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Sampling of water, soil and sediment to trace organic pollutants at a river-

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Anal Bioanal Chem (2006) 386: 1075–1088
DOI 10.1007/s00216-006-0486-2
REVIEW
Alain Hildebrandt . Sílvia Lacorte . Damià Barceló
Sampling of water, soil and sediment to trace organic pollutants
at a river-basin scale
Received: 17 February 2006 / Revised: 4 April 2006 / Accepted: 7 April 2006 / Published online: 24 May 2006
# Springer-Verlag 2006
Abstract Sampling is considered a crucial step in the
analysis of organic compounds in the environment. This
review describes field sampling techniques and provides
detailed step-by-step procedures for collection and pre-
servation of all major environmental matrices (water,
sediment and soil) integrated as part of the river-basin
water cycle. Attention is given to the prerequisites for
obtaining reliable samples, and the practical issues of
sample collection (planning, field sampling, sampling
strategies and equipment and data quality assessment)
are considered. Considering the heterogeneity of environ-
mental matrices, special considerations for each matrix
are given to solve typical problems and to find the
most appropriate solutions to ensure the quality of the
sample. The procedures described in the next sections
are commonly used protocols that reflect true field con-
ditions and current state-of-the-art techniques used in the
sampling of organic compounds. The aim is to signify
the importance of sampling to the overall analytical pro-
cedure. Finally, quality control issues to be considered in
environmental sampling are given.
Keywords Sampling . Environment . Trace . Organic .
Pollutant
Introduction
Within monitoring river-basin programs, continuous track-
ing of the main environmental parameters constitutes a
method of evaluating the state of the local environment.
River basins are dynamic systems that can vary according
to catchments and water flows, and they depend on the
inflow of their effluents and climatic conditions. Due to the
A. Hildebrandt . S. Lacorte (*) . D. Barceló
Department of Environmental Chemistry,
IIQAB-CSIC Jordi Girona 18–26,
08034 Barcelona, Spain
e-mail: slbqam@iiqab.csic.es
Tel.: +34-934006169
Fax: +34-932045904
urban, industrial and agricultural activities that commonly
take place along rivers, most river basins are exposed to
diffuse pollution due to the release of compounds that
might be persistent, toxic and deleterious for the environ-
ment. To control the quality of river basins, monitoring
programs have been established for many years, with their
main objective to determine target compounds responsible
for low water quality, identify non-target compounds that
could be potentially toxic for the environment, and thresh-
old levels and environmental processes that affect the
final fate of contaminants within a river basin. Monitoring
programs begin with the establishment of a list of priority
pollutants and other toxic compounds; measures to limit
the presence of a toxic compound in the different com-
partments; or the designation of maximum levels (accord-
ing to directives), action levels (to detect levels above
background, identify sources and pathways of contami-
nation and determine interactions with environmental
levels) or target levels (to indicate the levels to be achieved
to decrease human/environmental exposure). Monitoring
programs not only operate in emergency situations but may
remain permanently active from the outset. This makes it
possible to detect potentially critical situations and plan
appropriate measures for the protection of the local pop-
ulation and the environment.
To study the health of a river basin, all interrelated
matrices should be considered, since the physico-chemical
properties of each contaminant will determine its compart-
ment distribution. Parameters that should be taken into
consideration prior to sampling are the polarity of target
compounds, solubility, vapor pressure, Henry’s constant,
octanol-water partition coefficient (Kow), octanol-organic
carbon partition coefficient (Koc), acid–base constant,
compound half-life and GUS index. Such information
will be useful to establish the most likely compartment to
be monitored for a specific chemical compound or family.
Water is the main actor in the river basin transport of
pollutants through the mechanisms of the “water cycle.”
Only the part of the water cycle directly in contact with the
land will be discussed here, that is surface water (streams,
rivers, lakes and dams), wastewater [wastewater treatment
Table 1 Environmental sampling devices: strengths and weaknesses
1076

Sampling device Construction Strengths Weaknesses Use

Water Simple bottle Glass Simple, inexpensive, easy to clean Fixed capacity, breakable, no depth control All water types
Syringe Glass Simple, inexpensive Little sample volume, breakable, All water types
no depth control
Simple bottle SS Simple, easy to clean, unbreakable Fixed capacity, no depth control All water types
Kemmerer bottle Teflon and/or SS Vertical sampling profile Fixed capacity Groundwater, lakes
and dams
Van Dorn bottle Teflon and/or SS Horizontal sampling profile Fixed capacity, heavy Rivers
Pumps SS + tubing material Continuous sampling, large volume Possible loss of VOCs; All water types
complex clean or purge
SPMD Hydrophobic membrane, Commercially available, well-tested Susceptible to biofouling All water types,
hydrophobic filling passive sampling
Chemcatcher C-18 Empore disks Commercially available, well-tested Scarcely used in in situ sampling All water types,
or other sorbents passive sampling
Dialysis membrane Hydrophilic membrane, No biofouling Poor sensitivity for strong All water types,
hydrophobic filling hydrophobic compounds passive sampling
Soil Spoon/shovel SS Simple, inexpensive, easy clean Uncharacterized sample All soil types, subsampling
Ring SS and/or Teflon Simple, inexpensive, easy clean Little sample volume All soil types,
results per area units
Auger type, corer SS Simple, inexpensive, easy to clean, Little sample volume Exist for each soil type
may sample undisturbed soil
Little corer SS and/or Teflon Simple, inexpensive, single use, Very little sample volume Sampling for VOCs
or PVC sample undisturbed soil
Probes, long corer SS Simple, inexpensive, easy to clean, Depth sampling All soil types
may sample undisturbed soil
Sediment Spoon SS Simple, inexpensive, easy to clean Fine material may wash out, Streams, shallow rivers
little sample volume
Van Veen, Ponar, Petersen SS Simple, easy to clean Poor jaw shape, stones and branches Calm waters
