Application of semipermeable membrane device for assessing toxicity in drinking water

Semipermeable membrane devices (SPMDs) mimic passive diffusive transport of bioavailable hydrophobic organic compounds through biological membranes and their partitioning between lipids and environmental levels. Our study was developed on a surface water treatment plant based in Turin, Northern Italy. The investigated plant treats Po River surface water and it supplies about 20% of the drinking water required by Turin city (about one million inhabitants). Surface water (input) and drinking water (output) were monitored with SPMDs from October 2001 to January 2004, over a period of 30 days. The contaminant residues, monthly extracted from SPMDs by dialysis in organic solvent, were tested with the Microtox^TM acute toxic test and with the Ames mutagenicity test. Same extracts were also analyzed with gaschromatography—mass spectrometry technique in order to characterise the organic pollutants sampled, especially Polycyclic Aromatic Hydrocarbons (PAHs).

Although the PAHs mean concentration is about one hundred times lower in the output samples, the mean toxic units are similar in drinking and surface water.

Our data indicate that the SPMD is a suitable tool to assess the possible toxicity in drinking water.     

Use of semi-permeable membrane devices to monitor pollutants in water and assess their effects: a laboratory test and field verification

Uptake of eight pesticides of different classes (organochlorines, synthetic pyrethroids, dinitroanilines, amides) by semi-permeable membrane devices (SPMDs) was studied in a laboratory continuous-flow system. After 20 days of exposure, membrane concentration factors were in the range of 50 000-120 000 for all the analytes except for the amide herbicides propachlor and alachlor, which were not detected in any of the SPMDs. The kinetic data and mathematical models were used to calculate analyte uptake rate constants, SPMD lipid/water partition coefficients, average sampling rates and concentrations of the pesticides in water. To assess the effects of concentrated pesticides, standard bioassays (Salmonella/histidine reversion assay and bioluminescence inhibition in Vibrio fischeri test) were incorporated in the SPMD technique. To test the method in an environmental situation, SPMDs were deployed in polluted sites in Lithuania. Polynuclear aromatic hydrocarbons were the major pollutants detected in the SPMDs deployed in the field. All the SPMD dialysates were highly toxic in the bioluminescence inhibition test but no mutagenic activity was observed in the Salmonella/histidine reversion assay.     

Acute toxicity and genotoxicity of aquatic hydrophobic pollutants sampled with semipermeable membrane devices

Triolein-filled semipermeable membrane devices (SPMDs) were deployed for 4 weeks in polluted water sources in Lithuania. The mixtures of pollutants sampled by the SPMDs were fractionated by size-exclusion chromatography (SEC). The fraction containing average molecular weight compounds such as polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides was screened by gas chromatography and mass spectrometry. The whole (non-fractionated) samples and their SEC fractions were tested in bioassays including Microtox, Mutatox, Daphnia pulex immobilization assay and the sister chromatid exchange (SCE) in human lymphocytes in vitro test. The Microtox test was most sensitive with the estimated EC(50) values in the range of milligrams or even micrograms per milliliter based on the amount of the SPMD triolein. Part of the observed toxicity was caused by elemental sulfur co-sampled by the SPMDs from sediments. The sum of toxicity equivalents of the SEC fractions was smaller than the relative toxicity of the whole samples indicating the presence of synergistic interactions in the complex mixtures of chemical pollutants. The toxic or genotoxic response induced by the chemical mixtures and their fractions was smaller in the D. pulex, Mutatox and SCE tests. In Mutatox, a positive response was only detected without the S9 metabolic activation which indicates the presence of mainly direct-acting mutagens in the samples. Interpretation of the Mutatox data was difficult due to the complexity of dose-response and time-response relationships. The study has demonstrated the potential as well as some limitations of SPMDs in the monitoring of biological effects of bioavailable organic pollutants in the aquatic environment.     

