Higher Chlorinated Polychlorinated Biphenyls Research Articles

Concentrations and fingerprints of PAHs and PCBs adsorbed onto marine plastic debris from the Indonesian Cilacap coast and theNorth Atlantic gyre

We investigated the contamination of marine plastic debris from the Indonesian Cilacap coast and the North Atlantic gyre by polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). The mean concentrations of 15 PAHs in gyre were 58 and 142 ng/g in polyethylene (PE) and polyethylene terephthalate (PET) debris, respectively, while PE and polypropylene (PP) Indonesian debris exhibited an average content of 552 ng/g (mainly naphthalene). The mean concentration of 61 PCBs in open ocean debris was 12.2 ng/g, while coastal debris showed a worryingly high mean value of 1.4×104 ng/g, with the notable presence of CB6, 101 and 173. PE gyre debris contained mostly high molecular weight PAHs such as benzo(g,h,i)perylene and indeno(1,2,3-cd)pyrene and low-chlorinated PCBs such as CB52, 77 and 105, whereas PET debris contained low molecular weight PAHs (mainly acenaphthylene and phenanthrene) and high-chlorinated PCBs such as CB204.

Serum organochlorines and non-Hodgkin lymphoma: A case-control study in Israeli Jews and Palestinians

Associations of organochlorine (OC) pesticides and polychlorinated biphenyls (PCBs) with non-Hodgkin lymphoma are controversial. We compared serum levels of 6 OC pesticides and 38 PCBs in Israeli Jews (IJ) and Palestinian Arabs (PA) and assessed possible associations with B-cell non-Hodgkin lymphoma (B-NHL). Ninety B-NHL cases (50 IJ and 40 PA) and 120 controls (65 IJ and 55 PA) were included. Median concentrations of analytes in controls were compared across ethnic groups using quantile regression, adjusting for age and sex. We used logistic regression to derive odds ratios (OR) and 95% confidence intervals (CI) for detectable analytes and B-NHL, adjusting for age, ethnic group, faming and body mass index. Median values of PCBs and dichlorodiphenyldichloroethylene (DDE) were higher in IJ vs PA controls (P = 0.0007), as were several PCBs (74, 99, 118, 138, 146, 153, 156, 163, 170, and 180). Overall, OC pesticide and PCB exposures were comparable with reports from high-income countries. B-NHL was associated with PCB 146 (OR 1.70, 95% CI: 1.02, 2.83), PCB 156 (OR 1.75, 95% CI: 1.06, 2.89), and high-chlorinated PCBs (OR 1.55, 95% CI: 1.00, 2.40) in all study subjects. These associations were robust in quantile as well as sensitivity analyses. An association of DDE with B-NHL was noted in PA (OR 1.72, 95% CI: 1.07, 2.77), but not in IJ (OR 0.87, 95% CI: 0.59, 1.27). Although high-chlorinated PCB concentrations did not indicate high exposure levels, our findings indicate that B-NHL may be associated with this exposure.

Revolatilisation of soil-accumulated pollutants triggered by the summer monsoon in India

Abstract. Persistent organic pollutants that have accumulated in soils can be remobilised by volatilisation in response to chemical equilibrium with the atmosphere. Clean air masses from the Indian Ocean, advected with the onset of the summer monsoon, are found to reduce concentrations of hexachlorocyclohexane (HCH), dichlorodiphenyltrichloroethane (DDT) and its derivatives, endosulfan and polychlorinated biphenyls (PCBs) in air at a mountain site (all in the range 5–20 pg m−3) by 77 %, 70 %, 82 % and 45 %, respectively. The analysis of fugacities in soil and air suggest that the arrival of summer monsoon triggers net volatilisation or enhances ongoing revolatilisation of the now-banned chemicals HCH and PCBs from background soils in southern India. The response of the air–soil exchange was modelled using a regional air pollution model, WRF-Chem PAH/POP. The results suggest that the air is increasingly polluted during transport by the south-westerly monsoon winds across the subcontinent. Using a multidecadal multimedia mass balance model, it is found that air–surface exchange of HCH and DDT have declined since the ban of these substances from agriculture, but remobilisation of higher chlorinated PCBs may have reached a historical high, 40 years after peak emission.

