Polychlorinated Biphenyl

An expert meeting was organized by the World Health Organization (WHO) and held in Stockholm on 15-18 June 1997. The objective of this meeting was to derive consensus toxic equivalency factors (TEFs) for polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and dioxinlike polychlorinated biphenyls (PCBs) for both human, fish, and wildlife risk assessment. Based on existing literature data, TEFs were (re)evaluated

Numerical sediment quality guidelines (SQGs) for freshwater ecosystems have previously been developed using a variety of approaches. Each approach has certain advantages and limitations which influence their application in the sediment quality assessment process. In an effort to focus on the agreement among these various published SQGs, consensusbased SQGs were developed for 28 chemicals of concern in freshwater sediments (i.e., metals, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and pesticides). For each contaminant of concern, two SQGs were developed from the published SQGs, including a threshold effect concentration (TEC) and a probable effect concentration (PEC). The resultant SQGs for each chemical were evaluated for reliability using matching sediment chemistry and toxicity data from field studies conducted throughout the United States. The results of this evaluation indicated that most of the TECs (i.e., 21 of 28) provide an accurate basis for predicting the absence of sediment toxicity. Similarly, most of the PECs (i.e., 16 of 28) provide an accurate basis for predicting sediment toxicity. Mean PEC quotients were calculated to evaluate the combined effects of multiple contaminants in sediment. Results of the evaluation indicate that the incidence of toxicity is highly correlated to the mean PEC quotient (R 2 ϭ 0.98 for 347 samples). It was concluded that the consensus-based SQGs provide a reliable basis for assessing sediment quality conditions in freshwater ecosystems.

Estrogens are defined by their ability to induce the proliferation of cells of the female genital tract. The wide chemical diversity of estrogenic compounds precludes an accurate prediction of estrogenic activity on the basis of chemical structure. Rodent bioassays are not suited for the large-scale screening of chemicals before their release into the environment because of their cost, complexity, and ethical concerns. The E-SCREEN assay was developed to assess the estrogenicity of environmental chemicals using the proliferative effect of estrogens on their target cells as an end point. This quantitative assay compares the cell number achieved by similar inocula of MCF-7 cells in the absence of estrogens (negative control) and in the presence of 1 7,B-estradiol (positive control) and a range of concentrations of chemicals suspected to be estrogenic. Among the compounds tested, several "new" estrogens were found; alkylphenols, phthalates, some PCB congeners and hydroxylated PCBs, and the insecticides dieldrin, endosulfan, and toxaphene were estrogenic by the E-SCREEN assay. In addition, these compounds competed with estradiol for binding to the estrogen receptor and increased the levels of progesterone receptor and pS2 in MCF-7 cells, as expected from estrogen mimics. Recombinant human growth factors (bFGF, EGF, IGF-1) and insulin did not increase cell yields. The aims of the work summarized in this paper were a) to validate the E-SCREEN assay; b) to screen a variety of chemicals present in the environment to identify those that may be causing reproductive effects in wildlife and humans; c) to assess whether environmental estrogens may act cumulatively; and finally d) to discuss the reliability of this and other assays to screen chemicals for their estrogenicity before they are released into the environment. -Environ Health Perspect 1 03(Suppl 7): 113-122 (1995)

The weight-of-evidence approach to the development of sediment quality guidelines (SQGs) was modified to support the derivation of biological effects-based SQGs for Florida coastal waters. Numerical SQGs were derived for 34 substances, including nine trace metals, 13 individual polycyclic aromatic hydrocarbons (PAHs), three groups of PAHs, total polychlorinated biphenyls (PCBs), seven pesticides and one phthalate ester. For each substance, a threshold effects level (TEL) and a probable effects level (PEL) was calculated. These two values defined three ranges of chemical concentrations, including those that were (1) rarely, (2) occasionally or (3) frequently associated with adverse effects. The SQGs were then evaluated to determine their degree of agreement with other guidelines (an indicator of comparability) and the percent incidence of adverse effects within each concentration range (an indicator of reliability). The guidelines also were used to classify (using a dichotomous system: toxic, with one or more exceedances of the PELs or non-toxic, with no exceedances of the TELs) sediment samples collected from various locations in Florida and the Gulf of Mexico. The accuracy of these predictions was then evaluated using the results of the biological tests that were performed on the same sediment samples. The resultant SQGs were demonstrated to provide practical, reliable and predictive tools for assessing sediment quality in Florida and elsewhere in the southeastern portion of the United States.

The ligninolytic enzymes of white-rot fungi have a broad substrate specificity and have been implicated in the transformation and mineralization of organopollutants with structural similarities to lignin. This review presents evidence for the involvement of these enzymes in white-rot fungal degradation of munitions waste, pesticides, polychlorinated biphenyls, polycyclic aromatic hydrocarbons, bleach plant effluent, synthetic dyes, synthetic polymers, and wood preservatives. Factors relating to the feasibility of using white-rot fungi in bioremediation treatments for organopollutants are discussed.

