CALUX Bioassay of Dioxin-Like Compounds in Sediments from the Haihe River,China

Chemically Activated LUciferase gene eXpression (CALUX) bioassay is a rapid, effective, and cheap method to analyze dioxin-like compounds (DLCs). Using this method, total levels of DLCs, including PCDD/Fs (polychlorinated dibenzo-p-dioxin and dibenzofurans) fraction and DL-PCBs (dioxin-like polychlorinated biphenyls) fraction, in extracts of sediments from the Haihe River, China, were determined. It was found that the levels of PCDD/Fs in the sediments from the Haihe River were tens of times to hundreds of times higher than those of DL-PCBs. The DLC levels in sediments in March 2005 approximated those in November 2006. The CALUX toxic equivalents (TEQs) of DLCs were independent of the total organic carbon (TOC) of sediments. Significant correlation was observed between the PCDD/Fs TEQs and DL-PCBs TEQs. The two fractions of some samples were also analyzed by HRGC/HRMS (high-resolution gas chromatography/high-resolution mass spectrometry) method. Significant statistical correlations were observed between the CALUX TEQs and HRGC/HRMS TEQs. The difference between TEF (toxic equivalent factor) and REP (relative potency) can explain most of the discrepancy between CALUX and HRGC/HRMS analysis. A high level of DLCs was found at the sites near the influx into Bohai Bay. The dioxin pollution might be associated with industrial activities of pentachlorophenol (PCP) in the adjacent area. More attention should be paid to the increase of DLC levels and further investigation should be done for this area.     

On the isolation of polychlorinated dibenzo-p-dioxins and furans from serum samples using immunoaffinity chromatography prior to high-resolution gas chromatography–mass spectrometry

Immunoaffinity chromatography (IAC) for the purification of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) from biological samples was explored as a means to simplify the cleanup procedure and thereby decrease the time and cost of dioxin analysis. A monoclonal antibody (DD3) was used to produce IAC columns and to isolate the PCDD/Fs from serum. Native and ¹³C-labeled PCDD/Fs were spiked at the ppq to ppt range into serum. Quantitation of the PCDD/Fs was performed by a standard dioxin analytical method, i.e. high-resolution gas chromatography–mass spectrometry (GC–MS), which was easily compatible with IAC. Five of the most toxic PCDD/Fs consistently showed acceptable recoveries (>25%) and were reliably quantitated. The congeners specifically recovered by this method represent almost 80% of the toxic equivalency of dioxins and furans present in the serum samples. Dioxin-like polychlorinated biphenyls (PCBs) were not recognized by this antibody column. Compared to conventional dioxin cleanup methods, IAC decreased solvent usage by 1.5 l/sample and took only 2 h to process a sample for analysis.     

Anaerobic reductive dehalogenation of polychlorinated dioxins

Polychlorinated dibenzo-p-dioxins and -furans (PCDD/Fs) are among the most harmful environmental contaminants. Their widespread distribution due to unintentional or unknown release coincides with environmental persistence, acute and chronic toxicity to living organisms, and long-term effects due to the compounds’ tendency for bioaccumulation and biomagnification. While microbial aerobic degradation of PCDD/Fs is mainly reported for the turnover of low chlorinated congeners, this review focuses on anaerobic reductive dehalogenation, which may constitute a potential remediation strategy for polychlorinated compounds in soils and sediments. Microorganisms in sediments and in microcosms or enrichment cultures have been shown to be involved in the reductive dechlorination of dioxins. Bacteria related to the genus Dehalococcoides are capable of the reductive transformation of dioxins leading to lower chlorinated dioxins including di- and monochlorinated congeners. Thus, reductive dehalogenation might be one of the very few mechanisms able to mediate the turnover of polychlorinated dioxins by reducing their toxicity and paving the way for a subsequent breakdown of the carbon skeleton.     