may interfere with jaw closure
Ekman SS Simple, low sample disturbance Small sample Calm waters
Shipek SS Low sample disturbance Heavy, may need mechanical help/boat All sediment types
Box SS Low sample disturbance, Heavy, bulky, may need mechanical help/boat All sediment types
large sample size
Corer SS and/or Teflon Simple, inexpensive, easy to clean, Difficulties in sampling sands Shallow waters
undisturbed profiles
Gravity corer SS Undisturbed profiles Heavy, difficulties when sampling sands All sediment types
Vibro-corer SS Undisturbed profiles Heavy, difficulties when sampling sands, All sediment types
needs power supply
Table 2 Environmental sampling devices: uses and authors
Sampling device Construction Sampled matrix Target compounds Reference

Water Subsurface grab device Glass River Pesticides and chlorophenols [25]
Subsurface grab device Glass, PET, PE Drinking water Phthalic esters and endocrine-disrupting compounds 26
Subsurface grab device Polypropylene River (15 cm below surface) PFOS and PFOA (polyF) 27
Subsurface grab device Teflon and glass River (1 m below surface) Pharmaceuticals [28]
Subsurface grab device SS River Pharmaceuticals and pesticides [29]
Niskins bottle SS River VOCs [31]
Syringe (and tubing) Glass (and nylon) Groundwater PAHs, BTEX and OC [30]
Pump SS and PVC Groundwater PAHs, BTEX, OC, alkylBzs and others [23]
Multilevel well Polyethylene Groundwater MTBE, BTEX and other VOCs [36]
Dosimeter (passive sampler) Ceramic, Teflon and Groundwater PAHs, BTEX and OC [30, 44]
an unspecified sorbent
POCIS (passive sampler) SS and a sorbent (Oasis HLB; River Estrogenic compounds [51]
Isolute Env+ and Ambersorb 1500)
SPMD (passive samplers) SS and an unspecified sorbent Wastewater from WWTP 4-Methylbenzylidene camphor [46]
Soil Core surface grab Unspecified Wild/background soil (0–5 cm) PCBs, HCB and OC [56, 57]
Core surface grab Unspecified Seven different ecosystems (0–30 cm) Ergosterol [58]
Split-spoon sampler Unspecified Soils VOCs [61]
Surface grab Unspecified Soils (0–3 cm) PCDDs, PCDFs, PCBs and PCNs [62]
Sediment Gravity corer Unspecified Lake sediment OC [57]
Ekman grab SS River sediment (0–20 cm) Different organic compounds [64]
Ekman grab SS River sediment (0–10 cm) Phtalates [65]
Core sampler Unspecified River sediment (0–2 m) Different organic compounds [64]
Gravity corer Unspecified River sediment (0–50 cm) PCBs, DDTs and PBDEs [68]
PET Polyethylene terephthalate, PE polyethylene, PFOS perfluorooctane sulfonate, PFOA perfluorooctanoate, SS stainless steel, VOC volatile organic compounds, PAH polycyclic
aromatic hydrocarbons, BTEX benzene, toluene, ethylbenzene, xylenes, OC organochlorinated compounds, alkylBzs alkylbenzene compounds, MTBE methyl-tert-butylether, POCIS polar
organic chemical integrative sampler, SPMD semi-permeable membrane device, PCB polychlorinated biphenyls, HCB hexachlorobenzene, PCDD polychlorinated dibenzo-p-dioxin,
PCDF polychlorinated dibenzofuran, PCN polychlorinated naphthalene, DDT dichloro-diphenyl-trichloroethane, PBDE polybrominated diphenyl ethers
1077
1078
plants (WWTPs) along the basin], and interstitial water
entrapped in the soil and groundwater. Rain water and wet
deposition will not be considered in this review [1–3].
Water matrices are interconnected with soil and sediment,
and contaminants are distributed within these compart-
ments. The horizontal transport of contaminants is mainly
determined by surface water flows, and wastewater nowa-
days plays an important role as it might be the source of
contaminants through wastewater effluents. Within river
basins, sediments can act as a final drain of contaminants,
although processes of adsorption/desorption can take place
and remobilize organic contaminants. Similarly, ground-
water and interstitial waters reflect the quality of soil and all
activities performed. In the case of groundwater, its
monitoring is necessary to guarantee safe water, which is
used directly in many instances for drinking water or
irrigation.
This review will summarize existing sampling theory
and devices (see summary in Table 1) for monitoring trace
organic contamination within a river basin, placing
emphasis on the sampling of waters, sediments and soils.
Data on sampling protocols will be given (see summary in
Table 2). The review will focus on the sampling plan,
selection of monitoring points, cleaning protocols of the
sampling devices and types of sampling (grab, multilevel
and passive) for water, soil and sediment.
Sampling plan
Sampling is a critical part in analytical methods. If not
performed using adequate techniques and according to
specific objectives, the result of the analysis can have a
high bias. The sampling strategy should reflect the
composition of the environmental compartment. In addi-
tion, it should preserve the sample in order that the exact
concentration can be determined.
The design of the sampling plan is linked to the purposes
of the sampling and to the specific information one can
gather. The distribution of organic compounds can be
random, uniform, patchy, stratified or following a gradient
so it is recommended that preliminary testing be performed
to establish likely distribution. In addition, sampling can be
systematic, random or judgmental, and each will provide
different information. Also, sampling can be performed in a
Fig. 1 Sampling compartments
in a river-basin monitoring
qualitative or quantitative way. When the purpose of the
study is to have quantitative data of a sample, sampling
equipment must be accurately calibrated to avoid un-
certainties in the final results. This is especially important
when collecting samples for regulatory or legal purposes.
The sampling plan involves various decisions including
(1) the selection of sampling locations, (2) the frequency of
sampling, (3) the size of the sample, (4) the number of
samples, (5) the selection of the sampling devices, con-
tainers and their cleaning requirements, and (6) the type of
sample [discrete, composite, active (grab or multilevel) or
passive (diffusion)]. The sampling plan should be written,
and information about the sample procedures should be
compiled and used as feedback to the sampling plan [4].
Samples should be refrigerated and protected from light
to avoid photolysis during transport to the main laboratory,
where they will be stored and analyzed. The composition of
the sample should be preserved during transport and
storage, which means that biological action and the
hydrolysis of chemicals should be inhibited, and phenom-
ena such as volatility and adsorption should be avoided.