Polychlorinated biphenyls (PCBs) in the environment pose long-term risk to public health because of their persistent and toxic nature. This study investigates the degradation of PCBs using sulfate radical-based advanced oxidation processes (SR-AOPs). These processes are based on the generation of sulfate radicals through iron (Fe(II), Fe(III)) mediated activation of peroxymonosulfate (KHSO 5 , PMS) or persulfate (Na 2 S 2 O 8 , PS). This study is the first instance for coupling of Fe(II)/Fe(III) with PMS for PCB degradation in aqueous and sediment systems. The high oxidation efficiencies of the free radicals (SO 4 À), in combination with the slow rate of consumption of the oxidants, make these processes very effective for the degradation of recalcitrant organic compounds. The effectiveness of the process was evaluated based on the degradation of a model polychlorinated biphenyl, 2-chlorobiphenyl and total organic carbon (TOC) removal. The kinetics of 2chlorobiphenyl degradation along with the effect of oxidant and catalyst concentrations on the degradation efficiency was studied. Near complete removal of 2-chlorobiphenyl was observed when Fe(II) was used with PMS or PS. Fe(II) acts as a sulfate radical scavenger at higher concentrations indicating that there is an optimum concentration of Fe(II) that leads to most effective degradation of the target contaminant. A chelating agent, sodium citrate, was used to control the quantity of iron in the solution for activation of the oxidant. For the first time, we studied the feasibility of the activation of PMS using iron citrate complexes for PCB degradation. In the presence of sodium citrate, increase in degradation efficiency was observed up to a metal:ligand ratio of 1:2, after which the increase in citrate concentration led to a decrease in removal efficiency. Fe(II)/PMS systems were found to be very effective in degrading PCB in a sediment-slurry system with more than 90% PCB removal being observed within 24 h.

In a previous review of this topic, results from studies up to mid-2005 showed that several brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs, including BDE-209), hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA) were reaching the Arctic . Spatial trends of PBDEs and HBCD in top predators such as polar bears were similar to those seen for polychlorinated biphenyls (PCBs) indicating western Europe and eastern North America as source regions. Temporal trends indicated increasing concentrations of tetra-decaBDEs in several Arctic species and the tetra-hexaBDEs were found to biomagnify. The concentrations of the various BFRs were generally lower in the Arctic compared to more southerly regions and were lower than concentrations of legacy chemicals such as PCBs. The results indicated that most of these BFRs undergo long range transport to the Arctic.

The emission of black carbon is known to cause major environmental problems. Black carbon particles contribute to global warming, carry carcinogenic compounds and cause serious health risks. Here, we show another side of the coin. We review evidence that black carbon may strongly reduce the risk posed by organic contaminants in sediments and soils. Extremely efficient sorption to black carbon pulls highly toxic polycyclic aromatic hydrocarbons, polychlorinated biphenyls, dioxins, polybrominated diphenylethers and pesticides into sediments and soils. This increased sorption is general, but strongest for planar (most toxic) compounds at environmentally relevant, low aqueous concentrations. Black carbon generally comprises about 9% of total organic carbon in aquatic sediments (median value of 300 sediments), and then may reduce uptake in organisms by up to two orders of magnitude. This implies that current environmental risk assessment systems for these contaminants may be unnecessarily safe.

Liquids and sludges containing polychlorinated biphenyls (PCBs) can be treated to concentrate the PCBs in a solid residue. The latter can then be handled to destroy the PCBs. A study on sorption kinetics of PCBs on fly ash was conducted in controlled batch systems. TCB and HeCB are removed at 25°C by adsorption on fly ash up to 97% at pH 7, with an adsorbent dose of 5 g/l. An examination of the thermodynamic parameters shows that the adsorption of TCB and HeCB by fly ash is a process occuring spontaneously at ambient conditions. Activation energies for the sorption process ranged between 5.6 and 49.1 kJ/mol. It was observed that the rate at which TCB and HeCB are adsorbed onto fly ash showed a diffusion limitation. The uptake rate of TCB and HeCB increases with increasing initial concentration and gradually tends to a constant value. A decrease in the adsorption of TCB and HeCB was observed when interfering ions and other PCB congeners were present. Changing the pH in the aqueous solution from 2 to 10 had no effect on the adsorption process. Overall, fly ash can be used for an efficient removal of PCBs from several aqueous solutions.

Chronic low level polychlorinated biphenyls (PCB) exposures remain a significant public health concern since results from epidemiological studies indicate PCB burden is associated with immune system dysfunction, cardiovascular disease, and impairment of the developing nervous system. Of these various adverse health effects, developmental neurotoxicity has emerged as a particularly vulnerable endpoint in PCB toxicity. Arguably the most pervasive biological effects of PCBs could be mediated by their ability to alter the spatial and temporal fidelity of Ca 2+ signals through one or more receptor mediated processes. This review will focus on our current knowledge of the structure and function of ryanodine receptors (RyRs) in muscle and nerve cells and how PCBs and related non-coplanar structures alter these functions. The molecular and cellular mechanisms by which noncoplanar PCBs and related structures alter local and global Ca 2+ signaling properties and the possible short and long-term consequences of these perturbations on neurodevelopment and neurodegeneration are reviewed.

Pesticides as environmental pollutants are described in detail along with their sources and paths of entry into various elements of the environment. Comprehensive literature data on the concentration of these pollutants in natural and treated waters and wastewaters are discussed. A wide selection of isolation and preconcentration techniques for these pollutants in water is presented and discussed. An emphasis is put on solid-phase extraction. In the case of the authors' work, a more detailed description is given.

For the 1983 nesting season, Forster's tern (Sterna forsteri) reproductive success was significantly impaired on organochlorine contaminated Green Bay, Lake Michigan compared to a relatively uncontaminated inland location at Lake Poygan, Wisconsin. Compared with tern eggs from Lake Poygan, eggs from Green Bay had significantly higher median concentrations of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), other polychlorinated dibenzo-p-dioxins (PCDDs), total polychlorinated biphenyls (PCBs), total (three congeners) non-ortho, ortho' PCBs, five individual PCB congeners known to induce aryl hydrocarbon hydroxylase (AHH) and several other organochlorine contaminants. Conversions of analytical concentrations of TCDD and PCB congeners based on relative AHH induction potencies allowed for estimation of total 2,3,7,8-TCDD equivalents. Two PCB congeners, 2,3,3',4,4'-and 3,3',4,4',5-pentachlorobiphenyl (PeCB) accounted for more than 90% of the median estimated TCDD equivalents at both Green Bay and Lake Poygan. The median estimated TCDD equivalents were almost l 1-fold higher in tern eggs from Green Bay than in eggs from Lake Poygan (2175 and 201 pg/g). The hatching success of Green Bay sibling eggs from nests where eggs were collected for contaminant analyses was 75% lower at Green Bay than at Lake

