Anal Bioanal Chem (2005) 381: 279–301
DOI 10.1007/s00216-004-2830-8
R EV IE W
Jacek Namieśnik Æ Bo_zena Zabiegałła Æ Agata Kot-Wasik
Monika Partyka Æ Andrzej Wasik
Passive sampling and/or extraction techniques in environmental analysis:
a review
Received: 30 April 2004 / Revised: 10 August 2004 / Accepted: 24 August 2004 / Published online: 23 October 2004

Springer-Verlag 2004
Abstract The current state-of-the-art of passive sampling
and/or extraction methods for long-term monitoring of
pollutants in different environmental compartments is
discussed in this review. Passive dosimeters that have
been successfully used to monitor organic and inorganic
contaminants in air, water, sediments, and soil are pre-
sented. The application of new approaches to the
determination of pollutants at the sampling stage is
discussed. The main milestones in the development of
passive techniques for sampling and/or extraction of
analytes, and in biomonitors used in environmental
analysis, are summarized in this review. Passive samplers
and biomonitors are compared.
Keywords Sampling/extraction techniques Æ Passive
sampling Æ Environmental analysis Æ Solid-phase
microextraction Æ Biomonitoring Æ Speciation
Abbreviations ACC: Activated carbon cloth strips Æ
BTX: Benzene, toluene, and xylenes Æ CAR: Carboxen Æ
CAT: Capillary adsorption tubes Æ CW: Carbowax Æ
DNPH: 2,4-Dinitrophenylhydrazine Æ DSD: Carbonyl-
diffusive sampling device Æ DVB: Divinylbenzene Æ EPA:
Environmental Protection Agency Æ ePTFE: Expanded
polytetrafluoroethylene Æ GC: Gas chromatography Æ
IGFF: Impregnated glass fiber filters Æ LDPE:
Low-density polyethylene Æ LIPS: Liquid passive
sampler Æ LOCD: Lawrence Berkeley national
laboratory occupational carbon oxide dosimeter Æ
MESCO: Membrane-enclosed sorptive coating
sampler Æ NCPS: Nafion-coated passive sampler Æ
NITC: 1-Naphthylisothiocyanate Æ OC pesticides
(OCP): Organochlorine pesticides Æ OPFBHA:
O-(2,3,4,5,6-Pentafluorobenzyl)hydroxylamine Æ
OVM: Organic-vapor monitor Æ PA: Polyacrylate Æ
J. Namieśnik (&) Æ B. Zabiegała Æ A. Kot-Wasik Æ M. Partyka
A. Wasik
Department of Analytical Chemistry, Chemical Faculty,
Gdansk University of Technology,
11/12 Narutowicza Str., 80-952 Gdansk, Poland
E-mail: chemanal@pg.gda.pl
PAH: Polycyclic aromatic hydrocarbons Æ PAKS:
Personal aldehydes and ketones sampler Æ PAS: Passive
air samplers Æ PCB: Polychlorinated biphenyls Æ PCDD:
Polychlorinated dibenzodioxins Æ PCDF:
Polychlorinated dibenzofurans Æ PDBE:
Polybrominated diphenyl ethers Æ PDBS:
Passive diffusion bag sampler Æ PDMS:
Polydimethylsiloxane Æ PIMS: Passive integrative
mercury sampler Æ PISCES: Passive in-situ
concentration–extraction sampler Æ PLM: Permeation
liquid membrane Æ POG: Polymer-coated glass Æ POP:
Persistent organic pollutants Æ PPD: Parallel-plate
dialyzer Æ PTFE: Polytetrafluoroethylene Æ PUF:
Polyurethane foam Æ SBSE: Stir-bar-sorptive
extraction Æ SLM: Supported liquid membrane Æ SLMD:
Stabilized liquid membrane device Æ SPE: Solid-phase
extraction Æ SPM: Semipermeable membrane Æ SPMD:
Semipermeable membrane devices Æ SPME: Solid-phase
microextraction Æ SVOC: Semi-volatile organic
compounds Æ TEA: Triethanolamine Æ TPR: Templated
resin Æ TRIMPS: Trimethylpentane solvent passive
samplers Æ VOC: Volatile organic compounds Æ XRF:
X-ray fluorescence
Introduction
Monitoring of inorganic and organic environmental
pollutants is an ongoing challenge for the analytical
chemist. To establish the quality of different compart-
ments of our environment (atmosphere, indoor air,
water basins, soil, biota) a relatively large number of
samples must be taken from a given location over the
entire duration of sampling when the method of active
sampling is applied. This type of approach to sampling is
time-consuming and can be very costly.
Solutions for this situation are methods of passive
sampling and/or extraction of analytes, which involve
measurement of the concentration of any analyte as a
weighted average over the sampling and/or extraction
time. The concentration of the analyte is integrated over
280
the whole exposure time, making such a method immune
to accidental, extreme variations of pollutant concen-
trations. Information obtained in this way is a suitable
means of obtaining a long-term overview of pollutant
levels in a given environmental compartment.
In this respect the application of new approach to the
determination of inorganic and organic pollutants in
gaseous, aqueous, and soil environments, at the sam-
pling stage, is presented. This approach has been widely
applied to different types of substance in gaseous envi-
ronments (atmosphere, indoor air, atmosphere at work
places) [1–4]. Among analysts this new approach to
sampling and/or extraction has an accepted
name—passive dosimetry. By introducing that term
analysts aspire to emphasize the difference between dy-
namic and passive methods for sampling and/or
extraction of analytes from the medium surrounding the
sampler (air, water, soil, sediment). Both techniques are
based on absorption or adsorption of analytes in/on a
trap. In dynamic techniques, contrary to passive sam-
pling and/or extraction, active devices such as pumps are
required to force the flow of the sample through the trap
and flow meters are necessary to measure the volume or
flow rate of the sample.
Passive sampling is based on free flow (according to
the Fick’s first law of diffusion) of analyte molecules
from the sampled medium to a collecting medium. Dif-
fusion driving forces and separation mechanisms depend
on the different chemical potentials of trapped and non-
trapped (remaining in the sample) analytes [5]. The de-
vices used for passive sampling are usually based on
diffusion through a well-defined diffusion barrier or
permeation through a membrane. Living organisms can
also be used as passive samplers.
The equipment used for passive sampling and/or
extraction is simple and reliable; this is of great impor-
tance, because sampling sites are very often situated far
from the laboratory where further stages of the analysis
must be performed.
Because, after sampling, treatment of samples col-
lected by passive or dynamic sampling/extraction is al-
most the same, the use of passive dosimetry simplifies
the analytical procedure at the most critical step, sam-
pling, without subsequently introducing any further
inconveniences.
The next principal advantage of passive approach
over grab sampling and/or extraction is that only one
device is necessary at a given sampling location for the
duration of sampling. In grab sampling, where the
sample represents the conditions at the sampling site at a
given moment in time, the number of samples collected
over the duration of sampling can be large if the same
time-averaged information is to be obtained. Because
only a few analyses are necessary over the monitoring
period, analytical costs can be reduced substantially.
Moreover, decomposition of the sample during trans-
port and storage is also minimized. Passive sampling
and/or extraction methods are simple to perform and,
after the isolation and/or enrichment step, no further
sample preparation treatment is usually required. This
important feature is not, however, valid for the passive
sampler called the semipermeable membrane device
(SPMD); this sampler is described further because it is
the indicator of the bioavailability of organic and
organometallic pollutants most often used in all possible
compartments of our environment.
Several criteria are important and must be taken
into account in the proper design of an effective passive
monitor. The device commonly called either sampler or
dosimeter should be easy and inexpensive to manu-
facture, easy to deploy, even by an untrained lay-per-
son, small enough that it can be mailed inexpensively
to and from a remote location, sensitive to the pollu-
tants which are to be analyzed, and insensitive to
interfering matrix components such as humic material.
The method subsequently used analysis should, pref-
erably, not involve in-laboratory sample pretreatment
or extraction before final analysis. Other possible
advantageous properties which should be considered
are the capacity to withstand an indefinite storage time
before analysis without change in the concentration of
compounds sampled, and the ability to survive sample
preconcentration or extraction to increase the sensitiv-
ity of the analysis or to enhance the amount of infor-
mation obtained from the different techniques used for
analysis.
Historical overview of passive sampling
Much effort is focused on the development of reliable
sampling and sample-preparation (extraction) proce-
dures characterized by the simplicity of the operations
and devices involved in the process. Passive sampling
seems to be a promising alternative eliminating almost
every disadvantage of active extraction and/or sample
preparation techniques.
In general, passive sampling vastly simplifies the
sampling and sample preparation step by:
– eliminating power requirements,
– significantly reducing the analysis costs (only a few
analyses are necessary over the monitoring period),
and
– minimizing decomposition of the sample during
transport and storage and/or changes during the
analyte-enrichment step.
The main milestones in the development of passive
techniques for sampling and/or extraction of analytes,
which can be applied in environmental studies, are
summarised in Table 1.
Passive sampling
There is a clear need for rapid, effective and low-cost
integrated methods that enable direct monitoring of the
fate and concentrations of chemical pollutants in the
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Table 1 Milestones in the development of passive techniques for extraction (sampling) of trace constituents from environmental samples

