Stable isotopes, PCBs and pesticide concentrations in zooplankton, seawater and POM from Kongsfjorden and Liefdefjorden, Svalbard

Differences in bioaccumulation of persistent organic pollutants (POPs) between fjords characterized by different water masses were investigated by comparing POP concentrations, patterns and bioaccumulation factors (BAFs) in seven species of zooplankton from Liefdefjorden (Arctic water mass) and Kongsfjorden (Atlantic water mass), Svalbard, Norway. No difference in concentrations and patterns of POPs was observed in seawater and POM; however higher concentrations and BAFs for certain POPs were found in species of zooplankton from Kongsfjorden. The same species were sampled in both fjords and the differences in concentrations of POPs and BAFs were most likely due to fjord specific characteristics, such as ice cover and timing of snow/glacier melt. These confounding factors make it difficult to conclude on water mass (Arctic vs. Atlantic) specific differences and further to extrapolate these results to possible climate change effects on accumulation of POPs in zooplankton. The present study suggests that zooplankton do biomagnify POPs, which is important for understanding contaminant uptake and flux in zooplankton, though consciousness regarding the method of evaluation is important.

Body measurements and blood plasma lipid, PCB and OH-PCB content of polar bear (U. maritimus) mothers and cubs, Svalbard

The aim of this study was to examine the plasma concentrations and prevalence of polychlorinated biphenyls (PCBs) and hydroxylated PCB-metabolites (OH-PCBs) in polar bear (Ursus maritimus) mothers (n = 26) and their 4 months old cubs-of-the-year (n = 38) from Svalbard to gain insight into the mother-cub transfer, biotransformation and to evaluate the health risk associated with the exposure to these contaminants. As samplings were performed in 1997/1998 and 2008, we further investigated the differences in levels and pattern of PCBs between the two sampling years. The plasma concentrations of Sum(21)PCBs (1997/1998: 5710 ± 3090 ng/g lipid weight [lw], 2008: 2560±1500 ng/g lw) and Sum(6)OH-PCBs (1997/1998: 228 ± 60 ng/g wet weight [ww], 2008: 80 ± 38 ng/g ww) in mothers were significantly lower in 2008 compared to in 1997/1998. In cubs, the plasma concentrations of Sum(21)PCBs (1997/1998: 14680 ± 5350 ng/g lw, 2008: 6070 ± 2590 ng/g lw) and Sum(6)OH-PCBs (1997/1998: 98 ± 23 ng/g ww, 2008: 49 ± 21 ng/g ww) were also significantly lower in 2008 than in 1997/1998. Sum(21)PCBs in cubs was 2.7 ± 0.7 times higher than in their mothers. This is due to a significant maternal transfer of these contaminants. In contrast, Sum(6)OH-PCBs in cubs were approximately 0.53 ± 0.16 times the concentration in their mothers. This indicates a lower maternal transfer of OH-PCBs compared to PCBs. The majority of the metabolite/precursor-ratios were lower in cubs compared to mothers. This may indicate that cubs have a lower endogenous capacity to biotransform PCBs to OH-PCBs than polar bear mothers. Exposure to PCBs and OH-PCBs is a potential health risk for polar bears, and the levels of PCBs and OH-PCBs in cubs from 2008 were still above levels associated with health effects in humans and wildlife.

Polychlorinated and polybrominated biphenyls

This volume of the IARC Monographs provides evaluations of the carcinogenicity of polychlorinated biphenyls and polybrominated biphenyls. Polychlorinated biphenyls are a class of aromatic compounds comprising 209 congeners, each containing 1 to 10 chlorine atoms attached to a biphenyl nucleus. Technical products, which were manufactured to obtain a certain degree of chlorination, are mixtures of numerous congeners. These products were widely used as dielectric fluid in capacitors and transformers, and to a lesser extent in building materials. Although their production and use has been banned in most countries, these compounds are ubiquitous environmental pollutants, including in polar regions and the deep ocean, because they are persistent and bioaccumulate. Worldwide monitoring programmes have shown that polychlorinated biphenyls are present in most samples of human milk. An IARC Monographs Working Group reviewed epidemiological evidence, animal bioassays, and mechanistic and other relevant data to reach conclusions as to the carcinogenic hazard to humans of polychlorinated biphenyls, of the subclass of dioxinlike polychlorinated biphenyls, and of polybrominated biphenyls.

