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ABSTRACT: The applicability of silicone rubber and low density polyethylene (LDPE) as passive sampling materials for target and non-target analyses of moderately polar and non-polar substances was assessed through a field deployment of samplers along a small polluted stream in Oslo (Norway). Silicone and LDPE samplers of identical surface area (but different volumes) were deployed at six sites in the River Alna for 49 days. Quantitative target analysis by GC-MS (quadrupole, SIM mode) demonstrated that masses of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine compounds (OCs) absorbed in the two polymeric materials were consistent with the current understanding of the control and mode of accumulation in these sampler materials. Some deviation was observed for decabromodiphenyl ether (BDE 209) and may be linked to the large molecular size of this substance resulting in lower diffusivity in the LDPE. Target and non-target analyses with gas chromatography coupled to high resolution time-of-flight mass spectrometry (GC- HR ToFMS) allowed the identification of a wide range of chemicals including organophosphate compounds (OPCs) and musk compounds (galaxolide and tonalid). Semi-quantitative analysis revealed enhanced quantities of the OPCs in silicone material indicating some limitation in the absorption and diffusion of these substances in LDPE. Overall, silicone enables non-target screening analysis for compounds with a wider range of logKow values than what can be achieved with LDPE. Environ Toxicol Chem © 2013 SETAC.
Environmental Toxicology and Chemistry 04/2013; · 2.81 Impact Factor
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ABSTRACT: The implementation of strict environmental quality standards for polar organic priority pollutants poses a challenge for monitoring programs. The polar organic chemical integrative sampler (POCIS) may help to address the challenge of measuring low and fluctuating trace concentrations of such organic contaminants, offering significant advantages over traditional sampling. In the present review, the authors evaluate POCIS calibration methods and factors affecting sampling rates together with reported environmental applications. Over 300 compounds have been shown to accumulate in POCIS, including pesticides, pharmaceuticals, hormones, and industrial chemicals. Polar organic chemical integrative sampler extracts have been used for both chemical and biological analyses. Several different calibration methods have been described, which makes it difficult to directly compare sampling rates. In addition, despite the fact that some attempts to correlate sampling rates with the properties of target compounds such as log K(OW) have been met with varying success, an overall model that can predict uptake is lacking. Furthermore, temperature, water flow rates, salinity, pH, and fouling have all been shown to affect uptake; however, there is currently no robust method available for adjusting for these differences. Overall, POCIS has been applied to a wide range of sampling environments and scenarios and has been proven to be a useful screening tool. However, based on the existing literature, a more mechanistic approach is required to increase understanding and thus improve the quantitative nature of the measurements. Environ. Toxicol. Chem. © 2012 SETAC.
Environmental Toxicology and Chemistry 09/2012; · 2.81 Impact Factor
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ABSTRACT: The Stockholm Convention, which aspires to manage persistent organic pollutants (POPs) at the international level, was recently ratified in Bosnia and Herzegovina (BiH). Despite this fact, there is in general a paucity of data regarding the levels of POPs in the environment in BiH. In the present study, screening for POPs was conducted in one of the country's major rivers, the Bosna. A two-pronged approach was applied using passive samplers to detect the freely dissolved and bioavailable concentrations in the water phase and sediment analysis to provide an integrated measure of historical contamination. At several places along the river, the concentrations of polycyclic aromatic hydrocarbons (PAH) were high and exhibited potential for both chronic and acute effects to biota. River water also showed elevated concentrations of PAH, up to 480 ng L(-1) near the city of Doboj, and diagnostic ratios suggested combustion sources for the contamination present in both types of sample. The levels of the other contaminants measured-polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and polybrominated diphenyl ethers-were generally low in the water phase. However, PCBs and some OCPs were present in river sediments at levels which breach the international criteria and thus suggest potential for ecological damage. Additionally, the levels of heptachlor breached these criteria in many of the sites investigated. This study presents the first screening data for some of these Stockholm Convention relevant compounds in BiH and reveals both low concentrations of some chemical groups, but significant point sources and historic contamination for others.
Environmental Monitoring and Assessment 05/2012; · 1.40 Impact Factor
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ABSTRACT: The biological effects of a coastal process water (PW) discharge on native and caged mussels (Mytilus edulis) were assessed. Chemical analyses of mussel tissues and semi permeable membrane devices, along with a suite of biomarkers of different levels of biological complexity were measured. These were lysosomal membrane stability in haemocytes and digestive cells; micronuclei formation in haemocytes; changes in cell-type composition in the digestive gland epithelium; integrity of digestive gland tissue; peroxisome proliferation; and oxidative stress. Additionally the Integrative Biological Response (IBR/n) index was calculated. This integrative biomarker approach distinguished mussels, both native and caged, exhibiting different stress conditions not identified from the contaminant exposure. Mussels exhibiting higher stress responses were found with increased proximity to the PW discharge outlet. However, the biological effects reported could not be entirely attributed to the PW discharge based on the chemicals measured, but were likely due to either other chemicals in the discharge that were not measured, the general impact of the processing plant and or other activities in the local vicinity.