Year Passive sampling SPME techniques

1853 First use of passive exposure of ‘‘test papers’’ impregnated

with potassium iodide to measure ground-level ozone [6]
1927 Determination of carbon monoxide in air using passive
samplers—half-quantity analysis [7]
1968 Determination of hydrazine in air using passive
samplers—half-quantity analysis [8]
1973 First diffusion passive samplers—the Palmes tube—stainless-steel
mesh impregnated with triethanolamine (TEA) [9]
First permeation passive samplers—Reiszner–West Badge—for
sampling of SO2 [10]
1976 The Gasbadge Dosimeter—first bag diffusion passive sampler [11]
1979 Personal chlorine monitor utilizing permeation sampling [12]
1980 The Yanagisawa–Nishimura sampler for sampling NO2, SO2, O3
in atmospheric air—the most popular sampler in atmospheric
monitoring [13]
The Amaya–Sugiura sampler—for sampling NO2 in
atmospheric air [14]
Construction of Organic Vapor Monitor (OVM)—bag-type
passive sampler for determination of volatile organic
compounds in air—commercial available as OVM, 3 M Company;
Innovation—desorption in the body of the dosimeter [15]
1981 The Perkin–Elmer tube filled with Porapak Q; the sampler
was adapted for thermal desorption [16]
Ping-pong balls [17]
1984 First sampler for personal monitoring of N2O [18]
1985 First bag-type passive sampler adapted for thermal
desorption—requires special construction of thermal
desorber, which involves cost [19]
Thin ferromagnetic wire coated with activated charcoal—for
volatile compounds in soil [20]
1986 Diffusion sampler for passive enrichment of HCHO in
air—glassware filters impregnated with DNPH [21]
Modification of Amaya–Sugiura sampler to protect against impact
of atmospheric agents [22]
1987 Passive samplers filled with solvent—hydrophilic dialysis bag made
from regenerated cellulose filled with hexane; used for nonpolar
aqueous contaminant residues [237]
1988 Passive samplers filled with sorbent—this sampler can be applied to
detection of contaminants in water and air [24]
1989 Dual diffusion path and using two different sorbents—passive tube Invention of the technology. First paper on SPME
for enrichment of volatile organic compounds in air [25] (fused silica optical fibers coated with liquid and
solid polymeric phases, were dipped into an
aqueous solution containing the analyte
and then placed in a GC injector) [26]
1990 The Willems Badge—passive bag sampler for The first SPME device (coated fibers incorporated
determination of ammonium [27] into a microsyringe) [30]
Semipermeable membrane devices—SPMD [28]
Petrex tubes for sampling of soil [29]
1991 The Ferm dosimeter—diffusional sampler for use in ambient air. In-tube SPME concept (construction is based on
To avoid turbulent diffusion inside the sampler a thin porous a piece of internally coated tubing) [32]
membrane filter covers the inlet. [31]
1992 Copper-tube bailer—for traces of gases in soil [33] First paper on SPME automation published [35]
Supported liquid membrane (SLM) devices—sampler involves the
use of a porous PTFE membrane, separating two aqueous
solutions. Is in some ways similar to dialysis [34]
1993 Passive (bag-type) sampler for determination ozone in atmospheric SPME kit became commercially available from
air—commercially available as the Ogawa Passive Sampler for Supelco, initially with the choice of PDMS and
determination of ozone, NO2, SO2 [36, 37] polyacrylate fiber coatings. Varian forms partnership
Semipermeable membrane (SPM) sampler is a ‘‘lay-flat’’ with Supelco to develop an SPME autosampler
polyethylene tube for selective dialyses of lipophilic
organic compounds [38]
Diffusive sampler—for volatile compounds in soil [39]
Passive in-situ concentration/extraction sampler (PISCES) consists Introduction of head-space SPME into
of plumbing devices and chrome-plated brass slip-joint tee analytical practice [41]
soldered to slip-joint arm. [40]
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Table 1 (Contd.)

Year Passive sampling SPME techniques

1994 Flask description injector combined with

SPME–GC technique [42]
Application of SPME technique for the extraction
of analytes from solid slurries [43]
1995 Passive samplers consisting of polyethylene tubes filled with Implementation of SPME–HPLC interface [45]
iso-octane—for hydrophobic pollutants, including chlorinated
pesticides, in water environment [44]
Gore–sorber screening survey (for soil passive sampling). Introduction of field portable SPME–rapid GC [47]
Patented by W.L. Gore and Associates [46] Air analysis by SPME introduced [48]
1996 Radiello sampler for air analysis: the diffusive surface is cylindrical Indirect SPME extraction through a membrane [50]
instead of planar and the adsorbing substrate is contained in a
coaxial cylindrical cartridge. The diffusive path is therefore
parallel to the radius and not to the axis [49]
Passive diffusion bag for passive water sampling Samplers Derivatization techniques implemented in
were filled with air and water [51] combination with SPME [52]
Passive in-situ headspace sampler for soil sampling [53] Suitability of SPME for determination of pesticides
in water confirmed in an interlaboratory study [54]
First commercial SPME autosampler with sample
agitation introduced by Varian
1997 In-situ sampler via chelation on a textile-based solid Introduction of an SPME device for breath analysis
material—for heavy metals in water [55] in a non-invasive clinical application [56]
Time-integrated sampling of compounds by accumulation of the Use of the SPME technique to study the distribution
contaminant in a dosimeter packed with C18-coated solid phase, of analytes in a complex multiphase system [58]
XAD—and Amberlite resins—to determine PAH in water [57] US patent on SPME granted
In-tube SPME introduced for HPLC
1999 Twister—stir-bar-sorptive extraction [59] Evaluation of different configurations of SPME
units for field studies [60]
Use of the SPME technique to speciate different
forms of an analyte in a sample [61]
2000 Construction of Analyst for sampling volatile organic compounds
in air. Later Analyst was used to determine PAH and adapted for
determination of NO2 and ozone [62]
Tristearin-coated fiber-glass sheets were evaluated as passive samplers
for semivolatile organic chemicals in ambient atmospheres.
Conceived as a ‘‘synthetic leaf’’, combining the beneficial properties
of a leaf with the advantages of a standardized sampler [63]
Passive sampler with diffusion-limiting and solid
receiving membrane [64]
2001 A molecular-based sampling device (Analyst2) for determination of SPME (according to Analytical Chemistry) is one
semi-volatile polyaromatic hydrocarbons in air. It is open at of the great ideas of the decade [68]
both sides and holds the adsorbent in the middle [65, 66]
MESCO passive sampler for water [67]
2002 Modifications of LDPE samplers—LDPE filled with TRIMS [69]
for water analysis
Modifications of LDPE samplers—LDPE filled
with polysiloxane [70]
2002 Stabilized liquid membrane [71] for water analysis

environment and evaluation of their effects and assess-
ment of the hazards these chemicals pose to the envi-
ronment and to the human health. Many of these
requirements are fulfilled by passive sampling tech-
niques. They can be used to assess the quality of various
environmental compartments including air, water, and
soil [5, 29, 72–75]. Passive sampling has few disadvan-
tages; one is the relatively low sampling rate which
necessitates long sampling times at low concentrations.
This feature can, however, also be viewed as an advan-
tage of the technique, because it makes it easy to
determine time-weighted average (TWA) concentrations
of the analytes. In the overall assessment of the impact
of a pollutant on the environment, TWA concentrations
are more useful than short-term concentrations, because
they reflect the long-term action of these compounds.
Overall, however, the sampling mode is normally se-
lected on the basis of the goals of the actual measure-
ment (whether maximum or mean concentrations or
variations of concentration with time have to be deter-
mined).
Factors affecting the analytical result obtained by
application of passive sampling are: the detection limit,
environmental conditions such as temperature, and, for
air monitoring, humidity and air velocity also.
The limit of detection obtained by passive sampling is
a function of the sampling rate, the sampling time, blank
values of unexposed samplers, reproducibility, the sen-
sitivity of the detector used, and the selectivity of the
applied column.
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Passive samplers applied in gaseous media

Passive samplers, either diffusive or permeation, are, in

principle, prepared as tubes or boxes (badges). These
two main designs are the basis of all further modifica-
tions, which are performed to improve efficiency, reduce
sensitivity to air mass fluctuations, and simplify analyte
desorption. Tube-type samplers are usually character-
ized by a long, axial diffusion path length and a low
cross-sectional area; this results in relatively low sam-
pling rates. For badge-type samplers, which have a
shorter diffusion path length and a greater cross-sec-
tional area, uptake rates are typically higher.
Because particular designs of passive sampler used to Fig. 1 Design of the Radiello passive sampler [49]
monitor air quality have been extensively described in
the literature [5, 9–16, 25, 29, 31, 36, 49, 62, 65, 66, 74,
75] and catalogs, this review discusses only those sam-
plers which are widely applied in the practice.