Additives can be used to stop these problems. Although
some authors consider the storage procedure as part of the
sampling, sample preservation will not be discussed
because methods are specific to each compound or
chemical class and/or analysis technique [5–7].
The sampling procedure depends on the matrix to be
studied and its homogeneity. In sampling protocols, a
homogeneous sample would be one in which the variation
within five samples collected within the same spot was less
than 20%. When homogeneity does not exist, sampling
strategy gains in complexity and that can occur for any type
of matrix.
The sampling plan depends on the compartment to be
analyzed, since some are easier to monitor than others (see
Fig. 1). For a long time, water has been the most studied
environmental matrix because it is easy to collect and
analyze. Water is itself usually very homogeneous, and
sampling should avoid problems related to the sampling
technology (cross-contamination, stagnant water in pipe-
lines, etc.). Sampling can be aimed at determining the
chemical quality of a representative water body, where
discrete sampling is performed over a specific period of
time/depth. Another possibility is sample compositing
(usually 24 h to 1 week), which will depend on the water

flow variability. Sample compositing is generally applied
to sample all waters where the physico-chemical properties
may vary with time or space, i.e. wastewater, surface water
and groundwater. At present, water sampling can be
performed with passive samplers, directed to determine the
accumulation of specific chemical classes of contaminants
in a water body over a period of time. The frequency of
sampling depends on the objectives to be achieved. The
size of the sample depends basically on the type of water,
the concentration of particulate and organic matter and
likely concentrations of compounds to be monitored.
Within a water matrix, suspended matter should be
analyzed when monitoring compounds with an octanol-
water partition coefficient (Kow) >103, and the dissolved
phase should be analyzed for compounds with Kow<104.
When sampling river water, which contains around
100 mg/L of particulate matter, 50–99% of organic
compounds with octanol-organic carbon partition co-
efficients (Koc) of 105–107 will be present preferentially
in particulate matter, so 1 or 2 L of sample would be
enough. In contrast, coastal waters have 1 mg/L of
particulate matter, thus only 1–50% of compounds with
Koc 105–107 will be present in particulate matter so the
amount of sampled water should be increased to 150 L to
detect organic compounds. In any case, it is recommended
at least duplicate samples be collected.
Soil sampling strategies involve a new degree of
difficulty, and efforts are taken to achieve the proper
sample representation of the soil body. Soils are easy to
collect; sampling tools are technologically simple com-
pared to water or sediment sampling devices. What is
complicated about soil sampling is its heterogeneity. Soil
sampling strategy involves in a higher degree of effort in
the soil selection, establishing square or polar grids in
fields to collect samples that are as representative as
possible of the whole field. When sampling locations have
been identified, the collection is usually very simple to
carry out. A later compositing should be carefully studied
in order xto maintain or enhance the sampling quality.
Compositing will depend more on a strategy focused on
specific objectives than on a standard way of working.
Again, the sample size will depend on the compounds to be
monitored. In general, organic-rich soils have a higher
tendency to accumulate organic compounds, thus the total
organic carbon (TOC) content should be measured when
studying soil samples and can help determine the amount
of soil needed to obtain limits of detection of environ-
mental significance. The lower the TOC, the lower will
likely be the presence of organic contaminants and the
larger the amount of soil to sample.
Of the three compartments reviewed here, sediments are
the most difficult to collect because they involve complex
technological devices, and the location of the sampling site
is often problematic. When a grab sample is needed,
relatively simple devices are available, but when an
undisturbed sediment sample that preserves the strata is
needed, the sampling technology increases in complexity.
On the other hand, sediments are more homogeneous and
therefore, sampling is generally performed once a year. The
1079
sampling period depends on the area and climatic
conditions, and for comparison purposes within monitoring
programs, samples should be gathered at the same period of
the year. In rainy periods, sediments can be remobilized
and transported, and this might affect the results obtained.
As with soils, the TOC of the sample should be recorded.
Generally, a sample of sediment corresponds to the pooling
of three to six discrete grab samples.
For all matrices indicated above, the sampling plan
should be conducted with the firm purpose of keeping the
representative sample free from any environmental distur-
bance, which is not always easy or feasible. When
sampling in the field, any information that can affect the
analytical results should be collected; this is critical since
the working plan will be based on the acquired knowledge.
Wrong initial decisions will make any result illegitimate
and spoil all sampling efforts. In addition, local knowledge
is indispensable in establishing a quality sampling plan by
screening analyses that will adjust the sampling criteria to
the field reality. One should bear in mind that a poorly
designed sampling plan produces biased information, not
representative of the environmental body to be monitored.
It is for this reason that a lot of efforts have been made to
establish protocols for the collection of samples with the
aim of preserving the environmental characteristics in a
tiny sample.
Quality control in sampling
Sampling is considered the most critical step in environ-
mental determination of organic contaminants. As with
analytical uncertainty, sampling uncertainty can be derived
from several sources but the main cause is contaminant
heterogeneity within environmental matrices due to the
specific distribution of each compound in a matrix as well
as due to the non-homogeneity of environmental matrices.
When few samples are used to characterize a heterogeneous
matrix, there is little confidence in the results, e.g., can the
results from a 1-g sample legitimately be extrapolated to
represent the concentration of a contaminant in an area?
Sampling uncertainty can be reduced by collecting more
samples from an area of interest and by concentrating
samples in those areas of greatest decision uncertainty.
Experience has demonstrated that decision uncertainty
for most sites is attributed to sampling uncertainty rather
than analytical uncertainty. Analytical uncertainty is
properly managed by using standardized laboratory pro-
cedures, with quality assurance/quality control procedures
and internal/external audits, which produce results of
verifiable analytical quality. However, sampling plans
aimed at reducing sampling uncertainty are usually too
costly for any regional/national monitoring program. The
reason is that the sampling uncertainty is generally
inversely proportional to the square root of the number of
samples, so to decrease the uncertainty by a factor of 10
requires a 100-fold increase in the sample numbers. This
means that the higher the number of samples, the better
the management of sampling uncertainties, the better the
1080
understanding of the distribution of contaminants and the
more accurate conceptual site models can be designed.
However, the sampling plan has to be cost-effective with
regard to the information to be gathered with minimum
uncertainty.
