Monitoring of organotin compounds in seawater using semipermeable membrane devices (SPMDs)--tentative results

The impact of anthropogenic pollutants on the marine ecosystem is related to the concentrations experienced by the biota in the seawater and the resulting concentration in the organism. Results from monitoring of pollutants in water samples provide snapshots that can be high or low depending on a wide range of variables. To provide more integrated information, semipermeable membrane devices, SPMDs, have been used to monitor different organic pollutants. In this survey, SPMDs were used to monitor organotin compounds in the marine environment. Time-integrated sampling using SPMDs and direct water sampling was carried out at six stations in the inner Oslofjord, Norway. The sample work-up procedure for both water and SPMDs was based on direct derivatisation using NaBEt4 and simultaneous extraction with an organic solvent. Analysis was performed using a gas chromatograph equipped with an atomic emission detector. The results show that SPMDs do accumulate organotin compounds from the water phase. Both tributyl- (TBT) and dibutyltin were detected in all of the analysed membranes while no monobutyltin was found. Levels found in SPMDs range from < 1 to 220 ng Sn SPMD(-1). Water concentrations range from 0.4 to 10 ng Sn L(-1). An investigation of relative levels of TBT showed a similar concentration gradient in the inner Oslofjord using either direct water sampling or passive sampling by SPMDs. As the membranes are able to accumulate the organotins from the water it will be possible to locate lower concentrations than with direct analyses of water samples.     

Organotin compounds in the marine environment of the Bay of Piran,northern Adriatic Sea

In the year 2000, organotin pollution was investigated in the Bay of Piran, Slovenia, at the northern extremity of the Adriatic Sea. Gas chromatography-mass spectrometry with single ion monitoring GC/MS-SIM was applied for speciation analysis of pentylated organotin compounds in water and mussels. Sampling of marine waters was performed in summer and autumn at 8 locations. Mussels Mytilus galloprovincialis were collected only in summer at 3 locations. The highest concentrations of tributyltin (TBT) in marine water ranged from 500 to 630 ng L(-1) (as Sn) in summer and from 180 to 230 ng L(-1) (as Sn) in autumn. TBT concentration in mussels varied from 500 to 3500 ng g(-1) dry weight (d.w.) (as Sn). The study indicated remarkable butyltin pollution of the Slovenian coastline. Accuracy of the analytical procedure was verified by BCR CRM 477.     

Butyltin compounds and their relation with organic matter in marine sediments from San Vicente Bay—Chile

Tributyltin and its degradation products, mono-and dibutyltin have been determined in sediments collected in some representative sites in San Vicente Bay, Chile. The organic matter contents of sediments and water collected simultaneously from the same sampling sites were also determined. High levels of total organic carbon were found in sediments, especially in those from the northern part of the bay (1.80-8.87%). Good correlations were found between total organic carbon and the oxidizable and refractory carbon fractions. Among the butyltin species determined, TBT presented the highest levels, ranging from 14 to 1,560 ng Sn g(-1) dry weight. Concentration ratios of TBT to DBT ranged between 1.33 and 3.10, showing a high degree of contamination in sediments of this Chilean bay. All data obtained were analysed by the chemometric method of principal components analysis. A strong correlation was found between TBT and DBT concentrations in sediments, the different organic matter contents in sediments and water. In marine organisms only TBT was detected, containing the filterer organism Semele solida higher level than Perumytilus purpuratus and Pyura chilensis (220, 150 and 120 ng Sn g(-1) dry weight, respectively). For the alga Rodoficea iridae the TBT concentration was 60 ng Sn g(-1) dw. Comparatively, these values are higher than those reported for the same kind of marine organisms worldwide. The different samples from San Vicente Bay were found to be contaminated by TBT. This contamination can be attributed to the different anthropogenic activities taking place in the bay.     