Radiello passive sampler

The Radiello passive sampler was introduced to the

market and patented by the Fondazione Salvatore
Maugeri of Padova, Italy. It enables effective sampling
of organic and inorganic pollutants, for example ben-
zene–toluene–xylenes (BTX), volatile organic com-
pounds (VOC), nitrogen dioxide (NO2), sulfur dioxide
(SO2), ozone (O3), hydrogen fluoride (HF), hydrogen
chloride (HCl), aldehydes and anesthetic gases for
industrial, indoor, outdoor, and personal exposure
applications.
The Radiello system, shown in Fig. 1, exploits a
patented, radial geometry. It comprises a microporous
cylindrical diffusive body and an adsorbing cartridge,
also cylindrical, placed inside the diffusive body and
coaxial with it [49]. The sampler is light (less than 15 g)
and small (7 cm length and 1 cm internal diameter). The
system is included in ISO 16200-2 for sampling and
analysis of volatile organic compounds, and conforms to
the CEN/TC 264 WG 11 standard [76].
Analyst passive sampler
The Analyst passive sampler was been developed in 2000
[62]. It is designed to enable both collection and solvent
extraction of volatile organic air pollutants (sampled on
an active charcoal bed) in the same vial. The sampler can
be used for industrial, indoor, outdoor, and personal
exposure monitoring.
The sampler, shown in Fig. 2, consists of a glass
cylinder (20 mm I.D. · 20 mm diffusive path length)
closed at the base and threaded near the opening. The
plastic cap of the sampler is equipped with a Teflon-lined
rubber septum. The adsorbent, situated on the bottom
within a stainless-steel viewing ring, is active charcoal.
Situated on the viewing ring is a finely woven stainless-
steel net, which is kept in place by another stainless-steel
ring. The removable stainless-steel net, positioned in a
Fig. 2 Design of Analyst passive sampler [62]
threaded aluminium ring, is screwed into the mouth of
the device during sampling time. This extra barrier re-
sults in avoidance of random additional effects of eddy
diffusion.
The compactness of the structure and the inertness of
the materials used ensure the absence of unwanted ef-
fects, for example permeation through the walls during
long-term sampling or inverse migrating through the
walls during storage, and the absence of artefacts de-
rived from the construction materials.
The device is designed so it can be used also as an
‘‘extraction vial’’, so further transfer and manipulation
of the adsorbent is unnecessary. When sampling is
complete the cylinder is closed with the screw on top.
The solvent and the internal standard are injected into
the vial by means of a syringe, which pierces the seal.
After extraction, the aliquot of solution to be injected
into the gas chromatograph is withdrawn in the same
manner using a similar syringe.
This sampler has been modified for determination of
nitrogen dioxide [77]. NO2 is collected on a disc of
impregnated paper placed at the bottom of the vial and
held in position by a stainless-steel ring.
A modified version of the device (Analyst 2) can be
used to determine semi-volatile organic compounds (for
example polyaromatic hydrocarbons) in air. This model
is open at both sides and holds the adsorbent in the
middle [76].
284
ORSA-5-type passive sampler
The ORSA 5 (Drägerwerk, Lübeck, Germany) is a tube-
type diffusive passive sampler, open at both sides, con-
taining 400 mg activated charcoal, dedicated to sam-
pling of volatile organic compounds. The cross-sectional
area is 0.88 cm2 with a diffusion distance of 0.5 cm [78].
It can be used both as a personal sampler and for in-
door–outdoor air-quality monitoring.
OVM-type passive samplers
The organic vapor monitor (OVM) (introduced by 3 M,
Neuss, Germany) is a badge-type passive permeation
sampler consisting of a permeable membrane and an
activated-charcoal pad (180 mg) assembled in a disk-
shaped plastic holder. The cross-sectional area through
which diffusion occurs is 7.07 cm2, the diffusion dis-
tance (length) is 1 cm [78]. Similarly to the samplers
described above, it is dedicated to sampling of pollutants
in industrial, indoor, and outdoor environments.
PUF/POG passive sampler
In 2001 [79] a passive sampler consisting of thin films of
ethylene vinyl acetate coated on the inside and outside
surfaces of a hollow glass cylinder was developed. It was
used to measure chemical fugacity in fish tissues and
other solid substrates. It is referred to as a polymer-
coated glass (POG) sampler. The high surface-to-volume
ratio that can be achieved with POG enables rapid
equilibration (hours/days) of target analytes, and vary-
ing the surface area or coating thickness offers the
opportunity to vary the sensitivity and sampling time for
different analytes and to meet different study objectives.
This sampler (14 cm diameter and 1.35 cm thick) is used
for measuring elevated concentrations of POP in indoor
and ambient air [80].
Similar samplers (referred to as PUF disks and con-
taining polyurethane foam) have been used to monitor the
distribution of polychlorinated biphenyls (PCB), poly-
brominated diphenyl ethers (PDBE), and organochlorine
pesticides (OCP) in the European atmosphere [81].
PIMS passive sampler
A passive integrative mercury sampler (PIMS), based on
a sealed polymeric membrane, is effective for collection
and preconcentration of mercury Hg0 [82]. The PIMS air
sampler consists of segments of heat-sealed lay-flat
LDPE tubing filled with a solution of 10% HNO3 con-
taining 1 ppm Au3+.
UMEx passive sampler
The UMEx passive sampler (dimensions
8.6 · 2.8 · 0.89 cm and weight 10.9 g) shown in Fig. 3
is made of tough polypropylene and contains a paper
which can be impregnated with specific media for reli-
able collection of analytes (e.g. NITC (UMEx 400) for
collection of amines, DNPH (UMEx 100) for collection
of formaldehyde) [83].
Samplers are provided in individual aluminized
pouches that can be re-used to transport the sampler to
the laboratory after sampling. For convenience, insur-
ance against contamination, and quality control, each
sampler incorporates a ‘‘blank’’ section in addition to
the active sampling section so there is no need to send
extra samplers to the laboratory.
Samplers include a clip for attachment to a worker’s
collar for personal sampling or in an appropriate loca-
tion for area sampling.
Passive samplers applied in liquid media
Passive samplers filled with solvent
In 1987 a hydrophilic dialysis bag made from regener-
ated cellulose (1000 daltons cut-off) and filled with
hexane was used as an environmental monitor of non-
polar water contaminants [23]. In dialysis, solutes diffuse
from the donor side (water environment) to the acceptor
side of the membrane as a result of a concentration
gradient. Symmetric hydrophilic polymers are the
materials most commonly used to manufacture dialysis
membranes. Regenerated cellulose and cellulose acetate
are especially useful. They are readily available in a wide
range of configurations, resistant against several organic
modifiers, and can be used at pH 2–8. Apparent hexane
equilibrium in the dialysis bag can be reached in as little
as 48 h and interfering biogenic substances are ex-
cluded. The hexane concentration factors obtained for
PCB were approximately 300. Unfortunately, the poly-
meric materials used are susceptible to chemical, ther-
mal, and bacteriological degradation and they have also
Fig. 3 Design of the UMEx passive sampler [83]
 285