Lipid-Filled semipermeable membrane devices and mussels as samplers of organochlorine compounds in lake water

Semipermeable membrane sampling devices (SPMDs) and caged lake mussels (Anodonta piscinalis) were simultaneously deployed at four lake watercourse sites in Central Finland four weeks in August 1992. This study was part of the regular annual monitoring of the organochlorine compounds (OCC) in pulp-mill recipient watercourses of Finland with bivalves. Chlorohydrocarbons (CHCs), chlorophenol compounds (PCPs), chloroanisoles (PCAs) and chloroveratroles (PCVs) were analyzed from lipid extract of mussels and from the synthetic triolein lipid of the SPMDs. Hexane-diethyl ether (9:1, v/v) dialysis using polyethylene membrane was applied in dean up of the SPMD lipids and, for comparison, to six sets of the mussel fat. Dialysis recovered CHCs but not PCPs from the mussel fat. CHCs, PCPs, PCAs and PCVs were all recovered in dialysis of the SPMD lipid. Handling of SPMDs in the transport and deployment operations caused significant OCC contamination for the blank SPMDs. Similar trends were revealed in the OCC profiles for mussels ans SPMDs. An exception was the lack of PCPs appearing in SPMDs that did appear in mussels and in a complementary manner the appearance of the PCAs and PCVs in SPMDs.     

Assessment of bioavailable PAH, PCB and OCP concentrations in water, using semipermeable membrane devices (SPMDs), sediments and caged carp

Bioavailable water concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were assessed at several freshwater sites in and around the city of Amsterdam. Carp (Cyprinus carpio) were caged for 4 weeks at 10 sites, together with semipermeable membrane devices (SPMDs). In addition, sediment samples were taken at each site. SPMDs and sediments were analysed for PAHs, PCBs and OCPs. Carp muscle tissues were analysed for PCBs and OCP, while PAH metabolites were assessed in fish bile. Contaminant concentrations in the water phase were estimated using three different methods: 1. Using fish tissue concentrations and literature bioconcentration factors (BCFs), 2. Using SPMD levels and a kinetic SPMD uptake model, and 3. Using sediment levels and literature sorption coefficients (K_ocs). Since PAH accumulation in fish is not considered an accurate indicator of PAH exposure, calculated aqueous PAH concentrations from SPMD data were compared with semiquantitatively determined biliary PAH metabolite levels. Contaminant concentrations in the water phase estimated with fish data (Cw_fish) and SPMD data (Cw_spmd) were more in line for compounds with lower K_ow than for compounds with higher K_ow values. This indicates that the assumption of fish–water sorption equilibrium was not valid. At most sites, sediment-based water levels (Cw_sed) were comparable with the Cw_spmd, although large differences were observed at certain sites. A significant correlation was observed between biliary PAH metabolite levels in fish and aqueous PAH concentrations estimated with SPMD data, suggesting that both methods may be accurate indicators of PAH exposure in aquatic ecosystems.     

The identification of readily bioavailable pollutants in lake shkodra/skadar using semipermeable membrane devices (SPMDs), bioassays and chemical analysis

