Polychlorinated biphenyls (PCBs) are persistent organic pollutants which were not produced in Turkey, however both national and international studies illustrate a measurable amount of PCB pollution in receiving environments, aquatic fauna and people. In this study, various information sources such as the national and international scientific literature, official records and reports are investigated to obtain information regarding PCB pollution in Turkey. Furthermore, various PCB pollution analysis techniques for soil/sediment samples are investigated and the selected methods are established in the laboratories of METU. Satisfactory recoveries are obtained for methods for the extraction of PCBs, clean-up of extract and gas chromatographic (GC/ECD) analysis of the sample. Finally, field studies are performed in two locations in Ankara. The first one is a preliminary pollution investigation study around Lake Eymir. Lake Eymir is suspected to be contaminated with PCBs due to a nearby transformer repair facility. The second, more detailed study is performed for a 25 km reach of Ankara Creek, passing through the Industrial Zone, Sincan Dumpsite and Ankara Central Wastewater Treatment Plant. Total- PCB concentrations are in the range of 0.2 and 777 ng/g with the median of 37.1 ng/g. Toxic Equivalent Concentrations (TEQ) are assessed for dioxin-like congeners and Aroclor 1016/1260 basis. A Chemical Mass Balance Model is used to identify and apportion the sources of PCBs for Ankara Creek samples. Typically highly chlorinated Clophen mixtures are identified in sediments as the pollution sources.

This study examines the application of two receptor models, namely Positive Matrix Factorization (PMF) and Chemical Mass Balance (CMB), on the investigation of sites contaminated with PCBs. Both models are typically used for apportionment of pollution sources in atmospheric pollution studies, however have gained popularity in the last decade on the investigation of PCBs in soil/sediments. The aim of the study is four-fold / (i) to identify the status of PCB pollution in Lake Eymir area via sampling and analysis of PCBs in collected soil/sediment samples, (ii) to modify the CMB model software in terms of efficiency and user-friendliness (iii) to apply the CMB model to Lake Eymir area PCB data for apportionment of the sources as well as to gather preliminary information regarding degradation of PCBs by considering the history of pollution in the area (iv) to explore the use of PMF for both source apportionment and investigation of fate of PCBs in the environment via use of Monte-Carlo simulated artificial data sets. Total PCB concentrations (Aroclor based) were found to be in the range of below detection limit to 76.3 ng/g dw with a median of. 1.7 ng/g dw for samples collected from the channel between Lake Mogan and Lake Eymir. Application of the CMB model yield contribution of highly chlorinated PCB mixtures (Aroclor 1254 and Aroclor 1260 / typically used in transformers) as sources. The modified CMB model software provided user more efficient and user friendly working environment. Two uncertainty equations, developed and existing in literature, were found to be effective for better resolution of sources by the PMF model.

This study aims to investigate the fate of polychlorinated biphenyls (PCBs) in sediments via using an anaerobic dechlorination model (ADM). PCBs are ubiquitous environmental pollutants, accumulated mostly in aquatic sediments. Significant attention was placed on the anaerobic dechlorination of PCBs since this process leads to the conversion of highly-chlorinated biphenyls to lower chlorinated ones, resulting in less toxic and more biodegradable congeners. An ADM was developed previously for the identification and quantification of anaerobic dechlorination pathways. In the present study, this model was improved and applied to laboratory and environmental sediment PCB data from Baltimore Harbor (BH), Maryland, USA, where PCB contamination has been recorded. The laboratory PCB data was from a 500 day microcosm study conducted with BH sediments which was used to validate the model, as well as to gather information on dominant dechlorination pathways affecting the sediments. ADM predicted the laboratory PCB data almost perfectly and subsequently very well predicted the environmental sediment PCB profiles. A complete identification and quantification of the anaerobic dechlorination pathways occurring in the BH sediments is achieved with this study for the first time. The significant similarity between the sediment sample PCB profiles and the model predicted profiles reveals that the BH sediments have undergone anaerobic dechlorination via a combination of previously identified dechlorination activities (N, P, M) with selective pathways. Model findings are consistent with microbial analysis of the sediments. Better understanding of anaerobic dechlorination mechanisms should aid in predicting natural attenuation of PCBs or developing bioremediation strategies for contaminated sites.