been shown to interact with several classes of organic

solute in aqueous solutions [84].
The use of non-porous films, for example low-density
polyethylene and polypropylene, for solvent enclosures,
seemed to have advantages over traditional dialysis
membranes, because they are hydrophobic and more
resistant to solvents and biodegradation. Low-density
non-porous polymers such as polyethylene seem to have
cavities of transient holes in the range 5 to 10 Å and,
therefore, only dissolved organic compounds of low
molecular weight should diffuse into solvents enclosed in
the sampler. Non-porous plastic bags, filled with several
types of solvent, have been used to concentrate dissolved
organic contaminants in the aquatic environment [28,
85]. Solvent-filled dialysis membranes have been shown
to accumulate persistent lipophilic pollutants in a way Fig. 4 Design of PISCES [40]
similar to that of aquatic organisms [23, 86].
Passive samplers consisting of polyethylene tubes fil-
led with isooctane and deployed within weighted wire
biological origin. PISCES proved to be a field-capable
cages in estuaries and rivers for a period of 3 weeks were
device that can be successfully used for sampling low
reported in 1995 [44]. Hydrophobic compounds, for
levels of contaminants (e.g. PCB) in water. It has the
example chlorinated pesticides, can partition from the
additional benefit of delivering a sample already in sol-
water column into the solvent tube giving a solvent/
vent, thus eliminating the difficulty of shipping large
water concentration ratio of 200 to 300. Dialysis sam-
volumes of water that must be kept refrigerated and,
plers are part of a flow-through system. A multi-channel
furthermore, preconcentrated.
peristaltic pump-head enables four tubes to transfer
solutions at equal rates into the individual compart-
ments of the flow-through tank. The dialysis membrane Stabilized liquid-membrane device (SLMD) The pat-
comes in a form of lay-flat tubing closed with dialysis ented SLMD is a passive, integrative sampler that pro-
clips at both ends. The volume of solvent added to the vides an alternative or complementary approach for
samplers is 10 mL. Samplers working in field deploy- sampling of bioavailable metals in water. A water-
ments should be equipped with a protective cage con- insoluble organic complexing mixture diffuses in a con-
structed of bird wire. trolled manner to the exterior surface of the sampler
A novel application of dialysis, SPM for selective membrane; this enables continuous sequestration of la-
dialyses of lipophilic organic compounds, was intro- bile (bioavailable) forms of trace metals including cad-
duced in 1993 [38]. The SPM is lay-flat polyethylene mium (Cd), cobalt (Co), copper (Cu), nickel (Ni), lead
tube. The membrane is sealed by heat at one end and (Pb), and zinc (Zn) for up to several weeks. In-situ
this sealed tube is placed in a glass funnel equipped with deployment of SLMD enables passive, time-integrated
a PTFE (Teflon) stopcock. The extract is transferred to analysis of unfiltered and filtered samples. The SLMD
the tube. The outside solvent is changed several times can also be used for in-laboratory preconcentration and
and after 4 days the combined fractions are evaporated. speciation of labile trace metals from grab samples of
The dialysis reduces the lipid content to approximately water [71].
1–5%, depending on dialysis time, lipid nature, and
solvent system. The dialysate will contain lipophilic or-
ganic compounds of molecular mass below, approxi- Supported liquid-membrane devices
mately, 600 daltons. It is possible to use this technique
for cleaning other types of sample containing com- The supported liquid-membrane enrichment technique
pounds of relatively high molecular mass, which can be involves use of a porous PTFE membrane separating
difficult to remove, e.g. dirty pulp, tar, tissues, and two aqueous solutions. The membrane is impregnated
sediment extracts [28, 87–90]. with an organic solvent and mounted between two flat
In 1993, another sampling tool, the passive in-situ blocks made of PTFE (Fig. 5). In these blocks corre-
concentration–extraction sampler (PISCES), was de- sponding spiral grooves are machined, forming a flow
scribed in the literature [40]. The sampler, shown in channel on each side of the membrane. The whole device
Fig. 4, is filled with hexane, sealed, and suspended in the is connected to a flow system, enabling aqueous solu-
water column with the membranes downward. Sampling tions to be independently pumped through each of the
occurs by diffusion of organic contaminants from the channels. By proper selection of the solutions pumped
water through the membranes into the collecting sol- through each of the channels on each side of the mem-
vents. This technique can be applied not only to a brane, compounds can be selectively extracted from one
variety of environmental samples but also samples of solution (the donor) into the organic membrane liquid
286
Fig. 5 Design of a supported liquid-membrane device
and, subsequently, extracted into the other solution (the
acceptor).
The liquid-membrane technique is in some ways
similar to dialysis, and the equipment required is similar.
The selectivity of the techniques is different, because
dialysis, in principle, separates small analyte molecules
from macromolecules whereas supported liquid mem-
branes (SLM) also selectively enrich a particular class of
analyte (for example amines or acids). The use of or-
ganic solvents is minimal, which is a very important
advantage of the SLM technique. The flow system also
enables easy automation of the technique and its direct
combination with other sample-treatment methods (e.g.
column adsorption) and with the final analytical step;
this is valuable if many samples must be analyzed.
Liquid-membrane extraction has been applied to a
variety of samples of environmental and biological ori-
gin. Nowadays the SLM technique has three main
application areas as a selective and efficient method for
pretreatment of certain classes of analyte before final
analysis by chromatography or other methods:
– Cleanup and enrichment of analytes from complicated
matrices, e.g. blood plasma, urine, and manure. For
example, aliphatic and aromatic amines in urine have
been determined at low-ppb levels after enrichment
with a liquid membrane containing n-undecane [91]
and aliphatic amines have been analyzed in blood
plasma at sub-ppb levels [92]
– Enrichment of trace pollutants from environmental
samples, e.g. short-chain aliphatic amines [93], bio-
genic amines [94], phenolic compounds [95], triazines
[96]
– Field sampling of trace pollutants. For example,
acidic herbicides have been enriched from natural
waters by use of equipment for field sampling [97],
continuous sampling has been performed in Swedish
brooks where several herbicides [97, 98] were found at
low-ppt levels, and metals have been sampled from
natural waters [99, 100].
It is apparent from recent review articles that the use
of membrane-based extraction techniques in sampling
and sample preparation is on the increase [96, 101–107].
Semipermeable membrane devices (SPMD)
Of all passive systems, SPMD have proved most effec-
tive in their capacity to accumulate lipophilic sub-
stances. Chemicals can be concentrated in SPMD to
levels comparable with or even higher than the values of
their octanol/water partition coefficients or bioconcen-
tration factors in aquatic organisms. SPMD were orig-
inally developed in 1990 to study the bioavailabilty of
hydrophobic organic chemicals to aquatic organisms
[28]. A patent has been obtained for this technology [44]
and an exclusive license was sold to Environmental
Sampling Technologies (St Joseph, Missouri, MO,
USA). Semipermeable membrane devices consist of a
tubular low-density polyethylene (LDPE) lay-flat mem-
brane manufactured without additives and filled with a
high-molecular weight lipid—typically high-purity syn-
thetic triolein (Fig. 6) [28, 108].
When placed in an aquatic environment, SPMD
passively accumulate hydrophobic organic compounds.
The LDPE tubing mimics a biological membrane in its
ability to allow selective diffusion of organic com-
pounds. Triolein is a major non-polar lipid found in
aquatic organisms. Lipid–water partitioning drives the
passive sampling of hydrophobic organic chemicals.
Use of semipermeable membrane devices in passive
techniques have all advantages of traditional methods of
passive water sampling. They are easy to use, can be
standardized, and the extracts obtained might be rep-
resentative of the thermodynamically dissolved organic
phase in surface waters. They can be deployed for long
periods of time (days to months) and used to estimate
time-weighted mean concentrations of the hydrophobic
organic compounds in the water body. For a given non-
ionic organic chemical an SPMD will effectively sample
depending on the chemical’s hydrophobicity (as quan-
tified by its water solubility or octanol–water partition
coefficient (Kow).
Passive sampling with SPMD has been widely applied
for both water and air monitoring. Selected applications
of SPMD filled with triolein are:
– Polyaromatic hydrocarbons in rivers after flooding
[109], in an irrigation water canal [110], in air [111], in
an urban creek [87, 112], in groundwater [113–115],
and in sediment [116, 117]
– Polychlorinated biphenyls in sea water [115, 118–120],
in a river [121], in indoor and outdoor air [122, 123],
and in a laboratory atmosphere [124]
– Organochlorine pesticides in sea water [118, 125], in
sea water after flooding [118], in river water [126], in
water and coastal air [127], in streams receiving irri-
gation drainwater [128], in pulp mill effluent [129], and
in compost [130]

Fig. 6 Semipermeable membrane device (a) and a typical deploy-
ment apparatus (b) [28, 108]
– Dioxins and furans in upstream and downstream river
water [121, 131, 132]
– Organotin compounds in sea water [133, 134].
Generally it can be estimated that any non-ionic
species having Kow>1 will preconcentrate in SPMD.
However, using the standard SPMD configuration, only
non-electrolytes or non-ionic compounds are extracted,
because the membrane is not permeable to charged
species.
By virtue of their design, SPMD exclude contami-
nants that are associated with humic acids or sediments.
In contrast with conventional sampling techniques, a
prefiltration step is unnecessary [131].
After a typical deployment period (approximately
30 days), the SPMD are removed from the aquatic
environment, sealed in the original can or Tedlar bag,
and placed on ice in a cooler for shipping. SPMD should
be stored in a freezer at 20C until analysis. Samples
then undergo dialysis with a non-polar solvent. This
287
extract is thereafter reduced, cleaned, and enriched [87,
112]. The enriched extract, with analytes, can then be
analyzed for target compounds using chromatographic
techniques. Analyte recovery and enrichment procedures
for SPMD usually require less effort than those for tissue
and sediment matrices. SPMD extracts are not readily
amenable to toxicity identification to elucidate the
identity of causal agents or toxicants, which is one the
most important disadvantages of the technique. A sec-
ond problem is the time-consuming sample-treatment
procedure (dialysis) necessary when SPMD are
used—without this the triolein extracts obtained are not
suitable for analytical analysis by any technique.
In 2002 an interesting modification of the SPMD
device was reported [69]. Passive samplers were con-
structed from low-density polyethylene membrane bags
containing 2,2,4-trimethylpentane solvent (TRIMPS).
Periphytic growth has not been observed on the mem-
branes of trimethylpentane-containing samplers, and
analysis of the medium does not require clean-up or
dialysis procedures. One disadvantage of TRIMPS has
been release of the solvent to the surrounding water.
TRIMPS have been successfully applied for sampling of
pesticides, for example endosulfan, chlorpyrifos-ethyl,
profenofos, and sulprofos [69].
Passive samplers filled with sorbent
Trace organic contaminants can be successfully deter-
mined in water, after sampling, by using passive sam-
plers filled with suitable sorbents. As early as 1998 a
dosimeter made from two disks of acrylic plastic was
proposed [24]. The diffusion pathways consist of holes,
clustered at the centre of the upper disk, as shown in
Fig. 7. The lower disk contains a cut-out section that
holds sorbent (granular activated carbon) directly below
the holes in the upper disk when the two disks are
screwed together. A window screen is placed between the
disks to prevent the carbon from falling out of the dif-
fusion holes. The dosimeters are typically exposed for 5–
50 days. After exposure, analytes are extracted from the
sorbent (carbon) and the extract is analyzed. The
dosimeter has been used for determination of atrazine in
water and air.
Time-integrated samplers for organic pollutants
which collect compounds by accumulation of the con-
taminant in a dosimeter packed with C18-coated solid
phase or XAD or Amberlite resins were reported in
1997 [57]. Two types of diffusion dosimeter system were
described:
– accumulation by steady-state diffusion across a
membrane into an adsorber and
– accumulation by non-steady-state diffusion in a water-
saturated packed adsorber bed.
In the first of these the analytes accumulate linearly
with time whereas in the second the accumulated mass of
the contaminant increases with the square root of time.
In both it was assumed that equilibrium between water/
288
Fig. 7 Example of a design of a passive sampler filled with sorbent
[24]
gas and adsorber bed concentrations was not achieved.
The adsorbents tested were of high polarity; recovery
rates were excellent, wetting properties good, and dif-
ferent sorption capacities were available. Passive sam-
plers were tested for PAH in water.
The system, based on the diffusion of target organic
compounds through a rate-limiting membrane and the
subsequent accumulation of these species in a bound,
hydrophobic, solid-phase material has been further
developed [64]. Accumulation rates are regulated by
choice of diffusion-limiting membrane and bound solid-
phase material and have been found to be dependent on
the physicochemical properties of the individual target
analytes. Two separate prototype systems have been
described—one suitable for sampling of non-polar or-
ganic species with log octanol/water partition coefficient
(log P) values greater than 4, the other for more polar
species with log P values between 2 and 4. Both systems
use the same sorbent (47 mm C18 Empore disk) as a
receiving phase but are fitted with different rate-limiting
membrane materials (polysulfone and polyethylene for
the polar and non-polar analytes, respectively). The two
systems complement each other and together can be
used to sample a wider range of organic analytes than is
usually possible using current passive sampling tech-
niques. The passive sampling system is shown in Fig. 8.
The successful determination of the concentrations of
polar biocides illustrates the wide scope of the new
passive sampling device compared with earlier systems.
This passive sampler has also been applied for metals
such as zinc and copper [135].
A simple, inexpensive, passive monitor based on a
textile-bound polyacryloamidoxime chelating agent
(polyacryloamidoxime cloth) has been evaluated for
Fig. 8 Schematic diagram of SLMD [64]
analysis of selected trace heavy metal in water [55, 136].
The device consists of amidoxime chelating groups
covalently bound to a polyacrylonitrile textile encased in
a common commercial slide holder made of plastic. The
idea for this approach came from previous work on
passive monitors for organic compounds in air and
water [137]. Placement of this device in the water to be
analyzed resulted in uptake of heavy metals by the
chelating groups. After removal of the monitor from
water, the metals taken up can be analyzed directly on
the cloth, both qualitatively and quantitatively, by X-ray
fluorescence (XRF). In-vitro experiments demonstrated
the feasibility of passive in-situ sorption of trace metals
by the cloth with sensitivity in the mg L 1 or sub
mg L 1 range. In addition, the size of the monitor is
convenient for delivery by mail. The choice of amidox-
ime as ligand proved to be selective to metals of interest
and not the alkali and alkaline earth metals.
Membrane-enclosed sorptive coating sampler (MESCO)
Adaptation of the novel solventless technique, stir-bar-
sorptive extraction (SBSE) [59], to enable integrative
passive sampling of persistent, hydrophobic organic
pollutants in the aqueous environment has recently been
reported [67]. The passive sampling device, referred to as
the MESCO, consisted, in the investigation, of a stirrer
bar used for SBSE enclosed in a dialysis membrane bag
made from regenerated cellulose and filled with bidis-
tilled water. The stir bar moved freely inside the mem-
brane. The selectivity of the MESCO extraction
technique is enhanced in two ways:
– The dissolved molecules become separated from col-
loids during their diffusion across the dialysis mem-
brane
– Hydrophobic target analytes are selectively extracted
from the inner aqueous solution by the PDMS sorbent
coating.
The MESCO sampling system combines the passive
sampling approach with solventless preconcentration of
organic solutes from aqueous matrices and subsequent
desorption of the analytes on-line into a chromato-