半渗透膜采样技术监测城市污水处理流程中的难降解有毒有机污染物

应用新型半透膜采样技术（ＳＰＭＤ），监测某城市污水处理流程中８个点污水中两类难降解有毒有机污染物多氯联苯（ＰＣＢ）和多环芳烃（ＰＡＨ），同时同地采集水样，气相色谱质谱联机，选择性离子扫描方式对各ＰＣＢ异构体和ＰＡＨ定性定量。与水样液液萃取相比，ＳＰＭＤ采样技术显著提高了分析的准确度。根据测定的采样器中污染物浓度，推算采样期间该点污水中的平均浓度，与瞬间水样分析结果符合程度较好。半透膜采样方法可用于污水处理工艺流程中多氯联苯和多环芳烃污染物的定性和半定量监测     

Comparison of the use of mussels and semipermeable membrane devices for monitoring and assessment of accumulation of mutagenic pollutants in marine environment in combination with a novel microbiological mutagenicity assay

A novel microbiological mutagenicity assay, based on bioluminescence of a marine bacterium Vibrio harveyi mutant strain, potentially suitable for monitoring and assessment of mutagenic pollution of marine environment, has been described recently. Here, we tested the use of this assay, in combination with either mussels (Mytilus sp.) or semipermeable membrane devices (SPMDs), in assessment of accumulation of mutagens in marine water (samples of Baltic Sea water were tested). Either similar results were obtained in both systems or higher signals in the SPMD-based system were detected, depending on the tested water samples. We conclude that the use of both mussels and SPMDs in combination with the V. harveyi bioluminescence mutagenicity assay is a method suitable for monitoring and assessment of accumulation of mutagenic pollutants in marine environment, but in some cases the SPMD-based system may provide a more sensitive test.     

One-year monitoring survey of organic compounds (PAHs, PCBs, TBT), heavy metals and biomarkers in blue mussels from the Arcachon Bay, France

Marine mussels Mytilus sp. were transplanted on a monthly basis in cages over one year to oyster farms and harbours in the Arcachon Bay (France) in order to assess the water quality of the bay. Contaminant levels (organotin compounds, trace metals, PCBs and PAHs) were measured in tissues of transplanted mussels and mussels from a reference station, along with physiological parameters of the mussels (condition indexes, lipid content and dry weight). Four biomarkers (AChE: acetylcholinesterase activity, GST: gluthathione S-transferase activity, CAT: catalase activity and TBARS: thiobarbituric acid-reactive substance content) were also monitored. The remote stations monitored (oyster parks) exhibited no accumulation pattern of pollutants. Their respective concentrations therefore constitute a background level of the contamination in the bay ([TBT]= 30 ng Sn g(-1) dw, [SigmaHAPs]= 100 ng g(-1) dw, [SigmaPCBs]= 35 ng g(-1) dw). The elevated chemical contamination of the largest harbour of the bay, the Arcachon harbour, can be interpreted in terms of persistence of organotin compounds ([SigmaOTs]= 1500-2000 ng Sn g(-1) dw) and PAHs ([SigmaHAPs]= 4500-5000 ng g(-1) dw) in sediments and, to a lesser extent, of direct inputs of copper ([Cu]= 20 microg g(-1) dw in harbours versus 7 in oyster parks) and petrogenic PAHs ([methylphenanthrenes]= 1600 ng g(-1) dw in the dockyard versus 170 at the gas stations), related to the use of copper-based antifouling paints and to dockyard activity, respectively. However, the Arcachon Bay presents a low contamination level by PCBs and metals, including harbour stations. Furthermore, higher levels of other PAHs (particularly alkyl PAHs such as methylphenanthrenes/1600 ng g(-1) dw) not included in the 16 PAHs from the EPA priority list (usually studied in biomonitoring programmes/1500 ng g(-1) dw) in the Arcachon harbour underline the need to integrate these compounds in biomonitoring of highly PAH-polluted areas such as harbours in order to avoid misinterpretation of the biological responses observed. Biomarker responses were not able to discriminate the different chemical contamination levels recorded in the Arcachon Bay and rather reflected changes in environmental factors. Furthermore, the strong intraspecies variability of biological responses could be due to genetic differences of mussels from the Arcachon Bay. It is the first time that such an integrated monitoring is performed in the Arcachon Bay, also taking into account seasonal variations of chemical contents and biomarkers levels in mussel tissues.     