We thank C. Koopman-Esseboom for initiating the study and for collecting the maternal and cord samples; L. Birnbaum, R. Smialowicz, and J.E. Vos for critically reviewing this paper; and all parents and their children for participating in this study. This study is part of the Dutch PCB/Dioxin Study, a larger prospective longitudinal study on possible adverse health effects of these pollutants on human children, and was supported by the Dutch Toxicology Research Promotion Program and the European Commission for Environmental and Health Programs contract EV5V-CT92-0207.

Blubber biopsy samples were obtained for contaminant analysis from two discrete populations of killer whales (Orcinus orca) which frequent the coastal waters of British Columbia, Canada. Detailed life history information for the ®sh-eating`resident' population, comprising two distinct communities, and the marine mammal-eating transient' killer whale population, provided an invaluable reference for the interpretation of contaminant concentrations. Total PCB concentrations (sum of 136 congeners detected) were surprisingly high in all three communities, but transient killer whales were particularly contaminated. PCB concentrations increased with age in males, but were greatly reduced in reproductively active females. The absence of age, sex and inter-community dierences in concentrations of polychlorinated-dibenzo-p-dioxins (PCDDs) and-dibenzofurans (PCDFs) may have partly re¯ected low dietary levels, but more importantly, metabolic removal of dioxin-like compounds in killer whales. While information on toxic thresholds does not exist for PCBs in cetaceans, total 2,3,7,8-TCDD Toxic Equivalents (TEQ) in most killer whales sampled easily surpassed adverse eects levels established for harbour seals, suggesting that the majority of free-ranging killer whales in this region are at risk for toxic eects. The southern resident and transient killer whales of British Columbia can now be considered among the most contaminated cetaceans in the world. Ó

Passive air samplers consisting of polyurethane foam (PUF) disks were deployed simultaneously over 2-4 month periods from April to July 2008 at 19 locations throughout the Tuscany Region at urban (n = 9), rural (n = 7) and agricultural sites (n = 3). The purpose of the study was to assess the gas-phase air concentrations of PCBs, OCPs, PBDEs and PAHs on a local and regional scale. Derived air concentrations (pg m -3 ) ranged from below detection limit (BDL) to 300 for ∑ 6 PCBs and from BDL to 30 for ∑ 3 PBDEs. As expected, the highest PCB concentrations (pg m -3 ) were observed at urban sites, peaking in Piombino (300). PBDEs, however, exhibited a "reverse gradient" (i.e. rural>agricultural>urban) with highest air concentration at the rural site, Arcidoso (30). Levels of OCPs showed less distinct differences among the three site types. The most frequently detected OCPs were Endosulfan I, γ-HCH and α-HCH. Endosulfan I ranged from BDL to 2 200 pg m -3 , α-HCH from BDL to 610, and γ-HCH from BDL to 1 100. The high air concentrations of HCHs were surprising and possibly due to continued and illegal use -especially at agricultural and urban sites that exhibited the highest levels in air. PAHs showed highest concentrations (pg m -3 ) at agricultural and urban sites, ranging from 290 to 4 700 and were generally consistent with other data sets from Europe. PAHs were dominated by the 3-ring PAHs (76 ± 6)%, with phenanthrene alone accounting for (45 ± 11%) of the total PAHs. This study demonstrates the feasibility of using PUF disks as time-integrating passive air samplers for assessing local and regional scale concentrations of a wide range of POPs in central Italy. Given their low cost and simplicity, passive air samplers are the preferred option for conducting concurrent sampling at multiple sites for monitoring and research purposes.

Contamination of persistent organochlorines (OCs) such as PCBs (polychlorinated biphenyls), DDT and its metabolites (DDTs), HCH (hexachlorocyclohexane) isomers (HCHs), chlordane compounds (CHLs), and HCB (hexachlorobenzene) were examined in mussels collected from coastal waters of Asian countries such as to elucidate the contamination status, distribution and possible pollution sources and to assess the risks on aquatic organisms and human. OCs were detected in all mussels collected from all the sampling sites investigated. Considerable residue levels of p; p 0 -DDT and a-HCH were found in mussels and the concentrations of DDTs and HCHs found in mussels from Asian developing countries were higher than those in developed nations suggesting present usage of DDTs and HCHs along the coastal waters of Asian developing countries. On the other hand, lower concentrations of PCBs detected in mussels from Asian developing countries than those in developed countries indicate that PCBs contamination in mussels is strongly related to industrial and activities. To our knowledge, this is a first comprehensive report on monitoring OCs pollution in the Asia-Pacific region.

This is the second of two papers demonstrating the feasibility of using passive air samplers to investigate persistent organic pollutants along an urban-rural transect in Toronto. The first paper investigated spatial trends for polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs). This second paper investigates the seasonality of air concentrations for polycyclic aromatic hydrocarbons (PAHs), PCBs, and OCPs along this transect. Air samplers, consisting of polyurethane foam (PUF) disks housed in stainless steel domed chambers, were deployed for three 4-month integration periods from June 2000 to July 2001. The seasonal variations of derived air concentrations for PAHs, PCBs, and OCPs reflected the different source characteristics for these compounds. PAHs showed a strong urban-rural gradient with maximum concentrations at urban sites during the summer period (July-October). These high summer values in Toronto were attributed to increases in evaporative emissions from petroleum products such as asphalt. PCBs also exhibited a strong urban-rural gradient with maximum air concentrations (∼2-3 times higher) during the spring period (April-June). This was attributed to increased surface-air exchange of PCBs that had accumulated in the surface layer over the winter. R-HCH was fairly uniformly distributed, spatially and temporally, as expected. This pattern and the derived air concentration of ∼35 to ∼100 pg m -3 agreed well with high volume air data from this region, adding confidence to the operation of the passive samplers and showing that site-to-site differences in sampling rates was not an issue. For other OCPs, highest concentrations were observed during the spring period.

