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Article history: Passive sampling is highly complimentary to spot sampling in environmental analysis. A
Received 30 August 2007 polar organic chemical integrative sampler (POCIS) was extensively tested to optimize its
Received in revised form performance under both controlled and field conditions. The passive sampler was subse-
8 November 2007 quently used for the sampling and analysis of estrone, 17-estradiol, 17␣-ethynylestradiol,
Accepted 15 November 2007 bisphenol A, propranolol, sulfamethoxazole, meberverine, thioridazine, carbamazepine,
Published on line 21 November 2007 tamoxifen, indomethacine, diclofenac and meclofenamic acid in sewage effluent and river
water. Under laboratory conditions, the kinetics of compound uptake by POCIS were linear
Keywords: during 10-day of exposure. POCIS sampling rates of the target compounds were signifi-
Passive sampling cantly greater by using polyethersulfone instead of polysulfone membrane, and enhanced
Pharmaceuticals with increasing sorbent exposure area. Together with spot water sampling, the optimized
Endocrine disrupting chemicals POCIS was deployed in the River Ouse, West Sussex, UK to obtain field-derived sampling
Liquid chromatography–tandem rates which, for endocrine disrupting chemicals (EDCs), were significantly higher than those
mass spectrometry from laboratory experiments. Both spot and passive sampling demonstrated that most of
Gas chromatography–mass the target chemicals were frequently detected in sewage effluent and river waters, and that
spectrometry the daily changes in the pollutant concentrations were greater for pharmaceuticals than
for EDCs. The aqueous concentrations of all compounds were elevated at a sewage outfall,
which is confirmed to be an important source of the target compounds in the river. The
validated POCIS was then successfully used to estimate the concentrations of the target
compounds in effluent and river water, which were in good agreement with those from spot
sampling for pharmaceuticals.
© 2007 Elsevier B.V. All rights reserved.
∗
Corresponding author. Tel.: +44 1273 877318; fax: +44 1273 678937.
E-mail address: j.zhou@sussex.ac.uk (J.L. Zhou).
0003-2670/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.aca.2007.11.024
38 a n a l y t i c a c h i m i c a a c t a 6 0 7 ( 2 0 0 8 ) 37–44
Considering the potential impacts of EDCs and PPCPs, they and behavior of emerging contaminants in sewage effluent
should be routinely monitored in aquatic systems. The most and river waters. Robust extraction and analytical methods
widely used technique for performing such monitoring is spot have been developed based on solid-phase extraction (SPE)
sampling followed by laboratory-based extraction and analy- followed by gas chromatography–mass spectrometry (GC–MS)
sis [6–8]. This approach, however, yields only an instantaneous for EDCs [20,21] and liquid chromatography–tandem mass
measurement of pollutant levels and suffers from the uncer- spectrometry (LC–MS–MS) for pharmaceuticals [22]. Labora-
tainty of short- and long-term concentration variations. An tory calibration was performed to evaluate the sampling rate
increase in sampling frequency or the use of flow- and time- of the modified POCIS for the target compounds. The effects
weighted automatic samplers may reduce such uncertainty; of different conditions (e.g. size of sampler) on POCIS sam-
however, the associated increase in costs may prove unfeasi- pling rates were evaluated. The POCIS sampling rates derived
ble [9,10]. from laboratory conditions were compared with those from
There has been rapid development in the use of passive field experiments. Estimation of the ambient aqueous concen-
sampling devices that allow continuous monitoring of aque- tration of target chemicals was achieved by using field-based
ous pollutants without the disadvantages of using organisms sampling rates.