利用Triolein半渗透膜采样技术测定洋河水中的优先污染物

应用Ｔｒｉｏｌｅｉｎ半渗透膜采样器采集了河北洋河宣化至官厅水库河段水样，根据测定采样器中多氯联苯污染物（ＰＣＢｓ）及其它优先污染物浓度，可以估算这些污染物在河段水体中的平均浓度。将结果与同时同地采集的水样，经萃取浓缩后分析得到的结果比较，发现对于不同类型污染物，二者符合程度不同。本研究证明半渗透膜被动采样技术可用于水中多氯联苯等难降解污染物的定量监测，有可能在我国的优先污染物监测工作中发挥作用     

利用Triolein-半渗透膜采样技术测定淮河水中的有毒有机污染物

利用 Triolein 半渗透膜采样技术 ( Triolein SPMD)采集了淮河信阳、淮南断面水样 ,测定了采样器中多氯联苯、多环芳烃、取代苯等有毒有机污染物浓度。污染物在 SPMD酯中高浓度富集 ,使其定性和定量更加容易和准确。根据SPMD酯 水分配平衡理论 ,进一步估算得到目标污染物在水中的平均浓度。本研究证明 Triolein SPMD技术可用于水中多氯联苯、多环芳烃、取代苯等污染物的采集和定量分析 ,可在我国的优先污染物监测、控制工作中发挥作用。     

Polybrominated diphenyl ethers (PBDEs) in freshwater mussels and fish from Flanders, Belgium

The levels and distribution of PBDEs in zebra mussels and several freshwater fish species (eel, carp and gibel carp) were investigated for different sites in Flanders, Belgium. In parallel, other organohalogenated contaminants, such as polychlorinated biphenyls (PCBs), p,p[prime or minute]-DDE and hexachlorobenzene (HCB) were also measured and their relationship with PBDEs was investigated. At most sites, individual PBDE congeners were present at detectable levels in mussel tissue, with the mean [summation operator]PBDE concentration ranging from 0.15 to 1.8 ng g(-1) wet weight (ww). The PCB concentrations in mussels ranged from 6.2 to 102 ng g(-1) ww. HCB and p,p[prime or minute]-DDE could be measured in mussels from most sites, mean values ranging from below the limit of quantification (LOQ) to 0.58 ng g(-1) ww and from 0.66 to 6.5 ng g(-1) ww, respectively. Except for one site (Blokkersdijk, Antwerp) where PBDEs were below the LOQ in carp muscle, all fish samples from other sites contained detectable PBDE levels, with the highest concentrations (14 +/- 14 ng g(-1) ww) being measured in eel liver from Watersportbaan (Ghent). The sampled sites covered a broad concentration range of organohalogenated pollutants with the highest values being consistently measured in eel liver. With few exceptions, all correlations between PBDEs and organochlorine pollutants for each species were low (r < 0.50) and most were statistically not significant (p > 0.05). This suggests that the exposure to contaminants arises from local sources possessing different signatures of PBDEs and organochlorine pollutants.     

Time trend of Butyl- and Phenyl-Tin contamination in organisms of the Lagoon of Venice (1999–2003)

In the period 1999-2003 a monitoring study on the accumulation of organotin compounds in edible organisms in the Lagoon of Venice was conducted. Butyl and Phenyl derivatives were determined in pooled samples of Mytilus galloprovincialis and Tapes spp. with the aims of assessing organotin contamination in the Lagoon of Venice in the period just preceding their ban in Europe, monitoring the concentrations in organisms with a high commercial use, evaluating a potential hazard for human health due to seafood and identifying the possible contamination sources. Sampling stations (up to 20) were distributed around the Lagoon and particularly concentrated in the area close to the town of Chioggia. Significantly higher (analysis of variance (ANOVA), p < 0.05) tributyltin (TBT) concentrations were found in mussels (from 38 +/- 8 to 6,666 +/- 1,333 microg kg(-1) d.w., as TBT(+)), than in clams (from 6 +/- 1 to 2,256 +/- 451 microg kg(-1) d.w., as TBT(+)). During the 3 years of the survey no increase in average concentrations of the butyltin compounds (tributyltin (TBT) + dibutyltin (DBT) + monobutyltin (MBT)) was observed (ANOVA, p > 0.05) in either species. Furthermore, by analyzing the entire data set, it is evident that most stations show analogous concentrations in the 3 years for both species, whereas few have anomalously higher concentrations. If organotin concentrations in specimens from some sites are compared with the Tolerable Average Residue Level, a possible risk for human health must be considered.     