Polychlorinated biphenyls (PCBs) are ubiquitous environmental persistent contaminants giving rise to potential health hazard. Some PCBs exert dioxin-like activities mediated through the aryl hydrocarbon receptor. Although reports on interaction with other nuclear receptors are sparce, some congeners are hypothesized to possess endocrine disruptive potential. Here we present evidence that the three PCBs most abundant in biological extracts, 2,2%,3%4,4%,5hexachlorobiphenyl (PCBc138), 2,2%,4,4%,5,5%-hexachlorobiphenyl (PCB c 153), and 2,2%,3,4,4%,5,5%-heptachlorobiphenyl (PCBc 180) have pleiotropic effects on the estrogen-and androgen-receptor. In MCF-7 cells a slightly increased cell proliferation was observed at low concentrations (1 -10 nM) in cells co-treated with 0.01 nM 17b-Estradiol, whereas the compounds inhibited cell growth significantly at 1 and 10 mM. In reporter gene (ERE-tk-CAT) analysis the three congeners exhibited a significantly estrogen receptor-ligand mediated decrease of the chloramphenicol transferase activity in both control and 10 nM 17b-estradiol induced MCF-7 cells. In addition, PCBc138 elicited a dose-dependent antagonistic effect on androgen receptor activity in transiently co-transfected Chinese Hamster Ovary cells with an IC 50 , of 6.2 mM. In summary, this study indicate that the di-ortho, multiple-chloro substituted biphenyls, PCB c138, PCB c153 and PCB c180, can compete with the binding of the natural ligand to two nuclear receptors and thus possess the ability to interfere with sexual hormone regulated processes.

Abbreviations: BPA, Bisphenol A; -OH, hydroxylated metabolite of; PAPS, 3Ј-phosphoadenosine-5Ј-phosphosulfate; PBDE, polybrominated diphenylether; PCB, polychlorinated biphenyl; PCDD, polychlorinated dibenzo-p-dioxin; PCDF, polychlorinated dibenzofuran; PHAH, polyhalogenated aromatic hydrocarbon; SULT1E1, estrogen sulfotransferase.

Background, aim and scope Once they have been generated, polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and other persistent organic pollutants (POPs) can persist in soils and sediments and in waste repositories for periods extending from decades to centuries. In 1994, the US EPA concluded that contaminated sites and other reservoirs are likely to become the major source of contemporary pollution problems with these substances. With this in mind, this article is the first in a new series in ESPR under the title ‘Case Studies on Dioxin and POP Contaminated Sites—Contemporary and Future Relevance and Challenges’, which will address this important issue. The series will document various experiences from sites contaminated with PCDD/F and other POPs. This article provides an overview of the content of the articles comprising the series. In addition, it provides a review of the subject in its own right and identifies the key issues arising from dioxin/POP-contaminated sites. Additionally, it highlights the important conclusions that can be drawn from these examples. The key aim of this article and of the series as a whole is to provide a comprehensive overview of the types of PCDD/F contaminated sites that exist as a result of historical activities. It details the various processes whereby these sites became contaminated and attempts to evaluate their contemporary relevance as sources of PCDD/Fs and other POPs. It also details the various strategies used to assess these historical legacies of contamination and the concepts developed, or which are under development, to effect their remediation. Main features Special sessions on ‘Contaminated sites—Cases, remediation, risk and policy’ were held at the DIOXIN conferences in 2006 and 2007, and this theme will be continued at DIOXIN 2008 to be held in Birmingham. Selected cases from the approximately 70 contributions made to these sessions, together with some additional invited case studies are outlined together with the key issues they raise. By evaluating these cases and adding details of experiences published in the current literature, an overview will be given of the different features and challenges of dioxin and POP-contaminated sites. Results This article provides a systematic categorisation of types of PCDD/F and POP-contaminated sites. These are categorised according to the chemical or manufacturing process, which generated the PCDD/Fs or POPs and also includes the use and disposal aspects of the product life cycle in question. The highest historical PCDD/F and dioxin-like polychlorinated biphenyl (PCB) contamination burdens have arisen as a result of the production of chlorine and of chlorinated organic chemicals. In particular, the production of chlorinated pesticides, PCBs and the related contaminated waste streams are identified being responsible for historical releases of toxic equivalents (TEQs) at a scale of many tonnes. Along with such releases, major PCDD/F contaminated sites have been created through the application or improper disposal of contaminated pesticides, PCBs and other organochlorine chemicals, as well through the recycling of wastes and their attempted destruction. In some extreme examples, PCDD/F contaminated sites have also resulted from thermal processes such as waste incinerators, secondary metal industries or from the recycling or deposition of specific waste (e.g. electronic waste or car shredder wastes), which often contain chlorinated or brominated organic chemicals. The examples of PCDD/F and dioxin-like PCB contamination of fish in European rivers or the impact of contaminated sites upon fishing grounds and upon other food resources demonstrate the relevance of these historical problems to current and future human generations. Many of the recent food contamination problems that have emerged in Europe and elsewhere demonstrate how PCDD/F and dioxin like PCBs from historical sources can directly contaminate human and animal feedstuffs and indeed highlight their considerable contemporary relevance in this respect. Accordingly, some key experiences and lessons learnt regarding the production, use, disposal and remediation of POPs from the contaminated sites are summarised. Discussion An important criterion for evaluating the significance and risks of PCDD/Fs and other POPs at contaminated sites is their present or future potential for mobility. This, in turn, determines to a large degree their propensity for off-site transport and environmental accessibility. The detailed evaluation of contaminated site cases reveals different site-specific factors, which influence the varied pathways through which poor water-soluble POPs can be mobilised. Co-contaminants with greater water solubility are also typically present at such sites. Hence, pumping of groundwater (pump and treat) is often required in addition to attempting to physically secure a site. At an increasing number of contaminated sites, securing measures are failing after relatively short time spans compared to the time horizon, which applies to persistent organic pollutant contamination. Due to the immense costs and challenges associated with remediation of contaminated sites ‘monitored natural attenuation’ is increasingly gaining purchase as a conceptual remediation approach. However, these concepts may well prove limited in their practical application to contaminated sites containing persistent organic pollutants and other key pollutants like heavy metals. Conclusions It is inevitable, therefore, that dioxin/POP-contaminated sites will remain of contemporary and future relevance. They will continue to represent an environmental issue for future generations to address. The securing and/or remediation of dioxin/POP-contaminated sites is very costly, generally in the order of tens or hundreds of millions of dollars. Secured landfills and secured production sites need to be considered as constructions not made for ‘eternity’ but built for a finite time scale. Accordingly, they will need to be controlled, supervised and potentially repaired/renewed. Furthermore, the leachates and groundwater impacted by these sites will require ongoing monitoring and potential further remediation. These activities result in high maintenance costs, which are accrued for decades or centuries and should, therefore, be compared to the fully sustainable option of complete remediation. The contaminated site case studies highlight that, while extensive policies and established funds for remediation exist in most of the industrialised western countries, even these relatively well-regulated and wealthy countries face significant challenges in the implementation of a remediation strategy. This highlights the fact that ultimately only the prevention of contaminated sites represents a sustainable solution for the future and that the Polluter Pays Principle needs to be applied in a comprehensive way to current problems and those which may emerge in the future. Recommendations and perspectives With the continuing shift of industrial activities in developing and transition economies, which often have poor regulation (and weak self-regulation of industries), additional global challenges regarding POPs and other contaminated sites may be expected. In this respect, a comprehensive application of the “polluter pays principle” in these countries will also be a key to facilitate the clean-up of contaminated areas and the prevention of future contaminated sites. The threats and challenges of contaminated sites and the high costs of securing/remediating the problems highlight the need for a comprehensive approach based upon integrated pollution prevention and control. If applied to all polluting (and potentially polluting) industrial sectors around the globe, such an approach will prove to be both the cheapest and most sustainable way to underpin the development of industries in developing and transition economies.