A combination of ternary classification models and reporter gene assays for the comprehensive thyroid hormone disruption profiles of 209 polychlorinated biphenyls

Computational toxicology is widely applied to screen tens and thousands of potential environmental endocrine disruptors (EDCs) for its great efficiency and rapid evaluation in recent years. Polychlorinated biphenyls (PCBs) with 209 congeners have not been comprehensively tested for their ability to interact with the thyroid receptor (TR), which is one of the most extensively studied targets related to the effects of EDCs. In this study, we aimed to determine the thyroid-disrupting mechanisms of 209 PCBs through the combination of a novel computational ternary classification model and luciferase reporter gene assay. The reporter gene assay was performed to examine the hormone activities of 22 PCBs via TR to classify their profiles as agonistic, antagonistic or inactive. Thus, six agonists, eleven antagonists and seven inactive chemicals against TR were identified in in vitro assays. Then, six relevant variables, including molecular structural descriptors and molecular docking scores, were selected for describing compounds. Machine learning methods (i.e., linear discriminant analysis (LDA) and support vector machines (SVM)) were used to build classification models. The optimal model was obtained by using SVM, with an accuracy of 88.24% in the training set, 80.0% in the test set and 75.0% in 10-fold cross-validation. The remaining 187 PCB congeners' hormone activities were predicted using the obtained models. Out of these PCBs, the SVM model predicted 38 agonists and 81 antagonists. The findings revealed that higher chlorinated PCBs tended to have TR-antagonistic activities, whereas lower chlorinated PCBs were agonists. This study provided a reference for further exploring PCBs' thyroid effect.

Polychlorinated biphenyl (PCB) contamination in Galveston Bay, Texas: Comparing concentrations and profiles in sediments, passive samplers, and fish.

The industrialized portion of the Houston Ship Channel (HSC) is heavily contaminated with anthropogenic contaminants, most prominent of which are the polychlorinated biphenyls (PCBs). This contamination has driven adaptive evolution in a keystone species for Galveston Bay, the Gulf killifish (Fundulus grandis). We investigated the geographical extent of PCB impacts by sampling 12 sites, ranging from the heavily industrialized upper portion of the HSC to Galveston Island. At each site, PCB concentrations and profiles were determined in three environmental compartments: sediment, water (polyethylene passive samplers), and fish tissue (resident Gulf killifish). We observed a steep gradient of PCB contamination, ranging from 4.00 to 100,000 ng/g organic carbon in sediment, 290-110,000 ng/g lipid in fish, and 4.5-2300 ng/g polyethylene in passive samplers. The PCB congener profiles in Gulf killifish at the most heavily contaminated sites were shifted toward the higher chlorinated PCBs and were highly similar to the sediment contamination profiles. In addition, while magnitude of total PCB concentrations in sediment and total fish contamination levels were highly correlated between sites, the relative PCB congener profiles in fish and passive samplers were more alike. This strong correlation, along with a lack of dependency of biota-sediment accumulation factors with total contamination rates, confirm the likely non-migratory nature of Gulf killifish and suggest their contamination levels are a good site-specific indicator of contamination in the Galveston Bay area. The spatial gradient of PCB contamination in Galveston Bay was evident in all three matrices studied and was observed effectively using Gulf killifish contamination as an environmentally relevant bioindicator of localized contamination in this environment.

Assessment of the Pollution Status of Eleyele Lake, Ibadan, Oyo State, Nigeria.