Levels of Polychlorinated Dibenzo-P-Dioxins (PCDDs) and Polychlorinated Dibenzo-P-Furans (PCDFs) in the Atmosphere (PM10) of a Coastal Area of West Bengal,India

Particle-bound polychlorinated dibenzo-p-dioxins and dibenzo-p-furans (PCDDs/Fs) were analyzed in the coastal air of West Bengal, India. Total PCDD/Fs ranged from 4–2491 fg m^–3 with a mean of 355 fg m^–3 and their I-TEQ values ranged between 1 to 62.6 fg I-TEQ m^–3, with an average of 17.1 fg I-TEQ m^–3. The dominant congeners were OCDD (46%) OCDF (14%) 1,2,3,4,6,7,8-HpCDF (11%) and 1,2,3,4,6,7,8-HpCDD (10%) and accounted for >80% to the total PCDDs/Fs. TCDD (29%) > PeCDF (28%) > HxCDF (16%) > PeCDD (13%) were the dominant TEQ contributors. Rough estimates of tolerable daily intake (TDI) show a low health risk of exposure to PCDD/Fs measured in the ambient air of a rural coastal area of West Bengal, India.     

Oral Bioavailability of Polychlorinated Dibenzo-p-Dioxins/Dibenzofurans in Industrial Soils

In this study, the oral bioavailabilities of numerous 2,3,7,8-PCDD/F congeners were evaluated in soil samples from an industrial site. The purpose of this study is several-fold: (1) to compare the soil bioavailability results of the different PCDD/F congeners; (2) to evaluate the consistency of the bioavailability results with those obtained in an in vitro bioaccessibility study with simulated GI tract fluids; and (3) to develop quantitative bioavailability measurements that are appropriate for use in a health risk assessment for this site. Soil samples containing PCDD/F toxic equivalent (TEQ) concentrations ranging from 0.53–45.2 ng/g were administered to female Sprague Dawley rats via oral gavage. Reference formulations of PCDD/Fs were administered intravenously or by oral gavage. The overall relative bioavailability of PCDD/Fs in the soil samples on a TEQ basis ranged from 17 to 51%, with a mean of 38%. The results of the in vitro bioaccessibility study were consistent with the bioavailability results (mean extracted TEQ of 22%). Because of the clear relationship between increasing chlorination and decreasing bioavailability and bioaccessibility observed in this study, we suggest that simply extrapolating results from one congener to another may be associated with a high degree of uncertainty.     

Toward the bioremediation of dioxin-polluted soil: structural and functional analyses of in situ microbial populations by quinone profiling and culture-dependent methods

In order to obtain basic information toward the bioremediation of dioxin-polluted soil, microbial communities in farmland soils polluted with high concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were studied by quinone profiling as well as conventional microbiological methods. The concentration of PCDD/Fs in the polluted soils ranged from 36 to 4,980 pg toxicity equivalent quality (TEQ) g(-1) dry weight of soil. There was an inverse relationship between the levels of PCDD/Fs and microbial biomass as measured by direct cell counting and quinone profiling. The most abundant quinone type detected was either MK-6 or Q-10. In addition, MK-8, MK-8(H2), and MK-9(H8) were detected in significant amounts. Numerical analysis of quinone profiles showed that the heavily polluted soils (> or = 1,430 pg TEQ g(-1)) contained different community structures from lightly polluted soils (< or = 56 pg TEQ g(-1)). Cultivation of the microbial populations in the heavily polluted soils with dibenzofuran or 2-chlorodibenzofuran resulted in enrichment of Q-10-containing bacteria. When the heavily polluted soil was incubated in static bottles with autoclaved compost as an organic nutrient additive, the concentrations of PCDD/Fs in the soil were decreased by 22% after 3 months of incubation. These results indicate that dioxin pollution exerted a significant effect on microbial populations in soil in terms of quantity, quality, and activity. The in situ microbial populations in the dioxin-polluted soil were suggested to have a potential for the transformation of PCDD/Fs and oxidative degradation of the lower chlorinated ones thus produced.     

Dioxin/polychlorinated biphenyl body burden,diabetes and endometriosis: findings in a population-based study in Belgium