The multiple cascades of signal transduction pathways that lead from receptors on the cell membrane to the nucleus, thus translating extracellular signals into changes in gene expression, may represent important targets for neurotoxic compounds. Among the biochemical steps and pathways that have been investigated are the metabolism of cyclic nucleotides, the formation of nitric oxide, the metabolism of membrane phospholipids, the activation of a multitude of protein kinases and the induction of transcription factors. This brief review will focus on the interactions of three known neurotoxicants, lead, ethanol and polychlorinated biphenyls, with signal transduction pathways, particularly the family of protein kinase C isozymes, and discusses how such effects may be involved in their neurotoxicity.

We have measured the concentrations of polychlorinated dibenzo-p-dioxins (PCDD/F), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDE) in 10 market baskets consisting of almost 4000 individual food samples representing 228 different food items, and also in the total diet basket. Lower bound concentrations of PCDD/Fs ranged between 0.0057 and 5.6 pg/g fresh weight in the market baskets and the corresponding values for PCBs from 39 to 25,000 pg/g. The fish basket contributed most to the concentrations of dioxins and PCBs, and also to concentrations of PBDEs in which the lower bound range was from 0.82 to 850 pg/g. We also assessed the average daily intakes of these substances by the Finnish adult population. The average daily intake of sum of PCDD/Fs and PCBs as WHO toxic equivalents was assessed to be 115 pg, which was 1.5 pg WHO-TEq/kg body weight using an average mean weight of 76 kg for the general population in Finland. The contribution of fish to the intake of PCDD/Fs was between 94% and 72%, depending on whether lower or upper bound concentrations were used. With respect to PCBs, the contribution of fish was 80%. The calculated intake of PBDEs of 44 ng/day was comparable to intake assessments from other countries. Fish also contributed most to the PBDE intake, but there was some other source of PBDEs that distinguishes the exposure to PBDEs from exposure to PCDD/Fs and PCBs. This additional source seemed to be found in the market basket that included beverages, spices, and sweets. D

Prenatal exposure to polychlorinated biphenyls (PCBs) was examined by analysis of cord tissue from 435 children from a Faroese birth cohort. Analysis of 50 paired cord blood samples showed excellent correlation with the cord tissue concentration (r =.90). Among 17 neuropsychological outcomes determined at age 7 years, the cord PCB concentration was associated with deficits on the Boston Naming Test (without cues, two-tailed P =.09 not adjusted for mercury; with cues, P =.03), the Continuous Performance Test reaction time ( P =.03), and, possibly, on long-term recall on the California Verbal Learning Test ( P =.15). The association between cord PCB and cord-blood mercury (r =.42) suggested possible confounding. While no PCB effects were apparent in children with low mercury exposure, PCB-associated deficits within the highest tertile of mercury exposure indicated a possible interaction between the two neurotoxicants. PCB-associated increased thresholds were seen at two of eight frequencies on audiometry, but only on the left side, and no deficits occurred on evoked potentials or contrast sensitivity. The limited PCB-related neurotoxicity in this cohort appears to be affected by concomitant methylmercury exposure. D