Background.Lakes are a vital water resource, but are adversely affected by pollutants such as heavy metals and polychlorinated biphenyls (PCBs) from urban, agricultural and industrial activities. This can give rise to potential pollution-related health problems such as cancer and infectious diseases. Risk assessments are necessary to determine the degree of pollution and its effects on human health and ecological systems.Objectives.This study assessed the pollution status and a risk assessment was calculated to determine the degree of the pollution and its effects on the human health and the ecological system of Eleyele Lake in Ibadan, Nigeria.Methods.Physical and chemical parameters, heavy metals and PCBs were determined in the lake water using standard methods from December 2013 to February 2014 at ten different sites of anthropogenic activity.Results.Water pH ranged from 6.00–7.50, while electrical conductivity ranged from 205.00–221.00 μs/cm3. Dissolved oxygen ranged from 0.30–6.00 mg/L and total dissolved solids ranged from 105.00–113.00 mg/L. Phosphate levels ranged from 13–0.99 mg/L. Nitrate and sulphate in the dry season ranged from (3.10–3.80 and 35.81–40.97 mg/L) and (0.12–0.37 and 6.10–10.30 mg/L) in the wet season. Heavy metal concentrations were in the order cadmium (Cd) > zinc (Zn) > copper (Cu) > chromium (Cr) > lead (Pb) for the dry season and Cd > Zn > Cr > Pb > Cu for the wet season. Total PCBs ranged from 493.90–732.55 μg/L and 52.00–390.03 μg/L for the dry and wet seasons, respectively. All determined physical and chemical parameters were within permissible levels, while heavy metals and PCB concentrations were higher than permissible levels.Discussion.The hazard quotients and carcinogenic risk values were greater than acceptable limits, indicating that PCBs in Eleyele lake water pose adverse health effects to the local population. It was observed in this study that lower chlorinated PCBs were more prevalent than higher chlorinated PCBs. This may be attributed to the fact that the lower chlorinated PCBs are influenced by atmospheric deposition as a result of their volatility, and they are more susceptible to atmospheric transport than highly chlorinated PCBs.Conclusions.PCBs possess serious health risks to the population that depends on the lake as a source of domestic water and its aquatic organisms. Efforts are needed to reduce anthropogenic influence on the lake through strict environmental controls.

Long-term time trends in human intake of POPs in the Czech Republic indicate a need for continuous monitoring

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) from the group of persistent organic pollutants are detected in human tissues years or even decades after their ban. Exposure to PCBs and OCPs can pose risks to human health. In the present study, we calculated the daily intakes of PCBs and OCPs in the Czech population and investigated the long-term trends of human exposure to POPs. Data on POP concentrations from a 16-year period of breast-milk monitoring were used. A toxicokinetic model with consideration of compound-specific elimination half-lives was used to calculate the mothers' daily intake of PCBs and OCPs representing the intake of POPs by all exposure routes. The calculated intakes were compared with dietary intakes calculated by the Czech National Institute of Public Health. The comparison shows good agreement of both intake estimates with decreasing intake trends of POPs in the Czech population in the time period studied. However, several fluctuations with peaks of higher levels were observed in both datasets which are not typical for the period after the ban of use and production of POPs. The available evidence suggests that the increases in chemical concentrations might be caused by food contamination. The calculated intakes of compounds with longer elimination half-lives, such as higher-chlorinated PCBs, were higher in older mothers. This “memory effect” was already observed in other studies and indicates higher exposure in earlier life periods of the mother. Our results suggest that exposure to POPs is still relevant for the Czech population in the period after the ban of the use and production of POPs (post-ban period), especially via food ingestion, though the intake trends are decreasing. Possible food contamination by POPs in the post-ban period requires further assessment.

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.

Biomagnification of persistent organic pollutants along a high-altitude aquatic food chain in the Tibetan Plateau: Processes and mechanisms

Biomagnification of some persistent organic pollutants (POPs) has been found in marine and freshwater food chains; however, due to the relatively short food chains in high-altitude alpine lakes, whether trophic transfer would result in the biomagnification of POPs is not clear. The transfer of various POPs, including organochlorine pesticides and polychlorinated biphenyls (PCBs), along the aquatic food chain in Nam Co Lake (4700 m), in the central Tibetan Plateau, was studied. The POPs levels in the water, sediment and biota [plankton, invertebrates and fish (Gymnocypris namensis)] of Nam Co were generally low, with concentrations comparable to those reported for the remote Arctic. The composition profiles of POPs in the fish were different from that in the water, but similar to their food. DDEs, DDDs, PCB 138, 153 and 180 displayed significant positive correlations with trophic levels, with trophic magnification factors (TMFs) ranged between 1.5 and 4.2, implying these chemicals can undergo final biomagnification along food chain. A fugacity-based dynamic bioaccumulation model was applied to the fish with localized parameters, by which the simulated concentrations were comparable to the measured data. Modeling results showed that most compounds underwent net gill loss and net gut uptake; only when the net result of the combined gut and gill fluxes would be positive, bioaccumulation could eventually occur. The net accumulation flux increased with fish age, which was caused by the continuous increase of gut uptake by aged fish. Due to the oligotrophic condition, efficient food absorption is likely the key factor that influences the gut POPs uptake. Long residence times with half-lives up to two decades were found for the higher chlorinated PCBs in Gymnocypris namensis.