Dioxins and polychlorinated biphenyls (PCBs) are persistent organic pollutants widely distributed in the food chain, which is the main source of human exposure. Their effects on human health at background exposure levels are still poorly understood. Recent epidemiological evidence suggests a possible association between these pollutants and diabetes. We report here the results of a population-based study in Belgium on 257 (142 women and 115 men) environmentally exposed subjects, including 10 cases of endometriosis and nine cases of diabetes. Seventeen 2,3,7,8-polychlorinated dibenzodioxins/dibenzofurans (PCDD/Fs or dioxins), four coplanar PCBs (International Union of Pure and Applied Chemistry [IUPAC] nos 77, 81, 126 and 169) and 12 PCB markers (IUPAC nos 3, 8, 28, 52, 101, 118, 138, 153, 180, 194, 206 and 209) were quantified in serum fat from fasting blood samples in order to estimate the body burden of these pollutants. Whilst no difference was found between women with endometriosis and their controls, diabetic patients had significantly increased serum levels of dioxins, coplanar PCBs and the 12 PCB markers. After adjustment for age and other covariates, serum total toxic equivalent activity (sum of PCDD/Fs and coplanar PCBs) and 12 PCB marker concentrations in diabetics were 62% (p=0.0005) and 39% (p=0.0067) higher, respectively, than in controls. The risk of diabetes was significantly increased in subjects in the top decile for adjusted concentrations of dioxins (odds ratio 5.1, 95% confidence interval [CI] 1.18–21.7), coplanar PCBs (odds ratio 13.3, 95% CI 3.31–53.2) or 12 PCB markers (odds ratio 7.6, 95% CI 1.58–36.3). These findings warrant further studies to assess the significance of the associations between diabetes and environmental exposure to polychlorinated pollutants.     

Simultaneous Treatment of Dioxins and Heavy Metals in Tagonoura Harbor Sediment by Two-Step Pyrolysis

This paper describes the simultaneous treatment of PCDD/PCDF and toxic heavy metals contaminated sediment by pyrolysis with emphasis on complete removal and destruction of PCDD/PCDF in Tagonoura harbor sediment during a two-step pyrolysis process. Pyrolysis was conducted at different temperatures and N ₂ gas flow rates. Results showed that almost all PCDD/PCDF (99.998%) can be removed from the sediment by treatment at 800°C for 30 minutes in single-step pyrolysis; however, PCDD/PCDF remained in the gas phase without destruction. Analysis also revealed that some PCDD/PCDF formation occurred during the single-step pyrolysis. However, by the use of two-step pyrolysis, where off-gases from the first furnace are heated at 1000°C, PCDD/PCDF in the final gas effluent was dramatically reduced by a thermal degradation mechanism. Stabilization of toxic heavy metals was also observed. Specifically, their leaching activity drastically decreased with increasing pyrolysis temperature. Significant metal volatilization did not occur. Though the low temperature pyrolysis was effective in removing PCDD/PCDF, the leachability of toxic heavy metals such as Cr and Ni was higher that of 800°C; however, lower than untreated. Two-step pyrolysis at 800°C for 30 minutes in the single-step and 1000°C in the two-step pyrolyzer would be effective for the treatment of sediments contaminated with PCDD/PCDF, toxic heavy metals and organic matters simultaneously.     

The application of hybrid mass spectrometry/mass spectrometry and high-resolution mass spectrometry to the analysis of fish samples for polychlorinated dibenzo-p-dioxins and dibenzofurans

A hybrid mass spectrometer operated in low-resolution selected decomposition monitoring (SDM) mode was used for the analysis of whole fish samples for the 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins and poly-chlorinated dibenzofurans (PCDD/Fs). These fish samples were previously analyzed for PCDD/Fs using a high-resolution mass spectrometer following EPA protocols. The hybrid tandem mass spectrometric method using loss of COCl gave similar quantification results to those obtained by high-resolution mass spectrometry and eliminated the interferences attributed to polychlorinated biphenyls that were encountered in the high-resolution mass spectrometric analysis. Comparison of the two methods shows that the high-resolution mass spectrometric method surpasses the tandem mass spectrometric method in other analytical figures of merit, such as detection limit, linearity and reproducibility.     

Long-Term Environmental Surveillance and Health Risks of Metals and PCDD/Fs Around a Cement Plant in Catalonia,Spain

In this study, environmental data concerning the potential impact of a cement plant were updated, 10 years after a previous monitoring study. In 2011 and 2012, samples of soil, vegetation, and air were collected in the vicinity of a cement plant located in Santa Margarida i els Monjos (Barcelona, Catalonia, Spain). The concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and those of a number of metals (As, Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, Sb, Sn, Tl, V, and Zn) were determined. The results were compared with data from two previous sampling campaigns, performed in 2000 and 2001. Vanadium was the only element presenting a significant increase in the three monitors. In turn, a significant decrease of PCDD/Fs was noted in vegetation, from 0.2 to 0.1 ng WHO-TEQ/kg. The Hazard Quotient (HQ) of exposure to all pollutants was below the safety limit, while cancer risk associated with the exposure to metals and PCDD/Fs was within the range considered as assumable (10^?6–10^?4). Despite the long period of time elapsed between campaigns (10 years) and the use of alternative fuels, the impact of the cement plant seems to be low, based on the emissions of the contaminants here evaluated.     

