECD (Electron Capture Detector) (GCxGC)
-etc.

Gas Chromatography

GC-HRMS (High Resolution MS Dual column GC (MDGC)

methods) MDGC-HRMS MDGC-MS

Figure 9.6: Gas chromatographic techniques that are used in the analysis of environmental
toxicants.

most difficult applications in environmental analysis of PCBs. One way to improve

identification is by using the hyphenated technique of GC-MS: GC coupled to a mass
spectrometric detector; but it still has problems as it is not possible to distinguish
co-eluting congeners with the same chlorine number. They have the same or very
similar mass spectra.
A different way to improve separation and therefore identification is to run
the sample in two columns of different polarity to obtain a second set of retention
times [5], although in this case it is not still possible to get a complete resolution when
different polarities and efficiencies of both columns are optimized.
One alternative to improve separation is by fitting in parallel traps, columns,
valves, flow switches, etc., but all this will only lead to longer analysis times and tech-
nical difficulties. Another way is by using the corresponding analytical procedure to
clean up the sample prior to its separation by GC, which will lead to a cleaner sample
and therefore less compounds present to interfere. Although it must be made many
times when the samples are complex, it is also convenient to reduce these steps to a
minimum as it is time-consuming, and difficult to automate and reproduce. It is also
difficult to get good recoveries with these steps and the samples are susceptible to be
contaminated when working at trace levels.
A different alternative to reduce the sample handling steps and increase resolution
is the use of multidimensional gas chromatography (MDGC). It is based on the sepa-
ration that takes place in two or more independent separation steps/mechanisms [6]
and the components remain separated until the overall analysis is completed; there-
fore it becomes the only practical alternative to increase resolution. Although GC-MS
might be considered a good alternative, there is still isomer co-elution because the
separation takes place in one single column so that MDGC will be a valuable tool to
improve or completely separate complex mixtures of toxicants [7].

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 9 Analysis of environmental toxicants 255

Second detector
First detector
Injector

first column second column

First oven Second oven

Figure 9.7: Typical schematic diagram of a MDGC setup.

A typical schematic diagram of a MDGC setup is shown in Figure 9.7. As can be seen,
it consists of two independent ovens and detectors, a T-piece allows quantitative and
reproducible transfer of small, unresolved selected fractions of the eluate from the
first column to the second column, where separation takes place.
All types of detectors can be used for two-dimensional GC, like electron capture
detector and the MS, operated in the selected/single-ion monitoring (SIM) mode
because of their high sensitivity and specificity, for organohalogen analysis.
The resolution of a MDGC system is determined by the column(s)’ dimensions and
the difference in separation power between the two stationary phases. The longer the
columns and the smaller internal diameters, the better the separation. A key aspect is
the difference in selectivity for the two columns, which will remarkably affect the final
separation; for instance, if polarity is quite different for both stationary phases it may
be expected to improve separation.
Some of the applications of MDGC analysis are tabulated in Table 9.2. There are
hundreds of papers published on this topic when MDGC technique is used, so this list
is just indicative of the need to use it to improve resolution in separation for volatile
compounds in environmental analysis. A common goal in all the research is the reso-
lution in specific congener analysis and the isolation of the components of interest for
subsequent measurement of chiral ratios [8].
Although MDGC has many attractive points of interest, it is not the only tech-
nique used for analysis of volatile and semivolatile contaminants. The lack of robust-
ness has restricted its use in routine laboratories where 1-D GC is still used. On the
other hand, it has the relevant limitation that its increased separation power can only
be applied to a few regions of the chromatogram, rather than to the whole sample.
Thus, in many cases analysis of environmental toxicants is based on GC followed by

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 256 Ana M. Botana

Table 9.2: List of analysis of some environmental toxicants employing multidimensional gas
chromatography.

Environmental toxicants studied Analysis goals

Organophosphorus pesticides Identification of pesticides in food

Halogenated and organophosphorus Identification of pesticide residues in food samples
pesticides employing two columns of different polarity
PCBs Analysis of PCBs congeners using column switching
Non-ortho-chlorinated CBs Showed analysis of samples without preseparation will
underestimate planar CB concentration
TCDD isomers Detection of complex isomeric mixtures of TCDDs
Polychlorinated dibenzo-p-dioxins Study of gas-phase photodegradation of PCDDs; MDGC
toxaphene interfaced to photoreactor analysis of technical toxaphene
mixture containing many congeners and biological samples
Polycyclic xenobiotics Detection of the enantiomer ratios of polycyclic xenobiotics
Dioxins, PCBs Determination of dioxins and PCBs

(high-resolution) mass spectrometric detection [9]. The mass spectrometer is often

the detector of choice in MDGC as well because it can operate in a universal detection
mode (similar to a flame ionization detector) and in a specific ion mode, the latter
property being of particular importance for the analysis of a specific target compound.