graphic system. This combination is a low-cost and ro-
bust alternative to currently used passive sampling
techniques. The samplers are miniature and do not re-
quire use of large deployment devices in the field. ME-
SCO samplers have been applied for pesticides, PCB,
and PAH [67, 138].
Passive samplers in soil
For sites with permeable soils and abundant levels of
volatile organic compounds (VOC) in the vapor phase,
both passive and active soil gas methods have been pro-
ven effective. On sites with low-permeability soils, low
VOC levels and SVOC and PAH in the soil gas, passive
soil gas technology has proven more effective than active
techniques. If the depths of organic materials are great
(e.g. deep fossil fuel reserves and deep groundwater
contaminant plumes) or the soils poorly drained, passive
soil gas technology is superior for detecting and reporting
the target compounds of interest.
Typically, soil gas sampling involves collection of va-
por occupying the pore space of soils. The vapor is com-
posed of air and water vapor, naturally occurring organic
compounds, anthropogenic organic compounds, organic
compounds migrating from deep fossil fuel reserves, and
other constituents capable of partitioning from liquid and
solid materials into the vapor phase under ambient con-
ditions. Passive soil-gas techniques are a sensitive and
representative means of measuring soil gases, and are,
therefore, capable of detecting and reporting volatile and
semi-volatile compounds under a wider range of site
conditions than any other similar technology. Passive
methods are less susceptible to changing ambient and
subsurface conditions and do not disturb the natural
equilibrium of the vapors in the subsurface.
Gore-Tex sampler
In 1992, W.L. Gore et al. [46] pioneered the use of ex-
panded polytetrafluorethylene (ePTFE) in environmen-
tal site-characterization applications, using the Gore-
Sorber module to sample analytes from both soil and
water. The module is a passive soil-gas sampler that
consists of several separate sorbent collection units called
sorbers (Fig. 9). Each sorber contains sorbent materials
selected for their affinity for a broad range of volatile and
semivolatile organic compounds and for their hydro-
phobic properties. The sorbers are sheathed in a vapor-
permeable insertion and retrieval cord, constructed of
inert, hydrophobic material (Gore-Tex) that allows va-
por to move freely across the membrane and on to the
sorbent material, and which protects the granular
adsorbents from physical contact with soil and water.
The membrane facilitates vapor transfer across the
entire surface area while providing strength for retrieval
from the subsurface. Organic vapor present in the soil
gas migrates unimpeded through the membrane to the
adsorbent housed in the sorbers. This design prevents
289
Fig. 9 The Gore–Sorber module [46]
soil particles and liquid water from affecting sample
integrity. The module itself is approximately 30 cm long
and contains enough sorbers for two samples. This en-
ables duplicate analyses, if required, or a back up
analyses in the event of instrument malfunction. Addi-
tional sorbers can be placed in the module if more
samples are required.
Different samplers applied for soil and sediment
compartment
Soil air can be sampled passively via stainless-steel pipes
[139]. The pipe is hammered into the soil. To prevent soil
entering the pipe during hammering a stainless-steel ball
is put in front of the pipe. The pipe is driven into the soil
about 10 cm deeper than its final position, to create
sufficient space for the volatile compounds to diffuse
into it. A snugly fitting adsorbent tube is inserted into
the pipe with the open end facing the lower part of the
tube; a plastic plug seals top end of the pipe.
Another measurement method that uses a thin fer-
romagnetic wire coated with activated charcoal to col-
lect organic compounds has been described in the
literature [20].
An alternative to other soil-gas techniques was de-
scribed in the literature in 1993 [39]. The principal
advantage of this approach is that the device has the
flexibility to monitor a site over a short- or long-term
time-frame either by quantitative analysis by thermal
desorption into a GC–MS or determining concentra-
tions in the field. Moreover, installation is accomplished
by hydraulically pressing the device into the soil to the
desired sampling depth or by conventional monitoring
well-installation techniques. The device is also simple,
rugged, and can be easily retrieved and deployed at the
surface by non-technical personnel. Quantitative mea-
surements can be made for most of the VOC on the EPA
priority pollutant list. The sampling device consists of a
290
small sorbent tube that is lowered from the ground
surface down a 25-mm-diameter borehole or an existing
monitoring well, until it seats in a sampling chamber.
Vapor from organic compounds contaminating the soil
that have high relative vapor pressures enter the sam-
pling chamber by molecular diffusion and are collected
by the sorbent. The sorbent tube is retrieved after a
predetermined exposure period and sent to a laboratory.
Around the outside of the sampling chamber is a
porous polyethylene membrane. The sorbent tube is
constructed from a small glass tube filled at one end with
Carbotrap sorbent to retain organic molecules. The
other end of the tube is left open to the atmosphere
inside the sampling chamber to enable transfer of or-
ganic vapor through the tube by diffusive flux.
Naturally occurring and anthropogenic dissolved
gases have been used as tracers for many years in
oceanography and hydrology. The use of ping-pong
balls and latex tubing for sampling the helium content of
lake sediments has been discussed in the literature [17].
Special sample-collection methods are needed to prevent
loss of these gases during sampling. The three most
common methods are:
1. copper-tube bailers [33],
2. gas-tight syringes [140], and
3. vacuum flasks [141].
All these methods can produce high-quality samples
under favorable conditions, but analyte collection is
time-consuming and expensive. An alternative approach
is the use of in-situ headspace samplers in which a
semipermeable membrane attached to a gas-filled reser-
voir is immersed in a solution containing dissolved ga-
ses. A passive in-situ headspace sampler employing a
semipermeable membrane and copper tubing equipped
with a Schrader valve has been described in the literature
[53]. A conceptual approach for such passive monitoring
is illustrated in Fig. 10.
Solid-phase microextraction as a passive
sampling technique
Solid-phase microextraction (SPME) is one of the most
promising solvent-free techniques of sample prepara-
Fig. 10 Schematic design of the components of a passive diffusive
sampler [53]
tion. It does not require the use of any liquid solvents
and can therefore by considered as proecological. SPME
is used either for sampling or for simultaneously isola-
tion and enrichment of a very wide range of analytes
from gaseous and liquid media and indirectly from solid
samples. Two ways of sampling can be distinguished:
– direct—in this approach the extraction fiber of the
SPME device is immersed in the medium being stud-
ied (e.g. in gaseous or relatively ‘‘pure‘‘ liquid med-
ium);
– indirect—the extraction fiber of the SPME device is
placed in the headspace layer, which is at equilibrium
with the sample studied (e.g. liquid heavily loaded
with different contaminants, soil, or sediments).
The SPME fiber can be used to extract target analytes
directly in the field without collecting a sample. Analyte
sampling is based on transport to and sorption in a thin
film of stationary phase coated on an SPME fiber. The
coated fiber can be replaced by stainless-steel capillary
with a modified inner surface. Stationary phase in both
cases acts like a ‘‘sponge‘‘ concentrating the analytes on
its surface so they can be transferred to the gas or liquid
chromatograph.
Solid-phase microextraction is a combination of
passive and dynamic methods. Because of the way
analytes are sampled from the medium, which is con-
trolled similarly to passive sampling, flow of analytes
from the sample surrounding microextractor to the trap,
the fiber, is completely free. The main driving force is the
difference between concentrations. Also, the equipment
used for sampling in SPME is not complicated. But the
sampling time required to reach equilibrium of the order
of several seconds and minutes for volatile organic
compounds and of the order of several minutes up to
half an hour for POP. Thus this type of sampling cannot
be used for long-term monitoring, because the results
obtained are only comparable with those obtained by
grab sampling.
The scope of practical application of the SPME
technique has been described in many reviews [142–151].
We decided to report publications according to the
classes of compound sampled from different matrices; in
SPME these are determined by the analyte-sampling
step and by introduction to the analytical instru-
ment (Table 2).
Biomonitoring
Biomonitoring surveys are based upon measurements of
the accumulation of pollutants in the tissues of living
organisms. The process of active and passive accumu-
lation might result in concentrations of lipophilic com-
pounds in the tissues of the test organisms far exceeding
those found in the surrounding environment. Biomoni-
toring is an integrative technique and as such has the
advantage over spot sampling that the aquatic envi-
ronment is effectively sampled continuously throughout
 291