Science of The Total Environment 04/2012; 426:375-86. · 3.29 Impact Factor
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Norsk Epidemiologi 12/2011; 21(1).
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Environmental Science & Technology 11/2011; 45(21):9120-1. · 4.80 Impact Factor
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Environmental Science & Technology 07/2011; 45(15):6233-4. · 4.80 Impact Factor
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ABSTRACT: Polar organic chemical integrative samplers (POCIS) were calibrated in situ for selected illicit drugs and their metabolites at a sewage treatment works. Eleven out of 13 target compounds were detected and eight of those exhibited linear uptake kinetics with sampling rates between 0.035 and 0.150 L d(-1). Subsequently POCIS were deployed for 2 week periods over the course of a whole year, in order to examine trends in drug usage. Amphetamine and methamphetamine showed several similar peaks in concentration during the course of the year as did cocaine and two of its metabolites. Low levels of ecstasy were observed, with a prominent peak in May and a steady increase toward the end of the year. The antihistamine Cetirizine showed a clear increase in use during the summer months as expected and back calculation of the yearly dosage from POCIS accumulations yielded very similar results to that registered in the Norwegian prescription database. Estimations of cocaine usage using the parent compound averaged between 0.31 and 2.8 g d(-1) per 1000 inhabitants. POCIS is a cost-effective technique for the long-term monitoring of drug usage of a defined population and may overcome the difficulties of representative sampling associated with autosampling equipment.
Environmental Science & Technology 06/2011; 45(13):5676-82. · 4.80 Impact Factor
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Environmental Science & Technology 05/2011; 45(10):4191; author reply 4192. · 4.80 Impact Factor
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ABSTRACT: Polycyclic aromatic hydrocarbons (PAH) and alkylphenols (AP) that are present in routine discharges of produced water (PW) from the offshore industry continue to cause concern. The suitability of biological methods and chemical based passive samplers to determine exposure to these compounds was tested by deploying them around an oil installation and at reference locations in the North Sea. PAH and AP were analysed either as parent compounds in passive samplers and mussel tissue or as metabolites in fish bile. Generally the pattern of exposure relative to proximity to the discharge was represented by mussels, SPMDs and fish for PAH. Fish and SPMDs showed good correlation for PAH accumulations, whereas some differences were apparent between mussels and SPMDs. POCIS was the only technique tested that could accurately measure the most abundant AP in PW. The advantages of biologically independent measures of exposure for inclusion in discharge monitoring studies are outlined.
Marine pollution bulletin 02/2011; 63(5-12):141-8. · 2.63 Impact Factor
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Steven J Brooks, Christopher Harman,
Merete Grung,
Eivind Farmen,
Anders Ruus,
Sjur Vingen,
Brit F Godal,
Janina Barsiene,
Laura Andreikenaite,
Halldóra Skarpheðinsdottir,
Birgitta Liewenborg,
Rolf C Sundt
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ABSTRACT: The Norwegian water column monitoring program investigates the biological effects of offshore oil and gas activities in Norwegian waters. In three separate surveys in 2006, 2008, and 2009, bioaccumulation and biomarker responses were measured in mussels (Mytilus edulis) and Atlantic cod (Gadus morhua) held in cages at known distances from the produced water (PW) discharge at the Ekofisk oil field. Identical monitoring studies performed in all three years have allowed the biological effects and bioaccumulation data to be compared, and in addition, enabled the potential environmental benefits of a PW treatment system (CTour), implemented in 2008, to be evaluated. The results of the 2009 survey showed that caged animals were exposed to low levels of PW components, with highest tissue concentrations in mussels located closest to the PW discharge. Mussels located approximately 1-2 km away demonstrated only background concentrations of target compounds. Concentrations of polycyclic aromatic hydrocarbons (PAH) and alkyl phenol (AP) metabolites in the bile of caged cod were elevated at stations 200-250 m from the discharge. There was also a signal of exposure relative to discharge for the biomarkers CYP1A in fish and micronuclei in mussels. All other fish and mussel biomarkers showed no significant exposure effects in 2009. The mussel bioaccumulation data in 2009 indicated a lower exposure to the PW effluent than seen previously in 2008 and 2006, resulting in an associated general improvement in the health of the caged mussels. This was due to the reduction in overall discharge of PW components (measured as oil in water) into the area in 2009 compared to previous years as a result of the improved PW treatment system.