Another problem related to sampling uncertainty is
that in most cases, sampling plans are programmed in
such a way that sample numbers, locations and ana-
lytical methods to be used are pre-determined. However,
there is an uncertainty about the contamination status
in any given area, so it impossible to determine the
number of samples required and the specific sampling
location. This produces situations such as not identifying
contaminants where they are expected and vice versa.
This means that sampling plans should be revised regu-
larly to resolve these uncertainties.
Besides sampling uncertainties, quality control issues
are applied in sampling procedures to obtain accurate data.
For effective sampling, it is compulsory to select suitable
sampling devices and procedures, provide adequate train-
ing to sampling personnel and to design the sampling plan
so that environmental heterogeneity is minimized. Quality
control protocols in the sampling procedures should
include the following:
1. Routine tests on the effectiveness of the cleaning of
sample devices and containers. It should be verified
that the materials used during sampling do not cause
contamination of the sample, so laboratory tests should
be conducted prior to sampling and if contamination
problems appear, corrective actions should be under-
taken to optimize efforts and resources.
2. Field blanks to provide routine checks on contamina-
tion. Field blanks are samples of deionized water that
are taken to the field and treated in the same way as
environmental samples, from sampling to analysis.
Blanks of soils can be collected from remote sites
known to be away from contamination sources, but soil
characteristics would probably differ. Sediment blanks
are usually taken close to the source of the river.
3. Field check samples to provide routine checks on
sample stability. The concentration of target com-
pounds in storage media should be checked, either in
water, solid-phase extraction cartridges (or any adsor-
bent), or freeze-dried sediment or soil samples. The
check sample is prepared by dividing the problem
sample into two and spiking one of them to test the
recoveries in different conditions (temperature, light,
pH, etc) to optimize storage conditions.
4. Duplicate samples as an indication of sample uncer-
tainty. Collection of samples in duplicate can provide a
check on the contribution of sampling and handling to
overall random error.
With proper sample planning and effective sampling
procedures, and provided the analytical protocols are
under control, accurate and precise data regarding organic
contaminants in the environment can be measured, thus
making decision-making more powerful.
Sample contamination and equipment maintenance
Adsorption of organic pollutants to the sampling devices
and containers leads to contamination of the sample and
biased results. The degree of contamination depends on
the type of sampling material, the hydrophobicities and
concentrations of the contaminants and the contact time
between them. To avoid sample contamination, sampling
devices and containers should be carefully chosen ac-
cording to the matrix and compound to be monitored.
Cross-contamination can also lead to biased results. Cross-
contamination occurs when sampling devices are used
more than once. To prevent sample contamination, clean-
ing protocols and sampling procedures have been devel-
oped to assure and preserve the quality of the sample
during sampling.
When sampling for organic compounds, plastic materi-
als should be avoided since they contain phthalates and
other plastic additives that might migrate to the sample thus
contaminating it by interfering with the analysis of target
compounds. In addition, they are porous and lead to losses
of volatile compounds, and their surface facilitates micro-
bial colonization, leading to the degradation of target
compounds. When using glass containers, 10% of high
lipophilic compounds might be absorbed, thus it is
recommended to add up to 10% methanol to the sample.
Addition of 10% methanol is only recommended in
some cases and depends strongly on the organic compound
(it is not recommended for very polar and water-soluble
compounds) and analytical extraction procedures that
are performed afterwards (addition of methanol can
interfere with liquid–liquid extraction procedures). The
most common materials for the sampling of trace organic
pollutants in waters are as follows:
Borosilicate amber glass Glass is inert and has great
chemical stability; its weak point is its breakability. It is
usually used alone to sample from the bank of the stream
or inside a robust cage of stainless steel.
Stainless steel Samplers made of stainless steel are inert
and have great chemical stability, but high acidic con-
ditions might oxidize them.
Teflon Even though it is a plastic material, Teflon is inert
and has great chemical stability even in corrosive sit-
uations; its use is banned when polyfluorinated organic
compounds are among the studied analytes.
PET PET (polyethylene terephthalate) is a plastic polymer
known to be inert with non-corrosive water samples; very
light and break-resistant, it replaces glass when glass is
prohibited due to its high weight or breakability, or when
glass would interfere with sample analytes. PET can be of
amber type. The weak point of the PET that is almost
exclusively used for bottle manufacture is its photode-
gradability with time [8].
All of these materials are considered to not significantly
adsorb trace organic pollutants when there is a short contact

period (typically, under 15 min) between the sample and
the sampler [9, 10].
There are several cleaning protocols to remove traces of
organic contamination from these materials [11, 12]. For
decontaminating water-sampling devices, the system is
rinsed with potable water or hot pressurized potable water;
next, the material is washed with a non-phosphate deter-
gent and rinsed again with potable water. For trace
determination, the sampling material is rinsed with acetone
and finally with high-quality water [10]. This protocol can
be applied to monitor any natural waters (surface water,
interstitial water, groundwater and wastewater). When
no significant differences in terms of types and concentra-
tions of contaminants are expected, the same devices
and containers can be used. However, sampling devices
and containers for samples with high organic load and
high concentration of organic compounds (e.g., waste-
water), sampling material should be exclusive to collect
these samples. This measure is to avoid field blank
contamination.
Cleaning protocols for soil sampling devices are es-
tablished by the Environmental Protection Agency (EPA)
and include the following: (1) wash with tap water and a
steel brush to remove adhered soil, (2) rinse with a low-
purity organic solvent and air-dry or acetone-dry, (3) rinse
twice with distilled water, (4) rinse with acetone of spec-
trographic grade [waste may be used in (2)], (5) rinse twice
with hexane of spectrographic grade and air-dry, and
finally, (6) package in clean aluminum foil [13]. Another
proposed simple and fast cleaning method, when cleaning
materials are not available, is to push the probe sampler
several times into the surrounding soil before taking the
sample [13].
Samplers for sediment collection are subjected to both
organic hydrophobic- and hydrophilic-pollutant contami-
nation. That means that a more exhaustive cleaning pro-
tocol must be performed considering hydrophobic and
hydrophilic washes. The suggested protocol is the use of a
phosphate-free detergent to clean the surface followed by
multiple rinses: first with tap water, then with high purity
water, with methanol and finally with hexane. Then, the
material must be air-dried and wrapped in aluminum foil
[14].
