Lower Chlorinated Polychlorinated Biphenyls Congeners Research Articles

Occurrences and possible sources of persistent organic pollutants (POPs) in ice-free area soils in East Antarctica

Antarctica is widely regarded as a sink for persistent organic pollutants (POPs). However, there is a scarcity of data on the occurrence and spatial pattern of POPs in Antarctica, especially in the cold-xeric East Antarctica. Here, organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) in soils from the Larsemann Hills, the second-largest ice-free area along East Antarctica, were investigated. It is shown that the main OCP contaminants were HCB, p,p’-DDD and δ-HCH (3.7–1522.3 pg g−1, 38.2–2276.6 pg g−1 and < LOD–570 pg g−1, respectively). OCPs in soils were primarily caused by long-distance atmospheric transport, but local sources can be found in areas heavily impacted by local human activities. Among DDTs and HCHs, only p,p’-DDD and δ-HCH were detected, indicating that DDTs and HCHs have aged. For PCBs (14.1–993.4 pg g−1), low-chlorinated PCB congeners were found in soil samples far from the station areas (Zhongshan, Progress II, and Progress I), possibly due to long-range atmospheric transport, while high levels of high-chlorinated PCB were found in the soils inside the station area (Law Base) and close to the main road, possibly associated with local station activities. Among the measured PBDEs (81.8–695.5 pg g−1), BDE-209 was the most frequently observed species, and the low-BDE found in soil samples could be from BDE-209 photodegradation. The majority of samples containing high concentrations of BDE-209 are concentrated in the station areas, implying that its source may be related to local station activities.

Spatial and temporal distribution of Persistent Organic Pollutants and current use pesticides in the atmosphere of Argentinean Patagonia

XAD-based passive air samplers (PAS) were used to evaluate organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and some current use pesticides (chlorotalonil, trifluralin and dichlofluanid) in the atmosphere of Argentinian Patagonia. The PAS were deployed for 12 months during three consecutive years along a longitudinal (Rio Negro watershed) and a latitudinal (Patagonian coast) transect. Endosulfan, trifluralin and DDT-related substances were the most prevalent pesticides in the Rio Negro watershed, an intensive agricultural basin, consistent with ongoing use of endosulfan at the time of sampling. Concentrations of industrial contaminants were low (mean 25 pg/m3 and 1.9 pg/m3 for Σ38 PCBs, and Σ5PBDEs, respectively) and similar among sites. However, along the Patagonian coast, air concentrations of total contaminants were highly variable (14–400 pg/m3) with highest values recorded at Bahia Blanca, an important industrial area that is also downwind of the most intensively agriculturally used area of Argentina. Contaminant levels decreased toward the south, with the exception of the southernmost sampling site (Rio Gallegos) where a slight increase of total pollutant levels was observed, mainly due to the lower chlorinated PCB congeners. Interannual variability was small, although the last year tended to have slightly higher levels for different contaminant groups at most sampling sites. This large-scale spatial atmospheric monitoring of POPs and some CUPs in the South of Argentina highlights the important and continuing role of rural and urban areas as emission sources of these chemicals.

Informal e-waste recycling and plasma levels of non-dioxin-like polychlorinated biphenyls (NDL-PCBs) – A cross-sectional study at Agbogbloshie, Ghana

Informal e-waste recycling leads to a contamination of the workers with several hazardous substances, in particular heavy metals and persistent organic pollutants (POPs). Polychlorinated biphenyls (PCBs) belong to the group of POPs and are suspected to be associated with adverse health effects. In particular lower chlorinated PCBs, such as the congeners PCB 28 and PCB 52 are a marker of occupational exposure. The aim of our study was to assess the occupational PCB exposure in e-waste workers in relation to their specific recycling task (e.g. dismantling, burning). Altogether, n = 88 e-waste workers and n = 196 control subjects have been included in this study. All plasma participant's samples were evaluated for the PCB congeners PCB 28, 52, 101, 138, 153, 180 and sum of NDL-indicator congeners by human biomonitoring. A significant difference could be detected for the lower chlorinated PCB congeners (PCB 28, 52, and 101) for e-waste workers in comparison to the control group. Analyzing specific recycling tasks, workers who dismantle and those who burn e-waste showed the highest plasma levels of PCB 28 and 52. In conclusion, e-waste workers showed occupational related elevated PCB levels. Although those levels did not exceed the BAT value, workers were contaminated with PCBs during their task. Occupational health and safety measure are therefore necessary to protect the worker's health.