Isotope Ratio Mass Spectrometry (IRMS) is a specialized technique used to provide information about the geographic, chemical, and biological origins of substances. The ability to determine the source of an organic substance stems from the relative isotopic abundances of the elements which comprise the material. Because the isotope ratios of elements such as carbon, hydrogen, oxygen, sulfur, and nitrogen can become locally enriched or depleted through a variety of kinetic and thermodynamic factors, measurement of the isotope ratios can be used to differentiate between samples which otherwise share identical chemical compositions. Several sample introduction methods are now available for commercial isotope ratio mass spectrometers. Combustion is most commonly used for bulk isotopic analysis, whereas gas and liquid chromatography are predominately used for the real-time isotopic analysis of specific compounds within a mixture. Here, highlights of advances in instrumentation and applications within the last three years are provided to illustrate the impact of this rapidly growing area of research. Some prominent new applications include authenticating organic food produce, ascertaining whether or not African elephants are guilty of night-time raids on farmers' crops, and linking forensic drug and soil samples from a crime scene to a suspected point of origin. For the sake of brevity, we focus this Minireview on the isotope ratio measurements of lighter-elements common to organic sources; we do not cover the equally important field of inorganic isotope ratio mass spectrometry. His research interests include ion trap development, forensic applications of isotope ratio mass spectrometry and the construction of miniature, portable mass spectrometers. He also teaches workshops on Forensic Applications of Mass Spectrometry.

Consumption of polyunsaturated fatty acids (PUFA) improves the lipid metabolism of diabetics, leading to prevents of arteriosclerosis. Exact relationship between saturated fatty acids (SFA) or PUFA and the insulin resistance of diabetics are unknown. We investigated the relationship between the serum concentrations of saturated and unsaturated fatty acids and the homeostasis model insulin resistance index (HOMA-R) in Japanese patients with type 2 diabetes mellitus. The SFA, i.e., lauric acid, myristic acid, palmitic acid, and stearic acid; the monounsaturated fatty acids (MUFA), i.e., palmitoleic acid, oleic acid, and erucic acid; and the PUFA, i.e., eicosadienoic acid, dihomo-gamma-linolenic acid, docosatetraenoic acid, and docosapentaenoic acid were positively correlated with HOMA-R. However, no correlations were found between HOMA-R and SFA, i.e., arachidic acid, behenic acid, and lignoceric acid; the MUFA, i.e., eicosenoic acid and nervonic acid; and the PUFA, i.e., linoleic aci...

1973. Degradation of polychlorinated biphenyls by two species of Achronzobacfer. Can. J. Microbiol. 19: 47-52. Two species of Achromobacter were isolated from sewage effluent using biphenyl (BP) and p-chlorobiphenyl (PCB) respectively as sole carbon sources. Achrotnobacfer BP grown on biphenyl accumulated a product with an ultraviolet absorption maximum at 257 nm which could not be identified. Washed cell suspensions of both isolates oxidized biphenyl, o-phenylphenol, phenylpyruvate, catechol, p-chlorobiphenyl, m-chlorobiphenyl, o-chlorobiphenyl, o,of-dichlorobiphenyl, and p,pl-dichlorobiphenyl. Both isolates produced meta cleavage products by fission of the benzene ring. However, spectral characteristics of degradation products from respective substrates were different between the two isolates, indicating divergent degradation pathways. Benzoic and p-chlorobenzoic acids were produced from the degradation of BP and PCB, respectively, by Achromobacter PCB. Chloride was not produced by either isolate during the degradation of all chlorobiphenyls tested including the growth of Aclrromobacfer pCB on p-chlorobiphenyl.

A technique using Tenax TA beads as ''sink'' for desorbed solute was employed to measure the kinetics of desorption of chlorobenzenes, polychlorinated biphenyls, and polycyclic aromatic hydrocarbons from laboratory-contaminated sediment. Firstorder rate constants of rapid and slow desorption were in the order of 10 Ϫ1 /h and 10 Ϫ3 /h, respectively. The rate constants of slow desorption correlate well with the molecular volumes of the compounds used and decrease between 2 and 34 d of equilibration. Slowly desorbing fractions increase with both increasing solute hydrophobicity and increasing equilibration time.

Vitellogenins (Vg) are the major precursor of the egg-yolk proteins, vitellins (Vn), which provide energy reserves for embryonic development in oviparous organisms. In mature females, Vg are generally synthesised in response to endogenous estrogens, such as 17β-estradiol (E2), released into the bloodstream and then stored in developing oocytes. In males, the Vg gene, although present, is normally silent. However, it may be activated by (xeno)-estrogens. These substances belong to a large and heterogeneous group of environmental contaminants capable of altering endocrine functions in organisms. For this reason, they are named endocrine disrupting chemicals (EDCs). Natural steroidal estrogens [E2, estrone (E1), estriol (E3)] and synthetic chemicals, such as pesticides, polychlorinated biphenyls (PCBs) and household products (surfactants) are estrogenic compounds widespread in aquatic ecosystems. The main sources of contamination mostly stem (or originate) from municipal and industrial effluents, agricultural practices, livestock wastes and sewage treatment plants (STP). Recently, Vg induction, mainly in males and immature females, has been proposed as a useful biomarker to assess estrogenic contamination in aquatic environments. Indeed, estrogenicity of individual chemicals and mixtures has extensively been evaluated, in both laboratory and field studies, albeit mostly in fish. In contrast, limited attention has centred on evaluating xenoestrogen effects in aquatic invertebrates, probably owing to limited knowledge of their endocrinology. This review focuses on a brief description of xenoestrogens and their occurrence in aquatic environments, and on Vg induction in aquatic invertebrates in response to both experimental and environmental exposure to estrogenic compounds. Results of recent field and laboratory studies are presented. In addition, new perspectives about the use of Vg induction as a biomarker of exposure to estrogenic compounds are also discussed.