Water sampling (surface water, wastewater, interstitial
water and groundwater)
Whereas interstitial and groundwater can be considered as
stable matrices, surface and especially wastewater fluctuate
greatly in terms of chemical quality. As a result, it is
common to record the total and dissolved organic carbon
content of these waters as well as parameters that can be
monitored in situ during sampling (temperature, pH,
conductivity, salinity, oxygen, etc.). This information is
complementary to the chemical characterization and over-
all will provide a better insight into water quality. There is a
literature collection from ISO (International Organization
1081
for Standardization) that provides guidance on sampling
the different water compartments [15].
Sampling strategy
The sampling strategy includes the selection of sample
points, the size of the sample and the number of sample
units in each sample. Contamination by organic com-
pounds can be random, uniform, patchy, stratified or along
a gradient, thus preliminary tests are recommended to
establish likely distribution. The timing of the sampling is
another parameter to be considered. Sampling can be
performed over hours and days to determine, e.g., fast
degradation or can be performed over weeks or months or
years for long-term monitoring.
The geographical choice of a water sampling point must
follow defined criteria and can be briefly summarized as
follows: the sampling site must be representative of the
water body so the sample composition characterizes the
water-body quality [16, 17]. Sites that are supposed to be of
environmental concern should be selected either covering
impacted areas or pristine areas. The type of pollution will
determine where and when the sample must be taken,
according to specific sampling objectives:
– Chemical and toxicological characterization of a
sample
– Analysis of target compounds according to regulatory
agencies
– Evaluation of environmental processes to determine
the fate and transformation of organic compounds
Regarding surface water, the sample can be collected
from several points, depending on availability. Streams that
are normally shallow are more subject to bank sampling.
On the other hand, river water should be collected from
boats, bridges or from a shore platform. Lakes and dams
are usually sampled from boats, even if platforms or docks
are in some cases available. Sampling should be performed
either upstream or downstream of agricultural, industrial
areas, urban discharge, inflows and outflows of lakes,
dams, WWTPs or water supply units, but also in the main
streams of rivers, lakes or dams, or at the mouths of
significant tributaries [16]. Exact information on the
sample location should be gathered, preferably through
GPS systems.
More complex is the sampling of groundwater since it
can only be collected from wells or springs (also defined as
streams when sampling protocols are considered). Location
of wells is not always straightforward and the exact
location for sampling is not always available. Groundwater
can be sampled over hot spots and near locations following
the subterranean stream in order to establish contaminant
plume movements. One objective of groundwater sampling
is to gather information on the concentration of a chemical
compound versus depth and spatial position to determine
the leaching potential and transport of organic compounds
within an aquifer. Stagnant water should be pumped and
the system purged till pH and conductivity are constant
1082
(drawdown volume) as slowly as possible (100–400
mL/min) to control turbidity. The sampling system should
be purged over the system volume (tubing and pump) plus
the drawdown volume before sampling [18]. This topic is
extensively described in the literature [19–21]. When
sampling groundwater, information on the depth of the
well, type of soil material, type of crop (if any) and land
activities upstream should be recorded to allow a better
interpretation of results.
Wastewater is easy to sample as the WWTPs always
have pipes directly linked to the inflow, intermediate
treatment processes and outflow for the continuous
monitoring of water-quality parameters; if a different
sample is required, wastewater samples can be collected
from bridges and platforms located within the WWTP. The
strategy to be used when sampling wastewater depends on
the objective of the study. In many instances, an inventory
of toxic compounds in influent and effluent waters is
needed to evaluate the treatment efficiency within the
WWTP. Sampling can be performed in a discrete way, but
provides little information on the overall contamination.
More common in wastewater is gathering composite
samples (multiple discrete samples or a continuous sample
during 24 h or a whole week). In WWTPs, it is common to
collect samples simultaneously at different sites of the plant
(influent, effluent and at each treatment) to evaluate the
efficiency of the different treatment processes.
Finally, interstitial water entrapped in soil is sampled
following the sample selection protocols that are used for
soils that will be discussed below. Interstitial waters are
sampled with pumps over a period of time (from a few
hours to days to collect enough sample volume) or by
passive samplers using the diffusion property or the lixiv-
iation by gravity.
The number of sample replicates needed to characterize
a sampling point will depend mainly on the statistical
parameters of the sample population as well as the required
confidence. The frequency of sampling has also been
mathematically studied using different methods, all sup-
ported by historical data, meaning that a previous knowl-
edge of the studied site is needed to establish a sampling
schedule. For some kinds of samples, the frequency is
established by regulatory agencies. Both number of
samples and frequency are exhaustively discussed in the
literature [16, 22].
According to the EPA, water samples containing organic
compounds should be analyzed within 15 days. After
sampling, samples should be stored at 4 °C and acidifica-
tion might be required (ascorbic, hydrochloric, phosphoric
acid) to inhibit bacterial growth. In some cases the samples
have to be analyzed within hours rather than days
(e.g., DIN EN ISO 17993: determination of 15 PAHs by
HPLC-FD where extraction has to be performed within
24 h, without stabilization, or 72 h).
Sampling devices
Grab sampling and composite sampling
Water sample devices should provide a rapid descent in
water, drift minimally from the vertical, have a suitable
closing/sealing mechanism to retain the sample, be easy to
use and maintain and have an appropriate sample capacity.
A discrete sample, or grab sample, is the sample collected
at a given point within a short period of time, no longer
than 15 min. This kind of sample represents the water body
at the exact moment of the sampling but does not
necessarily represent it at any other time. Grab samples
are simple and easy to obtain and are most recommended
when it is known that the source quality remains essentially
constant [16, 22].