PCB11 Metabolite, 3,3'-Dichlorobiphenyl-4-ol, Exposure Alters the Expression of Genes Governing Fatty Acid Metabolism in the Absence of Functional Sirtuin 3: Examining the Contribution of MnSOD.

Although the production of polychlorinated biphenyls (PCBs) is prohibited, the inadvertent production of certain lower-chlorinated PCB congeners still threatens human health. We and others have identified 3,3’-dichlorobiphenyl (PCB11) and its metabolite, 3,3’-dichlorobiphenyl-4-ol (4OH-PCB11), in human blood, and there is a correlation between exposure to this metabolite and mitochondrial oxidative stress in mammalian cells. Here, we evaluated the downstream effects of 4OH-PCB11 on mitochondrial metabolism and function in the presence and absence of functional Sirtuin 3 (SIRT3), a mitochondrial fidelity protein that protects redox homeostasis. A 24 h exposure to 3 μM 4OH-PCB11 significantly decreased the cellular growth and mitochondrial membrane potential of SIRT3-knockout mouse embryonic fibroblasts (MEFs). Only wild-type cells demonstrated an increase in Manganese superoxide dismutase (MnSOD) activity in response to 4OH-PCB11–induced oxidative injury. This suggests the presence of a SIRT3-mediated post-translational modification to MnSOD, which was impaired in SIRT3-knockout MEFs, which counters the PCB insult. We found that 4OH-PCB11 increased mitochondrial respiration and endogenous fatty-acid oxidation-associated oxygen consumption in SIRT3-knockout MEFs; this appeared to occur because the cells exhausted their reserve respiratory capacity. To determine whether these changes in mitochondrial respiration were accompanied by similar changes in the regulation of fatty acid metabolism, we performed quantitative real-time polymerase chain reaction (qRT-PCR) after a 24 h treatment with 4OH-PCB11. In SIRT3-knockout MEFs, 4OH-PCB11 significantly increased the expression of ten genes controlling fatty acid biosynthesis, metabolism, and transport. When we overexpressed MnSOD in these cells, the expression of six of these genes returned to the baseline level, suggesting that the protective role of SIRT3 against 4OH-PCB11 is partially governed by MnSOD activity.

Tracking polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in sediments and soils from the southwest of Buenos Aires Province, Argentina (South eastern part of the GRULAC region)

PCBs and PBDEs (7 and 10 congeners, respectively) were analyzed in four coastal surface sediments collected from the northern shore of Bahía Blanca estuary and in nine soils from different locations of Bahía Blanca city and the surrounding region (Southwest of Buenos Aires Province, Argentina). Sediment samples showed PCBs(Σ7) concentrations ranged from 0.61 to 17.6ngg−1 (dry weight=dw) and PBDEs(Σ10) from 0.16 to 2.02ngg−1 dw, whereas in soil samples ranged from 0.04 to 1.67ngg−1 dw for PCBs(Σ7) and 0.04 to 10.7ngg−1 dw for PBDEs(Σ10). The highest concentrations of both chemicals were detected in the urban and industrial/port areas showing a dominance of the higher chlorinated PCB congeners: in sediments for PCB-180 (56±33%) and PCB-153 (11±6%); and in soils for PCB-138 (23±3%), PCB-153 (22±2%) and PCB-180 (18±7%). In contrast, lower chlorinated PCB congeners were predominant at more distant sites; in sediments for congeners PCB-28 (33±4%) and PCB-52 (14.5±0.2%); and in soils PCB-28 (56±14%) and PCB-52 (33±19%). PBDE-209 (high brominated PBDE) showed the highest relative abundance in both sample types i.e., sediment (94±7%) and soil (80±12%). These findings can be considered lower or similar when compared with other sites of the world, and are likely associated with anthropogenic activities in their surrounding area, which has experienced a fast industrial growth in the last decade. This is the first investigation of PBDEs levels in the whole study area and of PCBs in soils from the Bahía Blanca city and surrounding region. This article provides new and useful information on POP levels in the South eastern part of the GRULAC region.