Investigations into the determination of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) by capillary gas chromatography

Factors involved in the determination of PAHs (16 priority PAHs as an example) and PCBs (10 PCB congeners, representing 10 isomeric groups) by capillary gas chromatography coupled with mass spectrometry (GC/MS, for PAHs) and electron capture detection (GC/ECD , for PCBs) were studied, with emphasis on the effect of solvent. Having various volatilities and different polarities, solvent studied included dichloromethane, acetonitrile, hexan e, cyclohexane, isooctane, octane, nonane, dodecane, benzene, toluene, p-xylene, o-xylene, and mesitylene. Temperatures of the capillary column, the injection port, the GC/MS interface, the flow rates of carrier gas and make-up gas, and the injection volume were optimized by one factor at a time method or simplex optimization method. Under the optimized conditions, both peak height and peak area of 16 PAHs, especially the late-eluting PAHs, were significantly enhanced (1 to 500 times) by using relatively higher boiling point solvents such as p-xylene and nonane, compared with commonly used solvents like benzene and isooctane. With the improved sensitivity, detection limits of between 4.4 pg for naphthalene and 30.8 pg for benzo[g,h,i]perylene were obtained when p-xylene was used as an injection solvent. Effect of solvent on peak shape and peak intensity were found to be greatly dependent on temperature parameters, especially the initial temperature of the capillary column. The relationship between initial temperature and shape of peaks from 16 PAHs and 10 PCBs were studied and compared when toluene, p-xylene, isooctane, and nonane were used as injection solvents. If a too low initial temperature was used, fronting or split of peaks was observed. On the other hand, peak tailing occurred at a too high initial column temperature. The optimum initial temperature, at which both peak fronting and tailing were avoided and symmetrical peaks were obtained, depended on both solvents and the stationary phase of the column used. On a methyl silicone column, the alkane solvents provided wider optimum ranges of initial temperature than aromatic solvents did, for achieving well-shaped symmetrical GC peaks. On a 5% diphenyl: 1% vinyl: 94% dimethyl polysiloxane column, when the aromatic solvents were used, the optimum initial temperature ranges for solutes to form symmetrical peaks were improved to a similar degree as those when the alkanes were used as injection solvents. A mechanism, based on the properties of and possible interactions among the analyte, the injection solvent, and the stationary phase of the capillary column, was proposed to explain these observations. The effect of initial temperature on peak height and peak area of the 16 PAHs and the 10 PCBs was also studied. The optimum initial temperature was found to be dependent on the physical properties of the solvent used and the amount of the solvent injected. Generally, from the boiling point of the solvent to 10 0C above its boiling point was an optimum range of initial temperature at which cthe highest peak height and peak area were obtained.

Organochlorine pesticides and polychlorinated biphenyls in soil and water samples in the northeastern part of São Paulo State, Brazil

Detailed analyses of persistent organic pollutants (POPs) such as organochlorine pesticides (OCPs), hexachlorocyclohexane (HCH) isomers (HCHs), dichlorodiphenyltrichloro ethane (DDT) and its metabolites (DDTs) and congeners of polychlorinated biphenyls (PCBs) in soil and surface water from the northeastern São Paulo, Brazil allowed the evaluation of the contamination status, distribution and possible pollution sources. The pesticides and PCBs demonstrated markedly different distributions, reflecting different agricultural, domestic and industrial usage in each region studied. The ranges of HCH, DDT, and PCBs concentrations in the soil samples were 0.05-0.92, 0.12-11.01, 0.02-0.25 ng g(-1) dry wt, respectively, and in the surface water samples were 0.02-0.6, 0.02-0.58 and 0.02-0.5 ng l(-1), respectively. Overall elevated levels of DDT and PCB were recorded in region 2, a site very close to melting, automotive batteries industries, and agricultural practice regions. High ratios of metabolites of DDT to DDT isomers revealed the recent use of DDT in this environment. The sources of contamination are closely related to human activities, such as domestic and industrial discharge, street runoff, agricultural pesticides and soil erosion, due to deforestation as well as atmospheric transport. (c) 2006 Elsevier Ltd. All rights reserved.