Uptake of some selected aquatic pollutants in semipermeable membrane devices (SPMDs) and the polar organic chemical integrative sampler (POCIS)

The uptake characteristics of semipermeable membrane devices (SPMDs) and polar organic chemical integrative samplers (POCISs) were examined for mono, di and tributyltin, triphenyltin, pyrene, benzo[a]pyrene, 4-tert-butylphenol, 4-n-nonylphenol, PCBs 77 and 153, PBDE 47, lindane, triclosan and DDT. Exposure in a flow through system continued for 28 days with samplers removed every 7 days in order to study the relevant uptake kinetics. Uptake remained linear for POCISs with sampling rates (Rs) of up to 0.2 L d(-1). For SPMDs uptake varied from linear to approaching equilibrium with Rs values of up to 14 L d(-1). 7 out of 9 results for SPMDs could be explained by an empirical model (nonylphenol and lindane were exceptions). None of the four organo-tin compounds studied were detected in POCISs and only tributyltin was accumulated significantly by SPMDs. The establishment of these sampling rates allows the calculation of time weighted water concentrations for several important contaminants. Using presented methods, sampling rates and exposure conditions, theoretical detection limits for selected compounds by SPMDs were between 11-68 pg L(-1), which is well below the environment quality standard proposed for those compounds that are included in the European Water Framework Directive.     

Spatial and temporal distribution of butyltin compounds in a Northern Chesapeake Bay Marina and river system

This study was designed to: determine dibutyltin (DBT), tributyltin (TBT) and tetrabutyltin (TTBT) bi-weekly for a four month period (June-September 1986) in the Port Annapolis Marina, Mears Marina, Back Creek and Severn River area of Northern Chesapeake Bay; measure DBT, TBT and TTBT for five successive days (Thursday-Monday) to determine possible daily effects (weekday versus weekend) and determine DBT, TBT and TTBT every two hours for one full tidal cycle in the study area. Maximum concentrations of TBT were reported at both Port Annapolis Marina (1801 ng L^–1) and Mears Marina (1171 ng L^–1) during early June followed by significant reductions in TBT during late summer and early fall. All 4 Back Creek Stations also had highest concentrations of TBT in early June; significant reductions occurred during the next three months. The highest concentration of TBT reported in the Severn River (48 ng L^–1) occurred in September. The lowest TBT value (5 ng L^-1) at this station occurred in June. TTBT was not detected in any of the samples. The day of week sampled (Thursday-Monday) during the daily experiments was not found to significantly affect TBT concentrations. TBT evaluations every two hours during the tidal cycle demonstrated that values peaked at 1400 and 1600 hr time intervals. Peak concentrations of TBT occurred during a rising tide. The possible consequence of the measured TBT concentrations for aquatic biota are discussed.     

Butyltin and copper monitoring in a Northern Chesapeake Bay marina and river system in 1989: An assessment of tributyltin legislation