Indirect Evidence Link PCB Dehalogenation with Geobacteraceae in Anaerobic Sediment-Free Microcosms.

Although polychlorinated biphenyls (PCBs) production was brought to a halt 30 years ago, recalcitrance to degradation makes them a major environmental pollutant at a global scale. Previous studies confirmed that organohalide-respiring bacteria (OHRB) were capable of utilizing chlorinated congeners as electron acceptor. OHRB belonging to the Phyla Chloroflexi and Firmicutes are nowadays considered as the main PCB-dechlorinating organisms. In this study, we aimed at exploring the involvement of other taxa in PCB dechlorination using sediment-free microcosms (SFMs) and the Delor PCB mixture. High rates of congener dehalogenation (up to 96%) were attained in long-term incubations of up to 692 days. Bacterial communities were dominated by Chloroflexi, Proteobacteria, and Firmicutes, among strictly simplified community structures composed of 12 major phyla only. In a first batch of SFMs, Dehalococcoides mccartyi closely affiliated with strains CG4 and CBDB1 was considered as the main actor associated with congener dehalogenation. Addition of 2-bromoethanesulfonate (BES), a known inhibitor of methanogenic activity in a second batch of SFMs had an adverse effect on the abundance of Dehalococcoides sp. Only two sequences affiliated to this Genus could be detected in two (out of six) BES-treated SFMs, contributing to a mere 0.04% of the communities. BES-treated SFMs showed very different community structures, especially in the contributions of organisms involved in fermentation and syntrophic activities. Indirect evidence provided by both statistical and phylogenetic analysis validated the implication of a new cluster of actors, distantly affiliated with the Family Geobacteraceae (Phylum δ-Proteobacteria), in the dehalogenation of low chlorinated PCB congeners. Members of this Family are known already for their dehalogenation capacity of chlorinated solvents. As a result, the present study widens the knowledge for the phylogenetic reservoir of indigenous PCB dechlorinating taxa.

Polychlorinated Biphenyls in a Temperate Alpine Glacier: 2. Model Results of Chemical Fate Processes.

We present results from a chemical fate model quantifying incorporation of polychlorinated biphenyls (PCBs) into the Silvretta glacier, a temperate Alpine glacier located in Switzerland. Temperate glaciers, in contrast to cold glaciers, are glaciers where melt processes are prevalent. Incorporation of PCBs into cold glaciers has been quantified in previous studies. However, the fate of PCBs in temperate glaciers has never been investigated. In the model, we include melt processes, inducing elution of water-soluble substances and, conversely, enrichment of particles and particle-bound chemicals. The model is validated by comparing modeled and measured PCB concentrations in an ice core collected in the Silvretta accumulation area. We quantify PCB incorporation between 1900 and 2010, and discuss the fate of six PCB congeners. PCB concentrations in the ice core peak in the period of high PCB emissions, as well as in years with strong melt. While for lower-chlorinated PCB congeners revolatilization is important, for higher-chlorinated congeners, the main processes are storage in glacier ice and removal by particle runoff. This study gives insight into PCB fate and dynamics and reveals the effect of snow accumulation and melt processes on the fate of semivolatile organic chemicals in a temperate Alpine glacier.

