Compositional effects on leaching of stain-guarded (perfluoroalkyl and polyfluoroalkyl substance-treated) carpet in landfill leachate.

Perfluoroalkyl and polyfluoroalkyl substances (PFASs) from stain-guard treated carpets in landfills continue to be released into the environment. To understand the leaching of PFASs from carpets to landfill leachate as a function of environmental factors, leaching concentrations of ten perfluoroalkyl carboxylic acids and four perfluoroalkyl sulfonic acids were quantified for different pHs, contact times, mixing speeds, and temperatures. Partitioning from carpet to leachate and distilled water at different pHs showed negligible differences. The total concentration of leaching PFASs in distilled water was approximately 1 ng L(-1) higher than in landfill leachate, indicating that the presence of multivalent cations in leachate could have a negative effect on leaching of PFASs. For all PFASs monitored, leaching increased with increasing contact time and temperature. Perfluorohexanoic and perfluoroheptanoic acids experienced the largest increases with contact time and temperature. Gibbs free energy (ΔG > 0), enthalpy (ΔH > 0), and entropy energy (ΔS < 0) indicated that PFAS leaching from carpet was dominantly controlled by entropy-driven processes and did not differ significantly among individual PFASs. PFAS concentrations in leachate with rotation of an end-over-end contactor were higher than under static conditions, but otherwise, varying the rotation speed had negligible influence. The results provide useful information for management of discarded stain-guard carpets in landfills.

Distinctive metabolite profiles in in-migrating Sockeye salmon suggest sex-linked endocrine perturbation.

The health of Skeena River Sockeye salmon (Onchorhychus nerka) has been of increasing concern due to declining stock returns over the past decade. In the present work, in-migrating Sockeye from the 2008 run were evaluated using a mass spectrometry-based, targeted metabolomics platform. Our objectives were to (a) investigate natural changes in a subset of the hepatic metabolome arising from migration-associated changes in osmoregulation, locomotion, and gametogenesis, and (b) compare the resultant profiles with animals displaying altered hepatic vitellogenin A (vtg) expression at the spawning grounds, which was previously hypothesized as a marker of xenobiotic exposure. Of 203 metabolites monitored, 95 were consistently observed in Sockeye salmon livers and over half of these changed significantly during in-migration. Among the most dramatic changes in both sexes were a decrease in concentrations of taurine (a major organic osmolyte), carnitine (involved in fatty acid transport), and two major polyunsaturated fatty acids (eicosapentaenoic acid and docosahexaenoic acid). In females, an increase in amino acids was attributed to protein catabolism associated with vitellogenesis. Animals with atypical vtg mRNA expression demonstrated unusual hepatic amino acid, fatty acid, taurine, and carnitine profiles. The cause of these molecular perturbations remains unclear, but may include xenobiotic exposure, natural senescence, and/or interindividual variability. These data provide a benchmark for further investigation into the long-term health of migrating Skeena Sockeye.

Biodegradation of N-ethyl perfluorooctane sulfonamido ethanol (EtFOSE) and EtFOSE-based phosphate diester (SAmPAP diester) in marine sediments.

Investigations into the biodegradation potential of perfluorooctane sulfonate (PFOS)-precursor candidates have focused on low molecular weight substances (e.g., N-ethyl perfluorooctane sulfonamido ethanol (EtFOSE)) in wastewater treatment plant sludge. Few data are available on PFOS-precursor biodegradation in other environmental compartments, and nothing is known about the stability of high-molecular-weight perfluorooctane sulfonamide-based substances such as the EtFOSE-based phosphate diester (SAmPAP diester) in any environmental compartment. In the present work, the biodegradation potential of SAmPAP diester and EtFOSE by bacteria in marine sediments was evaluated over 120 days at 4 and 25 °C. At both temperatures, EtFOSE was transformed to a suite of products, including N-ethyl perfluorooctane sulfonamidoacetate, perfluorooctane sulfonamidoacetate, N-ethyl perfluorooctane sulfonamide, perfluorooctane sulfonamide, and perfluorooctane sulfonate. Transformation was significantly more rapid at 25 °C (t(1/2) = 44 ± 3.4 days; error represents standard error of the mean (SEM)) compared to 4 °C (t(1/2) = 160 ± 17 days), but much longer than previous biodegradation studies involving EtFOSE in sludge (t(1/2) ∼0.7-4.2 days). In contrast, SAmPAP diester was highly recalcitrant to microbial degradation, with negligible loss and/or associated product formation observed after 120 days at both temperatures, and an estimated half-life of >380 days at 25 °C (estimated using the lower bounds 95% confidence interval of the slope). We hypothesize that the hydrophobicity of SAmPAP diester reduces its bioavailability, thus limiting biotransformation by bacteria in sediments. The lengthy biodegradation half-life of EtFOSE and recalcitrant nature of SAmPAP diester in part explains the elevated concentrations of PFOS-precursors observed in urban marine sediments from Canada, Japan, and the U.S, over a decade after phase-out of their production and commercial application in these countries.