Journal of Toxicology and Environmental Health Part A 01/2011; 74(7-9):582-604. · 1.83 Impact Factor
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ABSTRACT: The biological impact of a treated produced water (PW) was investigated under controlled laboratory conditions in the blue mussel, Mytilus edulis. Mussel health status was assessed using an integrated biomarker approach in combination with chemical analysis of both water (with SPMDs), and mussel tissues. Acyl-CoA oxidase activity, neutral lipid accumulation, catalase activity, micronuclei formation, lysosomal membrane stability in digestive cells and haemocytes, cell-type composition in digestive gland epithelium, and the integrity of the digestive gland tissue were measured after 5 week exposure to 0%, 0.01%, 0.1%, 0.5% and 1% PW. The suite of biomarkers employed were sensitive to treated PW exposure with significant sublethal responses found at 0.01-0.5% PW, even though individual chemical compounds of PW were at extremely low concentrations in both water and mussel tissues. The study highlights the benefits of an integrated biomarker approach for determining the potential effects of exposure to complex mixtures at low concentrations. Biomarkers were integrated in the Integrative Biological Response (IBR/n) index.
Marine pollution bulletin 11/2010; 62(2):327-39. · 2.63 Impact Factor
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ABSTRACT: Semipermeable membrane devices (SPMDs) and polar organic integrative chemical samplers (POCIS) were deployed in vicinity of an offshore oil production platform discharging production water (produced water) to the North Sea. Extracts from SPMDs and POCIS were subjected to chemical analysis for polycyclic aromatic hydrocarbons (PAHs) and alkylphenols (APs) respectively, and also assessed for acute toxicity (cytotoxicity), estrogen receptor (ER)-mediated production of vitellogenin (Vtg) and induction of 7-ethoxyresorufin-O-deethylase (EROD) activity in primary hepatocytes from rainbow trout (Oncorhynchus mykiss). Chemical analysis of the extracts revealed a gradient of exposure away from the platform for low molecular weight PAH and AP, whereas no exposure gradient was apparent for high molecular weight PAH, as expected. These data coupled with earlier work allowed a tentative general exposure scenario to be determined. The passive sampler extracts also caused modulation of the bioassay toxicity endpoints, although a clear gradient of response relative to the discharge point could not be identified.
Journal of Environmental Monitoring 09/2010; 12(9):1699-708. · 1.99 Impact Factor
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ABSTRACT: Increasing demand for simple and reliable passive samplers for monitoring hydrophobic organic contaminants in water has led to increased frequency of use of single-phase polymeric sampling devices. In this study, we evaluate the effect of sampler material on the passive sampling of polycyclic aromatic hydrocarbons (PAHs) in two Norwegian rivers. Low density polyethylene membranes (LDPE), silicone strips and semipermeable membrane devices (SPMDs) with the exact same surface area and conformation were exposed in the Drammen River for overlapping exposures of 24 and 51 d, under identical hydrodynamic conditions. Dissipation rates of performance reference compounds (PRCs) spiked in all samplers were consistent and demonstrated no significant differences in sampler-water analyte exchange kinetics between the two exposures. The transition to fully boundary layer-controlled uptake shown by PRC dissipation rates was confirmed by investigating PAH masses absorbed by the samplers. Masses of analytes with log K(ow)>4.5 absorbed into the samplers were similar and independent of the sampler material used, generally indicating for these compounds that the boundary layer dominated the resistance to mass transfer. The very low variability in analyte masses absorbed across sampler types observed here indicates that much of the overall variability in dissolved contaminant concentrations seen in passive sampler intercomparison studies is likely the result of the uncertainty associated with sampler-water partition coefficients and PRC dissipation rates. PRC dissipation rates and ratios of masses absorbed over 51 and 24 d for these compounds demonstrated integrative sampling over 51 d and no major effects of biofouling on sampling. The equivalence of data obtained using silicone strips and SPMDs supports the use of single-phase polymeric passive sampling devices.
Chemosphere 02/2010; 79(4):470-5. · 3.21 Impact Factor
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ABSTRACT: In order to assess the environmental impact of aquatic discharges from the offshore oil industry, polar organic chemical integrative samplers (POCIS) and semipermeable membrane devices (SPMDs) were deployed around an oil platform and at reference locations in the North Sea. Exposure to polycyclic aromatic hydrocarbons (PAH) and alkylated phenols (AP) was determined from passive sampler accumulations using an empirical uptake model, the dissipation of performance reference compounds and adjusted laboratory derived sampling rates. Exposure was relatively similar within 1-2 km of the discharge point, with levels dominated by short chained C1-C3 AP isomers (19-51 ngL(-1)) and alkylated naphthalenes, phenanthrenes and dibenzothiophenes (NPD, 29-45 ngL(-1)). Exposure stations showed significant differences to reference sites for NPD, but not always for more hydrophobic PAH. These concentrations are several orders of magnitude lower than those reported to give both acute and sub-lethal effects, although their long term consequences are unknown.