GOAL, SCOPE AND BACKGROUND: Lake Shkodra/Skadar is the largest lake in the Balkans region and located on the border between Albania to the south and Montenegro to the north. Because of the wide range of endemic, rare or endangered plant and animal species it supports, Lake Shkodra/Skadar and its extensive associated wetlands are internationally recognised as a site of significance and importance (Ramsar site). In recent years, social and economic changes in both Albania and Montenegro have lead to unprecedented levels of urban and industrial effluent entering the lake. Of particular concern is the increasing input of toxic hydrophobic organic pollutants (HOPs) into the lake and the degree to which these compounds are available for uptake by aquatic biota. Semipermeable membrane devices (SPMDs) have been shown to sample the readily bioavailable fraction (dissolved phase) of waterborne HOPs and in doing so provide relevant data for exposure assessment. The aim of the current study was to use SPMD-based sampling in conjunction with appropriate bioassays and chemical analysis to identify readily bioavailable HOPs in the lake. METHODS: SPMDs were constructed and deployed at three sites in the Albanian sector and three sites in the Montenegrin sector of Lake Skadar/Shkodra for 21 days. Following the dialytic recovery of target analytes and size exclusion chromatographic clean-up, aliquots of SPMD samples were subjected to GC-MS scan analysis for major components, GC-MS SIM analysis for 16 priority pollutant polycyclic aromatic hydrocarbons (PP-PAHs) and assayed for EROD-inducing, estrogenic and mutagenic potential using rainbow trout liver cells (RTL-W1), the yeast estrogen screen (YES) and the Ames Test, respectively. RESULTS AND DISCUSSION: A total of 39 compounds were tentatively identified in SPMD samples from the six sampling sites. Alkylated PAHs were the most abundant and ubiquitous compounds present along with various sterols and sterol derivatives. Numerous other compounds remain unidentified. 15 of the 16 targeted PP-PAHs were present in samples from one or more of the sampling sites indicating these compounds are both readily bioavailable and widely distributed in Lake Shkodra/Skadar. Total PP-PAH concentrations ranged between 3991 ng/SPMD and 10695 ng/SPMD. Bioassays carried out on SPMD samples revealed significant EROD-inducing and estrogenic potential at five of the six sampling sites indicating toxicologically relevant compounds are readily available for uptake by resident aquatic biota. EROD-inducing potential was positively correlated with targeted PP-PAH concentration (r2 = 0.74). However, comparison of bioassay- and analytically-derived toxicity equivalents revealed targeted PP-PAHs were responsible for less than 0.06% of the total EROD-inducing potential. CONCLUSIONS AND OUTLOOK: The combination of SPMD-based sampling with appropriate bioassays and chemical analysis provided an effective tool for the identification of environmentally relevant waterborne pollutants in Lake Shkodra/Skadar. Our results show that toxicologically relevant HOPs including EROD-inducing and potentially estrogenic compounds are widely distributed in the lake and readily available for uptake by aquatic biota. Our results also suggest that alkylated PAHs rather than parent compounds may be of greater toxicological relevance in the lake. As anthropogenic influences continue to increase, SPMD-based sampling is expected to play a central role in future research concerned with the identification, monitoring and assessment of the risk posed by HOPs to Lake Shkodra/Skadar's aquatic biota.     

Long-term air monitoring of organochlorine pesticides using Semi Permeable Membrane Devices (SPMDs) in the Alps

Atmospheric sampling of organochlorine pesticides (OCPs) was conducted using Semi Permeable Membrane Devices (SPMDs) deployed in the Alps at different altitudinal transects for two consecutive exposure periods of half a year and a third simultaneous year-long period. Along all the altitude profiles, the sequestered amounts of OCPs increased in general with altitude. SPMDs were still working as kinetic samplers after half a year for the majority of the OCPs. However, compounds with the lowest octanol-air partition coefficient (K_oa), reached equilibrium within six months. This change in the SPMD uptake was determined for the temperature gradient along the altitude profile influencing K_oa, OCPs availability in the gaseous phase, and SPMD performance. In sum, it seems two effects are working in parallel along the altitude profiles: the change in SPMD performance and the different availability of OCPs along the altitudinal transects determined by their compound properties and concentrations in air.     

In situ monitoring of urban air in Southern Italy with the Tradescantia micronucleus bioassay and semipermeable membrane devices (SPMDs)

This study was designed to assess toxic and genotoxic compounds in the urban air of Caserta, South Italy using cuttings from the plant Tradescantia #4430. In situ monitoring of gaseous pollutans was made at 17 sampling points in two seasons of the year. Genotoxicity was evaluated by recording the micronuclei in meiotic pollen mother cells (Trad-MCN assay). In addition, the passive sampler semipermeable membrane devices (SPMDs) were deployed at the sampling points with a significant increase in micronuclei frequency. SPMDs concentrated priority organic pollutants were identified by high performance liquid chromatography and gas chromatography, while toxicity and mutagenesis were assessed on the bacterium Vibrio fischeri using the Microtox and Mutatox systems respectively. Significant toxic and mutagenic effects were observed at different points on the town grid and SPMDs effectively concentrated trace contaminants. The relationship between what was present in the air sampled by SPMDs and the micronuclei frequency was also explored.     