Phylogenetic characterization of a polychlorinated-dioxin- dechlorinating microbial community by use of microcosm studies

Microcosms capable of reductive dechlorination of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) were constructed in glass bottles by seeding them with a polluted river sediment and incubating them anaerobically with an organic medium. All of the PCDD/F congeners detected were equally reduced without the accumulation of significant amounts of less-chlorinated congeners as the intermediate or end products. Alternatively, large amounts of catechol and salicylic acid were produced in the upper aqueous phase. Thus, the dechlorination of PCDD/Fs and the oxidative degradation of the dechlorinated products seemed to take place simultaneously in the microcosm. Denaturing gel gradient electrophoresis and clone library analyses of PCR-amplified 16S rRNA genes from the microcosm showed that members of the phyla Firmicutes, Proteobacteria, and Bacteroidetes predominated. A significant number of Chloroflexi clones were also detected. Quantitative real-time PCR with specific primer sets showed that the 16S rRNA genes of a putative dechlorinator, "Dehalococcoides," and its relatives accounted for 0.1% of the total rRNA gene copies of the microcosm. Most of the clones thus obtained formed a cluster distinct from the typical "Dehalococcoides" group. Quinone profiling indicated that ubiquinones accounted for 18 to 25% of the total quinone content, suggesting the coexistence and activity of ubiquinone-containing aerobic bacteria. These results suggest that the apparent complete dechlorination of PCDD/Fs found in the microcosm was due to a combination of the dechlorinating activity of the "Dehalococcoides"-like organisms and the oxidative degradation of the dechlorinated products by aerobic bacteria with aromatic hydrocarbon dioxygenases.     

Recent developments in microbial biotransformation and biodegradation of dioxins

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), commonly known as dioxins (PCDD/Fs), are toxic environmental pollutants formed from various sources. Elimination of these pollutants from the environment is a difficult task due to their persistent and ubiquitous nature. Removal of dioxins by biological degradation (biodegradation) is considered a feasible method as an alternative to other expensive physicochemical approaches. Biodegradation of dioxins has been extensively studied in several microorganisms, and details concerning biodiversity, biodegradation, biochemistry and molecular biology of this process have accumulated during the last three decades. There are several microbial mechanisms responsible for biodegradation of dioxins, including oxidative degradation by dioxygenase-containing aerobic bacteria, bacterial and fungal cytochrome P-450, fungal lignolytic enzymes, reductive dechlorination by anaerobic bacteria, and direct ether ring cleavage by fungi containing etherase-like enzymes. Many attempts have been made to bioremediate PCDD/Fs using this basic knowledge of microbial dioxin degradation. This review emphasizes the present knowledge and recent advancements in the microbial biotransformation, biodegradation and bioremediation of dioxins.     

Atmospheric and riverine inputs of metals,nutrients and persistent organic pollutants into the lagoon of Venice

Atmospheric deposition in the lagoon of Venice and river inputs from the watershed were collected and analysed from 1998 to 1999 using the same analytical methods. The input from riverine sources largely prevails (>70%) over that from the atmosphere for As, Cr, Fe, Mn, Ni, nitrogen and phosphorus. Equivalent amounts of Hg, Pb, PCBs, HCB are discharged into the lagoon from the two sources, whilst atmospheric inputs prevail for Cd, ammonia and dioxins. A comparison with figures of maximum allowable discharges (MAD) for various compounds, recently set by the Italian Ministry for the Environment, showed that total inputs (riverine + atmospheric) of trace metals were below the MAD thresholds only for Cr, Cu, Ni and Zn. The total inputs of Cu and Ni, and Cr and Zn were approximately 20 and 40% of the MAD limit, respectively. The total phosphorus input of 284 t was close to the imposed limit, whilst the inorganic nitrogen load alone (>4000 t) was much higher than the MAD for total nitrogen. For those metals (As, Cd, Hg and Pb) and persistent organic pollutants, such as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) where the MAD states that the load should tend to ‘0’ (no discharge), the measured inputs of 4.8 (As) and 5.1 t (Pb), 151 (Cd) and 39 kg (Hg), 18 g (PCDD/Fs) and 440 mg (Toxicity Equivalents, TEQs, of PCDD/Fs) are by definition ‘above’ the MAD. The principal component analysis (PCA) of loading data and input profiles (markers) of production typologies showed that river and atmosphere contributions can be easily separated and recognised due to their different fingerprints. Riverine inputs were similar to chemical and glass work production markers, whereas atmospheric loadings were mainly influenced by chemical industry (PVC and VCM production), metallurgy and paper-mill.     