Per- and polyfluoroalkyl substances in landfill leachate: patterns, time trends, and sources.

Concentrations and isomer profiles for 24 per- and polyfluoroalkyl substances (PFASs) were monitored over 5 months (February-June, 2010) in municipal landfill leachate. These data were used to assess the role of perfluoroalkyl acid (PFAA) precursor degradation on changes in PFAA concentrations over time. The influence of total organic carbon, total suspended solids, pH, electrical conductivity (EC), leachate flow rates, and meteorological data (precipitation, air temperature) on leachate PFAS concentrations was also investigated. Perfluoropentanoate and perfluorohexanoate were typically the dominant PFASs in leachate, except for March-April, when concentrations of perfluorooctane sulfonate, perfluorooctanoate, and numerous PFAA-precursors (i.e., (N-alkyl) perfluorooctane sulfonamides and fluorotelomer carboxylic acids) increased by a factor of 2-10 (~4 µg/L to ~36 µg/L ΣPFASs). During this time, isomer profiles of PFOA became increasingly dominated by the linear isomer, likely from transformation of linear, telomer-manufactured precursors. While ΣPFAA-precursors accounted for up to 71% of ΣPFASs (molar basis) in leachate from this site, leachate from a second landfill displayed only low concentrations of precursors (<1% of ΣPFASs). Overall, degradation of PFAA-precursors and changes in leachate pH, EC, and 24-h precipitation were important factors controlling PFAS occurrence in leachate. Finally, 8.5-25 kg/yr (mean 16 kg/yr) of ΣPFASs was estimated to leave the landfill via leachate for subsequent treatment at a wastewater treatment plant.

Observation of a novel PFOS-precursor, the perfluorooctane sulfonamido ethanol-based phosphate (SAmPAP) diester, in marine sediments.

The environmental occurrence of perfluorooctane sulfonate (PFOS) can arise from its direct use as well as from transformation of precursors ((N-alkyl substituted) perfluorooctane sulfonamides; FOSAMs). Perfluorooctane sulfonamidoethanol-based phosphate (SAmPAP) esters are among numerous potential PFOS-precursors which have not been previously detected in the environment and for which little is known about their stability. Based on their high production volume during the 1970s-2002 and widespread use in food contact paper and packaging, SAmPAP esters may be potentially significant sources of PFOS. Here we report for the first time on the environmental occurrence of SAmPAP diester in marine sediments from an urbanized marine harbor in Vancouver, Canada. SAmPAP diester concentrations in sediment (40-200 pg/g dry weight) were similar to those of PFOS (71-180 pg/g). A significant (p < 0.05) correlation was observed between SAmPAP diester and N-ethyl perfluorooctane sulfonamido acetate (an anticipated degradation product of SAmPAP diester). ∑PFOS-precursor (FOSAM) concentrations in sediment (120-1100 pg/g) were 1.6-24 times greater than those of PFOS in sediment. Although SAmPAP diester was not detected in water, PFOS was observed at concentrations up to 710 pg/L. Among the per- and polyfluoroalkyl substances monitored in the present work, mean log-transformed sediment/water distribution coefficients ranged from 2.3 to 4.3 and increased with number of CF(2) units and N-alkyl substitution (in the case of FOSAMs). Overall, these results highlight the importance of FOSAMs as potentially significant sources of PFOS, in particular for urban marine environments.

Molecular profiling of marine fauna: integration of omics with environmental assessment of the world's oceans.