Determination of organochlorine pesticides and polychlorinated biphenyls residues in municipal solid waste compost by gas chromatography with electron-capture detection

A simple and efficient method for the simultaneous gas chromatographic determination of ten organochlorine pesticides (alpha-HCH, beta-HCH, gamma-HCH, p,p'-DDT, o,p'-DDT, p,p'-DDD, p,p'-DDE, aldrin, endrin, and dieldrin) and six congeners of PCBs (PCB 28, 52, 118, 138, 153, and 180) in municipal solid waste compost is described. The procedure involves a solid-phase dispersion matrix using celite as dispersant sorbent, alumina as clean up sorbent and hexane-dichloromethane (7:3, v/v) mixture as eluting solvent. An additional purification step with copper was necessary to eliminate sulphur. Analysis of the sample was performed by GC-ECD. The method was validated with fortified samples at two concentration levels (0.025 and 0.05 mg kg(-1)). Average recovery ranged from 77 to 121% with relative standard deviation between 1 and 18%. The detection limits, which ranged from 0.003 to 0.01 mg kg-1, were lower than those established by the Baden-Wurttemberg directive (0.033 mg kg(-1)).

Polychlorinated Biphenyls in Glaciers. 2. Model Results of Deposition and Incorporation Processes

In previous work, Alpine glaciers have been identified as a secondary source of persistent organic pollutants (POPs). However, detailed understanding of the processes organic chemicals undergo in a glacial system was missing. Here, we present results from a chemical fate model describing deposition and incorporation of polychlorinated biphenyls (PCBs) into an Alpine glacier (Fiescherhorn, Switzerland) and an Arctic glacier (Lomonosovfonna, Norway). To understand PCB fate and dynamics, we investigate the interaction of deposition, sorption to ice and particles in the atmosphere and within the glacier, revolatilization, diffusion and degradation, and discuss the effects of these processes on the fate of individual PCB congeners. The model is able to reproduce measured absolute concentrations in the two glaciers for most PCB congeners. While the model generally predicts concentration profiles peaking in the 1970s, in the measurements, this behavior can only be seen for higher-chlorinated PCB congeners on Fiescherhorn glacier. We suspect seasonal melt processes are disturbing the concentration profiles of the lower-chlorinated PCB congeners. While a lower-chlorinated PCB congener is mainly deposited by dry deposition and almost completely revolatilized after deposition, a higher-chlorinated PCB congener is predominantly transferred to the glacier surface by wet deposition and then is incorporated into the glacier ice. The incorporated amounts of PCBs are higher on the Alpine glacier than on the Arctic glacier due to the higher precipitation rate and aerosol particle concentration on the former. Future studies should include the effects of seasonal melt processes, calculate the quantities of PCBs incorporated into the entire glacier surface, and estimate the quantity of chemicals released from glaciers to determine the importance of glaciers as a secondary source of organic chemicals to remote aquatic ecosystems.

Análise dos parâmetros que interferem no metabolismo da microbiota anaeróbia e anóxica na remoção de bifenilas policloradas