Marine pollution bulletin 09/2009; 58(11):1671-9. · 2.63 Impact Factor
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ABSTRACT: Semipermeable membrane devices (SPMD) and polar organic chemical integrative samplers (POCIS) were exposed to a cocktail of organic chemicals using a flow-through system. Samplers were removed and analyzed every 7 d over a four-week period in order to determine sampling rates (Rs) for individual compounds. Prior to laboratory exposure, half of the samplers were allowed to foul naturally for six weeks, in order to examine differences in uptake due to fouling. The amount of fouling ranged from 0.2 to 2.8 g dry weight/dm2 for POCIS and 0.1 to 1.4 g dry weight/dm2 for SPMDs, and the pattern of accumulation was also different between them. The Rs values were determined by fitting curves to time course uptake data and also by using performance reference compounds (PRCs) for SPMDs. Sampling rates ranged from 2.7 to 14.2 L/d for SPMDs and 0.01 to 0.27 L/d for POCIS. Fouled SPMDs showed a reduction in Rs (<20%) for all but one compound, and there was a similar reduction in the release of PRCs. However, PRC-predicted R, values were overall somewhat higher than those from fitted curves. Uptake of alkylated phenols in POCIS was generally higher (up to 55%) in fouled samplers. The reason for this is not known, but is possibly due to some reduction in interactions with the membrane in fouled samplers. There was no overall pattern in the relationship of sampling rate differences with log Kow or over time for either sampler. Release of compounds from POCIS after a drop in exposure water concentrations provides some encouragement for the application of a PRC approach to polar passive samplers.
Environmental Toxicology and Chemistry 07/2009; 28(11):2324-32. · 2.81 Impact Factor
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ABSTRACT: The extent to which accumulations of polycyclic aromatic hydrocarbons (PAH) by semipermeable membrane devices (SPMD) may be correlated to the concentration of PAH metabolites in fish was examined. Atlantic cod (Gadus morhua) and SPMD were exposed over a 4-wk period to a mixture that was designed to simulate the composition of PAH in produced water discharges in the North Sea. Fish bile and whole SPMD were analyzed after exposure in a high, low, and a control treatment tank. PAH metabolites were detected and quantified by means of high-performance liquid chromatography (HPLC) or gas chromatography-time-of-flight mass spectroscopy (GC-ToF-MS) and PAH in SPMD by gas chromatography-mass spectroscopy (GC-MS). The level and duration of exposure were generally reflected in both matrices. Exposure water concentrations, calculated from SPMD accumulations, showed some considerable differences from nominal concentrations for volatile compounds. Concentration factors (CF) for fish based on SPMD-derived water concentrations ranged from 2.9 to 354.3 L/g. CF increased with hydrophobicity with more variation at higher log K(ow). Regression analysis of accumulations of individual compounds in fish and SPMDs showed reasonable but compound-specific correlation, r2 = .54-.85 (C1-phenanthrenes/anthracenes and pyrene, respectively). Comparison of the two exposures suggests that fish CF may not be entirely independent of water concentrations. Overall the results show that accumulation of up to four-ring PAH in SPMD may be related to internal exposure of fish to these substances when exposed through water, as evidenced by metabolite concentrations. The usefulness of using SPMD to measure exposure concentrations in a large-scale flow-through study is also examined.
Journal of Toxicology and Environmental Health Part A 02/2009; 72(3-4):234-43. · 1.83 Impact Factor
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ABSTRACT: 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.
Journal of Environmental Monitoring 03/2008; 10(2):239-47. · 1.99 Impact Factor
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ABSTRACT: The in vitro estrogen receptor (ER) agonist and androgen receptor (AR) antagonist potencies of offshore produced water effluents collected from the Norwegian Sector were determined using recombinant yeast estrogen and androgen screens. Solid phase extraction (SPE) concentrates of the effluents showed E2 agonist activities similar to those previously reported for the United Kingdom (UK) Continental Shelf (<0.1-4 ng E2 L(-1)). No activity was detected in the filtered oil droplets suggesting that produced water ER activity is primarily associated with the dissolved phase. Targeted analysis for methyl- to nonyl-substituted alkylphenol isomers show the occurrence of known ER agonists in the analysed samples. For the first time, AR antagonists were detected in both the dissolved and oil associated phase at concentrations of between 20 and 8000 microg of flutamide equivalents L(-1). The identity of the AR antagonists is unknown, however this represents a significant input into the marine environment of unknown compounds that exert a known biological effect. It is recommended that further analysis using techniques such as bioassay-directed analysis is performed to identify the compounds/groups of compounds that are responsible in order to improve the assessment of the risk posed by produced water discharges to the marine environment.
Marine Pollution Bulletin 03/2007; 54(3):277-83. · 2.50 Impact Factor