9.5 Liquid chromatography (LC)

It is a fact that there is an overwhelming number of chemicals in use in the world, there-
fore they are affecting all environmental areas and the ecosystems where they enter.
As it has already been mentioned at the beginning of this chapter, the transformation
products of these chemicals or their metabolites can alter even more the environmental
balance. The number of organic micropollutants increases and their eco-toxicity can be
comparable or even higher than that of the original compound [10, 11]. The problem at
this stage is that, when this happens, their chemical structures and toxicological effects
are not completely known; so, it is important to develop analytical strategies to monitor
as many chemicals as possible and trace their fate in the environment.
The first list of priority pollutants created by the EPA (US Environmental Protec-
tion Agency) contained analyzable compounds by GC-MS; however, since the late 80s
the hyphenated technique LC-MS has grown very quickly to determine and control
environmental toxicants. It offers a series of advantages with regard to the chemical
nature of those compounds, because most of them are polar organic contaminants:
compared to GC-MS, it is possible to avoid the step of derivatization for those nonvol-
atile compounds, it increases the number of pollutants that is possible to analyze and
reduces the total analysis time [12].

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 9 Analysis of environmental toxicants 257

A total of 700 substances have been categorized into 20 classes (NORMAN network)
in the European surface waters. The most relevant classes are: pesticides, pharma-
ceuticals, disinfection by-products, wood preservation, and industrial chemicals. In
general, there are several groups of compounds that emerged as particularly relevant:
– Algal and cyanobacterial toxins
– Brominated flame retardants
– Disinfection by-products
– Hormones and other endocrine disrupting compounds
– Drugs of abuse and their metabolites
– Organometallics
– Organophosphate flame retardants and plasticizers
– Nanomaterials (nanoparticles)
– Perfluorinated compounds
– Pharmaceuticals and personal care products
– Polar pesticides and their degradation/transformation products
– Surfactants and their metabolites

However, the different physicochemical properties of those compounds make impos-

sible to develop one method to screen and determine all, as well as their degradation
products. The scientific community needs to take up the challenge to develop more
advanced instrumentation, to search for new chromatographic materials and to make
more effective analytical approaches. Since the impact on aquatic life and human
health can be dramatic, a rigorous evaluation of analytical methodology is crucial for
contaminants that can compromise flora, fauna, and public health integrity.
Simple and fast sample treatments have been developed to extract and analyze as
many compounds as possible simultaneously, in the last years: the main objective has
been to save time, expense, and labor. As different pollutants have different physico-
chemical properties, a balance must be found between handling “dirty” extracts and
accepting low recoveries; on the other hand, in case of samples like aqueous ones con-
taining pesticides and drugs, which are very polar and hydrophilic, it has been neces-
sary to lyophilize and evaporate under reduced pressure to enrich them. However, con-
ventional offline SPE on discs and cartridges has still been the most common and used
technique due to its high simplicity and flexibility for many different samples. The clas-
sical materials for SPE include: C18, graphitized carbon black, N-vinylpyrrolidone-di-
vinylbenzene copolymers, mixed mode cation-exchange cartridges, mixed mode ani-
on-exchange cartridges, weak anion-exchange cartridges and many others. Therefore,
depending on the compound a different sorbent is chosen which allows to obtain high
recovery percentages and enrichment factors. They vary between 20 and 1,000.
In the last years, research has been focused on the development of nanomate-
rials (carbon nanostructured materials, metallic nanosized structures, and metal
organic frameworks) because of their potential as sorbents in SPE operations either
on conventional or miniaturized scales. Their properties of chemical stability;

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 258 Ana M. Botana

thermal, mechanical, and electronic properties [13–15], as well as their large surface
area and durability make them suitable for a broad variety of environmental appli-
cations. Fullerenes, nanotubes, nanofibers and graphene are the carbon nanostruc-
tured materials where more research is developed. They show a very good affinity
for hydrophobic compounds, especially aromatic compounds that strongly interact
with their graphitic portion. They are also very good for polar compounds, because
a preliminary oxidizing treatment introduces polar functionality (hydroxyl, carboxyl,
and carbonyl groups) and makes them suitable to interact with polar compounds and
for chemical derivatizations [16, 17]. These materials, oxidized or not, can be used in
generic sample treatments to extract a large number of organic micropollutants, and
with an adequate functionalization they can change their selectivity in a dramatic
way, thus becoming specialized sorbents for specific methods of interest.
As an example of the goals accomplished, here is the description of the analysis
of a group of marine toxins that are a serious problem in environmental analysis:
STX and analogs. They are commonly known as PSP (paralytic shellfish poisoning)
toxins, and are rather common worldwide and the most lethal of marine toxins intox-
ication. They are a group of more than 21 tetrahydropurines, usually quantified by a
semiquantitative MBA [18], which is the reference method internationally accepted in
monitoring programs. The chemical methods used to determine PSP toxins are fluori-
metric assays, HPLC with fluorimetric detection (either pre-column or post-column
oxidation), LC-MS, and capillary electrophoresis methods.
The HPLC methods are widely used to quantify PSP toxins present in seafood
samples, but they are also useful in providing the PSP profile because in chromatogra-
phy it is possible to identify each toxin as well. These toxins have only a weak chromo-
phore group and it should be modified before detection: when they are oxidized in
an alkaline solution, a purine is formed that becomes fluorescent at acidic pH. This
reaction can either be a pre-column or post-column one, and obtained purines are
monitorized with a fluorescence detector. Figure 9.8 describes the general outline of
these two procedures, where in the post-column method different types of columns
have been used (1 and 2 options in the scheme) [19, 20].
Pre- and post-column HPLC methods present as advantages a high sensitivity
for low concentrations and low variability for results; but their drawbacks are also
important. In the case of hydrophobic analogs, they are retained by C18 resins [21];
therefore, HPLC methods do not allow determining their presence in monitoring pro-
grams [22, 23]. LC-MS methods are actually being developed to get a good charac-
terization of these compounds, hence it is recommended that the presence of PSP
toxins is confirmed by MS. However, the use of reversed-phase conditions, which gen-
erally consist of some organic solvent and nonvolatile salts, is not suitable for LC-MS;
mobile phases with phosphate content as well as ion-pair formers are a handicap for
an efficient application of the LC-MS technique. Therefore, the application of ionic
exchange chromatography with eluents containing only volatile compounds to quan-
tify PSP toxins either with fluorimetric or MS detection has been proposed.