A elevada concentração de cloro das bifenilas policloradas provoca alta toxicidade do composto, o qual dificulta sua biodegradação. A contaminação de PCB no Brasil foi confirmada em estudo realizado na Bahia de Santos-São Vicente (São Paulo), o qual revelou a necessidade de um plano de ação para o controle e remoção de PCB no Brasil. Pretendeu-se assim, na realização da presente pesquisa, verificar quatro hipóteses: (1) A técnica de Microextração em fase sólida é uma metodologia eficaz para avaliação de bifenilas policloradas de amostras de reatores; (2) A condição fermentativa-metanogênica abriga comunidade resistente ao PCB, e removê-lo; (3) A condição desnitrificante abriga comunidade resistente ao PCB, e removê-lo e (4) A remoção de PCB, bem como, a composição microbiana é distinta em cada condição metabólica. Para tanto, reatores em batelada foram montados separadamente com biomassa anaeróbia proveniente de reator UASB usado no tratamento de água residuária de avicultura e biomassa de sistemas de lodos ativados de tratamento de esgoto sanitário. Os reatores operados em condição mesófila foram alimentados com meio sintético, co-substratos, sendo etanol (457 mg.L-1) e formiato de sódio (680 mg.L-1) para os reatores anaeróbios, e somente etanol (598 mg.L-1) para os reatores anóxicos, além de PCB padrão Sigma (congêneres PCBs 10, 28, 52, 153, 138 e 180) em diferentes concentrações, dependendo do objetivo do ensaio. A aplicação do método de extração por SPME com análise em cromatógrafo gasoso com detector por captura de elétrons foi adequada para a determinação dos seis congêneres de PCB. Obteve-se ampla faixa de linearidade, seletividade frente aos vários interferentes, além da robustez do método, utilidade e confiabilidade na identificação e quantificação específica dos seis congêneres de PCB. A Hipótese 1 foi aceita; ou seja, por meio da aplicação da metodologia SPME foi possível quantificar os PCB nos reatores em batelada. Apesar de ter sido comprovada a inibição metanogênica na presença de PCB, com IC50 de 0,03 mg.L

Toxicity of polychlorinated biphenyls and N-phenyl-1-naphthylamine in the juvenile turtle, Chelydra serpentina

Polychlorinated biphenyls (PCBs) and substituted phenylamine antioxidants (SPAs) are two chemical groups that have been used in multiple Canadian industrial processes. Despite the production ban of PCBs in North America in 1977, they are still ubiquitous in the environment and in wildlife tissues. Previous studies of fish, amphibians, birds, and mammals have shown that PCBs are toxic and act as endocrine disruptors. In contrast, SPAs, specifically N-phenyl-1-naphthylamine (PANA), have received very little attention despite their current use in Canada and their expected environmental releases. The effects of PCB and PANA exposures in reptiles remain unknown thus, juvenile Chelydra serpentina were used in this thesis as a model vertebrate to fill in missing toxicity research gaps due to their importance as an environmental indicator. First, food pellets were spiked at an environmentally relevant concentration of the PCB mixture Aroclor 1254 (A1254) to model hepatic bioaccumulation (0.45 μg/g A1254 for 31 days) and depuration (clean food for 50 days) of PCBs in turtles. No significant differences in PCB concentrations were observed between the control and treated animals, suggesting that juvenile turtles exposed to environmentally relevant concentrations of PCBs can likely detoxify low concentrations of PCBs. Additionally, two dose-response experiments were performed using A1254 or PANA spiked food (0-12.7 μg/g and 0-3,446 μg/g, respectively) to determine hepatic toxicity and bioaccumulation in juvenile C. serpentina. An increase in hepatic cyp1a was observed when exposed to the highest dose of both chemicals: 1) for A1254, induction correlated to the significant increase in hepatic PCB congeners that are known to be metabolized by CYP1A; and 2) for PANA, induction suggested that CYP1A has a potential role in its detoxification. PCBs are known endocrine disruptors, but no significant changes were observed for both thyroid receptors (alpha and beta) or by estrogen and androgen receptors. This lack of response, also noted in the PANA exposure, suggests that C. serpentina is less sensitive to endocrine disruption than other vertebrates. Furthermore, the expression of genes involved in cellular stress was not altered in PCB and PANA exposed animals, supporting the resilience of turtles to oxidative stress. This is the first study to demonstrate the toxicity of PCBs and PANA in C. serpentina, demonstrating the turtle’s high tolerance to contamination.

