Legacy and new halogenated persistent organic pollutants in polar bears from a contamination hotspot in the Arctic, Hudson Bay Canada.

A large and complex suite of 295 legacy and new halogenated persistent organic pollutants (POPs) were investigated in fat or liver tissue samples of polar bears collected in 2013-2014 from Southern (SHB) and Western (WHB) subpopulations of the Canadian Arctic contaminants hotspot of Hudson Bay. A total of 210 POPs were detected and/or quantifiable with some frequency in all fat or liver samples. POP profile and concentration differences were investigated both within (e.g. age and sex) and between the two subpopulations. Two time-point comparisons were made relative to POPs reported for Hudson Bay polar bears harvested in 2007-2008. ΣPolychlorinated biphenyl (PCB) concentrations at both time points were the most concentrated of the POP groups, and were spatially uniform with no detectable influence of sex or age, as were concentrations of the dominant congener CB153. ΣChlordanes (ΣCHLs, 74-79% oxychlordane) and the Σperfluoroalkyl substances (ΣPFASs, ≈60% perfluorooctane sulfonate (PFOS)) had the second greatest POP group concentrations in SHB and WHB respectively, with ΣPFASs and ΣCHLs being significantly influenced by age and/or sex. ΣCHLs were spatially uniform but ΣPFASs were greater in the SHB bears, as were e.g. some flame retardants, due to e.g. local contamination and/or changes in bear behavior and diet. Endosulfans and hexabromocyclododecane were detectable in samples from 2007-2008 but not from 2013-2014, which is consistent with their global POP regulations. ΣPolychlorinated naphthalenes (ΣPCNs) were consistently detected at relatively high concentrations compared to other arctic wildlife, however these concentrations were low relative to legacy POPs. ΣShort-chain chlorinated paraffins (ΣSCCPs) were major contributors to the overall POPs burden with concentrations comparable to other legacy POPs, though there was no significant difference between or within subpopulations for PCNs or SCCPs. Except for octachlorostyrene, POPs concentrations were generally lower in female and male bears from SHB in 2013-2014 relative to 2007-2008, however those of WHB males were greater over the same timeframe for almost all POPs.

Congener specific determination of polychlorinated naphthalenes in sediment and biota by gas chromatography high resolution mass spectrometry.

An isotope dilution congener-specific method for the determination of the most abundant and most toxic polychlorinated naphthalenes (PCNs) was developed using gas chromatography with high resolution mass spectrometry (GC-HRMS). The method was used to determine the concentration of 24 target congeners and total PCN concentrations in fish and sediment samples. Tissue samples were extracted using pressurized liquid extraction (PLE) and sediment samples were extracted using Soxhlet extraction. Sample extracts were cleaned up using either a manual two-stage open column procedure or an automated FMS Power Prep System with multi-analyte and multi-sample capability using a three-column cleanup procedure. Sediment extracts were cleaned up with a dual open column cleanup technique involving the use of both a multi-layered silica (silver nitrate/acid/base/neutral silica) column followed by column containing carbon-activated silica. Fish tissue extracts were cleaned up on the automated system involving the use of a high capacity ABN (acid/base/neutral column), carbon celite column, and a basic alumina column. The method is capable of producing instrument detection limits (IDLs) between 0.06 and 0.13pg for each PCN (on column), with method detection limits (MDLs) for the fish extracts ranging from 1.3 to 3.4pg/g (wet weight) and 0.46 to 1.2pg/g (dry weight) for sediments. The average accuracy of 34 spiked fish samples analysed over a period of several months was 100% with a precision (%RSD) of 12%. Similarly, the average accuracy for 28 spiked sediment samples was 104% with a precision (%RSD) of 12%. The application of the method to environmental samples was demonstrated through the analysis of sediment and fish samples obtained from Lake Ontario, Canada. The method is used both for the determination of 24 PCNs and to perform non-targeted screening for the remaining 51 PCN congeners, which are included in the total PCN quantification result. It is currently one of the most comprehensive and accurate congener-specific methods available and was developed from the existing techniques used for the determination of polychlorinated dioxins and furans to produce high quality data with only minor modifications in the clean-up procedure. It can therefore be readily adopted by other laboratories performing dioxin and POP analyses.

Wild fish from the Bay of Quinte Area of Concern contain elevated tissue concentrations of PCBs and exhibit evidence of endocrine-related health effects.