Design and testing of a new sampler for simplified vacuum-assisted headspace solid-phase microextraction

The design and testing of a new and low-cost experimental setup used for vacuum-assisted headspace solid-phase microextraction (Vac-HSSPME) is reported here. The device consists of a specially designed O-ring seal screw cap offering gas-tight seal to commercially available headspace vials. The new polytetrafluoroethylene (PTFE) cap was molded by a local manufacturer and had a hole that could tightly accommodate a septum. All operations were performed through the septum: air evacuation of the sampler, sample introduction and HSSPME sampling. The analytical performance of the new sampler was evaluated using 22 mL headspace vials with 9 mL water samples spiked with polychlorinated biphenyls (PCBs). Several experimental parameters were controlled and the optimized conditions were: 1000 rpm agitation speed; 30 min extraction time; 40 °C sampling temperature; polydimethylsiloxane-divinylbenzene (PDMS-DVB) fiber. The lack of accurate Henry's law constant (KH) values and information regarding how they change with temperature was a major limitation in predicting the phase location of evaporation resistance during Vac-HSSPME. Nevertheless, the combined effects of system conditions indicated the increasing importance of gas phase resistance with increasing degree of PCBs chlorination. Stirring enhancements were not recorded for the higher chlorinated PCBs suggesting that the hyperhydrophobic gas/water interface was the preferred location for these compounds. Analytically, the developed method was found to yield linear calibration curves with limits of detection in the sub ng L−1 level and relative standard deviations ranging between 5.8 and 14%. To compensate for the low recoveries of the higher chlorinated PCB congeners in spiked river water the standard addition methodology was applied. Overall, the compact design of the new and reusable sample container allows efficient HSSPME sampling of organic analytes in water within short extraction times and at low sampling temperatures compared to other published HSSPME methods.

Effects of RAMEB and/or mechanical mixing on the bioavailability and biodegradation of PCBs in soil/slurry

Microbial remediation is preferred as a clean and cost-effective method for restoring environments polluted by organics. But the biodegradation rates of hydrophobic organic contaminants (HOCs) are usually extremely restricted by their low bioavailability, especially in soil. Here, a physical method (mechanical mixing) and a chemical method (randomly methylated-β-cyclodextrins, RAMEB) were adopted to improve the bioavailability and biodegradation of polychlorinated biphenyls (PCBs) of an aged soil. The bioavailability of tri-CBs was increased by adding RAMEB in soil/slurry or assisting mechanical mixing in slurry, but these methods had no effects on the bioavailability of tetra-CBs and high chlorinated PCBs (Cl > 4). The degradation rate of tri-CBs could be obviously enhanced by adding RAMEB in soil or assisting mechanical mixing in slurry. The highest removal amount of tri-CBs reached 43.8% in 100 d with a first-order decay kinetics constant of 0.0059 d−1. But the removal of tetra-CBs and high chlorinated PCBs (Cl > 4) were not significant in all mesocosms, possibly due to the lack or weakness of the native degrading microflora. Based on the analysis of the richness and diversity of bacterial communities, the characteristics of the heatmap and the variation of bphC copy numbers in the soil/slurry mesocosms, it could be inferred that there was no obvious corresponding relationship between the variation of the bacterial communities and the physical/chemical measures.

Distribution Characteristics of Polychlorinated Biphenyls in Sediments inside Jeju Harbor

In this paper, polychlorinated biphenyls (PCBs) were measured in surface sediments collected three times (June, October, December, 2013), inside Jeju Harbor as major harbors of Jeju Island. The concentration of PCBs inside Jeju Harbor was in the range of 1.62~4.45 (mean) ng/g on a dry weight basis and the levels were very low. In the analysis of PCBS homologue patterns, high-chlorinated PCB congeners were dominant in surface sediments inside Jeju Harbor, indicating that their sources were originated from shipping activity. In the relationships between PCBs concentrations and particle size (mud, sand and gravel) in surface sediments, PCBs concentrations were higher in the sediments with higher mud content, indicating that higher PCBs were distributed with increasing sediments of fine gradules. The PCBs concentrations in surface sediments in this study were very low, compared with ER-L (effect range-low) and TEL (threshold effects level) among sediment quality guideleines (SQGs) applied in foreign countries, such as USA, Canada, and Australia, etc), indicating that their biological effects on the bottom organisms in marine environment were expected to be very low.