Polychlorinated Dibenzodioxins and Dibenzofurans in Butter from Different States in Australia

Nine samples of butter from producers in various states of Australia were analysed for polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). Detectable concentrations of 2,3,7,8-chlorine substituted PCDD/Fs were found in all samples. The mean PCDD/F concentration expressed as 2',3,7,8-TCDD equivalents (TEQs) was 0.19 pg TEQ g(-1) fat. The highest concentration (0.46 pg TEQ g(-1) fat) was observable in a sample from Victoria which is the most densely populated state. Overall the results indicate that PCDD/F concentrations in dairy products from Australia are low in comparison to the levels in dairy products of industrialized countries on the Northern Hemisphere. As expected, this study provides evidence that the environmental and consequently the human body burden of PCDD/ Fs to be relatively low in Australia.

PCDDs in the water/sediment-seagrass-dugong (Dugong dugon) food chain on the Great Barrier Reef (Australia)

Polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) concentrations were measured in sediment and seagrass from five locations in or adjacent to the Great Barrier Reef Marine Park. A full spectrum of Cl(5-8)DDs were present in all samples and, in particular, elevated levels of Cl8DD were found. PCDFs could not be quantified in any samples. The PCDD concentrations ranged over two orders of magnitude between sites, and there was a good correlation between sediment and seagrass levels. There were large quantities of sediment present on the seagrass (20-62% on a dry wt. basis), and it was concluded that this was a primary source of the PCDDs in the seagrass samples. The PCDD levels in the seagrass samples were compared with the levels in the tissue of three dugongs stranded in the same region. The relative accumulation of the 2,3,7,8-substituted PCDD congeners in the dugongs decreased by over two orders of magnitude with increasing degree of chlorination. This was attributed to the reduced absorption of the higher chlorinated congeners in the digestive tract, a behaviour that has been observed in other mammals such as domestic cows. (C) 2001 Elsevier Science Ltd. All rights reserved.

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in sediments from Hong Kong

Concentrations of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were determined in 14 sediment samples collected from four sites in the Mai Po Marshes Nature Reserve (within a RAMSAR Site) and from another six sites in Victoria Harbour and along the Hong Kong coastline. Elevated levels of PCDDs, and particularly OCDD, were detectable in all samples collected from the Mai Po Marshes and five of the six sites. In contrast to PCDDs, PCDFs were mainly found in sediment samples collected from industrial areas (Kwun Tong and To Kwa Wan) in Victoria Harbour. PCDD/F levels and congener profiles in the samples from the Mai Po Marshes Nature Reserve in particular show strong similarities to those reported in studies which have attributed similar elevated PCDD concentrations to nonanthropogenic PCDD sources. (C) 2002 Elsevier Science Ltd. All rights reserved.

Transformation processes, pathways, and possible sources of distinctive polychlorinated dibenzo-p-dioxin signatures in sink environments

In recent years, studies on environmental samples with unusual dibenzo-p-dioxin (PCDD) congener profiles were reported from a range of countries. These profiles, characterized by a dominance of octachlorinated dibenzodioxin (OCDD) and relatively low in dibenzofuran (PCDF) concentrations, could not be attributed to known sources or formation processes. In the present study, the processes that result in these unusual profiles were assessed using the concentrations and isomer signatures of PCDDs from dated estuarine sediment cores in Queensland, Australia. Increases in relative concentrations of lower chlorinated PODS and a relative decrease of OCDD were correlated with time of sediment deposition. Preferred lateral, anaerobic dechlorination of OCDD represents a likely pathway for these changes. In Queensland sediments, these transformations result in a distinct dominance of isomers fully chlorinated in the 1,4,6,9-positions (1,4-patterns), and similar 1,4-patterns were observed in sediments from elsewhere. Consequently, these environmental samples may not reflect the signatures of the original source, and a reevaluation of source inputs was undertaken. Natural formation of PCDDs, which has previously been suggested, is discussed; however, based on the present results and literature comparisons, we propose an alternative scenario. This scenario hypothesizes that an anthropogenic PCDD precursor input (e.g. pentachlorophenol) results in the contamination. These results and hypothesis imply further investigations are warrented into possible anthropogenic sources in areas where natural PCDD formation has been suggested.