This study was designed to: (1) evaluate dibutyltin (DBT) and tributyltin (TBT) bi-weekly in the water column for four months during the peak boating season (June–September, 1989) at seven stations in the Back Creek and Severn River area of Maryland waters of Chesapeake Bay; (2) compare butyltin values from the 1989 study with values obtained from a similar butyltin monitoring study conducted in 1988 (after Maryland TBT legislation) and 1986 (before Maryland TBT legislation); (3) determine the extent of TBT paint use in the Back Creek area by surveying boat owners; (4) determine dissolved copper concentrations from three of the seven stations bi-weekly during the four-month study; and (5) compare dissolved copper concentrations at these stations with previous copper data collected in 1988.Mean four-month DBT concentrations ranged from 10 to 73 ng/L at the seven stations. Highest DBT concentrations occurred at Station 1 in a marina; lowest concentrations occurred at Station 7 in the Severn River. Mean four-month TBT concentrations ranged from 177 ng/L at Station 1 (marina) to 21 ng/L at Station 7 (Severn River). Maximum TBT concentrations of 361 and 570 ng/L occurred at marina SDtations 1 and 3, respectively. Temporal trends in both DBT and TBT (station mean concentrations by date) showed that peak concentrations occurred during the early part of the boating season followed by reductions in late summer and early fall. Spike concentrations of both DBT (117 and 62 ng/L) and TBT (308 and 366 ng/L) were reported on two sampling dates near a boat maintenance facility in Back Creek.There was a significant reduction in DBT concentrations from 1986 to 1989 when date was treated as a fixed effect. However, TBT concentrations were not significantly reduced between 1986 and 1989 when mean concentrations of TBT were averaged across stations and dates for each year. A significant reduction was reported at Station 1 (marina station) when each station was examined for differences between years. TBT was also reported to significantly decrease (p=0.0442) at Station 7 between 1988 and 1989. A boat owner survey in the study area showed that 6% of the recreational boats that were surveyed were painted with TBT paint in 1989. This was a significant decrease in TBT paint use from the previous year when 31% of recreational boat owners surveyed used TBT paints.An evaluation of dissolved copper concentrations at three stations in the study area in 1989 showed that mean concentrations from bi-weekly sampling for four months was 10 g/L at Station 1, 7.8 g/L at Station 4 and 2.7 g/L at Station 7. Copper concentrations decreased with distance away from the Back Creek marinas. Copper concentrations at all three stations were significantly lower in 1989 than in 1988.     

Field uptake rates of hydrophobic organic contaminants by semipermeable membrane devices: environmental monitoring considerations

The uptake rates of selected hydrophobic organic contaminants (HOCs) by semipermeable membrane devices (SPMDs)--a polyethylene layflat containing the lipid triolein--were investigated under natural conditions. SPMDs were exposed in three sampling sites (industrial, urban, and agricultural areas) in the Tajo River (Toledo, Spain) for 5, 11 and 20 d. The organochlorine compounds 4,4'-DDT, 4,4'-DDE, alpha-HCH, gamma-HCH, pentachlorobenzene, hexachlorobenzene, and polychlorinated biphenyls (PCBs), and the 16 priority pollutant polycyclic aromatic hydrocarbons (PAHs) were detected in the SPMDs deployed in the three sampling sites. A linear uptake rate was found for DDTs and for 4-Cl- and 5-Cl-substituted PCB congeners in all sampling sites. Concentrations of HCHs (80.3 ng g(-1) SPMD for alpha-HCH and 109 ng g(-1) SPMD for gamma-HCH after 20 d of exposure) increased according to a linear uptake rate in the SPMDs deployed in the sampling site located in the agricultural area. Likewise, a marked increase of total PAH concentration (up to 300 ng g(-1) SPMD after 20 d of exposure) was solely found in the sampling site situated near a thermoelectric power station. Examination of individual PAHs revealed that PAHs with log K(OW) between 4.2 and 5.7 displayed a linear uptake rate over the 20 d of exposure. Water concentrations (ng L(-1)) of HCB (0.80-2.48), lindane (1.30-11.5), 4,4'-DDT (0.61-2.02), 4,4'-DDE (6.89-11.6) and total PAHs (12.0-26.7) estimated by a linear uptake kinetic model were found to be high in comparison with other polluted aquatic systems, and similar to concentrations in other Spanish rivers. Our results suggest that SPMD kinetic uptake studies in the natural environment are recommended for identifying point-pollution sources, and that shorter times of SPMD exposure (approximately 1 week) are desirable to minimize one of the main problems of field SPMD deployment, i.e., the biofouling, which negatively affects the estimation of the dissolved HOC concentrations.     