Exposure to polychlorinated biphenyls and the thyroid gland – examining and discussing possible longitudinal health effects in humans

BackgroundMany previous studies have dealt with the effect of polychlorinated biphenyls (PCBs) on the thyroid gland, but their findings are inconsistent. One problem of these studies has been their use of cross-sectional designs. ObjectivesThe aim of the current study is to investigate longitudinal effects of PCBs on the thyroid gland, focusing on: morphological changes in thyroid tissue (i.e. thyroid volume), changes in thyroid hormones and in thyroid antibodies. MethodsA total of 122 individuals (Mage=44.7) were examined over a period of four years (t1 until t4). Medical history was collected via interviews, an ultrasound examination was performed and blood samples were taken to determine plasma PCB levels, thyroid stimulating hormone (TSH), free triiodthyronine (fT3), free thyroxine (fT4), thyroid peroxidase antibodies (TPOab), thyreoglobulin antibodies (TGab) and thyroid-stimulating hormone receptor antibodies (TSHRab). Rank correlation coefficients and mixed effect models were performed controlling for age and total lipids. ResultsThere were negative correlations between higher chlorinated biphenyls and fT3, cross-sectionally as well as longitudinally. We also found an interaction effect of higher-chlorinated PCBs over time for fT4 as well as TSHRab. In case of high exposure, a decrease in fT4 and an increase in TSHRab level were found over time. In regards to the other variables, our findings yielded no clear results in the examined time period. ConclusionThis is the first study to shows a PCB-related effect on fT3, fT4 and TSHRab over a four year period. The data also suggest that morphological and antibody findings remain inconsistent and do not allow for unambiguous interpretation.

Diurnal Variations of Air-Soil Exchange of Semivolatile Organic Compounds (PAHs, PCBs, OCPs, and PBDEs) in a Central European Receptor Area.

Concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), and polybrominated diphenyl ethers (PBDEs) in air and soil, their fugacities, and the experimental soil-air partitioning coefficient (KSA) were determined at two background sites in the Gt. Hungarian Plain in August 2013. The concentrations of the semivolatile organic compounds (SOCs) in the soil were not correlated with the organic carbon content but with two indirect parameters of mineralization and aromaticity, suggesting that soil organic matter quality is an important parameter affecting the sorption of SOCs onto soils. Predictions based on the assumption that absorption is the dominant process were in good agreement with the measurements for PAHs, OCPs, and the low chlorinated PCBs. In general, soils were found to be a source of PAHs, high chlorinated PCBs, the majority of OCPs and PBDEs, and a sink for the low chlorinated PCBs and γ-hexachlorocyclohexane. Diurnal variations in the direction of the soil-air exchange were found for two compounds (i.e., pentachlorobenzene and p,p'-dichlorodiphenyldichloroethane), with volatilization during the day and deposition in the night. The concentrations of most SOCs in the near-ground atmosphere were dominated by revolatilization from the soil.

What determines PCB concentrations in soils in rural and urban areas? Insights from a multi-media fate model for Switzerland as a case study

Polychlorinated biphenyls (PCBs) are banned worldwide under the Stockholm Convention on Persistent Organic Pollutants. However, PCBs are still emitted in appreciable amounts from remaining primary sources in urban areas or landfills and are ubiquitous environmental contaminants, inter alia in soil and air. Concentrations of PCBs have been measured in various media by numerous studies worldwide. However, monitoring data do not always provide quantitative information about transport processes between different media, deposition fluxes to ground, or distribution of PCBs between environmental compartments. Also future trends in environmental contamination by PCBs cannot be predicted from monitoring data, but such information is highly relevant for decision-makers. Here, we present a new regionally resolved dynamic multimedia mass balance model for Switzerland to investigate the origin of PCBs in air and to investigate their long-term fate and mass balance in the environment. The model was validated with existing field data for PCBs. We find that advective inflow of PCBs from outside Switzerland into the atmospheric boundary layer is responsible for 80% of PCBs present in air in Switzerland, whereas Swiss emissions cause the remaining 20%. Furthermore, we show that the atmospheric deposition of the higher-chlorinated PCBs is dominated by particle-bound deposition, whereas the deposition of the lower-chlorinated PCBs is a combination of particle-bound and gaseous deposition. The volume fraction of particles in air is in both cases an important factor driving the deposition of PCBs to ground and, thus, contributing to the higher concentrations of PCBs generally observed in populated and polluted areas. Regional emissions influence the deposition fluxes only to a limited extent. We also find that secondary emissions from environmental reservoirs do not exceed primary emissions for all PCB congeners until at least 2036. Finally, we use our model to evaluate the effect of chemical regulation on future environmental contamination by PCBs.