Use of semipermeable membrane devices (SPMDs)

Triolein-containing semipermeable membrane devices (SPMDs) were employed as passive samplers to provide data on the bioavailable fraction of organic, waterborne, organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polynuclear aromatic hydrocarbons (PAHs) in streams flowing through a highly polluted industrial area of Bitterfeld in Saxony-Anhalt, Germany. The contamination of the region with organic pollutants originates in wastewater effluents from the chemical industry, from over one-hundred years of lignite exploitation, and from chemical waste dumps. The main objective was to characterise time-integrated levels of dissolved contaminants, to use them for identification of spatial trends of contamination, and their relationship to potential pollution sources. SPMDs were deployed for 43 days in the summer of 1998 at four sampling sites. The total concentration of pollutants at sampling sites was found to range from a low of 0.8 microgram/SPMD to 25 micrograms/SPMD for PAHs, and from 0.4 microgram/SPMD to 22 micrograms/SPMD for OCPs, respectively. None of the selected PCB congeners was present at quantifiable levels at any sampling site. A point source of water pollution with OCPs and PAHs was identified in the river system considering the total contaminant concentrations and the distribution of individual compounds accumulated by SPMDs at different sampling sites. SPMD-data was also used to estimate average ambient water concentrations of the contaminants at each field site and compared with concentrations measured in bulk water extracts. The truly dissolved or bioavailable portion of contaminants at different sampling sites ranged from 4% to 86% for the PAHs, and from 8% to 18% for the OCPs included in the estimation. The fraction of individual compounds found in the freely dissolved form can be attributed to the range of their hydrophobicity. In comparison with liquid/liquid extraction of water samples, the SPMD method is more suitable for an assessment of the background concentrations of hydrophobic organic contaminants because of substantially lower method quantification limits. Moreover, contaminant residues sequestered by the SPMDs represent an estimation of the dissolved or readily bioavailable concentration of hydrophobic contaminants in water, which is not provided by most analytical approaches.     

Simultaneous monitoring of PCDD/Fs and PCBs in contaminated air with semipermeable membrane devices and fresh spruce needles

The contaminated air with burning plastic floor and electronic scrap was monitored with semipermeable membrane devices (SPMDs) and fresh unpolluted spruce needles at the same time for polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs). It was found that there were more polychlorinated dibenzofurans (PCDFs) than polychlorinated dibenzo-p-dioxins (PCDDs) collected from contaminated air. The total amounts of PCBs were much higher than that of PCDD/Fs, but the contribution of them to the WHO-TEQ was less than that of PCDD/Fs. Triolein-containing SPMDs can absorb much more PCDD/Fs and PCBs than spruce needles when they were exposed in contaminated air simultaneously. The logarithm of the concentrations of PCDD/Fs and PCBs in SPMDs and in spruce needles at the same sampling time exhibited a significant linear correlation, the correlation coefficients were larger than 0.86 for PCDD/Fs and 0.92 for PCBs. SPMDs and spruce needles are effective passive air sampler for PCDD/Fs and PCBs. SPMDs and spruce needles can complement each other in passive air sampling.     

Prediction of PCB content in sportfish using semipermeable membrane devices (SPMDs)

Triolein-filled semipermeable membrane devices (SPMDs) were immersed at three locations along the St. Joseph River in northern Indiana for 30 days to see if the PCB content of fish from the same location could be predicted with this model device. Triolein from the SPMD's was analyzed for PCB using enzyme-linked immunosorbent assay (ELISA) and compared to residues detected in fish collected from the same locations. There was a significant difference (p < 0.05) in total PCB concentrations between SPMD samples. However, due to variability in PCB residues between species and low PCB residues in SPMDs, a direct correlation between PCBs in sportfish and SPMDs could not be determined.     