China had the highest yield of loquat in the world. Fujian province was the main loquat production area in China. On the basis of the consideration of the thermostability of the enzyme, a new simple and feasible method was developed for its purification. At the first step, the fresh seeds were soaked into 60 • C, 0.01 M pH 6.0 sodium phosphate buffer to wipe off some soluble coloring matters. Then the seeds were homogenized with 5% PVPP (polyvinylpolypyrolidone) in 0.01 M pH 5.0 sodium phosphate-vitamin C buffer. Afterwards, the supernatant was precipitated by 80% saturation of ammonium sulfate, and the enzyme solution was loaded onto a 100 ml DEAE-Sepharose anion exchange chromatograph column (1.6 cm × 50 cm) after dialyzation. All unbound impurities were washed through the column by at least 300 ml 0.01 M sodium phosphate buffer. The column was then eluted with a linear gradient of NaCl (0-0.3 M). Aliquots with the mandelonitrile lyase activity were collected and then concentrated with 60% PEG 20000. Subsequently, a homogeneous enzyme containing FAD as the prosthetic group could be obtained.

Air samples were collected at the urban center, a background site, and the adjacent coastal area of the metropolitan area of Athens during July 2000. Gas and particle phase concentrations of aliphatic hydrocarbons, α,β-hopanes, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and 2,3,7,8-substituted polychlorinated dibenzo-pdioxins and dibenzofurans (PCDD/Fs) were identified and measured. Total concentrations of aliphatic hydrocarbons, ranged from 380.7 ng m -3 (background site) up to 947.0 ng m -3 (coastal area) in the gas and from 154.4 ng m -3 (background site) up to 469.0 ng m -3 (urban center) in the particulate phase. The total concentration of α,β-hopanes (14 homologues) in the urban area was ca. 0.2 ng m -3 in the gas and 1.0 ng m -3 in the particulate phase. Total PAH concentrations (∑PAHs of 20 members) ranged from 3.5 ng m -3 (background site) to 26.0 ng m -3 (urban center) in the gas and from 1.3 ng m -3 (coastal area) up to 5.0 ng m -3 (urban center) in the particulate phase. The total concentration of PCBs (∑PCBs of 54 congeners) in the gas plus the particulate phase of the atmosphere ranged from 85.5 pg m -3 (background site) up to 367.0 pg m -3 (urban center) and the corresponding concentration of PCDD/Fs ranged from 166.6 fg m -3 (background site) up to 701.5 fg m -3 (urban center), respectively. Gas-particle partition coefficient K p of n-alkanes, PAHs, PCBs and PCDD/Fs were well correlated (R 2 = 0.43-0.91) with the subcooled liquid vapor pressure o L P . The average slopes m r of log K p versus log o L P for n-alkanes (-0.46) and PCBs (-0.44) were low compared to other urban areas. The corresponding m r values for PAHs (-0.57), PCDDs (-0.78) and PCDFs (-0.75) are comparable to those obtained in other urban areas.

Results of three hybrid receptor models, potential source contribution function (PSCF), concentration weighted trajectory (CWT), and residence time weighted concentration (RTWC), were compared for locating polychlorinated biphenyl (PCB) sources contributing to the atmospheric concentrations in Chicago. Variations of these models, including PSCF using mean and 75% criterion concentrations, joint probability PSCF (JP-PSCF), changes of point filters and grid cell sizes for RTWC, and PSCF using wind trajectories started at different altitudes, are also discussed.

The bacterial diversity assessed from clone libraries prepared from rRNA (two libraries) and ribosomal DNA (rDNA) (one library) from polychlorinated biphenyl (PCB)-polluted soil has been analyzed. A good correspondence of the community composition found in the two types of library was observed. Nearly 29% of the cloned sequences in the rDNA library were identical to sequences in the rRNA libraries. More than 60% of the total cloned sequence types analyzed were grouped in phylogenetic groups (a clone group with sequence similarity higher than 97% [98% for Burkholderia and Pseudomonas-type clones]) represented in both types of libraries. Some of those phylogenetic groups, mostly represented by a single (or pair) of cloned sequence type(s), were observed in only one of the types of library. An important difference between the libraries was the lack of clones representative of the Actinobacteria in the rDNA library. The PCB-polluted soil exhibited a high bacterial diversity which included representatives of two novel lineages. The apparent abundance of bacteria affiliated to the beta-subclass of the Proteobacteria, and to the genus Burkholderia in particular, was confirmed by fluorescence in situ hybridization analysis. The possible influence on apparent diversity of low template concentrations was assessed by dilution of the RNA template prior to amplification by reverse transcription-PCR. Although differences in the composition of the two rRNA libraries obtained from high and low RNA concentrations were observed, the main components of the bacterial community were represented in both libraries, and therefore their detection was not compromised by the lower concentrations of template used in this study.