Composite sampling is the collection of grab samples
over time, mixed in the same container. This kind of sample
represents the average characteristics of the water body
during the sampling period. Composite samples are a
mixture of grab samples, so the number of samples that
must be analyzed is reduced compared to a battery of
discrete samples, but there is also a loss of information if
the quality of the water body changes with time. There are
six types of composite samples depending on the com-
positing method: a continuous collection with a constant
pumping flow; a continuous collection with a rated
pumping flow (the higher the flow of the water body, the
higher the pumping); a periodic collection of samples with
a constant sample volume; a periodic collection of samples
with a rated sample volume (the higher the flow of the
water body, the higher the volume); a periodic collection of
samples with a constant time between samples; and a
periodic collection of samples with a rated time between
samples (the higher the flow of the water body, the shorter
the time between samples) [16].
Manual devices for grab or composite sampling are
usually of technical simplicity. The model that will be used
in the sampling depends on the type of compounds studied.
For instance, VOC sampling must be done while avoiding
degassing or volatilization [10, 16, 23].
The water-sampling devices include the following:
Glass bottles The bottle is placed inside a heavy cage,
which is held by a rope; it is filled at the desired depth,
with the plug being controlled with another rope. Glass
bottles are useful for almost all kinds of grab sampling.
Plastic bottles Made of Teflon or PET, they should be used
when glass is to be avoided and analytes will not interfere
with such plastic materials. Their use is similar to that
described above for glass bottles. PET bottles are for a
single use only due to their photodegradability with time.
Kemmerer bottles These bottles consist of a rigid cylinder
sliding along a rope to the desired depth, remaining
vertical; one or two plugs will seal the system after
collection. These are used especially for nonflowing
waters: groundwater and lake/dam sampling.
 1083

Syringes These sample a limited volume by suction; they characteristics and quality may vary and the study of those
are used as samplers but can also be used as containers. differences may be of interest.
Syringes are more appropriate for groundwater or stream This technique is mainly applied to groundwater sam-
sampling. pling through multilevel wells (see Fig. 2) that are usually
built for the occasion and may be unique in terms of
Van Dorn bottles These bottles consist of a rigid cylinder materials, depths or pumping systems. Materials used in
held by a rope and mounting fins that orient the system the construction of such wells must be chemically inert in
horizontally and parallel to the flowing stream; two plugs order to prevent adsorption of organic pollutants onto
seal the cylinder after collection. They are used especially the well casing [32–35]. Sampling at different levels is
for river-water sampling. a technique that is acquiring popularity, especially to
follow contamination plumes within groundwater systems
Pumps There are many different pumps [10]; the choice [36–38].
will mainly depend on the distance to the sampling point
and the kind of studied analytes (VOCs or SVOCs). The
most popular is the so-called bladder pump, which consists Passive sampling
of a flexible membrane inside a rigid container. The
membrane is compressed or expanded using a gas that is Passive sampling is the collection of a sample over time
outside the bladder so the gas and the sample are never in through the free flow of analyte molecules from the
contact. The sample is pumped by successive expansions sampled medium to the collecting medium lodged in a
and compressions through a valve to the surface. The sampling device. The movement of analyte molecules
bladder pump is the most recommended pump for occurs thanks to differences in chemical potentials until the
sampling VOCs or SVOCs [24]. Pumping systems must equilibrium state is reached or until the end of the
first be purged before obtaining the sample to avoid sampling. The time needed to reach chemical equilibrium
sampling of stagnant water that would not be representa- is established by the physical and chemical properties of
tive of the water body. Pumping systems are the usual the analytes. For proper performance, the kinetics should
method to obtain grab samples from monitoring wells be studied for each type of compound. The detailed theory
(i.e., wells built for environmental monitoring purposes). about passive sampling is described in the literature [39]
Interstitial water is also sampled using pumping tech- (see Fig. 3). Passive sampling for organic pollutants in the
niques as the water is more or less linked to the soil; water
is obtained through filters by suction.
Grabbing of water samples is the most common type of
sampling in environmental monitoring, but the proof that
the sampling is usually undervalued in environmental
research is that very little information is given in research
publications. Sampling is even not considered at all in
many published papers, leading to an uncertainty about the
results obtained. Among ones that relate the sampling
techniques and technology used to collect samples, we can
cite the use of the grab sampling technique with glass
bottles to monitor pesticides and chlorophenols [25]; glass,
PET and PE bottles for phthalic esters and endocrine-
disrupting compounds [26]; and polypropylene bottles
placed into subsurface devices for monitoring poly-
fluorinated compounds [27]. River water has also been
monitored for pharmaceuticals and pesticides [28, 29].
Glass syringes have been used for groundwater sampling in
order to monitor PAHs, BTEX and some chlorinated
compounds [30]. A paper reports the use of a Niskins bottle
(similar to a Kemmerer bottle) for river-water sampling
[31], even if this sampling device is more designed for
seawater sampling. Pumping systems are often used in
groundwater monitoring [21].

Multilevel sampling

Multilevel sampling can be defined as the collection of

discrete samples taken at different locations at the same
time over a vertical line. Within the vertical profile, water Fig. 2 Diagram of a multilevel well
1084
aquatic environment has already been described exten-
sively [40–42]. It applies basically to surface water but also
to groundwater for integrated time screening or for sites
where it is not easy to collect or pump water. In many
instances, information on passive samplers is compared
with historical data from traditional sampling.
There is a variety of passive sampling methods but three
are or have been particularly employed:
Solvent-filled dialysis membranes These passive samplers
were the first to be used and are particularly useful for
metal monitoring but have some limitations when con-
centrating organic pollutants. They permit pollutant mig-
ration from the water to the hydrophobic receiving phase
(usually hexane) through a dialysis membrane; the main
problem of such devices is that the dialysis membrane
is hydrophilic, which limits the diffusion of the most
hydrophobic compounds. Interstitial waters might be
sampled using dialysis membranes placed in soils of
environmental concern. They are now in minor use since
the emergence of the semipermeable membrane devices.
Semipermeable membrane devices (SPMD) These are
becoming more and more popular. Using a hydrophobic
membrane (usually polyethylene) with a specific hydro-
phobic receiving phase, SPMDs allow the monitoring of a
wide range of organic pollutants with values of log Pow
higher than 3.
Chemcatchers Some have been used until now for ex-
traction, but due to their high surface-to-volume ratio, they
can be used as sampling devices in the field. The most
commonly used phase is C18 but others are commercially
available. They benefit from a well-known history.