Table 2 Analytical applications of the SPME technique [142–151]

Group of analytes Fiber types Type of matrix

Aliphatic and aromatic PDMS, CAR/PDMS, PDMS/DVB, Atmospheric air (industrial air)
hydrocarbons CW/DVB, CAR/PDMS, CAR/DVB, Indoor air (homes, swimming pool, cars, trains, laboratory)
porous carbon Workplace air
Groundwater, running water, pure water, drinking water
Sludge, sand, soil, wastewater and sediments
Aldehydes PDMS/DVB, PDMS, CAR/PDMS, Workplace air
and ketones CW/DVB, PA, DVB/CAR/PDMS, Groundwater
Building materials
Water rich in humic organic matter, compost
Mainstream smoke
Alcoholic beverages, alcohol, wine, beer, fruit juices
Coffee beans, vegetable oils, butter
Alcohols PDMS, PDMS/DVB, CW/DVB, Groundwater, running water, pure water, drinking water
CAR/PDMS, DVB/CAR/PDMS, PA Alcoholic beverages, alcohol, wine, beer, fruit juices
Coffee beans, vegetable oils, butter
Human urine
Phenols PDMS, CAR/PDMS, CAR/DVB, Workplace air
CW/TPR, PA Organic layer on building materials
Groundwater near leaking underground storage tanks with gasoline,
water polluted with petroleum hydrocarbons, wastewater discharges
Human urine
Chlorinated PDMS, CAR/PDMS, PA, CAR/DVB, Indoor air (homes, swimming pool, cars, trains, laboratory)
compounds porous carbon, CW/DVB Workplace air
Groundwater, running water, pure water, drinking water
Groundwater near leaking underground storage tanks with
gasoline, wastewater discharges
Milk
Sludge, sand, soil, wastewater and sediments
Nitro compounds PDMS Groundwater, running water
Sludge, sand, soil, wastewater and sediments
Amines PDMS, PDMS/DVB, Workplace air
CW/TPR, CAR/DVB Sludge, sand, soil, wastewater and sediments
Human urine
PAH PDMS, CAR/PDMS, PDMS/DVB, Atmospheric air (industrial air)
CW/TPR, CAR/DVB, porous carbon Groundwater near leaking underground storage tanks with
gasoline, water polluted with petroleum hydrocarbons,
wastewater discharges
Workplace air
Bituminous materials, sludge
Human urine
Alkaloids Polyimide, CAR/PDMS Fruit juices, coffee, tea
Fruit
Organosulfur CAR/PDMS Atmospheric air (industrial air)
compounds Workplace air
Wine
PCB PDMS, Carbopack B Workplace air
Sludge, sand, soil, wastewater and sediments
Pesticides PA, PDMS/DVB, CAR/PDMS, Workplace air
and biocides PDMS, CW/TPR Sludge, sand, soil, wastewater and sediments
Groundwater near leaking underground storage tanks with gasoline,
water polluted with petroleum hydrocarbons, wastewater discharges
Wine and fruit juices
Organic layer on building materials
Fruit
Honey
Human urine
Carboxylic acids PA, PDMS, CAR/PDMS, Workplace air
and esters DVB/CAR/PDMS, PDMS/DVB, Groundwater near leaking underground storage tanks with gasoline,
CAR/DVB, porous carbon water polluted with petroleum hydrocarbons, wastewater
discharges, aqueous sludge
Sludge, sand, soil, wastewater and sediments
Alcoholic beverages, alcohol, wine, beer, fruit juices
Coffee beans, vegetable oils, butter
292
Table 2 (Contd.)
Group of analytes Fiber types
Ethers PDMS/DVB/CAR, CAR/PDMS,
PDMS, PA, CAR/DVB,
porous carbon
Organometallic PDMS, CW/DVB
compounds
Drug derivatives CAR/PDMS, PA, PDMS
deployment. Information obtained in that way refers to
the time-integrated concentrations to which the test
organisms are exposed. However, the use of living
organisms as in-situ sampler is fraught with technical
difficulties. A chosen biomonitoring species will be re-
stricted to a particular water type and temperature.
Some compounds might not be accumulated, because
they are metabolized by the test organisms. Rates of
bioaccumulation vary between individuals of the same
species, being affected by the age, sex, and general
condition of the organism. Lipophilic chemicals accu-
mulate at a much faster rate and to a greater extent than
lipophobic substances. This effectively precludes the use
of biomonitoring for polar organic compounds, with
log octanol/water partition coefficient (log P) less than
four. Bioaccumulation depends on intake from material
dissolved in the water column and present in the food.
This is in contrast with passive samplers, which measure
only the freely dissolved fraction of an analyte [64].
The idea of using organisms or communities of
organisms is to reflect the state of water environment.
Biological indicators can reveal problems otherwise
missed or underestimated. Literature data relating to
application of different types of organism, or suitable
tissue, as integrative samplers for a wide range of ana-
lytes have been summarized in Table 3.
Living organisms and passive samplers—comparative
studies
Of all passive samplers SPMD have the greatest potential
as monitoring tools and, to some extent, can overcome
the problems associated with the use of living organisms
as monitoring tools, for example natural variability,
different age, sex, and physical condition. Trials of
SPMD in several countries and for different contami-
nants (for example organotin compounds [133], poly-
brominated diphenyl ether fire retardants [197–200],
organochlorine pesticides and PCB [125, 201–204], and
PAH [205]) have indicated that SPMD might be even
Type of matrix
Workplace air
Groundwater near leaking underground storage tanks with gasoline,
water polluted with petroleum hydrocarbons, wastewater
discharges, aqueous sludge
Beer
Workplace air
Groundwater near leaking underground storage tanks with
gasoline, water polluted with petroleum hydrocarbons,
wastewater discharges, aqueous sludge
Sludge, sand, soil, wastewater, and sediments
Fish tissues
Human urine and human blood
Workplace air
Human urine and blood
Human hair
Human saliva
more efficient than living organisms at indicating trace
organic contaminants in the water column, as they enable
more standardized comparison of different sites in widely
differing localities. Moreover, in highly polluted waters
where organisms such as mussels might not be able to
survive, SPMD can provide invaluable information.
Although in most papers SPMD are compared with
mussels [125, 133, 198, 201, 202, 204], other biota sam-
ples were also studied in parallel with SPMD—Dunge-
ness crab (Cancer magister) [199], English sole
(Pleuronectes vetulus) [199], harbor porpoise (Phocoena
phocoena) [199], oligochaete worm (Lumbriculus varie-
gates) [200, 206], freshwater clams (Corbicula fluminea)
[203], and benthic amphipod (Diporeia spp.) [205] to
mention only a few.
Living organisms can absorb substances present in
their environment by respiration (dissolved phase) and
feeding (dissolved phase and suspended matter) whereas
SPMD sample the bioavailable dissolved phase only. As
a consequence, this sampling method does not enable
quantification of total concentrations for many target
analytes. An SPMD cannot model biomagnification, but
it can alert us to the presence of contaminants that can
be biomagnified.
The relationship between fish lipids and triolein varies
with the type of fish lipid, the sex, age, and species of
fish, and whether the fish can metabolize contaminants
such as PAH. The concentrations of contaminants in
triolein and whole fish tissue correlate only for some
chemicals, because fish metabolize and eliminate many
contaminant residues from their tissues. Thus, residues
in SPMD represent what a fish was exposed to and not
necessarily what was retained in the tissue. In other
words, SPMD provide an estimate of potential bioac-
cumulation, not actual.
Passive sampling and/or extraction in speciation
It is possible to distinguish two quite different ap-
proaches in speciation chemical analysis. In the first,
 293