Atmospheric concentration characteristics and gas/particle partitioning of PCBs from the North Pacific to the Arctic Ocean

Polychlorinated biphenyls (PCBs) were measured in atmospheric samples collected from the North Pacific to the Arctic Ocean between July and September 2012 to study the atmospheric concentration characteristics of PCBs and their gas/particle partitioning. The mean concentration of 26 PCBs (vapor plus particulate phase) (ΣPCBs) was 19.116 pg/m3 with a standard deviation of 13.833 pg/m3. Three most abundant congeners were CB-28, −52 and −77, accounting for 43.0% to ΣPCBs. The predominance of vapor PCBs (79.0% to ΣPCBs) in the atmosphere was observed. ΣPCBs were negative correlated with the latitudes and inverse of the absolute temperature (1/T). The significant correlation for most congeners was also observed between the logarithm of gas/particle partition coefficient (logKP) and 1/T. Shallower slopes (from −0.15 to −0.46, average −0.27) were measured from the regression of the logarithm of sub-cooled liquid vapor pressures (logpL○) and logKP for all samples. The difference of the slopes and intercepts among samples was insignificant (p>0.1), implying adsorption and/or absorption processes and the aerosol composition did not differ significantly among different samples. By comparing three models, the J-P adsorption model, the octanol/air partition coefficient (KOA) based model and the soot-air model, the gas/particle partitioning of PCBs in the Arctic atmosphere was simulated more precisely by the soot-air model, and the adsorption onto elemental carbon is more sensitive than the absorption into organic matters of aerosols, especially for low-chlorinated PCB congeners.

Diurnal Variability of Persistent Organic Pollutants in the Atmosphere over the Remote Southern Atlantic Ocean

A diel (24-h) cycle with daytime atmospheric concentrations higher than nighttime concentrations by a factor of 1.5–3 was observed for several low molecular weight polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) in remote areas of the tropical South Atlantic during a cruise in October–November 2005. In contrast, high molecular weight PCBs and PAHs did not display diurnal variability. A model which has successfully explained diel variability of persistent organic pollutants (POPs) over land could not reproduce the observed diel cycle by considering variability in temperature, atmospheric OH radical concentrations, atmospheric boundary layer height and wind speed as causal factors. We used the model to conduct two bounding scenarios to explore the possibility that phytoplankton biomass turn-over in the surface ocean drives the observed variability in air concentrations. The model could only qualitatively reproduce the field observations of diel variability for low chlorinated PCB congeners when the ocean acts as a source of pollutants to the atmosphere, and when variability in biomass drives variability in the capacity of the surface ocean.

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.

An interdisciplinary approach to the problem of neutralization of man-made polychlorinated biphenyls

19 Currently, biological methods of degradation of manmade polychlorinated biphenyls (PCBs) are becoming increasingly important in connection with the selection of new efficient PCB degrading strains. The most successful studies in the field of biodegrada tion of PCBs are associated with the use of low chlo rinated PCB congeners [1, 2]. It has been found that the biodegradability of PCB congeners increases with decreasing number of chlorine atoms in the initial sub strates. At the same time, interest persists in the search for surfactants capable of transferring more hydropho bic medium and high chlorinated PCB congeners into an aqueous medium in order to create stable emulsions available for efficient operation of bacterial strains [3, 4].

소나무잎을 Passive Air Sampler(PAS)로 이용하여 대기 중 PCBs 농도 추정

Objective: This study was carried out to use pine needles as a passive air sampler (PAS) of atmospheric Polychlorinated Biphenyls (PCBs). Methods: PCB concentrations in ambient air (<TEX>$C_a$</TEX>, ng/<TEX>$m^3$</TEX>) and deposited on pine needles (<TEX>$C_p$</TEX>, ng/g dry) were analyzed simultaneously from June 1 to December 31. Air samples were taken using a low volume PUF active air sampler and the overall average air volume was about 900-1,000 <TEX>$m^3$</TEX>. Pine needles were collected at the end of August and December near the air sampler. Results: <TEX>$C_a$</TEX> were higher at higher air temperature and lower chlorinated PCB congeners, but <TEX>$C_p$</TEX> showed irregular distribution. The average PCB sampling rates from air to pine needles were 0.116 (0.002-0.389) <TEX>$m^3$</TEX>/day - g dry. Conclusions: A poor correlation was shown between <TEX>$C_a$</TEX> and <TEX>$C_p$</TEX>. However, a good correlation was shown between the logarithm of octanol-air partitioning coefficient (<TEX>$logK_{oa}$</TEX>) and log (<TEX>$C_p/C_a$</TEX>), and the interrelation was better with longer sampling time (June to December) than shorter sampling time (June to August). The average PCB sampling rates from air to pine needles were the lowest with respect to PUF disk, XAD-2 resin and semipermeable membrane devices (SPMDs) PAS. The average ratio (<TEX>$C_{a-calc}/C_{a-meas}$</TEX>) of calculated (<TEX>$C_{a-calc}$</TEX>) and measured (<TEX>$C_{a-meas}$</TEX>) PCB concentration was 0.69 with a shorter sampling time and 1.24 with a longer, so <TEX>$C_{a-calc}$</TEX> was close to <TEX>$C_{a-meas}$</TEX>. It was found that pine needles can be used as PAS of atmospheric PCBs, and are especially suitable for long-time PAS.