With the aim of studying levels of antioxidant and peroxisomal enzymes and the structure of peroxisomes in relation to body burdens of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs), mussels Mytilus gallopro6incialis, oysters Crassostrea sp., crabs Carcinus maenas and mullets Mugil cephalus were sampled in two Basque estuaries (Bay of Biscay): Urdaibai (Laida, Txatxarramendi, Arteaga, and downstream a sewage treatment plant-STP) and Plentzia. In general, animals showed higher concentrations of contaminants in winter than in summer and no relevant differences were detected among locations. Conversely, antioxidant enzyme activities were higher in summer. Enzyme expression was studied in mullets using immunochemical methods. By immunoblotting season-dependent differences were detected for Mn-superoxide dismutase (Mn-SOD). As for the immunohistochemical staining, mullets sampled in summer in Plentzia showed significantly higher optical densities for acyl-CoA oxidase and lower for both Cu,Zn-SOD and Mn-SOD than those collected downstream a STP as well as higher catalase immunostaining than those collected in winter. Peroxisomal volume density (V vp ) of mussels sampled in Laida and Txatxarramendi did not show seasonal variations, while for oysters collected in Laida and Arteaga V vp was higher in summer. Crab and mullet V vp were also higher in summer. In conclusion, the estuaries of Urdaibai and Plentzia can be considered as low to moderately polluted areas and levels of PAHs and PCBs do not show marked variations apart from seasonal variations. Animals can be adapted to low pollution conditions and, under these circumstances, seasonal factors might affect biomarker responses to a greater extent than pollution variations.

PAHs and PCBs were measured in the mussel Perumytilus purpuratus (Lamarck) collected from three different sites along the coast of Valdivia and Valparaiso, South-Central and Central Chile, respectively. Pollution at these sites is considered low with PAHs originating mainly from pyrolytic sources according to the Phenanthrene/Anthracene and Fluoranthene/Pyrene ratios. Temporal variation of PAHs was observed in Valdivia, while site variation was observed along the Valparaiso area. Total PAH concentrations in Valdivia ranged from 29.2 ng/g to 89.5 ng/g in 2001 and from 31.0 ng/g to 48.6 ng/g in 2002 while in Valparaiso samples the total PAHs ranged from 27.3 ng/g to 253.1 ng/g and from 12.1 ng/g to 26.3 ng/g in 2001 and 2002, respectively. Polychlorinated biphenyls were not found in mussels from Valdivia; however five non-planar congeners were detected in samples from Valparaiso with total concentrations between 1.0 ng/g and 16.6 ng/g in 2001 and between 3.4 ng/g and 29.0 ng/g in 2002. The pesticide heptachlor epoxide was detected in all sampling sites of Valdivia during the years 2001-2002 at concentrations ranging between 1 and 3.5 ng/g.

Research on environmentally related chemical contaminants in breast milk spans several decades and dozens of countries. The ability to use this research as an environmental indicator is limited because of a lack of consistent protocols. Data on xenobiotics in breast milk are influenced by choices in sample selection, sample pooling, analysis, and reporting. In addition, most studies have focused only on a small panel of persistent organic pollutants, despite indications that a wide range of additional chemical contaminants may also enter breast milk. Despite these limitations, however, it is possible to draw some generalizations. In this paper we review available data on levels of organochlorine pesticides, polychlorinated biphenyls (PCBs), polychlorinated dibenzodioxins (PCDDs), polybrominated diphenyl ethers (PBDEs), metals, and solvents in breast milk. Examples drawn from around the world illustrate the available data and the patterns that have appeared in various areas over time. Over the past few decades, levels of the organochlorine pesticides, PCBs, and dioxins have declined in breast milk in countries where these chemicals have been banned or otherwise regulated. In contrast, the levels of PBDEs are rising. Regional differences in levels of xenobiotics in breast milk are related to historical and current local use patterns. Diet is a major factor that influences breast milk levels of persistent organic pollutants, with patterns in fish consumption playing a particularly significant role. Improved global breast milk monitoring programs would allow for more consistent data on trends over time, detection of new xenobiotics in breast milk, and identification of disproportionately exposed populations.

BACKGROUND: Obesity, an inflammatory condition linked to cardiovascular disease, is associated with expansion of adipose tissue. Highly prevalent coplanar polychlorinated biphenyls (PCBs) such as 3,3´,4,4´-tetrachlorobiphenyl (PCB-77) accumulate in adipose tissue because of their lipophilicity and increase with obesity. However, the effects of PCBs on adipocytes, obesity, and obesity-associated cardiovascular disease are unknown. OBJECTIVES: In this study we examined in vitro and in vivo effects of PCB-77 on adipocyte differentiation, proinflammatory adipokines, adipocyte morphology, body weight, serum lipids, and atherosclerosis. METHODS: PCB-77 or 2,2´,4,4,5,5´-hexachlorobiphenyl (PCB-153) was incubated with 3T3-L1 adipocytes either during differentiation or in mature adipocytes. Concentration-dependent effects of PCB-77 were contrasted with those of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). For in vivo studies, we treated C57BL/6 wild-type (WT) or aryl hydrocarbon receptor (AhR) -/mice with vehicle or PCB-77 (49 mg/kg, by intraperitoneal injection) and examined body weight gain. In separate studies, we injected ApoE -/mice with vehicle or PCB-77 over a 6-week period and examined body weight, adipocyte size, serum lipids, and atherosclerosis. RESULTS: Low concentrations of PCB-77 or TCDD increased adipocyte differentiation, glycerol-3phosphate dehydrogenase activity, and expression of peroxisome proliferator-activated receptor γ, whereas higher concentrations inhibited adipocyte differentiation. Effects of PCB-77 were abolished by the AhR antagonist α-naphthoflavone. PCB-77 promoted the expression and release of various proinflammatory cytokines from 3T3-L1 adipocytes. Administration of PCB-77 increased body weight gain in WT but not AhR -/mice. ApoE -/mice injected with PCB-77 exhibited greater body weight, adipocyte hypertrophy, serum dyslipidemia, and augmented atherosclerosis. CONCLUSIONS: Our findings suggest that PCB-77 may contribute to the development of obesity and obesity-associated atherosclerosis. KEY WORDS: adipocyte differentiation, aryl hydrocarbon receptor, ectopic lipid deposition, obesity, polychlorinated biphenyl.