Many species that contribute to the commercial and ecological richness of our marine ecosystems are harbingers of environmental change. The ability of organisms to rapidly detect and respond to changes in the surrounding environment represents the foundation for application of molecular profiling technologies towards marine sentinel species in an attempt to identify signature profiles that may reside within the transcriptome, proteome, or metabolome and that are indicative of a particular environmental exposure event. The current review highlights recent examples of the biological information obtained for marine sentinel teleosts, mammals, and invertebrates. While in its infancy, such basal information can provide a systems biology framework in the detection and evaluation of environmental chemical contaminant effects on marine fauna. Repeated evaluation across different seasons and local marine environs will lead to discrimination between signature profiles representing normal variation within the complex milieu of environmental factors that trigger biological response in a given sentinel species and permit a greater understanding of normal versus anthropogenic-associated modulation of biological pathways, which prove detrimental to marine fauna. It is anticipated that incorporation of contaminant-specific molecular signatures into current risk assessment paradigms will lead to enhanced wildlife management strategies that minimize the impacts of our industrialized society on marine ecosystems.

Development and validation of protocols to differentiate PCB patterns between farmed and wild salmon.

Polychlorinated biphenyl (PCB) congener patterns based on full congener PCB analyses of three farmed and five wild species of salmon from coastal British Columbia, Canada are compared using principal components analysis (PCA) and the best fit linear decomposition of the observed PCB composition in terms of Aroclor 1242, 1254, and 1260 end-members. The two complementary analysis methods are used to investigate congener composition pattern differences between species, trophic levels, feeding preferences, and farmed or wild feeding regimes, with the intent of better understanding PCB processes in both salmon and salmon consumers. PCA supports classification of PCB congeners into nine groups based on a) structure activity groups (SAG) related to the bioaccumulation potential in fish-eating mammals, b) Cl number, and c) the numbers of vicinal meta- and para-H. All three factors are needed to interpret congener distributions since SAGs by themselves do not fully explain PCB distributions. Farmed salmon exhibit very similar congener patterns that overlap the PCA and Aroclor composition of their food, while wild salmon separate into two distinct groups, with chinook and "coastal" coho having higher proportions of the higher chlorinated, Aroclor 1260 type, nonmetabolizable congeners, and chum, pink, sockeye, and "remote" coho having higher proportions of the lower chlorinated, more volatile and metabolizable Aroclor 1242 type, congeners. Wild chinook have the highest PCB and toxic equivalent (TEQ) concentrations, and the highest proportions of A1254 A1260, and PCB congeners in the most refractory SAG. Because both "coastal" and "remote" coho groups are likely to be consuming prey of similar size and trophic level, the PCB delivery mechanism (e.g., atmosphere vs runoff) apparently has more influence on the salmon PCB profile than biotransformation, suggesting that the wild chinook PCB profile is determined by feeding preference. Overall, wild salmon distributions primarily relate to trophic level, feeding preferences, and longevity, while metabolism appears at most a minor factor. The new classification protocol takes better advantage of individual congener PCB analyses and provides a better framework for understanding the PCB distributions in salmon and, potentially, the movement of individual PCB congeners through marine food chains than previous classification schemes.

Assessing exposure of sediment biota to organic contaminants by thin-film solid phase extraction.

Differences in bioavailability among sediments are a source of variability and uncertainty in sediment quality assessment. We present three sets of studies designed to test a thin-film solid phase extraction technique for characterizing the bioavailability of organic chemicals in sediments. Laboratory studies with spiked natural sediments reveal highly reproducible thin-film extractions for chemicals with octanol-water partition coefficients between 10(4.5) and 10(8.5), with 95% equilibration times between 1 and 600 h. Studies with field-collected sediments illustrate that method detection limits are sufficiently low for field application at contaminated sites. Bioaccumulation studies with clams (Macoma balthica) show excellent correlations between thin-film and animal tissue concentrations. We conclude that thin-film extraction provides an ecologically relevant, fugacity-based measure of chemical exposure that can be expected to improve sediment quality assessments.

Polychlorinated biphenyls and polybrominated diphenyl ethers in Galapagos sea lions (Zalophus wollebaeki).