Protective role of estrogen receptor-alpha on lower chlorinated PCB congener-induced DNA damage and repair in human tumoral breast cells

Polychlorinated biphenyls (PCBs) are ubiquitous environmental contaminants. Much of the research has focused on the carcinogenic potential of higher chlorinated PCBs, but accumulative evidence has shown that lower chlorinated PCB congeners have initiating and promoting activities. The goal of this study was to examine the potential of lower chlorinated PCBs, including 2,2',5,5'-tetrachlorobiphenyl (PCB52) and 3,3',4,4'-tetrachlorobiphenyl (PCB77), to induce DNA damage and apoptosis in human MDA-MB-231 (MDA) and MCF-7 breast cancer cells. Results confirmed that treatment of cells with PCB52 and PCB77 resulted in oxidative stress and caspase-dependent apoptosis in both MDA and MCF-7 cells. We noticed that at non-cytotoxic concentrations PCB52 and PCB77-induced decreases in intracellular NAD(P)H in MDA cells but not in MCF-7 cells. Further investigation confirmed that decreases in intracellular NAD(P)H in PCB-treated MDA cells are primarily due to reduction in intracellular NAD(+) pool mediated by poly(ADP-ribose)polymerase-1 activation through formation of DNA strand breaks. Antagonism was observed between PCB52 and PCB77 for the effect on induction of DNA strand breaks in MDA cells. Overall, this evidence demonstrates that at non-cytotoxic concentrations, lower chlorinated PCB congeners are capable of inducing oxidative DNA lesions in ERalpha(-)/MDA cells but not in ERalpha(+)/MCF-7 cells and that functional ERalpha plays a protective role in modulating the PCB-induced DNA damage in human breast cancer cells.

Chlorination Increases the Persistence of Semiquinone Free Radicals Derived from Polychlorinated Biphenyl Hydroquinones and Quinones

Polychlorinated biphenyls (PCBs) comprise a group of persistent organic pollutants that differ significantly in their physicochemical properties, their persistence, and their biological activities. They can be metabolized via hydroxylated and dihydroxylated metabolites to PCB quinone intermediates. We have recently demonstrated that both dihydroxy PCBs and PCB quinones can form semiquinone radicals (SQ(*-)) in vitro. These semiquinone radicals are reactive intermediates that have been implicated in the toxicity of lower chlorinated PCB congeners. Here we describe the synthesis of selected PCB metabolites with differing degrees of chlorination on the oxygenated phenyl ring, e.g., 4,4'-dichloro-biphenyl-2,5-diol, 3,6,4'-trichloro-biphenyl-2,5-diol, 3,4,6,-trichloro-biphenyl-2,5-diol, and their corresponding quinones. In addition, two chlorinated o-hydroquinones were prepared, 6-chloro-biphenyl-3,4-diol and 6,4'-dichloro-biphenyl-3,4-diol. These PCB (hydro-)quinones readily react with oxygen or via comproportionation to yield the corresponding semiquinone free radicals, as detected by electron paramagnetic resonance spectroscopy (EPR alias ESR). The greater the number of chlorines on the (hydro-)quinone (oxygenated) ring, the higher the steady-state level of the resulting semiquinone radical at near neutral pH.