Biomonitoring of tin and arsenic in different compartments of a limnic ecosystem with emphasis on Corbicula fluminea and Dikerogammarus villosus

Asian clam Corbicula fluminea, the amphipod Dikerogammarus villosus and the macrophyte Nuphar lutea were tested for investigating spatial and temporal variability in the bioavailability of tin and arsenic in the River Lippe, Germany. Samples were collected from September 2002 to May 2003 at a tin polluted site (source pollution) and a reference site. Additional screening sampling was carried out twice in April 2003 to test the extent of As and Sn concentration in periphyton (aufwuchs) samples. Accumulated Sn and As concentrations were measured with ICP-MS after sample processing (dissection, cryo-milling) and digestion. Quality control was performed by parallel analysis of three certified reference materials. Measurable As and Sn contents in plant tissues were only detectable in roots (below 30 microg kg(-1) and 20 microg kg(-1) for As and Sn, respectively). Homogenates from C. fluminea and D. villosus tissues showed site-dependent trace metal contents. Elevated bioavailability of Sn is present downstream of the sewage discharge of the world's biggest producer of tributyltin (TBT) at Luenen (northern Ruhr region). In comparison to C. fluminea, D. villosus shows higher concentrations of tin in samples from both sites. Arsenic concentrations in C. fluminea remain constant with increasing shell size, whereas tin shows a size-dependent accumulation. The results indicate that Corbicula fluminea and Dikerogammarus villosus are suitable passive biomonitoring organisms for Sn, but As levels might be actively regulated. The concentration of tin in the periphyton (aufwuchs) samples was found to be much higher in samples from a contaminated site (428 +/- 63 vs. 1949 +/- 226 microg kg(-1)).     

Occurrence of PAHs and PCBs in the Alna River, Oslo (Norway)

Thirty two polychlorinated biphenyl congeners (PCBs), hexachlorobenzene (HCB) and pentachlorobenzene (PeCB) were analysed in passive sampler extracts from surface water-exposed semipermeable membrane devices (SPMDs) and in bed sediment samples from a small urban watercourse, the River Alna (Oslo, Norway). Performance reference compound-corrected data from the passive samplers deployed at three sites along the river were used to track PCB contamination in the overlying water. SPMDs were able to detect an increase in dissolved PCB concentrations at the site furthest downstream that was corroborated by bed sediment concentrations. In comparison, no major increase in concentration of HCB, PeCB or PAHs could be observed. Comparison of passive sampling-based overlying water concentrations with total concentrations measured in bed sediments supports the possibility of further PCB sources upstream of the study area. Diagnostic PAH ratios (from SPMDs) and PCB congener pattern (from sediments) were used in an attempt to identify possible contaminant sources to the Alna River. Selected PAH diagnostic ratios support a multiple emission source scenario and demonstrate the complexity of identifying specific sources of these compounds to surface waters. PCB congener patterns in sediments from all three sites tend to indicate a source of highly chlorinated PCBs (of the Archlor 1260 type) and either a source of lower chlorinated PCBs or the less-likely occurrence of dechlorination in sediment. Information collected during the present screening study also confirms the Alna River as a continuous source of PCBs to the Oslofjord.     

Butyltin levels in several Portuguese coastal areas

This work aimed to report present levels (2007–2008 sampling) of tri- (TBT), di- (DBT), and monobutyltin (MBT) in surface sediments from 11 Portuguese coastal sites and discuss the evolution of BTs contamination in the last two decades. All the samples revealed quantifiable values of TBT, DBT, and MBT with total butyltin concentrations between 1 and 565 ng/g (of Sn in dry sediment). Maximum level of TBT, 66 ng/g, was observed in Sado estuary, at Lisnave site, in the proximity of a big shipyard. MBT decreased site by site by the same order as DBT and TBT did, but its concentrations were much higher in many cases, denoting that TBT contamination was much higher in the past. A comparison with the available previous data confirmed a marked decrease of TBT contamination all over the last years, indicating that the main sources of TBT in Portuguese coastwise stopped effectively.     