[9–12]. Of the various passive sampling devices, the most
widely used is the semi-permeable membrane device (SPMD)
2. Experimental
consisting of a tubular polyethylene membrane containing
a film of lipids such as triolein [13,14]. In comparison to
traditional water sampling, SPMD can be standardized and 2.1. Materials
deployed over a long period, can detect low levels of organic
contaminants, and mimics the bioconcentration of pollutants The solvents used including methanol and ethyl acetate were
in aquatic organisms [15]. However, SPMD is not suitable of distilled-in-glass grade from Rathburns Chemicals Ltd.
for polar organics, as either the membrane is impermeable (Scotland). Compounds E1, E2, EE2, E2-d2 , propranolol (pro),
to such compounds or accumulation is thermodynamically sulfamethoxazole (sul), meberverine, thioridazine, carba-
unfavorable due to the low affinity of the receiving phase for mazepine (carb), tamoxifen, indomethacine (indo), diclofenac
such analytes [16]. As it is the polar compounds (e.g. EE2) that (diclo) and meclofenamic acid were purchased from Sigma,
are primarily responsible for the estrogenic activities, recent UK, and bisphenol A (BPA) and BPA-d16 were supplied by
development has been focused on their passive sampling, Aldrich (Dorset, UK). Diuron-d6 and 13 C-phenacetin were
e.g. polar organic chemical integrative sampler (POCIS) and purchased from Cambridge Isotope Laboratories, USA. Sep-
Chemcatcher [17,18]. POCIS comprises a solid receiving phase arate stock solutions of individual compounds (1000 mg L−1 )
(sorbent) sandwiched between two microporous polyethersul- were prepared by dissolving an appropriate amount of each
fone (PES) membranes. POCIS samples from water and thereby substance in methanol. From these standards, a mixture
enables the chemical concentration to be estimated as follows of working standards or internal standards (BPA-d16 , E2-
[12,17]: d2 , diuron-d6 , 13 C-phenacetin) containing each compound
at 10 mg L−1 was prepared by diluting the stock solution in
Ms = Cw Rs t (1) methanol. All the standard solutions were stored at −18 ◦ C
prior to use. Ultrapure water was supplied by a Maxima Unit
where Ms is the mass of analytes in the receiving phase at from USF Elga, UK.
time t, Cw represents time-weighted average concentration in The passive sampling device was similar to POCIS [17]
water during the deployment period. Rs is the sampling rate of except the holder which supports both the diffusion-limiting
the system, which may be interpreted as the volume of water membrane and sorbent and seals them in place, was made of
cleared of analyte per unit of exposure time by the device [19]. PTFE rather than stainless steel (Fig. 1). In addition, the device
Chemcatcher uses a polytetrafluoroethylene (PTFE) sup- of different exposure diameters (27, 38, 54 mm) was tested.
port device to protect a layer of membrane which covers a solid The Oasis HLB sorbent (100 mg) from Waters Ltd., UK was
receiving phase (e.g. C18 Empore disk). Accumulation rates chosen because it sorbs a wider range and polar compounds
and selectivity are regulated by the choice of both the mem- better than C18 [20,22]. The Oasis sorbent was spread evenly
brane and the solid receiving material; both are supported between the membranes. The PES membrane (0.1 m pore
and sealed in place by an inert plastic housing [12,18]. Both of size) and polysulfone (PS) membrane (0.2 m pore size) were
these samplers have advantages over traditional methods of
sampling; however, further improvement and validation are
needed. For example, existing calibration experiments were
only performed in small systems, e.g. 1 L microcosms [17].
Certain factors (e.g. pollutant concentration, salinity) which
may affect the sampling rate were not reported [17,18]. Fur-
thermore, in order to estimate water concentration more
accurately, it is essential to validate laboratory-derived with
in situ sampling rates.