Maternal transfer of organochlorines and brominated flame retardants in blue tits ( Cyanistes caeruleus)

Although eggs have frequently been used as a biomonitoring tool for contamination with organohalogenated pollutants (OHPs), few studies have investigated the processes of maternal transfer in birds. Here, maternal transfer of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and polybrominated diphenyl ethers (PBDEs) was investigated through comparison of the concentrations and profiles between whole homogenised female blue tits ( Cyanistes caeruleus) and their eggs. In addition, we examined if there was an effect of laying order on the concentrations of PCBs, OCPs and PBDEs. PCBs were the most abundant contaminants in female blue tits and their eggs, followed by OCPs and PBDEs. Among the OCPs, p, p′-DDE was the most dominant compound and accounted for more than 80% of the sum OCPs. Egg concentrations decreased significantly in relation to the laying order from 1623 ± 148 ng/g lipid weight (lw) to 1040 ± 47 ng/g lw for the sum PCBs, from 342 ± 24 ng/g lw to 235 ± 17 ng/g lw for the sum OCPs and from 49 ± 5 ng/g lw to 27 ± 5 ng/g lw for the sum PBDEs. When reviewing all studies investigating laying order effects of OHPs in birds, no clear patterns emerged, which may be due to differences in study species and methodology among studies. Despite the fact that there were laying order effects in blue tit clutches, the variance in concentrations of PCBs and PBDEs was larger among clutches than within clutches. Variance in OCP concentrations among clutches was similar to the variance within clutches. These results suggest that one randomly collected blue tit egg from a clutch is useful as biomonitoring tool for PCBs and PBDEs, while for OCPs it is recommended to consistently use the same egg from the laying sequence as a biomonitoring tool. Lipid-normalized concentrations of sum PCBs, sum OCPs and sum PBDEs in female blue tits after clutch completion were comparable to the concentrations in the first-laid eggs. The egg/female lipid concentration ratios for sum PCBs, sum OCPs and sum PBDEs decreased significantly from 1.0 ± 0.09 to 0.7 ± 0.003, 1.1 ± 0.1 to 0.7 ± 0.02 and 1.2 ± 0.14 to 0.8 ± 0.05, respectively, during the course of egg laying. The profiles of the females and eggs differed significantly for the PCBs, OCPs and PBDEs. There was a higher contribution of lower chlorinated PCB congeners (CB 28, CB 52, CB 95, CB 101 and CB 110), BDE 183, p, p′-DDT and other less persistent OCPs in the females compared to their eggs. Maternal transfer in blue tits seemed to be selective for the more bioaccumulative and persistent congeners/compounds.

Selected organochlorine pesticide and polychlorinated biphenyl residues in house dust in Singapore

Although the use of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) has been prohibited in Singapore since 1980, OCPs and PCBs still can be detected in the environment and represent a potential threat to public health. In this study, OCPs and PCBs were measured in house dust samples collected from 31 homes across the island-state of Singapore. Organochlorine pesticides, such as hexachlorocyclohexanes (HCHs), chlordanes and dichlorodiphenyltrichloroethanes (DDTs) were tested, with a range of <LOD to 240ngg(-1) dust, <LOD to 110ngg(-1) dust and <LOD to 770ngg(-1) dust, respectively. Of 41 target PCB congeners measured, 28 were detected, and the median level of SigmaPCBs was 5.6ngg(-1) dust. The prevalence of these pesticides and industrial chemicals which have been banned many years ago suggests limited indoor degradation and on-going environmental accumulation. Weak negative correlations between an increased elevation of the residence and the concentration of DDTs and some low-chlorinated PCB congeners were noted, most likely due to increased ventilation and distance from ground-based sources at higher floors. Levels detected in several studies conducted in the USA were several orders of magnitude higher than concentrations observed in Singapore. Heavier use of chlorinated products in the USA, as well as different sampling methods, sampling time and site characteristics are likely explanations for the observed differences. Daily human intake of OCPs and PCBs via house dust was calculated, but values were low compared with dietary data from overseas. Ingestion of dust is indeed an exposure passway for these organochlorines, but may not be the predominant one.