Concentrations of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs) were measured in muscle-blubber biopsy samples from 21 Galapagos sea lion (Zalophus wollebaeki) pups that were live captured in the Galapagos Islands (Ecuador) using gas chromatography/high-resolution mass spectrometry. Only traces of PBDEs were detected in one male pup, whereas PCDDs and PCDFs were not detected in any sample. The total concentration of PCBs (ΣPCB) in the pups averaged 104 µg/kg lipid (range, 49-384 µg/kg). No statistically significant differences in ΣPCB were observed among the four study sites in the Galapagos Islands. Concentrations of PCB congeners in Galapagos sea lion pups were dominated by low-molecular-weight congeners. These results suggest that global transport is the main source for PCBs in Galapagos sea lions. The ΣPCB levels were below immunotoxic and endocrine-disruption thresholds in pinnipeds, suggesting a limited risk of adverse health effects. The present study indicates that Galapagos sea lions can serve as a useful sentinel of pollutants with a long-range transport capacity and that Galapagos Islands are not exempt from the threats of global pollutants despite its remote locale.

Large and growing environmental reservoirs of Deca-BDE present an emerging health risk for fish and marine mammals.

Polybrominated diphenyl ethers (PBDEs) have been the subject of intense scientific and regulatory scrutiny during recent years. Of the three commercial forms (Penta, Octa and Deca) of PBDEs that have been widely used as flame retardants in textiles, furniture upholstery, plastics, and electronics, only Deca-BDE remains on the general market in North America, while a recent ruling of the European Court spells an impending end to its use in Europe. We review here highlights of aquatic research documenting the rapid emergence of PBDEs as a high priority environmental concern in Canada. PBDEs are being introduced in large quantities to the aquatic environment through sewage discharge and atmospheric deposition. In certain environmental compartments, the single congener BDE-209, the main ingredient in the Deca-BDE formulation, has surpassed the legacy PCBs and DDT as the top contaminant by concentration. Limited biomagnification of BDE-209 in aquatic food webs reflects its high log K(ow) and preferential partitioning into the particle phase. As a result, large environmental reservoirs of BDE-209 are being created in sediments, and these may present a long-term threat to biota: BDE-209 breaks down into more persistent, more bioaccumulative, more toxic, and more mobile PBDE congeners in the environment.

Seasonal variability of the reduction in estrogenic activity at a municipal WWTP.

In vitro monitored estrogenicity of municipal wastewater influent/effluent samples (collected from September to December from a Northern Canadian biological nutrient removal (BNR) treatment plant serving an urban population of 750,000) were combined with operational, wastewater quality, and climate data to determine which of these latter variables may be related to the levels and reduction in the former parameter. Significant variability was present in operational and wastewater quality parameters throughout the sampling period including a 7 degrees C difference in wastewater temperature Most of the wastewater samples collected during this period show a considerable amount of recombinant yeast assay (RYA) activity with the greatest activity (estradiol (E2)-equivalents of 106-175ng/L) seen in the final effluents collected from mid-September to mid-October. Percent reduction in the levels of RYA measured E2-equivalents varied from -234% to 75%. No correlations were seen in RYA activity reduction with percent reduction in 5-day biochemical oxygen demand (BOD(5)), flow (i.e. inversely related to hydraulic retention time), solids retention time or even rainfall, and the reduction trends for RYA measured activity were explained best by ambient and effluent temperatures in an inverse fashion (% reduction in E2-equivalents=-10.8.(effluent temperature in degrees C)+191, p=0.005). Complementary instrumental analysis of select sample composites revealed that the free/conjugated estrogen ratio was indeed greater in the wastewater sampled during warmer temperatures.

Bioaccumulation behaviour of polybrominated diphenyl ethers (PBDEs) in a Canadian Arctic marine food web.

A comparative analysis of the bioaccumulation behaviour of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) was conducted involving simultaneous measurements of PBDE and PCB concentrations in organisms of a Canadian Arctic marine food web. Concentrations of individual PBDE congeners (BDE-28, -47, -99, -153, -154 and -183) in Arctic marine sediments (0.001-0.5 ng.g(-1) dry wt) and biota (0.1-30 ng.g(-1) wet wt) were low compared to those concentrations in biota from urbanized/industrial regions. While recalcitrant PCB congeners exhibited a high degree of biomagnification in this food web, PBDE congeners exhibited negligible biomagnification. Trophic magnification factors (TMFs) of PCBs ranged between 2.9 and 11, while TMFs of PBDEs ranged between 0.7 and 1.6. TMFs of several PBDE congeners (BDE-28, -66, -99, -100, -118, -153 and -154) were not statistically greater than 1, indicating a lack of food web magnification. BDE-47 was the only PBDE with a TMF (i.e. 1.6) statistically greater than 1, hence showing evidence of biomagnification in the food web. However, the TMF of BDE-47 (1.6) was substantially lower than TMFs of recalcitrant Cl(5)-Cl(7) PCBs (TMFs~9-11). Species-specific bioaccumulation factors (BAFs) of PBDEs in homeotherms were much smaller than those for PCBs. This further indicates the low degree or absence of biomagnification of PBDEs compared to PCBs in this food web. The field observations suggest PBDEs exhibit a relatively rapid rate of depuration though biotransformation in Arctic marine organisms, which is consistent with laboratory studies in fish and rats.