Pine needle and semi-permeable membrane device derived organochlorine compounds (OCPs) concentrations in air in Mersin Province to Taurus,Turkey

Abstract

Organochlorine pesticides (OCPs) were analyzed in three different ages (half-, 1.5-, 2.5-year-old) for needles and semi permeable membrane devices (SPMDs) at three deployment periods from sea level to 1881 meter above sea level. Individual HCHs concentrations ranged between 1.4 and 129?pg/g fw depending on the age and sampling season while 2.5-year-old needles showed higher HCHs levels compared to half and 1.5- year-old. Correlation between elevation and HCH concentration in SPMDs was found but not in needle samples. Concentrations of HCHs in SPMDs indicated clearly cold condensation effect on accumulation in winter period and increased with altitude. Concentrations of DDTs in half and 1.5-year-old needles were lower than 2.5-year-old needles. The highest total concentration of DDTs was detected in 1-year-period SPMD. Higher concentrations were found in 2.5-year-old needles for other OCPs. Seasonal and altitude-dependent changes were not observed for other OCPs in SMPDs. Total accumulation of OCPs in SPMDs were found higher than in needles. On the contrary, an increased accumulation rate was observed for HCHs in SPMD. In general, Total concentrations of DDTs and HCHs were similar to total of other OCPs in all altitudes when dominating endosulfan wasnot taken into account in the computation of total concentration of other OCPs.     

Purification of triolein for use in semipermeable membrane devices (SPMDs)

Analyses of triolein-containing semipermeable membrane devices (SPMDs) have sometimes been impeded by interferences caused by impurities endemic to triolein that codialyze with the analytes. Oleic acid and methyl oleate have been the most troublesome of these impurities because of their relatively high concentrations in triolein and because significant residues of both can persist even after size exclusion chromatographic (SEC) fractionation. These residues have also been blamed for false-positive signals during bioindicator testing of SPMD dialysates. To prevent these problems, a simple, cost-effective procedure was developed for purifying triolein destined for use in SPMDs: the bulk triolein is repeatedly (6x) partitioned against methanol. Tests of the procedure show that 14C-oleic acid is completely removed from the triolein. After SEC fractionation, dialysates of standard-size SPMDs made with the purified triolein contain less than 5 microg of methyl oleate as compared to sometimes more than 500 microg for dialysates (also after SEC) of SPMDs made with unpurified triolein. Gas chromatographic analyses with flame ionization and electron capture detection show that the purification treatment also greatly reduces the number and size of peaks caused by unidentified contaminants in the triolein. Microtox basic assay of dialysates of SPMDs shows that those made with the purified triolein have lower acute toxicities than dialysates of SPMDs made with unpurified triolein. Yeast estrogen screen (YES) testing of SPMDs fabricated with unpurified and purified triolein demonstrates that the purification process removes all background estrogenic activity.     

Monitoring PAHs in the Brisbane River and Moreton Bay, Australia, using semipermeable membrane devices and EROD activity in yellowfin bream, Acanthopagrus australis

Two water quality monitoring strategies designed to sample hydrophobic organic contaminants have been applied and evaluated across an expected concentration gradient in PAHs in the Moreton region. Semipermeable membrane devices (SPMDs) that sequester contaminants via passive diffusion across a membrane were used to evaluate the concentration of PAHs at four and five sites in spring and summer 2001/2002, respectively. In addition, induction of hepatic cytochrome P4501, EROD activity, in yellowfin bream, Acanthopagrus australis, captured in the vicinity of SPMD sampling sites following deployment in summer was used as a biomarker of exposure to PAHs and related chemicals. SPMDs identified a clear and reproducible gradient in PAH contamination with levels increasing from east to west in Moreton Bay and upstream in the Brisbane River. The highest PAH concentrations expressed as B(a)P-toxicity equivalents (TEQs) were found in urban areas, which were also furthest upstream and experienced the least flushing. Cytochrome P4501 induction in A. australis was similar at all sites. The absence of clear trends in EROD activity may be attributable to factors not measured in this study or variable residency time of A. australis in contaminated areas. It is also possible that fish in the Moreton region are displaying enzymatic adaptation, which has been reported previously for fish subjected to chronic exposure to organic contaminants. These potential interferences complicate interpretation of EROD activity from feral biota. It is, therefore, suggested that future monitoring combine the two methods by applying passive sampler extracts to in vitro EROD assays.     