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 9 Analysis of environmental toxicants 259

PSP toxins analysis

Bioassay LC-MS/MS

HPLC-
FLD
Pre- PCOX
Cox

Extraction Extraction
1 2

SPE-C18 Deproteination Deproteination

cleaning SPE-COOH
cleaning

peroxide periodate three STX-GTX

oxidation oxidation different C toxins toxins
fractions

graphitized
periodate carbon column C8 column C18 column
oxidation separation separation separation

LC LC LC
separation separation separation Post- Post- Post-
column column column
oxidation oxidation oxidation
FLD FLD FLD
detection detection detection FLD FLD FLD
detection detection detection

Figure 9.8: General outline of the pre-column and post-column oxidation procedures to determine
PSP toxins by HPLC.

Nowadays, environmental analysis is one of the most important application areas of

LC-MS, mainly related to the study of occurrence and fate of organic micropollutants,
that have been neither considered as a risk nor included in national monitoring plans
so far. Figure 9.9 provides a coarse idea of the wide application range of LC-MS and
how it is the technique of choice for analysis of most of these compounds.
In the last years, there has been a growing interest in the development of
high-throughput, robust, and sensitive chromatographic methods, regardless of the
specific research area. Ultra-high performance liquid chromatography (UPLC) tech-
nology is one of them, and it only dates back to 2004. It can deliver the mobile phase
at pressures up to 1,000 bar, allowing columns packed with very small particles
(17–18 μm) to reach their theoretical performance. Stationary phases based on sub-
2-mm particles enable elution of analytes in much narrower and more concentrated
bands, resulting in better chromatographic efficiency, resolution, and sensitivity with
negligible intra-column band dispersion. Compared to HPLC, this extra efficiency
occurs at a higher flow rate and can be achieved in a shorter analysis time. UPLC
columns with sub-2-μm porous particles have already successfully been employed to
speed up the analysis of a large variety of organic micropollutants in environmental

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 260

Lipid Surfactants Chelating agents

Estrogens Tranquilisers Antiepileptics B-blockers Antibiotics
regulators TPBS, ABS, EDTA, NTA, DTA

NONVOLATILE
LAS, APEO

Urea,
Nonsteroidal
Ana M. Botana

carbamate and Perfluorinated compounds

anti-inflammatory X-ray contrast
triazine pesticides PFOS, PFOA
drugs media

VOLATILITY
Benzotriazoles

Benzothiazoles
Methyl tert-butyl ether
MTBE

VOLATILE

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LIPOPHILIC POLARITY HYDROPHILIC

Figure 9.9: LC-MS and some of its applications.

 9 Analysis of environmental toxicants 261

samples: drugs [24, 25–27, 28] personal care products [25], pesticides [11, 25, 29, 30, 31,
perfluorinated compounds [32], and endocrine disruptors [33, 34].

Keywords: atomic spectrometry, gas chromatography, liquid chromatography,

metals, volatile compounds, non-volatile compounds

Abbreviations: 1-D GC: one-dimensional gas chromatography; CBs: chlorobiphenyls;

EPA: Environmental Protection Agency; GC: gas chromatography; GC-ECD: gas
chromatography with electron capture detector; GC-FID: gas chromatography
with flame ionization detector; GCxGC: comprehensive two-dimensional gas
chromatography; GC-HRMS: gas chromatography coupled to high resolution mass
spectrometry; GC-MS: gas chromatography-mass spectrometry; HPLC: high-pressure
liquid chromatography; LC: liquid chromatography; LC-MS: liquid chromato-
graphy-mass spectrometry; MBA: mouse bioassay; MDGC: multidimensional
gas chromatography; MDGC-MS: multidimensional gas chromatography-mass
spectrometry; PCBs: polychlorinated biphenyls; PCDDs: polychlorinated dibenzo-
dioxins; PSP: paralytic shellfish poisoning; SFE: supercritical fluid extraction; SIM:
single-ion monitoring; SPE: solid-phase extraction; SPME: solid-phase microext-
raction; TCDD: tetrachlorodibenzodioxin

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