Biodegradation of mono-alkyl phthalate esters in natural sediments.

Mono-alkyl phthalate esters (MPEs) are primary metabolites of di-alkyl phthalate esters (DPEs), a family of industrial chemicals widely used in the production of soft polyvinyl chloride and a large range of other products. To better understand the long term fate of DPEs in the environment, we measured the biodegradation kinetics of eight MPEs (-ethyl, -n-butyl, -benzyl, -i-hexyl, -2-ethyl-hexyl, -n-octyl, -i-nonyl, and -i-decyl monoesters) in marine and freshwater sediments collected from three locations in the Greater Vancouver area. After a lag period in which no apparent biodegradation occurred, all MPEs tested showed degradation rates in both marine and freshwater sediments at 22 degrees C with half-lives ranging between 16 and 39 h. Half-lives increased approximately 8-fold in incubations performed at 5 degrees C. Biodegradation rates did not differ between marine and freshwater sediments. Half-lives did not show a relationship with increasing alkyl chain length. We conclude that MPEs can be quickly degraded in natural sediments and that the similarity in MPE degradation kinetics among sediment types suggests a wide occurrence of nonspecific esterases in microorganisms from various locations, as has been reported previously.

Development of a magnetic particle immunoassay for polybrominated diphenyl ethers and application to environmental and food matrices.

A sensitive magnetic particle enzyme-linked immunoassay (ELISA) was developed to analyze polybrominated diphenyl ethers (PBDEs) in water, milk, fish, and soil samples. The assay was rapid and can be used to analyze fifty samples in about 1h after sample cleanup. The assay has a limit of detection (LOD) below 0.1 ppb towards the following brominated diphenyl ether (BDE) congeners: BDE-47, BDE-99, BDE-28, BDE-100, and BDE-153, with the LOD approximately the same as GC-NCI-MS. The congeners most readily recognized in the ELISA were BDE-47 and BDE-99 with the cross-reactivities of BDE-28, BDE-100, and BDE-153 being less than 15% relative to BDE-47. As anticipated, the sensitivities are proportional to the similarities between the hapten structure and the BDE congener structure. Some oxygenated congeners with structural similarity to the hapten showed high to moderate cross-reactivities. Very low cross-reactivity was observed for other PBDEs or chlorinated environmental contaminants. The assay gave good recoveries of PBDEs from spiked water samples and a very small within and between day variance. Comparison with GC-NCI-MS demonstrated the ELISA method showed equivalent precision and sensitivity, with better recovery. The lower recovery of the GC-NCI-MS method could be caused by the use of an internal standard other than an isotopically substituted material that could not be used because of the fragmentation pattern observed by this method. The cleanup methods prior to ELISA were matrix dependent, no pretreatment was needed for environmental water samples, while fish, milk, and soil samples required various degrees of cleanup. Analysis of this wide variety of environmental samples by both ELISA and GC-MS demonstrated ELISA provides a timely and cost-effective method to screen for PBDEs in a variety of samples.

Mercury and other trace elements in farmed and wild salmon from British Columbia, Canada.