Widespread Distribution of <Emphasis Type="Italic">Dehalococcoides mccartyi</Emphasis> in the Houston Ship Channel and Galveston Bay,Texas, Sediments and the Potential for Reductive Dechlorination of PCDD/F in an Estuarine Environment

Sediments in the Houston Ship Channel and upper Galveston Bay, Texas, USA, are polluted with polychlorinated dibenzo-p-dioxins/furans (PCDD/F; ≤46,000 ng/kg dry weight (wt.)) with 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), the most toxic congener, contributing >50 % of the total toxic equivalents (TEQ) at most locations. We measured PCDD/F concentrations in sediments and evaluated the potential for enhanced in situ biodegradation by surveying for Dehalococcoides mccartyi, an obligate organohalide respiring bacterium. Dehalococcoides spp. (98 % similar to D. mccartyi) and 22 other members of the class Dehalococcoidia were predominant 16S ribosomal RNA (rRNA) phylotypes. Dehalococcoides spp. were also present in the active fraction of the bacterial community. Presence/absence PCR screening detected D. mccartyi in sediment cores and sediment grab samples having at least 1 ng/kg dry wt. TEQ at salinities ranging from 0.6 to 19.5 PSU, indicating that they are widespread in the estuarine environment. Organic carbon-only and organic carbon + sulfate-amended sediment microcosm experiments resulted in ～60 % reduction of ambient 2,3,7,8-TCDD in just 24 months leading to reductions in total TEQs by 38.4 and 45.0 %, respectively, indicating that 2,3,7,8-TCDD degradation is occurring at appreciable rates.     

Phylogenetic Characterization of a Polychlorinated-Dioxin- Dechlorinating Microbial Community by Use of Microcosm Studies

Microcosms capable of reductive dechlorination of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) were constructed in glass bottles by seeding them with a polluted river sediment and incubating them anaerobically with an organic medium. All of the PCDD/F congeners detected were equally reduced without the accumulation of significant amounts of less-chlorinated congeners as the intermediate or end products. Alternatively, large amounts of catechol and salicylic acid were produced in the upper aqueous phase. Thus, the dechlorination of PCDD/Fs and the oxidative degradation of the dechlorinated products seemed to take place simultaneously in the microcosm. Denaturing gel gradient electrophoresis and clone library analyses of PCR-amplified 16S rRNA genes from the microcosm showed that members of the phyla Firmicutes, Proteobacteria, and Bacteroidetes predominated. A significant number of Chloroflexi clones were also detected. Quantitative real-time PCR with specific primer sets showed that the 16S rRNA genes of a putative dechlorinator, “Dehalococcoides,” and its relatives accounted for 0.1% of the total rRNA gene copies of the microcosm. Most of the clones thus obtained formed a cluster distinct from the typical “Dehalococcoides” group. Quinone profiling indicated that ubiquinones accounted for 18 to 25% of the total quinone content, suggesting the coexistence and activity of ubiquinone-containing aerobic bacteria. These results suggest that the apparent complete dechlorination of PCDD/Fs found in the microcosm was due to a combination of the dechlorinating activity of the “Dehalococcoides”-like organisms and the oxidative degradation of the dechlorinated products by aerobic bacteria with aromatic hydrocarbon dioxygenases.     