The Bay of Quinte (BOQ) is an Area of Concern listed under the Great Lakes Water Quality Agreement. The presence of dioxins and dioxin-like PCBs in fish in the BOQ AOC has led to restrictions on fish consumption by humans, which is a beneficial use impairment. Adult yellow perch (Perca flavescens) and brown bullhead (Ameiurus nebulosus) were sampled from Trenton, Belleville, and Deseronto (reference site) in the BOQ. A suite of hormone assays and various measures of exposure and/or sublethal health effects were used to assess the health status of fish of both species and sex. Condition factor, hepatosomatic index, ethoxyresorufin-O-deethylase activity, circulating steroid and thyroid hormones, thyroid activation, oocyte size distribution, spermatogenic cell stages, and plasma vitellogenin were among the endpoints that were significantly (p < 0.05) affected by location. Many of those effects corresponded with significantly (p < 0.05) greater tissue concentrations of polychlorinated biphenyls (PCBs) at Belleville and Trenton. Hepatic extracts from brown bullhead sampled from Trenton had significantly (p < 0.05) greater binding activity to the androgen receptor and sex steroid binding protein. Taken together, these data and preliminary data from a concomitant study suggest that PCBs are likely being hydroxylated in vivo, resulting in enhanced bioactivity at endocrine receptors and measurable health responses. The present study supports the growing body of evidence that PCBs and their metabolites can affect fish thyroid and steroid hormone systems.

Dechlorane-related compounds in franciscana dolphin (Pontoporia blainvillei) from southeastern and southern coast of Brazil.

Concentrations of Dechlorane (Dec) 603 (0.75 ng/g lipid weight (lw); mean) and Dec 602 (0.38 ng/g lw; mean) were quantified in more than 95% of the franciscana (Pontoporia blainvillei) dolphin samples, whereas the frequency of detection decreased to 75% for Dechlorane Plus (DP) (1.53 ng/g lw, mean). The presence of Chlordene Plus (CP) was also observed (0.13 ng/g lw, mean) in half of the samples. On the contrary, Dec 604, decachloropentacyclooctadecadiene (aCl(10)DP), and undecachloropentacyclooctadecadiene (aCl(11)DP) concentrations were below the limit of quantifications in all cases. To the best of our knowledge, this is the first article reporting the presence of Dec 603, Dec 602, and CP in mammals. For comparative purposes, levels of Mirex, polybrominated diphenyl ethers (PBDEs), and decabromodiphenylethane (DBDPE) are also reported. Considering geographic distribution evaluation together with the strong positive correlations found between DP and PBDEs (r(s) = 0.63; p < 0.01), highly anthropogenic areas were identified as potential sources of these chemicals in this dolphin species. However, local sources for Dec 602, 603, Mirex, CP, and DBDPE were not found indicating that in this case historical use and/or atmospheric transport and deposition may play an important role in their fate.

Characterization of mass-labeled [13C14]-decabromodiphenylethane and its use as a surrogate standard in the analysis of sewage sludge samples.

Very little data is available about the presence of the brominated flame retardant, DBDPE, in the environment. This study reports the characterization of [(13)C(14)]-decabromodiphenylethane and the use of this surrogate standard to positively identify and quantify the presence of DBDPE in sewage sludge samples. The large difference in response factors between BDE-209 and DBDPE predicates the use of [(13)C(14)]-decabromodiphenylethane as a surrogate standard to improve the accuracy when determining the levels of DBDPE in environmental samples.

Development of a reference material for routine performance monitoring of methods measuring polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and dioxin-like polychlorinated biphenyls.

Matrix-matched environmental certified reference materials (CRMs) are one of the most useful tools to validate analytical methods, assess analytical laboratory performance and to assist in the resolution of data conflicts between laboratories. This paper describes the development of a lake sediment as a CRM for polychorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (DLPCBs). The presence of DLPCBs in the environment is of increased concern and analytical methods are being developed internationally for monitoring DLPCBs in the environment. This paper also reports the results of an international interlaboratory study involving thirty-five laboratories from seventeen countries, conducted to characterize and validate levels of a sediment reference material for PCDDs, PCDFs and DLPCBs.

Differentiation and characterization of Klebsiella pneumoniae strains by pyrolysis-gas-liquid chromatography-mass spectrometry.

Nine coded duplicate strains of capsular nontypable Klebsiella pneumoniae were analyzed by pyrolysis-gas-liquid chromatography-mass spectrometry. All duplicate strains were correctly matched, and individual strains, including seven nontypable strains, were clearly distinguishable from one another. The addition of mass spectrometry to the analysis has aided the process of identification and has provided chemical structural information on K. pneumoniae strains. Application of this technique to the identification of some disease outbreaks or nosocomial problems could be of epidemiological importance, especially when conventional methods do not identify the epidemic strain.