Enhanced dechlorination of 2,2′,4,4′,5,5′-hexachlorobiphenyl in water-sediment mixture by adding anthraquinone-2,6-disulfonic acid

Dechlorination of polychlorinated biphenyls (PCBs) in aquatic sediments and anaerobic bioreactors has been widely observed, and mechanisms have also been studied. However, the role of humic acid in the biotic dechlorination of PCBs has not been studied. The present study investigated the role of humic acid as the redox mediator in the anaerobic biotransformation of PCBs in water and sediment mixture. Degradation of 2,2′,4,4′,5,5′-hexachlorobiphenyl (PCB 153) in water and sediment mixture was studied by adding different concentrations of anthraquinone-2,6-disulfonic acid (AQDS), which was a model substance for quinone moieties in humic acid. Chemical reduction of PCB 153 by sterile AH2QDS was performed to investigate the mechanisms involved. Decrease of PCB 153 was enhanced significantly by adding AQDS. The loss percentage of PCB 153 after 15 days of incubation was increased from 9.03 ± 2.73 % to 38.3 ± 3.27 % (P = 95 %) by adding 1 mM AQDS, while it was increased to 46.8 ± 4.41 % (P = 95 %) by adding 5 mM sodium acetate and 1 mM AQDS. Less chlorinated congeners PCB 101 and PCB 52 were identified as the products through the dechlorination of PCB 153 mainly in para positions. The results suggested that the quinone moieties in humic acid may play an important role in the dechlorination of PCBs in nature. This finding will help us to understand the natural attenuation of PCBs better and also provide a method to enhance the removal of higher chlorinated PCBs in waste treatment process.

Effects of occupational exposure to polychlorinated biphenyls on urinary metabolites of neurotransmitters: A cross-sectional and longitudinal perspective.

Polychlorinated biphenyls (PCBs) are chemicals which were used for industrial purposes and are known to induce various adverse health effects. They are also known to be neurotoxic and numerous targets within the central nervous system have been identified in previous studies. Specifically, the neurotransmitters dopamine (DA) and norepinephrine (NE) are influenced by PCBs as indicated in studies involving animals. However, limited evidence has been published documenting PCB induced changes in the neurotransmitter system in humans. In the present study, we examined the association between a higher PCB body burden following occupational exposure and possible changes in human neurotransmitter metabolites. Within a medical surveillance programme called HELPcB (Health Effects in High-Level Exposure to PCB) that monitors adverse health effects of occupational PCB exposure, urine samples were obtained (n(T1) = 166; n(T2) = 177 and n(T3) = 141). The urinary concentrations of the metabolites homovanillic acid (HVA; for DA) and vanillylmandelic acid (VMA; for NE) were analyzed. Blood samples were obtained by vena puncture in order to determine the internal exposure to PCBs with human biomonitoring. A cross-sectional analysis indicated a significant negative effect of PCB exposure on HVA and VMA. Longitudinally, an initially higher exposure to higher chlorinated PCBs was followed by constant reduced HVA level over three consecutive years. Exploratory analyses show different long-term effects for different PCBs according to their chlorination degree. A higher exposure with lower chlorinated PCBs leads to an increase of VMA and HVA. Conversely, a higher exposure to all PCBs results in a reduction of HVA. This study, to our knowledge, is the first to document changes in neurotransmitter metabolites after occupational PCB exposure in humans. This finding advances evidence obtained from past research, and identifies one potential pathomechanism in the central dopaminergic system of humans.