The influence of the Cucurbitaceae on mitigating the phytotoxicity and PCDD/PCDF content of soil amended with sewage sludge

The study evaluates the impact of sewage sludge on OECD - Organization for Economic Cooperation and Development and vegetable soil phytotoxicity, measured using three test species: Lepidium sativum, Sinapis alba and Sorghum saccharatum, and total and TEQ PCDD/PCDF (toxic equivalency polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans) soil concentration, measured using HRGC/HRMS - High Resolution Gas Chromatography/High Resolution Mass Spectrometry. It also evaluates the effect of zucchini and cucumber cultivation during 5-weeks period on mitigating these parameters. The application of 3, 9 and 18 t/ha of sewage sludge gradually increases the phytotoxicity of both OECD and vegetable soil. In the case of OECD soil, the highest roots growth inhibitions were observed for S. alba (73%, 86% and 87%, respectively) and the lowest for S. saccharatum (7%, 59% and 70%), while in vegetable soil inhibitions were averagely 25% lower. Sludge application also led to a 38% (3 t/ha), 169% (9 t/ha) and 506% (18 t/ha) increase in PCDD/PCDF concentration, and the TEQs were augmented by 15%, 159% and 251%. Both soil phytotoxicity and total and TEQ PCDD/PCDF concentrations were diminished as a result of zucchini and cucumber cultivation. The maximum reduction of soil phytotoxicity (83%) was observed as an effect of cucumber cultivation, while zucchini was 11% less effective. Zucchini, in turn, was more efficient in PCDD/PCDF removal (37% reduction), followed by cucumber (24%). Such differences were not observed in the case of TEQ reductions (68% and 66% for zucchini and cucumber cultivation, respectively).     

The Duisburg birth cohort study: influence of the prenatal exposure to PCDD/Fs and dioxin-like PCBs on thyroid hormone status in newborns and neurodevelopment of infants until the age of 24 months

Prenatal exposure to polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) can affect neurobehavioral development of infants and children. This effect may be mediated through disruption of thyroid hormone homeostasis. However, epidemiological studies reveal no consistent influence of PCDD/Fs and PCBs on thyroid status and neurodevelopment at environmental background levels. The effects may resolve with time of further decreasing exposure to these compounds. The aim of this study was to find out if there are still effects related to prenatal PCDD/F and PCB observable at the meanwhile decreased levels of exposure by using the same methods which have been applied in similar studies during the last 10 years in Europe. The birth cohort study was initiated in the year 2000 in the industrialized city of Duisburg, Germany. 232 healthy mother-infant pairs were recruited between 2000 and 2002. Dioxins, dioxin-like PCBs and six indicator PCBs were analyzed in maternal blood during pregnancy and in maternal milk following extraction and sample clean-up by HRGC/HRMS. Thyroid stimulating hormone (TSH), total thyroxine (T4), total triiodothyronine (T3), free thyroxine (FT4) and free triiodothyronine (FT3) were measured in serum samples of the pregnant women and in cord serum samples by chemiluminescent immunometric assay. Neurological examinations were performed at ages 2 weeks and 18 months using the neurological optimality score (NOS), mental and motor development were assessed using the Bayley Scales of Infant Development (BSID) at ages 12 and 24 months. Multiple linear regression analysis was used to describe the association of PCDD/F and PCB in maternal blood or milk with the outcome measurements after adjustment for confounding. Blood levels (n=182) of WHO 2005 toxic equivalents (TEQ) (PCDD/F+PCB) were in the range of 3.8-58.4 pg/glipid base (median: 19.3 pg/glipid base). The corresponding data for human milk (n=149) were 2.6-52.4 pg/glipid base (median: 19.7 pg/glipid base). Multiple regression analysis showed no decrease of thyroid hormones related to WHO 2005 TEQ in blood and milk of mothers and their newborns. Furthermore, no associations between exposure and neurological and developmental measures were observed. This study supports the view that the current decreased exposure to PCDD/Fs and PCBs does not impair thyroid function of newborns and neurodevelopment of infants until the age of 24 months.     