This paper focused on the validation and application of
POCIS for emerging contaminants in water, including evalua- Fig. 1 – The schematic diagram of the POCIS device (1) PTEE
tion of spot and passive sampling for studying the occurrence holder, (2) screw, (3) membrane, (4) sorbent and (5) hole.
a n a l y t i c a c h i m i c a a c t a 6 0 7 ( 2 0 0 8 ) 37–44 39
provided by Pall Gelman Sciences (VMR International, UK). (29 January to 9 February 2007). The samplers were suspended
PTFE used to construct the sampler was from Aquarius Plastics vertically at a water depth of 50–100 cm by attaching to a float-
Ltd., UK. Peristaltic pumps (Watson Marlow 401U/DM2) and ing ball. POCIS fitted with PES membrane and Oasis sorbent
tubes (0.5 mm × 1.6 mm and 3.2 mm × 1.6 mm) for controlling as the receiving phase with an exposure diameter of 54 mm,
the flow-through system were from Fisher, UK. were deployed at each site. Three spot water samples (1 L)
and POCIS were sampled each day. Water samples were fil-
2.2. Oasis sorbing capability for target chemicals tered through pre-combusted GF/F filters (0.7 m), spiked with
100 ng of internal standards and extracted by SPE. The ana-
Before the sorbents were used as the receiving phase of POCIS, lytes were eluted from the cartridges with 10 mL methanol,
it was necessary to determine their sorbing capacity for the which were concentrated to 0.3 mL under N2 , and analyzed
target chemicals. Samples of 50 mL of water spiked with 5 g of by LC-tandem-MS for pharmaceuticals and GC-MS for EDCs
each compound were passed through glass columns contain- [20–22]. The results were used to derive field-based sampling
ing 100 mg sorbent. The concentrations of target compounds rates for POCIS. Based on the field POCIS blanks, the limits of
were selected at levels above typical sequestered chemical quantification (LOQ) for selected target compounds in water,
residues from passive samplers to ensure future applications as calculated from Eq. (1), were from 6 to 487 pg L−1 .
of POCIS. Analysis of permeate from the sorbent beds showed The validated POCIS was deployed in the River Ouse (out-
concentrations of the chemicals below limits of detection fall, upstream, downstream) during 23–27 October 2006, for
(LOD), indicating that target chemicals had been retained by comparing performance with spot sampling. Again water
the sorbents. Recovery of the target compounds from the sor- samples were taken daily for monitoring the target com-
bents was achieved by eluting the sorbent beds with 20 mL pounds, while POCIS was sampled at the end of the week-long
of methanol, followed by concentration under N2 , and GC- experiment. In addition, water properties such as tempera-
MS analysis [20,21]. Good recovery (80–87%) of the target ture, pH and dissolved oxygen at each site were recorded at
compounds was achieved from replicate sampling and anal- each visit.
ysis, confirming that the sorbent has sufficient capacity for
trapping target compounds and can be used in POCIS for mon-
itoring purpose. 3. Results and discussion
Fig. 2 – Accumulation of BPA (1.63 g L−1 ), E1 (1.41 g L−1 ), E2 (2.14 g L−1 ) and EE2 (1.37 g L−1 ) from water by the passive
sampler under laboratory conditions.
aquatic environment. It allows polar organic chemicals to tors such as the biodegradability, pore size, strength and
pass through to the sorbent, while particulates with cross- durability.
sectional diameters greater than the membrane pore size will In this study, the performance of POCIS made by PES and
be excluded selectively. Without the membrane, direct contact PS membrane was compared, by calculating the sampling
of these excluded materials with the sorbent can result in a rates of POCIS following exposure. As shown in Fig. 3, the
site-specific bias of apparent contaminant concentrations in sampling rate of the target compounds varied from 0.033 to
the sorbent, reduce uptake due to enhanced biofouling in the 0.048 L day−1 (R.S.D. = 12.5–19.1%) for PES membrane, and from
membrane and sorbent, and potentially interfere with sam- 0.004 to 0.017 L day−1 (R.S.D. = 6.8–13.4%) for PS membrane. As
ple processing and analysis. Kingston et al. [18] suggested the PES membrane showed significantly higher Rs than PS
that PS membrane was suitable for polar organic compounds.
Alvarez et al. [17] however concluded that PES membrane
was preferred to sample polar organic contaminants, after
studying many types of membrane and considering fac-
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