The present study reports measured levels of Hg and other trace elements in commercial salmon feed; farmed Atlantic, coho, and chinook salmon (n = 110); and wild coho, chinook, chum, sockeye, and pink salmon (n = 91). Metal concentrations in farmed and wild salmon from British Columbia, Canada, were relatively low and below human health consumption guidelines. Methylmercury in all salmon samples (range, 0.03-0.1 microg/g wet wt) were below the 0.5 microg/g guideline set by Health Canada. Negligible differences in metal concentrations were observed between the various species of farmed and wild salmon. Metal concentrations generally were higher in commercial salmon feed compared to farmed salmon. Mercury showed slight bioaccumulation potential in farmed salmon, with biomagnification factors (BMFs) ranging between 0.8 and 1.9. Other metals, such as Cd, Pb, and Ni, exhibited biodilution, with BMFs of much less than one. The relatively low degree of biomagnification of metals observed in farmed salmon likely resulted from the combination of low gastrointestinal absorption efficiency, negligible transfer to muscle tissue relative to other compartments, and a high degree of growth dilution in these fish. Human dietary exposure calculations indicate intakes of Hg, Cd, Pb, Cu, As, and Ni via farmed and wild British Columbia salmon are a relatively small percentage of total intakes (0.05-32%) compared to other Canadian foodstuffs, such as fruits, vegetables, chicken, and beef (68-99%). Although total dietary exposure of Cd, Pb, and Cu approached provisional tolerable daily intake levels, the contribution from British Columbia salmon was less than 2%. Our findings indicate farmed and wild British Columbia salmon remain a safe source of omega-3 highly unsaturated fatty acid intake for cardioprotective and, possibly, other health benefits.

Ultra-trace analysis of multiple endocrine-disrupting chemicals in municipal and bleached kraft mill effluents using gas chromatography-high-resolution mass spectrometry.

A comprehensive gas chromatographic-high-resolution mass spectrometric (GC-HRMS)-based method was developed that permitted the simultaneous determination of 30 estrogenic endocrine-disrupting chemicals (EDCs) and related compounds, including surfactants, biogenic and synthetic steroids, fecal sterols, phytoestrogens, and plasticizers, in wastewater. Features of the method include low sample volume (~40 ml), optimized Florisil cleanup to minimize matrix interferences and optimized analyte derivatization to improve sensitivity via GC-HRMS. Detection limits were in the low- to mid-ng/L range, and recoveries were greater than 60% for most target analytes. This new method allows for high throughput analysis of many organic wastewater contaminants in a complex matrix with relative standard deviation of less than 15% for most measurable compounds. The applicability of the method was demonstrated by examining wastewater samples from different origins. Compounds such as di(2-ethylhexyl)phthalate, cholesterol, cholestanol, and other cholesterol derivatives were measured in much higher concentrations in untreated sewage and were reduced substantially in concentration by the treatment process. However, steroidal compounds, particularly estrone (E1), 17beta-estradiol (E2), and estriol (E3), as well as plant sterols (except stigmastanol), were greater in the treated municipal wastewater versus the untreated effluent. Plant and fungi sterols, stigmastanol and ergosterol, were found largely associated with bleached kraft mill effluent (BKME) as compared to the municipal effluents.

Ion-trap tandem mass spectrometry-based analytical methodology for the determination of polychlorinated biphenyls in fish and shellfish. Performance comparison against electron-capture detection and high-resolution mass spectrometry detection.

Optimization of the Varian Saturn 2200 ion-trap tandem mass spectrometry (IT-MS/MS) system and comparison of its data quality with two other detection methods [electron-capture detection (ECD) and high-resolution mass spectrometry (HRMS)] was pursued by measuring polychlorinated biphenyls (PCBs) levels in fish and shellfish samples. IT-MS/MS methodology provided limits of detection (LOD) comparable to those obtained by ECD but superior specificity for the detection of a selected number of 39 PCB native congeners and 9 (13)C-labelled PCB standards. The method detection limits (MDLs) established for IT-MS/MS ranged between 1.0 and 5.0 pg/g on a wet weight basis while those obtained by ECD and HRMS were 1.0-4.0 pg/g and 0.1-2.0 pg/g, respectively. Overall, the results obtained in the study demonstrate that gas chromatography (GC) combined with IT-MS/MS provide higher data quality than those achievable by GC-ECD. For this particular set of target analytes the specificity achievable with IT-MS/MS was comparable to that obtained by HRMS and both techniques provided comparable data in terms of accuracy and precision.

Assessment of environmental estrogens and the intersex/sex reversal capacity for chinook salmon (Oncorhynchus tshawytscha) in primary and final municipal wastewater effluents.