Butyltin Compounds in Sediments of the Bahía Blanca Estuary, Argentina

Systematic measurements of both Tributyltin (TBT) and Dibutyltin (DBT) in sediments along different locations in the inner zone of Bahía Blanca estuary were done. Two samples were taken near the main dry dock facility, at Puerto Belgrano naval base, in Argentina. TBT concentrations from non-detected to 170.3 ng Sn g⁻¹ were measured in the inner region of the estuary, and higher one of 3,288 ng Sn g⁻¹ near the dry dock at Puerto Belgrano. DBT values ranging between non-detected and 75.2 ng Sn g⁻¹ were obtained along the principal channel, but extreme concentration of 1,645 ng Sn g⁻¹ was measured at Puerto Belgrano. These values show that this estuary is affected by organotin pollution, mainly in areas of heavy shipyard activities.     

Investigation of hydrophobic contaminants in an urban slough system using passive sampling – insights from sampling rate calculations

Semipermeable membrane devices (SPMDs) were deployed in the Columbia Slough, near Portland, Oregon, on three separate occasions to measure the spatial and seasonal distribution of dissolved polycyclic aromatic hydrocarbons (PAHs) and organochlorine compounds (OCs) in the slough. Concentrations of PAHs and OCs in SPMDs showed spatial and seasonal differences among sites and indicated that unusually high flows in the spring of 2006 diluted the concentrations of many of the target contaminants. However, the same PAHs - pyrene, fluoranthene, and the alkylated homologues of phenanthrene, anthracene, and fluorene - and OCs - polychlorinated biphenyls, pentachloroanisole, chlorpyrifos, dieldrin, and the metabolites of dichlorodiphenyltrichloroethane (DDT) - predominated throughout the system during all three deployment periods. The data suggest that storm washoff may be a predominant source of PAHs in the slough but that OCs are ubiquitous, entering the slough by a variety of pathways. Comparison of SPMDs deployed on the stream bed with SPMDs deployed in the overlying water column suggests that even for the very hydrophobic compounds investigated, bed sediments may not be a predominant source in this system. Perdeuterated phenanthrene (phenanthrene-d (10)). spiked at a rate of 2 microg per SPMD, was shown to be a reliable performance reference compound (PRC) under the conditions of these deployments. Post-deployment concentrations of the PRC revealed differences in sampling conditions among sites and between seasons, but indicate that for SPMDs deployed throughout the main slough channel, differences in sampling rates were small enough to make site-to-site comparisons of SPMD concentrations straightforward.     

The polycyclic aromatic hydrocarbon composition of mussels (Mytilus edulis) from Scottish coastal waters

Blue mussels (Mytilus edulis) were collected from coastal areas and voes in Shetland and Orkney during March and April 1998 and from various coastal locations around mainland Scotland and from the Islands during October and December 1999. The polycyclic aromatic hydrocarbon concentration and composition (2- to 6-ring parent and branched) were determined for all samples. Additional analysis, including sensory assessment and the determination of n-alkanes and geochemical biomarkers, was also undertaken on the Shetland and Orkney mussels collected in 1998. Mussels from Shetland and Orkney exhibited a wide range of total PAH concentration (14.7 to 7,177 ng g(-1) wet weight). Those mussels collected in 1999 exhibited a narrower concentration range. The lowest value (mussels from Loch Kentra) was 8.4 ng g(-1) wet weight while the maximum concentration was 344.1 ng g(-1) wet weight and was determined in mussels from Granton East in the Firth of Forth. The PAH concentration ratios in mussels from Dury Voe (Grunna), Long Hope and Kirkwall Bay were consistent with a predominately petrogenic source for these contaminants. This was supported by both the sensory assessment and the n-alkane and triterpane profiles. Comparisons of the PAH concentrations in mussels with sediments collected from the same locations around Shetland and Orkney showed that in areas of high sediment PAH concentration the bioavailability of these contaminants was limited.