Dechlorination of polychlorinated biphenyls, naphthalenes and dibenzo-p-dioxins by magnesium/palladium bimetallic particles

The contamination of sediments with polychlorinated organics such as polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (Dioxins) and polychlorinated naphthalenes (PCNs) remains a significant problem in many rivers, harbors, and estuarine areas in the US and around the world. In this work, rapid dechlorination of PCBs, PCNs, and Dioxins by palladium—coated magnesium (0.01% by weight Pd) has been demonstrated in pure solvent systems (10% methanol in distilled water). This reaction was investigated with the goal of developing it as a future sediment treatment method. More than 90% of the initial single PCB congeners BZ 3 and 170 were removed in 1 to 10 minutes and about 58% of the total initial Arochlor 1260 was removed in 4 minutes. The removal of single Dioxin and PCN congeners also occurred rapidly resulting in a 69 to 95% reduction in 30 minutes. Rapid removal of biphenyl, the expected degradation end product for PCBs, was also observed (80% removal in 5 minutes). Experiments conducted with Arochlor 1260 and biphenyl did not identify significant volatile fractions. A significant amount of PCBs were extracted from the filtered Mg/Pd material suggesting that PCBs first adsorb to the surface of the bimetal and then dechlorination occurs; lesser chlorinated congeners and biphenyl were also found adsorbed to the Mg/Pd material. Experiments conducted with single PCB congeners BZ 194 and 204 demonstrated the formation of lower—chlorinated PCB congeners, indicating that dechlorination was occurring. A stepwise dechlorination process was suggested in which chlorines in the ortho position were removed last.

Identifying Sources and Biomagnification of Persistent Organic Contaminants in Biota from Mountain Streams of Southwestern British Columbia, Canada

We assessed whether biota occupying mountain streams accumulate and biomagnify remotely derived organic pollutants originating from atmospheric inputs to snowpack and glacial runoff and from marine sources introduced by migrating anadromous salmon. Several persistent organic pollutants including polychlorinated biphenyls (PCBs), p,p'-dichloro-diphenyl-dichloroethylene, hexachlorobenzene, and trans-nonachlor were commonly detected in benthic invertebrates, salmon fry (Oncorhynchus spp.), and eggs of an aquatic passerine, the American dipper (Cinclus mexicanus) from the Chilliwack River watershed, British Columbia, Canada. Total PCBs and several organochlorines (OCs) biomagnified from benthic invertebrate composites to salmon fry to dipper eggs. Invertebrate samples generally did not differ significantly in contaminant burdens between the river main stem where salmon are more abundant and higher-elevation tributaries where the salmon density is lower. Concentrations of total OCs and total PCBs in dipper eggs were positively related to drainage basin area and collection year but not to elevation. No differences in PCB congener patterns existed between dipper egg samples from the Chilliwack watershed and other watersheds in southwestern British Columbia. However, principal component analysis revealed significant spatial differences in egg PCB congener patterns between the main Chilliwack River and the higher-elevation tributaries. This difference was primarily due to a greater occurrence of lower chlorinated PCB congeners (66 and 105) in dipper eggs collected from the tributaries and higher loadings of the more stable and persistent congeners (153, 138, 130, and 128) in eggs from the river main stem. The results suggest that atmospheric sources are the main contributor of contaminants detected in biota from the region and that biomagnification is a common pathway for accumulation in lotic predators such as the American dipper.