‘‘chemical’’ speciation meant a process leading to iden-

PCB, polychlorinated biphenyls; POP, persistent organic pollutants; PAH, polycyclic aromatic hydrocarbons; PCDD, polychlorinated dibenzodioxins; PCDF, polychlorinated dibenzofurans; PCN,
Toxaphene
tification and determination of the different chemical

[183]

[188]

[196]
forms of an element present in a sample. Another ap-
proach in speciation analysis is ‘‘physical’’ specia-
tion—determination of different physical forms of an

[175, 182, 193]

analyte, e.g. POP dissolved in water and adsorbed on
particulate matter. Because speciation analysis can be
performed in very different ways [207], depending on the
PBDE

[175]

[182]

[188]
aim and scope of the analytical investigation, passive
samplers can be applied for different speciation pur-
poses. The possibilities of using SPME for speciation
Table 3 Literature data relating to application of different types of organism, or suitable tissue, as integrative samplers for a wide range of analytes

Organochlorine

analysis of mercury, tin, lead, arsenic, and selenium are

[172, 191, 192]

described in depth in a review paper [208].

[180, 181]

[187, 188]
Several authors have described typical, straightfor-
[155]

[155]
[161]

[174]

[176]

[184]
ward applications of passive sampling for chemical spe-
ciation. SPMD have been used to monitor mono,
dibutyl, and tributyltin compounds in the marine envi-
VOC

[154]

[160]

[154]

[154]

[154]
[154]
ronment [134]. The authors showed that SPMD do
accumulate organotins from water, and results obtained
were in good agreement with those obtained by use of
Organometallic

direct water sampling. Another passive sampler, con-

sisting of a diffusion-limiting membrane and a receiving
compounds

[176, 190]

phase surface, was applied for in-situ determination of

the electrochemically available fraction of metals (Cu,
[166]
[167]
[173]

[176]
[179]

Zn) in storm water [135]. Determination of hexavalent

chromium in high-particulate-containing surface water
PCN

was performed by using a conventional parallel-plate

[172]

[186]
[172]

polychlorinated naphthalenes; VOC, volatile organic compounds; PBDE, polybrominated diphenyl ethers

dialyzer (PPD) design that used planar membranes [209].

Application of a permeation liquid membrane (PLM) to
PCDD+PCDF

speciation of free metal ion and total dissolved metal

[163, 172, 191]

(Cu, Pb) was tested with various types of natural water

[163, 172]

[210].
Various passive devices can be used for group-type
[155]
[159]

[163]

[186]

[195]

speciation (chemical speciation). This type of speciation

analysis leads to determination of concentration levels
for a specific group of compounds. Tables 4 and 5
[156, 157]

summarize the main applications of passive samplers for

PAH

[155]

[162]

[171]

[181]

group and individual speciation.

[184, 185]

[176, 191]

Comparison of sampling techniques

[165]

[176]
[178]

[186]
PCB
POP

An evaluation of the different sampling techniques used

in environmental studies of water is presented in Table 6.
[168, 189, 190]

Comparison of sampling techniques commonly pre-

Heavy metals

sented in the literature shows that on a far-field scale

[152, 153]

[167, 168]
[169, 170]

living organisms (usually mussels) and SPMD both

[153]
[158]

[164]

[177]

[194]

provide important information about the presence and

bioavailability of organic contaminants. Both methods
are, moreover, extremely sensitive tools for determina-
Marine mammals (cetaceans)

tion of pollutants. In-situ, large-volume water sampling

(gastropods+crustaceans)

is also suitable for a wide range of this type of con-

taminant. This technique is, however, limited by low
Benthic invertebrates

break-though volume of the low-molecular-weight

Decorative plants

compounds. The small sampling volumes limited solid-

Birds and eggs
Aquatic plants
Mangrove leaf

Cephalopods
Zooplancton
Chinese teas
Pine needles

phase extraction (SPE) and whole water sampling tech-

Polar bears
Organism

niques, resulting in potential detection limit problems.

Bacteria
Lichens
Mosses

Fishes
Algae

Passive samplers or biomonitors have proven

Trees

advantages over other techniques in most respects.

294

Table 4 Application of passive samplers for group speciation

Group of analytes Passive sampler Application Refs

Dioxins and furans SPMD Water—field deployment [211]

(PCDD and PCDF) SPM Fat-rich environmental samples [212]
Polycyclic aromatic SPMD Sediment water, sediments (USA) [117, 213]
hydrocarbons (PAH) Surface water (Germany) [214]
Chemical factory [110, 203, 215]
SPM Water [38]
PUF following the glass fiber filter Outdoor air (Größhandsdorf, Germany) [216]
Analyst Air, laboratory tests, Italy [66]
Polychlorinated SPMD Indoor and outdoor air [217]
biphenyls (PCB) PISCES Water (NY, USA) [40]
Passive air sampling system, deploying Air monitoring—all Europe [81]
PUF disks monitoring studies
Polymer-coated glass (POG) Air monitoring [80]
passive sampler
Herbicides SLM Environmental waters [34, 98, 218, 219]
Passive diffusive sampler Laboratory batch experiments [220]
Organochlorine Samplers filled with solid sorbent Water [24]
pesticides (OCP) Solvent-filled device Lakes [221]
Estuarine waters [44]
SPM Compost [130]
PAS—passive air samplers with XAD-2 Air monitoring—laboratory and field [222]
experiments (Great Lakes
region, Canada)
Passive air sampling system, Air monitoring—all Europe [81]
deploying PUF disks monitoring studies
Kabis sampler Water [223]
Hydra sampler Water [223]
Discrete interval sampler Water [223]
Pneumo-bailer Water [223]
Passive diffusion bag sampler Water [223]
SPMD Aquatic environment [55, 87]
Water, coastal air [131, 224]
Polybrominated diphenyl Passive air sampling system, Air monitoring—all Europe [81]
esters (PDBE) deploying PUF disks monitoring studies
Aromatic hydrocarbons, OVM 3500, 3 M Company Indoor air monitoring [225]
aliphatic hydrocarbons, (Leipzig, München and Köln, Germany)
alcohols, esters Indoor/outdoor air (Germany) [78]
Workplace atmosphere [226]
OVM 3000, 3 M Company Indoor/outdoor air (Germany) [227]
ORSA-5, Drager Indoor/outdoor air (Germany) [78]
Perkin–Elmer tubes with Tenax GR Outdoor air, (The Netherlands) [228]
Stainless-steel tube with Tenax TA Indoor air (six cities, Kuwait) [229, 230]
Analyst Indoor, outdoor air (Italy) [62, 231]
Permeation passive sampler Indoor air, outdoor air (Gdansk, Poland) [232–234]
Radiello Outdoor air (Antwerp region, Belgium) [235]
Outdoor air (Madrid, Spain) [236]
ACC—activated carbon cloth strips Laboratory experiments and indoor air [137]
(local printing company)
GABIE Workplace/industrial atmosphere [237]
(methyl ethyl ketone)
Passive diffusion bag sampler (PDBS) Ground water [51]
Water [223]
Personal passive dosimeters (TK-200) Styrene—personal sampling—workers [238]
Kabis sampler Water [223]
Hydra sampler Water [223]
Discrete interval sampler Water [223]
Pneumo-bailer Water [223]
Porton diffusion sampler Styrene—personal sampling—workers [239]
Aldehydes and ketones GMD-570 diffusive samplers Inter-laboratory study [240, 241]
(formaldehyde analysis)
Laboratory study (glutaraldehyde) [242]
Laboratory study (acetaldehyde) [243]
OVM 3500 3 M, with Tenax TA Laboratory study (aldehydes) [244]
and OPFBHA
GABIE Workplace/industrial atmosphere [237]
(methyl ethyl ketone)
 295

Table 4 (Contd.)