Levels and profiles of chlorinated and brominated contaminants in Southern Hemisphere humpback whales, Megaptera novaeangliae

The study documents the levels and profiles of selected contaminants [polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polybrominated diphenyl ethers (PBDEs) and methoxylated PBDEs (MeO-PBDEs)] in blubber biopsy samples collected from humpback whales (Megaptera novaeangliae) in Antarctic Peninsula waters. In addition, we investigated year-to-year and sex-related differences in the bioaccumulation patterns. Except for hexachlorobenzene (HCB), whose concentrations were in the same range as those found in whales from the Northern Hemisphere, levels of all other compounds were lower in Southern Hemisphere whales compared to literature data on animals from the Arctic and subarctic region. The mean contribution to the sum of all anthropogenic organohalogen compounds (ΣOHC) decreased in the following order ΣPCBs (44%)>HCB (31%)>ΣDDXs (13%)>ΣCHLs (4.6%)>ΣHCHs (4.4%)>ΣPBDEs (0.9%). The predominant compounds within each chemical class were: PCBs 153, 149, 101 and 138; p,p′-DDE; γ-HCH; trans-nonachlor; PBDEs 99 and 47. The most dominant MeO-PBDE congener was 6-MeO-BDE 47. As samples were collected during three consecutive summer seasons, year-to-year trends could be assessed indicating a significant decrease from 2000 to 2003 for ΣCHL levels. Higher ΣPBDE concentrations and higher values of the ΣPBDE / ΣMeO-PBDE ratio, as well as higher ratios between the two MeO-BDEs (2′-MeO-BDE 68/6-MeO-BDE 47) were found in females compared to males. Higher ΣMeO-PBDE concentrations and higher values of the ratios between the lower chlorinated and the higher chlorinated PCBs were found in males than in females. In addition, five out of six significant differences found through discriminant function analysis were gender-related. The literature reports both feeding in mid- to low-latitudes and sex-related differences in migration patterns for humpback whales from the Southern Hemisphere, indicating that the hypothesis of dietary differences between males and females cannot be excluded. Nevertheless, additional studies are required for further investigation of this hypothesis.

Vertical distributions of organochlorine pesticides and polychlorinated biphenyls in an agricultural soil core from the Guanzhong Basin, China.

The concentrations and distributions of hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethanes (DDTs), and polychlorinated biphenyls (PCBs) in an agricultural soil core in the Guanzhong Basin, China were determined. Overall, p,p'-DDT and p,p'-DDE were dominant contaminants and accounted for approximately 48.4 and 23.3% of the total detected DDTs. Low chlorinated PCBs (PCB 28 and PCB 52) were generally detected at higher concentrations and more frequently than high chlorinated PCBs. The peak values of ∑DDT (12.92 ng/g), ∑HCH (2.25 ng/g), and ∑PCB (3.44 ng/g) occurred in the 10-15, 15-20, and 5-10 cm sections, respectively. The negative correlation between the organochlorine pesticide (OCP) concentrations and the soil depths and the relatively high p,p'-DDT/p,p'-DDE ratios in the surface soils indicated that these chemicals were recently used illegally, despite their official ban in 1983. The increase in the ratio of α-/γ-HCH with increasing soil depth indicated that the use of lindane decreased relative to the use of technical HCHs in recent years.

Determination of polychlorinated biphenyls by liquid chromatography-atmospheric pressure photoionization-mass spectrometry.

This study presents the atmospheric pressure photoionization (APPI) of high-chlorinated (five or more chlorine atoms) polychlorinated biphenyls (PCBs) using toluene as dopant, after liquid chromatographic separation. Mass spectra of PCB 101, 118, 138, 153, 180, 199, 206 and 209 were recorded by using liquid chromatography-APPI-tandem mass spectrometry (LC-APPI-MS/MS) in negative ion full scan mode. Intense peaks appeared at m/z that correspond to [M - Cl + O](-) ions, where M is the analyte molecule. Furthermore, a detailed strategy, which includes designs of experiments, for the development and optimization of LC-APPI-MS/MS methods is described. Following this strategy, a sensitive and accurate method with low instrumental limits of detection, ranging from 0.29 pg for PCB 209 to 8.3 pg for PCB 101 on column, was developed. For the separation of the analytes, a Waters XSELECT HSS T3 (100 mm × 2.1 mm, 2.5 µm) column was used with methanol/water as elution system. This method was applied for the determination of the above PCBs in water samples (surface water, tap water and treated wastewater). For the extraction of PCBs from water samples, a simple liquid-liquid extraction with dichloromethane was used. Method limits of quantification, ranged from 4.8 ng l(-1), for PCB 199, to 9.4 ng l(-1), for PCB 180, and the recoveries ranged from 73%, for PCB 101, to 96%, for PCB 199. The estimated analytical figures were appropriate for trace analysis of high-chlorinated PCBs in real samples.