At present there is increasing interest in passive sam-
pling, considering the ever-increasing number of papers
about this topic. Some examples include sampling with
permeation samplers for VOC monitoring [43]; the use of
ceramic dosimeters to monitor different families of organic
pollutants such as PAHs, BTEX or chlorinated hydro-
carbons in groundwater [30, 44]; the novel polar organic
chemical integrative sampler (POCIS) used in river water
to monitor estrogenic compounds [45] or SPMDs in
Fig. 3 Diffusion behavior in a passive sampling device
wastewater streams [46]. Interstitial waters have also been
monitored with passive samplers [47, 48]. More practical
examples can be found in [39–41].
Soil sampling
Soil is the unconsolidated mantle of mineral material lying
above solid rock and subjected to and influenced by
environmental factors [13]. Characteristics of the soil, such
as the clay percentage, organic matter content, pH, per-
meability and cation exchange capacity, will influence the
adsorption and potential leaching of pollutants. In fact, soil
acts as the organic phase of the water cycle, retaining the
most hydrophobic molecules and allowing lixiviation of
the most polar ones to groundwater.
Sampling strategy
The spatial variability of soil chemical properties is
enormous and critical so each soil has to be characterized
before any sampling campaign [49–52]. As for water, the
monitoring points should be representative of the study
site. The area, the type of soil, its use (agricultural,
industrial, urban or wild) and the organic pollutants of
interest will determine the selection of sample points. The
usual method consists of drawing a grid (squared or polar)
over the terrain, rationally choosing some squares for
sampling and mixing them altogether. A more simple
strategy is random sampling, mixing some collections to
form a composite sample, but this method can be subjected
to bias [53, 54].
The quantity of sample to collect is established by
mathematical relationships described in the literature [13,
55] and is determined by the following equation:

2
n
ðZa þ Zb Þ D þ 0:5  Za2
for one-sided, one-sample t-test, where n is the number of
samples, Z is the percentile of the standard normal
distribution, a is the probability of a Type I error, b is the
probability of a Type II error, and D is the minimum
relative detectable difference/coefficient of variation.
The quantity of sample to collect would be determined
by the following equations:
  

A ¼ w1  w2  S12  S22 w2  w1
B ¼ S12  ðA=w1 Þ ¼ S22  ðA=w2 Þ
wopt ¼ A=B
or for most environmental studies, the weight should be at
least six times the minimum weight (wmin):
.
wmin ¼ A ðXav  GÞ2

where A is the homogeneity constant, B is the segregation
constant, w1 is the weight of small random samples from a
preliminary study, w2 is the weight of large random
samples from a preliminary study (at least 10 times the
weight of w1), S2 is the variance, Xav is the average
concentration in small random samples, and G is the
background concentration.
Sampling devices
Grab sampling and composite sampling
Soil sampling is mainly done with a minimum of three
discrete samples that are mixed together. The word
“composite” is used in soil sampling as the pooling of
some discrete samples from nearby points. VOC monitor-
ing prohibits compositing because pooling of different
discrete samples would produce losses of target analytes.
Depending on the purpose of the study, either the organic
matter (vegetation) over the soil is removed before taking
the sample or left as it is to study air/soil interface. Surface
sampling is typically the upper 25 cm and involves
different sampling devices (see Fig. 4) than those used
for subsurface sampling (below 25 cm) [13].
Surface sampling
Shovel sampler The easiest sampler but the most biased
one. In fact, its use is only accepted to subsample soils that
have already been mixed for composite sampling.
Ring sampler A stainless steel circular sampler with a
fixed surface that is usually used to analyze compounds
with results in mass per unit area. They are basically used
by engineers.
Fig. 4 Examples of soil augers
1085
Little corers These are corers made for grab sampling.
Some are very short (2–4 cm) and suitable when soil
characteristics must be preserved. VOC sampling is done
with these little corers as soil aeration is not permitted.
Others are longer (5–10 cm) to allow a standardized way
of taking soil samples even if the collected soil is later
mixed. These types of corers are the most popular for
sampling soils.
Subsurface sampling
Trench sampling This is not properly a sampling device
but a way of sampling. A trench is dug and samples are
taken from the exposed soil wall with one of the previous
samplers. Soil sampling is carried out basically by grab
sampling when surface soil is of interest, and compositing
samples after their collection or collecting replicates. The
use of little corers is the most common practice: the
sampling of the first 5 cm after removing vegetation for
organochlorine-compound monitoring [56, 57] or the
sampling of the first 30 cm [58]. There are also sampling
procedures performed using scoops that are pooled to
provide a composite sample [59], and VOCs may be
sampled with coring devices after drilling the soil [60, 61].
Literature relates the sampling of PCDD/Fs, PCBs and
PCNs keeping the sample in polyethylene bags [62]. An
interesting study about grid sampling with soil core
collection and compositing is found in the literature [63],
even if the purpose of this work was soil nutrient
determination and not organic pollution monitoring.
Multilevel sampling
In soil science, multilevel sampling is defined as the
collection of a continuous sample (which will be later
studied as a sequence of discrete samples) over a line where
the characteristics of the soil may vary and where the
interest is to study those differences. The resulting sample
is called a core, which maintains the vertical profile of the
soil strata without disturbance. For organic pollution
monitoring, corers are made of stainless steel or Teflon
and sealed with Teflon caps. Glass corers exist but are
easily subjected to breakage and are not used for organic
trace contamination in environmental sampling. Some-
times corers are unable to retain some types of sand and
require special inserts for such a purpose. Another
limitation in core sampling is that the sample volume is
usually small, even smaller if the sample must be
subsampled for discrete sample analysis. Devices for
multilevel sampling are described below [13].
Surface sampling
Punch sampler These are made of stainless steel and are
pushed into the soil by hand or using a T-handlebar to
extract core samples. Punch samplers are the most
common multilevel samplers in soil monitoring.
1086
Subsurface sampling
Soil probe Probes are long corers; they can be manually
pushed into the soil with a mallet or mechanically with an
engine (power-driven corers).
Trench sampling A trench is dug and samples are taken
from the exposed soil wall with a core sampler; this
sampling technique is more expensive than others but is
sometimes the better way of sampling in places where
rocks are present that could hinder the advance of the
corer.