Group of analytes Passive sampler Application Refs

PAKS (personal aldehydes Indoor, outdoor, personal sampling [245]

and ketones sampler)
Radiello Ambient air at five locations in the [246]
north-west area of Milan (Italy)
(aldehydes and ketones)
Passive tube with silica gel Indoor air (formaldehyde and [247]
coated with o-PFBOA acetaldehyde), Japan
DSD-carbonyl—diffusive Air (aldehydes and ketones) [248]
sampling device
Porton diffusion sampler Methyl ethyl ketone—personal [239]
sampling—workers
Terpenes OVM 3500, 3 M Company Indoor air monitoring [225]
(Leipzig, München and Köln, Germany)
Perkin–Elmer tube with sorbent Air analysis (saw mill) [249]
Diffusive sampler SKC, model 530-16 Air sampling, saw mill (Sweden) [250]
Diffusive sampler SKC, model 575 Laboratory test, personal sampling, [250, 251]
and static sampling—saw mill (Sweden)
Amines Diffusive sampler Volatile amines in air, laboratory [252]
validation
Other Capillary adsorption tubes (CAT) Perfluorocarbon tracer gases, [253]
laboratory experiments and indoor
air (ice skating surface)
LIPS (liquid passive sampler) N,N-dimethylformamide and [254]
N,N-dimethylacetamide in air,
research purposes

Table 5 Application of passive samplers for individual chemical speciation

Group of Passive sampler Application Refs

analytes

NO2 Palmes tube Personal exposure, Sweden [255]

Indoor air, UK [256]
Amsterdam (NL), Huddersfield (UK), [257, 258]
Prague (CZ), Poznan (PL), air monitoring
Tubes contain stainless-steel Indoor air, Correr Museum, Venice, Italy [259]
mesh coated with a trapping
agent (TEA)
Ferm dosimeter Urban air [260]
Outdoor air, Australia [261]
Willems badge Laboratory experiments and field [262]
test—outdoor air, Sweden
Amsterdam (NL), Huddersfield (UK), [257, 258]
Prague (CZ), Poznan (PL), air monitoring
Ambient air, laboratory test and outdoor air, [263]
Rome, Italy
Passive sampling methods Indoor/outdoor, Korea [264]
using filter badges (Advantec)
Ogawa PS Air pollutants in Sequoia National Park, [265]
California, USA
Walden Gasbadge dosimeter Personal monitoring [266]
Yanagisawa-type dosimeter Atmospheric pollutants, mountains around [267]
Kyoto Basin, Japan
Analyst Laboratory experiments and field tests, Italy [77]
Amay-Sugiur modified sampler Urban and rural areas of Poland [268, 269]
Outdoor air (forest in Poland) [270]
SO2 Badge-type SO2 passive samplers Ambient air, indoor and/or outdoor air, Beijing, China [271]
Willems badge Amsterdam (NL), Huddersfield (UK), [258]
Prague (CZ), Poznan (PL), air monitoring
Ambient air, laboratory test and outdoor air, [263]
Rome, Italy
Palmes tube Amsterdam (NL), Huddersfield (UK), [258]
Prague (CZ), Poznan (PL), air monitoring
Ferm dosimeter Outdoor air, Australia [261]
Outdoor air, Asia, Africa [272]
Tubes contain stainless-steel mesh coated Indoor air, Correr Museum, Venice, Italy [259]
with a trapping agent (TEA)
296

Table 5 (Contd.)

Group of Passive sampler Application Refs

analytes

Walden Gasbadge dosimeter Personal monitoring [266]

Yanagisawa-type dosimeter Atmospheric pollutants, mountains around [267]
Kyoto Basin, Japan
Sampler described by Kasper Outdoor, Austria [273]
Amay-Sugiur modified sampler Urban and rural areas of Poland [268, 269]
Outdoor air [270]
(forest in Poland)
NH3 UC Davis passive sampler Airborne ammonia concentrations near [274]
large-scale animal facilities
Zürcher passive sampler Ammonia in ambient air, Switzerland [275]
Ferm dosimeter Outdoor air, Asia, Africa [272]
Sampler described by Kasper Monitoring ammonia in urban, inner alpine [276]
and pre-alpine ambient air
Carbon monoxide Dragger diffusion tubes Outdoor and indoor air at street [277]
level shops, Genoa, Italy
Passive electrochemical monitor Personal, preschool children, Helsinki, Finland [278]
LBNL/QGI occupational Workers exposure, Moscone Convention [279]
CO dosimeter (LOCD) Center (MCC), San Francisco
CO2 Passive diffusion sampler (5-L sampler) Measuring 14CO2 in air, laboratory experiments [280]
H2S Palmes-tube type dosimeter Indoor and outdoor air [281]
(Horniman Museum and the Dreadnought Study
Collection Centre), London, UK
Ozone O3 Yanagisawa-type dosimeter Atmospheric pollutants, mountains around [267]
Kyoto Basin, Japan
Passive sampling badges, Laboratory experiments [282]
consist of nitrite-IGFF
Ferm dosimeter Outdoor air, Asia, Africa [272]
Ogawa PS Air pollutants in Sequoia National Park, California, USA [266]
N2O Sampler develop by Cox Laboratory studies [283]
CS2 Diffusive sampling tubes (Perkin–Elmer) Personal sampling—viscose rayon factory, Japan [284]
OVM 3500 3 M Company Personal sampling—viscose rayon factory, Japan [284]
HNO3 Nylasorb nylon filters Air pollutants in Sequoia National Park, California, USA [266]
HF Dosimeter by Medical Air, laboratory [285]
University of Gdansk
Metals SPMD Sn: sea water—inner part of Oslofjord (Norway) [133, 134]
Diffusion sampler—PPD Cr: surface water—Black River (WI, USA) [209]
(parallel plate dialyzer) and Winnebago Lake (WI, USA)
SLMD Cd, Co, Cu, Ni, Pb, Zn—grab water (USA) [71]
Storm water [135]
PLM Cu, Pb, Zn, Cd: water [286, 287]
Textile-based solid sorbent Cu, Pb: water (Canada) [55]
Sampler by Kweitikus Hg: atmosphere monitoring and personal dosimetry [288]
NCPS (Nafion-coated diffusion Aquatic environment [289]
limiting membrane)
PIMS Hg: water–air, environment workplace [82]
Wisconsin modifications Hg: air, laboratory and field experiments, USA [290]
to Ferm sampler
Kabis sampler As, Cd, Cr, Pb: water [223]
Hydra sampler As, Cd, Cr, Pb: water [223]
Discrete interval sampler As, Cd, Cr, Pb: water [223]
Pneumo-bailer As, Cd, Cr, Pb: water [223]
Passive diffusion bag sampler As, Cd, Cr, Pb: water [223]
Mercury vapor monitor 3 M Hg: personal sampling—workers [291]

Detailed comparison of sampling techniques has been
performed for PAH in seawater [292]. Three methods
used for direct water sampling:
in-situ large-volume sampling of particulate and
dissolved hydrocarbons on to filters and XAD resins;
SPE using polystyrene-divinylbenzene disks; and
whole-bulk water sampling
have been compared with sampling by SPMD and blue
mussels (Mytilus edulis). This comparison of sampling
techniques for measurement of PAH in seawater has
shown that blue mussels and SPMD are both suitable for
near-field and far-field locations. The in-situ large-volume
water-sampling technique is useful for measuring higher
molecular weight PAH in the water, but this technique is,
currently, limited by low break-though volume of the low-
 297

Table 6 General evaluation of sampling techniques used in environmental studies of water

Passive Biomonitoring Dynamic techniques

sampler (mussels)
In-situ sampler SPE Grab
(large-volume sampling) disk sampler

Sensivity/detection limits + + NA NA NA
Captures dissolved organic compounds ++ + NA ++ NA
Captures particulate organic compounds NA + + NA
Captures total organic compounds NA + NA + +
Suitable for long-term integrated sampling ++ ++ NA - NA
Suitable for near-field monitoring ++ + + ++ +
Suitable for far-field monitoring ++ + NA + NA
Suitable for assessing bioavailability + ++ NA NA NA
Suitable for low molecular weight compounds NA NA NA NA +
Suitable for broad range of compounds NA NA NA + +
Potential for field contamination + + NA NA +
Easy sample handling + + NA ++ +
Easy sample preparation NA NA ++ +
Cost—initial investment NA + NA + +
Cost—sampling/analysis + NA NA ++ +

++ very good, + good, not suitable, NA not applicable

molecular weight compounds, for example naphthalenes.
SPE and whole/bulk water sampling are limited by the
smaller sampling volumes and, therefore, problems with
detection limits in the analysis. In addition, the SPE
technique could not effectively measure naphthalenes
because of interferences from the filter matrix.
Summary
Despite its relatively long history, passive sampling is
still developing. It has many significant advantages,
including simplicity, low cost, no need for expensive and
sometimes complicated equipment, no power require-
ments, unattended operation, and the ability to produce
accurate results.
There are also limitations that can sometimes be
difficult to overcome, probably the most important of
which is the possible effect of environmental conditions
(for example temperature, air humidity, and air and
water movement) on analyte uptake. Despite such con-
cerns, many users find passive sampling an attractive
alternative to more established sampling procedures. To
gain more general appeal, however, broader regulatory
acceptance would probably be required.
Passive sampling is used most often for determination
of time-weighted average concentrations, the response
time of the sampler is chosen according to the desired
length of the sampling period.
When the measurement session is complete, passive
sampling very often significantly simplifies further steps
in the analytical procedure, because it generally com-
bines handling and analyte preconcentration in a single
step. Thus, with few exceptions, passive sampling
shortens the time between sample collection and analy-
sis, improving the response time of the entire system.
It is also possible to apply the passive technique for
grab sampling, in which case the response time of the
analytical system can be very short compared with other
techniques.
Overall, it is clear that the full potential of passive
sampling techniques is not yet fully realized. Hopefully,
this will change in the not too distant future.
Acknowledgements The Department of Analytical Chemistry is part
of the ‘‘Centre of Excellence in Environmental Analysis and
Monitoring’’, a research project supported by the European
Commission under the Fifth Framework Programme and con-
tributing to the implementation of the Key Action ‘‘Sustainable
Management and Quality of Water’’ within the Energy, Environ-
ment, and Sustainable Development (Contract No.: EVK1-CT-
2002-80010). The authors acknowledge this generous support.
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