Chlorinated hydrocarbon contaminants and metabolites in polar bears ( Ursus maritimus) from Alaska, Canada, East Greenland, and Svalbard: 1996−2002

A suite of chlorinated hydrocarbon contaminants (CHCs) including organochlorine pesticides (OCPs) and by-products, polychlorinated biphenyls (PCBs), and methyl sulfone (MeSO 2) PCB and p, p′-dichlorodiphenyldichloroethylene ( p, p′-DDE) metabolites were determined in adipose tissue of 107 adult and sub-adult polar bears, almost exclusively females, sampled between 1996 and 2002 from populations spanning Arctic and Subarctic regions of Alaska, Canada, East Greenland, and Svalbard. The East Greenland and Svalbard populations of polar bears were distinguished by higher proportions of dichlorodiphenyldichloroethane (DDT)-related compounds, nonachlors, oxychlordane, and higher-chlorinated and persistent PCB congeners (hepta- to nona-chlorinated). Conversely, Alaska, the westernmost population of the North American Arctic, was characterized by higher proportions of relatively volatile compounds such as hexachlorocyclohexanes (HCHs) and pentachlorobenzene (PnCBz), lower-chlorinated PCB congeners (tri- to penta-chlorinated), and lower proportions of oxychlordane. Geometric mean (GM) with 95% confidence limits (CL) ΣHCH concentrations were highest in Alaska male polar bear fat samples (GM 593; CL 363−909 ng g − 1 lipid weight), ΣDDT concentration were highest in East Greenland female samples (GM 309; CL 249−490 ng g − 1 l.w.), and Σ 42PCB (GM 5972; CL 4637−9129 ng g − 1 l.w.) and ΣMeSO 2-PCB (GM 198; CL 162−279 ng g − 1 l.w.) concentrations were highest in female samples collected from Svalbard. The distribution of Σ-chlordane-related compounds (ΣCHL), ΣCBz, mirex, and dieldrin was relatively uniform among the populations of polar bears investigated. The present 1996−2002 data of female polar bear fat samples was compared to spatial assessments of female polar bear fat samples collected between 1989 and 1993 from comparable populations. The two-point temporal comparisons showed a general decrease for age-adjusted mean concentrations of ΣCHL, p, p′-DDE, Σ 42PCB, ΣMeSO 2-PCB and 3-MeSO 2- p, p′-DDE over a period of approximately 10 years. However, concentrations of dieldrin were comparatively unchanged. Comparisons of present 2001−2002 concentrations in fat of female polar bears from Western Hudson Bay showed great consistency with temporal trends (1991−1999) previously reported for the same region, i.e. the apparent non-decreasing trend of ΣCHL, β-HCH, ΣHCH and dieldrin, and the apparent declining trend for ΣPCB. However, present concentrations of α-HCH and ΣCBz were elevated, and ΣDDT was notably lower in Western Hudson Bay samples compared to the last measurements in fat samples collected in 1999, which was not in accord with reported temporal trends for this region. As a result of their relatively high degree of contamination, East Greenland and Svalbard polar bears are at higher health risk of contaminant exposure among Arctic and Subarctic populations. In addition to continued biomonitoring, further research on health and population status is needed to evaluate the impact from chronic exposure of polar bear populations to CHCs and their metabolites.

Airborne PCB as a contamination risk on freeze-drying of sediment

In a study of polychlorinated biphenyls (PCB) in freeze-dried sediments from Swedish lakes, the samples were found to contain unexpectedly high concentrations of PCBs. In one of the lakes (Björken), e.g. the concentration of PCB-28 was found to be 189 ng/g dw after freeze-drying compared to 7 ng/g dw after air-drying of the sediment and therefore our hypothesis was that the contamination had occurred during the freeze-drying procedure. Hence, a dry reference sediment (RS) was used in order to identify potential sources of PCB contamination. The investigation included freeze-drying of the dry RS in five different laboratories, exposure to the air in the freeze-drying room, storage at room temperature and air-drying in a certain fume hood and in a laminar flow clean bench. The pattern and concentrations of PCBs detected in the exposed RS were strongly influenced by low chlorinated PCB congeners under all of these conditions with exception for air-drying in the fume hood. Storage in the laboratory air resulted in a slight elevation in the concentrations of low chlorinated PCB congeners, whereas higher concentrations of all PCB congeners were observed after freeze-drying. In all experiments the contamination appeared to be due to adsorption of PCB from the laboratory air. On the basis of these findings we recommend that reference material be subjected to the entire procedure, including sample preparation, in order to monitor contamination and that a procedure involving solvent extraction of wet sediment samples is used, whenever possible, instead of procedures involving dry samples.