A trickling filter/solid contact (TF/SC) biological secondary treatment plant with chlorine disinfection serving a suburban population of 740,000 was assessed for environmental estrogens. Weekly grab samples were taken at established sampling points and analyzed for various pertinent environmental estrogens including industrial chemicals, and natural and synthetic steroidal estrogens. Additionally, human estrogen receptor (hER) activity and capacity to elicit intersex/sex reversal for the wastewater was monitored using a recombinant yeast assay and whole fish exposures, respectively. hER activity levels varied from 76 to 106 ng/L E2 equivalents in the primary effluent, and were reduced by 25% by biological treatment. For the primary and final effluent no evidence of sex reversal or intersex was apparent in any of the treatment groups (1%, 3%, 10%, or 100%) based on genetic sex determinations and histological examination of the gonads in alevin from 28 d exposed chinook salmon (Oncorhynchus tshawytscha) eggs.

An assessment of estrogenic organic contaminants in Canadian wastewaters.

A suite of 30 primarily estrogenic organic wastewater contaminants was measured in several influent/effluent wastewater samples from four municipal wastewater treatment plants and effluents from one bleached kraft pulp mill (BKME) using an ultra-trace analytical method based on gas chromatography-high resolution mass spectroscopy (GC-HRMS). In vitro recombinant yeast assay detection of the estrogenic equivalent (EEq) on whole and solid phase extracted (SPE) and fractionated wastewater was also performed. 19-norethindrone was the most frequently detected and abundant (26-224 ng/L) of all the synthetic estrogens/progesterones in the influent samples. 17alpha-ethinylestradiol was the more frequently detected synthetic estrogen/progesterone in the effluents occurring at or below 5 ng/L with some sporadic occurrences of up to 178 ng/L. The greatest levels of steroidal estrogens in municipal effluents were E1>E2>E3 which were all <20 ng/L. Nonylphenol and di(2-ethylhexyl) phthalate were found to be the highest non-steroidal synthetic compounds surveyed in both municipal influent and effluent samples, both occurring at 6-7 microg/L in municipal effluents. BKME contained relatively large amounts of the plant sterol stigmasterol (4 microg/L) but low amounts of fecal sterols, and steroidal estrogens (E2 only at 6 ng/L) when compared to the municipal effluents. In vitro EEq in the wastewater surveyed ranged from 9-106 ng E2/L and ranked from municipal influent>municipal effluent approximately BKME, with most of the estrogenicity fractionating in the 100% methanol SPE fraction followed by a secondary amount in the diethyl ether (for municipal) or methyl-tert butyl ether (for BKME) SPE fractions. Most correlations between chemical and in vitro estrogenic equivalency were weak (p>0.05 in most cases). Unexpected inverse correlations between in vitro estrogenic activity and concentrations of the estrogenic contaminant bisphenol A were found which likely contributed to the weakness of these correlations. A modified toxicity identification and evaluation procedure was continued with the SPE extracts from the more potent 100% methanol SPE fractions of municipal effluent. High performance liquid chromatography band elution retention times, based on in vitro estrogen detection, indicated that steroidal estrogens such as E2 were responsible for most of the estrogenicity of the samples. Subsequent collection and GC-MS analysis of active bands did not confirm the presence of steroidal estrogens, but expanded the possibility of phthalate esters (i.e. dibutyl phthalate) and natural sterols (i.e. beta-sitosterol) contributing to the overall estrogenic load.

Polybrominated diphenyl ethers in blood from Korean incinerator workers and general population.

This study was conducted to examine PBDE exposure in Koreans, with a special focus on incinerator workers due to their potential for occupational exposure to PBDEs. A total of 92 blood samples from 30 incinerator workers, 51 nearby residents and 11 controls were analyzed. The mean total PBDE concentration calculated from the 13 most concentrated congeners for all samples was 16.84+/-7.48 ng/g lipid, which was somewhat higher concentration than in other countries except North America and Canada. The PBDE levels and congener profiles detected in incinerator workers were not distinctly different from those found in the general population. In all groups tested, BDE-47 was dominant (mean contribution=32.5%) followed by BDE-153 (23.6%) and relatively high portions of BDE-183 (16.5%) were found. No strong trend was observed between PBDE levels and a number of key biological factors examined in this study, however, weak correlations were observed in PBDE levels measured against dietary habits, particularly in fish consumption frequency and gender. Overall, our data suggest that the occupational exposure of incinerator workers to PBDEs can be considered minor, while other lifestyle factors can have a greater contribution to PBDE exposure.