Sediment sampling
Sediments are unconsolidated material transported by
surface water or deposited under it. Sediments can have
different textures from thin dust to thick gravel. Like soils,
the composition percentage, the organic matter content,
pH, permeability and cation exchange capacity will modify
the characteristics of the sediment, influencing its content
in pollutants. Sediments will retain and accumulate the
most hydrophobic compounds carried by the surface water
body.
Sampling strategy
Selection of appropriate sediment monitoring points is
quite different from the sampling of any other environ-
mental sample described above. First, sediments are not
always present within river basins and secondly, they must
fulfill some physical specifications (clay content, grain
size, etc.). In this regard, the fine-material content (under
0.06 mm) must be over 30% [14] to obtain an equilibrated
sample with enough surface exchange with water. Some-
times it is difficult to meet both quality criteria within a
sampling location and selection of a new monitoring point
must be borne in mind. In this case, a detailed description
of the new sampling site and the sediment physical
composition should be undertaken. Another added dif-
ficulty is the mobility of sediments so that existing
monitoring points might not be suitable for future sam-
plings. Due to the movement of sediments, their chemical
composition can vary over years making comparisons
difficult.
Usually, the finest sediment is under still water; that is in
deep water, at stream margins, behind natural boulders or
obstructions or inside bends of river meanders [14].
Previous reconnaissance of the sampling site must be
carried out to assure the collection and the fulfillment of the
sampling plan.
Contamination in sediment particles is more equally
distributed than in soil particles, partly thanks to the
movement caused by water, which homogenizes it, and
partly because its contaminant phase exchanger is water,
which is itself highly homogeneous. As for water, sediment
samples are taken from boats, platforms, bridges or wading
in the stream if possible. Special care should be given to
avoiding disturbance of the sediment layer. The sampling
equipment must be selected not only according to the
sampling site, but also to the sample type (discrete or
continuous) and the characteristics of the sediment.
Sampling devices
Grab sampling and composite sampling
In contrast to soil where compositing is the most usual
methodology, in sediment sampling, compositing is also a
current methodology, but the higher homogeneity in
the contaminant distribution explains the fact that compo-
siting is not so critical to obtain a representative sample.
Again, VOC monitoring forbids compositing because the
mixing of the different discrete samples would produce
losses of target analytes. Sampling devices available for
grab sampling include the following:
Scoops and similar These are easy to use, portable and
inexpensive but are highly subjected to bias as result of the
sampling of an undefined surface and depth and the loss of
the finest particles that will be taken away by the water
stream. Scoops are only accepted for use in shallow and
still waters or for the collection of a subsample from a
composite sample.
Dredges These are widely used. Dredges are easy to
use, have simple functioning and maintenance and are
generally inexpensive. Some that are available on the
market with different mechanisms and sizes are Van Veen,
Ekman, Shipek and Box dredges. Dredge samplers should
be lowered slowly over the sediments to minimize fine
material dispersal resulting from an induced shock wave.
Dredges have some limitations. The two major disad-
vantages are that they have a low penetration into the
sediment layer and they lose the depth profile. Moreover,
they are not suitable in rivers with high flows where they
will shift from vertical, presenting some problems in
obtaining a representative sample (i.e., disturbance of the
sediment layer or even inability to set off the jaw closure).
Grab samples from the surface sediment layer are
usually taken with dredges. Ekman samplers have been
used to collect the upper 20 cm [64, 65] or Van Veen drags
to collect upper sediment layers. However, the sampler
type is not always cited [66].
Multilevel sampling
Sediment multilevel sampling is very similar to soil
multilevel sampling. The definition is the same and the
sampling devices do not really differ. Like soils, sediment
multilevel sampling is defined as the collection of a con-
tinuous sample (which will be later studied as a sequence
of discrete samples) over a line where the characteristics
of the sediment may vary and where the interest is in

studying those differences. All that has been said for
soil core samplers can be applied to sediment core
samplers, even if some technical differences exist between
them to avoid the conveyance of fine material by the
water stream. Sediment multilevel sampling devices in-
clude the following:
Corers These can be driven directly by hand in shallow
streams, or using a T-handlebar in some deeper waters.
Corers are easy to use and decontaminate and maintain the
sample profile undisturbed but are only useful in shallow
waters and for low sample volumes. Corers can be pushed
mechanically deeper in the sediment deposition, but the
engines are expensive and bulky.
Gravity corers These are specially designed to sample by
free fall into the river, lake or dam. Gravity corers are
stabilized by fins and carry an adjustable weight fitted to
the environmental and depth conditions.
Vibro-corers These sample after piercing sediment by
vibration using an electric motor.
Core samples are as common as grab samples but
usually their purpose is to establish a temporal contami-
nation either dating stratum with radioactive techniques
[64, 67, 68], or without dating [57, 69].
Conclusions
Sampling is a critical point in analytical procedures. If not
performed using adequate techniques and protocols and
according to specific objectives, the analysis can result in
significant errors. The sampling plan should be carefully
set up from previous knowledge, adjusted to the analytical
objectives and checked in the field to avoid any un-
certainties. Feedback is of great importance in amending
the sampling plan and completing records.
From a practical point of view, the sampling difficulty
increases with the heterogeneity of the sampled body.
When this happens, efforts must be made in the sample
collection step and/or in the sample compositing in order to
maintain the environmental characteristics of the sample.
There is a variety of existing sampling devices and
strategies and new ones under development that permit
the choice of the adequate tool to monitor the relevant
environmental compartments within a river basin. As part
of the analytical protocol, proper planning and quality
control during sampling should be carefully performed so
that the probability of making decision errors is reduced to
an acceptable level, thus increasing the quality of the
experimental environment and optimizing resources and
time.
1087
Acknowledgements This work is supported by the European
Union in “Integrate modeling of the river-sediments-soil-ground-
water system; advanced tools for the management of catchment areas
and river basins in the context of global change” [AQUATERRA,
GOCE 505428] and the Spanish Ministry of Education and Science
[CTM2005-25168-E] and reflects the authors’ views. The EU is not
liable for any use that may be made of the information contained in it.
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