Evaluation and in situ assessment of photodegradation of polyaromatic hydrocarbons in semipermeable membrane devices deployed in ocean water

Semipermeable membrane devices (SPMDs) were deployed in water using four different methods: a typical SPMD cage with and without a mesh cover, a bowl chamber and without any protection. In addition to routinely used performance reference compounds (PRCs), perdeuterated dibenz[a,h]anthracene was added. Due to its high sampler to water partition coefficient no measurable clearance due to diffusion was expected during the deployment period, hence any observed loss could be attributed to photodegradation. The loss of PRCs was measured and SPMD-based water concentrations determined. Results showed that a typical SPMD deployment cage covered with mesh provided the best protection from photodegradation. Samplers which had undergone the highest photodegradation underestimated PAH water concentrations by up to a factor of 5 compared to the most protected SPMDs. This study demonstrates that the potential for photodegradation needs to be addressed when samplers are deployed in water of low turbidity.     

Semipermeable membrane devices accumulate conserved ratios of sterane and hopane petroleum biomarkers

Semipermeable membrane devices (SPMDs) are commonly used as a time-integrated measure of aqueous concentrations of persistent hydrophobic chemicals, including PAH, pesticides, dioxins, and PCBs. Another class of persistent hydrophobic chemicals is petroleum biomarker compounds (hopanes and steranes) that are used for hydrocarbon source identification and allocation. In this study three different passive sampling device designs were exposed to a complex hydrocarbon mixture (Alaska North Slope crude) in a laboratory experiment to determine uptake rates of biomarkers into SPMDs. In addition to the standard triolein filled SPMDs, iso-octane filled SPMDs (ISPMDs) and unfilled low-density polyethylene strips (PESDs) were tested. Uptake rates and effective sampling rates were determined for 53 compounds. There was little variation in sampling rates among the individual biomarkers; average values (ld(-1)) for hopanes were 0.43+/-0.07 (PESD), 0.33+/-0.06 (SPMD), and 0.44+/-0.03 (ISPMD) and average sterane sampling rates were 0.57+/-0.04 (PESD), 0.42+/-0.03 (SPMD), and 0.53+/-0.03 (ISPMD). The primary reason for biomarker analysis is for source discrimination of petroleum. Nineteen different diagnostic ratios were measured, and were found to be remarkably well conserved between the oil, water, and all three devices. This indicates that SPMDs, PESDs, and ISPMDs should each be effective for source discrimination studies of petroleum contamination.     

Passive water sampling via semipermfable membrane devices (SPMDS) in concert with bivalves in the Sacramento/San Joaquin River Delta

Freshwater clams (Corbicula fluminea) and the Huckins et al. (1) semi-permeable membrane sampling device (SPMD) were simultaneously deployed at three sites on the Sacramento and San Joaquin rivers in 1990. Both clams and the SPMDs were analyzed for sequestered pesticides and polychlorinated biphenyls (PCBs) by gas chromatography with electron capture detection (GC/ECD). Polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and non-ortho PCBs were quantified by high resolution mass spectrometry (MS). In general, levels of organochlorine compounds were approximately 1.6 times higher in clams on a wet weight basis than in the SPMDs, and trends in accumulation were similar except where biofouling of the SPMD membranes decreased uptake rates. Comparisons between the normalized, average levels of PCDDs accumulated showed that while octachlorodibenzo-p-dioxin (OCDD) was most prevalent in both clams and SPMDs, much higher levels of 2,3,7,8 TCDD were found in the SPMDs than in the clams; 2,3,7,8 TCDD was 32% of the profile relative to the OCDD level for the SPMDs and <1% of the clam OCDD level. PCB levels showed the clams primarily accumulated hexachlorinated PCBs while the pentachlorinated and tetrachlorinated congeners were higher in the SPMDs. Differences in profiles for homologous series among the PCBs reveal that some congeners, especially those with 2,4,5 substitution, are more likely to bioaccumulate than those with lower chlorination or adjacent unsubstituted sites. GC/MS chromatograms indicate the SPMDs also sequestered several polyaromatic hydrocarbons. GC/ECD chromatograms indicate the presence of several unidentified, early eluting compounds in the SPMDs.     