Dioxin/polychlorinated biphenyl body burden, diabetes and endometriosis: findings in a population-based study in Belgium

Dioxins and polychlorinated biphenyls (PCBs) are persistent organic pollutants widely distributed in the food chain, which is the main source of human exposure. Their effects on human health at background exposure levels are still poorly understood. Recent epidemiological evidence suggests a possible association between these pollutants and diabetes. We report here the results of a population-based study in Belgium on 257 (142 women and 115 men) environmentally exposed subjects, including 10 cases of endometriosis and nine cases of diabetes. Seventeen 2,3,7,8-polychlorinated dibenzodioxins/dibenzofurans (PCDD/Fs or dioxins), four coplanar PCBs (International Union of Pure and Applied Chemistry [IUPAC] nos 77, 81, 126 and 169) and 12 PCB markers (IUPAC nos 3, 8, 28, 52, 101, 118, 138, 153, 180, 194, 206 and 209) were quantified in serum fat from fasting blood samples in order to estimate the body burden of these pollutants. Whilst no difference was found between women with endometriosis and their controls, diabetic patients had significantly increased serum levels of dioxins, coplanar PCBs and the 12 PCB markers. After adjustment for age and other covariates, serum total toxic equivalent activity (sum of PCDD/Fs and coplanar PCBs) and 12 PCB marker concentrations in diabetics were 62% (p=0.0005) and 39% (p=0.0067) higher, respectively, than in controls. The risk of diabetes was significantly increased in subjects in the top decile for adjusted concentrations of dioxins (odds ratio 5.1, 95% confidence interval [CI] 1.18-21.7), coplanar PCBs (odds ratio 13.3, 95% CI 3.31-53.2) or 12 PCB markers (odds ratio 7.6, 95% CI 1.58-36.3). These findings warrant further studies to assess the significance of the associations between diabetes and environmental exposure to polychlorinated pollutants.     

Heavy metal pollution in Antarctica: a molecular ecotoxicological approach to exposure assessment

Trematomus bernacchii sampled from two sites at Ross Island, Antarctica, were assessed for condition (gonadal and hepatic somatic indices and condition factor), pathological state (liver and gill histology), hepatic metal (Zn, Cu, Cd and Ni) concentrations, and metallothionein induction by quantitative competitive (qc) RT-PCR. Fish from a polluted site (Winter Quarters Bay) had pathological anomalies including necrosis and periductal inflammation in their livers, and X-cell disease, epithelial hyperplasia, lamellar fusion and aneurysms in their gills. Such anomalies were less common in fish from a relatively pristine site (Backdoor Bay, Cape Royds). Fish from both sites had similar liver concentrations of Zn, Cu and Cd and qcRT-PCR revealed similar levels of hepatic metallothionein mRNA. Ni in the livers of fish from Winter Quarters Bay were higher than those in fish from Backdoor Bay, but the differences were not great enough to affect hepatic metallothionein mRNA significantly. Despite the polluted state of Winter Quarters Bay waters, it seems that the heavy metals present may have only limited impact on the health status of fish collected from this locality. This may reflect a low bioavailability of the heavy metals in Ross Island marine sediments and suggests that other factors, such as relatively high levels of organic pollutants (PAHs, PCBs) or pathogens from the nearby sewage outlet, may play a more significant role in the aetiology of pathological conditions in fish from Winter Quarters Bay.     

Ecotoxicological assessment of several estuarine zones in the south of Primorsky Krai

A complex ecotoxicological assessment of several estuarine zones of the Razdol’naya, Barabashevka, Ryazanovka, and Gladkaya rivers in Amur Bay, and the Artyomovka and Sukhodol rivers in Ussyry Bay was carried out in 2007 and 2008. Bottom sediments in the estuary of the Kievka river were collected in 2009. The content of petroleum hydrocarbons was determined in the water and bottom sediments of riverine and marine sectors of estuaries and the total toxicity of bottom sediments was tested with the use of mysids. Bottom sediments from a small river on Reineke Island, in which the concentrations of primary pollutants corresponded to the background values for the entire Peter the Great Bay, were used as a control. The content of organochlorine pesticides in the muscles and liver of the Redeye Eastern Redfin (Tribolodon brandtii) was determined and molecular biomarkers of oxidative stress in organs of the Redlip Mullet (Liza haematocheila) analyzed. The amount of wastewater and pollutants flowing into Amur Bay and Ussyry Bay with some of the rivers was estimated. The correlation coefficient between the toxicity of bottom sediments and the petroleum hydrocarbons content in them was found. The higher sediment toxicity in the riverine zone, as compared to the marine zone, proves the concept of the “river-sea” biogeochemical barrier.