Feasibility of a simple laboratory approach for determining temperature influence on SPMD–air partition coefficients of selected compounds

Semipermeable membrane devices (SPMDs) are a widely used passive sampling methodology for both waterborne and airborne hydrophobic organic contaminants. The exchange kinetics and partition coefficients of an analyte in a SPMD are mediated by its physicochemical properties and certain environmental conditions. Controlled laboratory experiments are used for determining the SPMD–air (K_sa's) partition coefficients and the exchange kinetics of organic vapors. This study focused on determining a simple approach for measuring equilibrium K_sa's for naphthalene (Naph), o-chlorophenol (o-CPh) and p-dichlorobenzene (p-DCB) over a wide range of temperatures. SPMDs were exposed to test chemical vapors in small, gas-tight chambers at four different temperatures (−16, −4, 22 and 40 °C). The exposure times ranged from 6 h to 28 d depending on test temperature. K_sa's or non-equilibrium concentrations in SPMDs were determined for all compounds, temperatures and exposure periods with the exception of Naph, which could not be quantified in SPMDs until 4 weeks at the −16 °C temperature. To perform this study the assumption of constant and saturated atmospheric concentrations in test chambers was made. It could influence the results, which suggest that flow through experimental system and performance reference compounds should be used for SPMD calibration.     

Semipermeable membrane device (SPMD) for monitoring PCDD and PCDF levels from a paper mill effluent in the Androscoggin River, Maine, USA

Paper mill effluents may contain polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) that are normally generated due to chlorinated bleaching of pulp and paper. We used the semipermeable membrane device (SPMD) to monitor PCDD/F levels upstream and downstream of a paper mill on the Androscoggin River, in Jay (ME). Following the 36 day deployment, SPMD dialysis and cleanup, the samples were analyzed by HRGC/HRMS. Total concentrations of PCDD/Fs in SPMDs (sum of all tetra-through octachlorinated congeners) ranged from 4.71 pg g(-1) to 26.26 pg g(-1). Five out of the targeted 17 toxic congeners were detected, including: 2,3,7,8-TCDF; 1,2,3,7,8-PeCDF; 2,3,4,7,8-PeCDF; 1,2,3,4,6,7,8-HpCDD and OCDD. Permeability reference compounds (PRCs) were used for in situ calibration of the SPMD sampling rate (Rs). In all sites, water concentrations were the highest for OCDD (0.081-0.103 pg l(-1)), and the lowest for 1,2,3,7,8-PeCDF (0.005-0.009 pg l(-1)). There was not a consistent pattern of upstream-downstream gradient in the PCDD/F levels. This suggested that processes other than the mill in Jay (multiple sources, river dynamics) governed the flux of PCDD/Fs in the sampling locations. The SPMD results were validated by comparison to other studies on the Androscoggin River and elsewhere, confirming the potential of the device as a useful monitoring technique for PCDD/Fs in large river systems.     

Comparison of active and passive sampling for the determination of persistent organic pollutants (POPs) in sewage treatment plants

Semipermeable membrane devices (SPMDs) and conventional active sampling methods were used for the sampling of wastewater from the wastewater treatment plant of Thessaloniki, northern Greece. The occurrence of 22 POPs was shown by both sampling methods. The most abundant compounds were heptachlor-exo-epoxide and PCBs-52; -101 and -180. Concentrations of POPs detected by active sampling and those estimated by the SPMDs matched very well in some cases, but significant mismatches were also observed. Regression analysis of the results detected by both methods showed moderate correlations. The highest uptake rate of hydrophobic compounds by SPMDs was observed for analytes with log K(OW) between 5.5 and 6.0. Our data suggest that active and passive sampling are complimentary, and that at least for the outflow of a WWTP, SPMDs could be used for the routine monitoring of compounds that are listed at the Water Framework Directive of the European Commissions.