This paper uses the case of Polychlorinated Biphenyls (PCBs) to examine the dynamics of the public policy cycle in Canada. A process approach is applied to examine the principal stages of the cycle: problem identification, agenda-setting, decision-making, and implementation. In examining these stages, the factors that drive the policy cycle and those that impede its progress are identified. The regulatory history of PCBs is traced to demonstrate some of the complexities of the policy cycle. As one of the better known hazardous wastes in Canada, PCBs have been the catalyst for the introduction of new toxic chemical regulations throughout the 1970s and 1980s. Since the late 1970s, regulatory policies have been developed and implemented for PCB use and handling. After major PCB accidents occurred during the second half of the 1980s, regulations were introduced for their transport, storage and disposal. This case study provides seven major conclusions: (1) before the right policy solution is found and implemented, several stages in the cycle may need to be repeated; (2) public perception is a key determinant of the policy problem; (3) focusing events are a critical factor in setting the agenda; (4) decision-making often takes an incremental approach due to incomplete information and divided policy jurisdictions; (5) successful implementation, particularly in divided jurisdictions, requires sympathetic officials who are supportive of the enabling legislation; (6) constituency group support is a necessary condition for policy implementation; and (7) to deal with public concerns which may impede the implementation process, officials need political and managerial skills.

In 2001, a population-based cross-sectional study was conducted to compare levels of total polychlorinated biphenyls (PCBs) in residents of Calcasieu Parish and Lafayette Parish, Louisiana. A demographic, lifestyle, and food consumption questionnaire was collected for each participant. Overall, weighted geometric means and medians of total serum PCB concentrations in residents of Calcasieu and Lafayette Parishes were similar among all risk subgroups. However, 15-29 year olds had higher total serum PCB weighted geometric means in Calcasieu (64.4 ppb) than did this age group in Lafayette (46.6 ppb) (p=0.0059); conversely, in the 60 and older age group, geometric means of 293.7 ppb and 392.5 ppb were observed for Calcasieu and Lafayette, respectively (p=0.0059). In general, total PCB serum levels in Calcasieu and in Lafayette Parish, Louisiana residents were similar to each other and to levels observed in the U.S. general population in this time period.

No description available.

Eighteen-month-old adult female Peking Ducks (Anas platyrhynchos) were placed in the Ottawa, and St. Lawrence rivers for periods varying between 14 and 72 days during the summers of 1987, 1988 and 1989. Two stations located on Lake St. Francis were selected for establishing a time-curve for the accumulation of organochlorine pesticides (OC) and PCB in the liver. The ducks rapidly lost weight during their first 20 days in the natural environment but stabilised after about 40 days. This weight loss was caused by the stress of habitat, change, the energetic costs in searching for food and moulting. / There was a rapid increase in the number and concentration of contaminants detected in the livers of ducks exposed to pollutants in the natural environment. The concentrations found were low (99.9% of OC-PCB are under 1 mg/kg wet weight basis). These individuals were generally from 10 to 1000 times more contaminated than the control ducks for 40 days of exposure. / The use of domestic ducks as bioindicators has several advantages. They can be obtained readily and cheaply, and the sex and age of the individuals can be controlled. Since they are not very mobile and therefore are easy to locate, they provide information on the contamination (metals or OC-PCB) of specific sites. The use of Peking ducks has some limitations. There is a need for appropriate habitats to ensure their survival, and there is considerable stress caused by transferring the ducks from the breeding farm to the natural environment, thereby obliging them to search for food and exposing them to predators and poachers. (Abstract shortened by UMI.)

A major factor complicating the cleanup at many sites is co-contamination by both organic compounds and heavy metals. Whereas much research has focused on the removal of either organic compounds or metals, relatively few studies have investigated simultaneous removal of organic and inorganic pollutants from soil. / The studies reported in this thesis have evaluated a novel technique for the simultaneous mobilization of polychlorinated biphenyl (PCB) compounds and heavy metals (HMs) from a field contaminated soil. Soil extraction with washing aids {surfactants/cyclodextrin in combination with chelating reagent(s)} was optimized for mobilization efficiency, recovery/recycle of washing additives, and in parallel detoxification of mobilized contaminants. PCB extraction efficiencies were determined with a method that converted all the PCB congeners to dicyclohexyl by hydrogenation over palladium. Studies demonstrated that 10 minutes of ultrasonic mixing of field contaminated soil with a combination of surfactant (30 mL L-1) or cyclodextrin (100 g L-1) and a sparing quantity (2 mmoles) of EDTA, simultaneously mobilized appreciable quantities of PCBs and most analyte metals (Cd, Cu, Mn, Pb, Zn, Ni, Cr). / Relative to individual reagents, combinations of surfactant (Brij 98, Triton X-301, or Triton XQS-20) or cyclodextrin (RAMEB or HPCD) with EDTA did not influence PCB extraction efficiencies perceptibly. The presence of surfactant or cyclodextrin in admixture with EDTA did not appreciably change the efficiency of mobilization of most heavy metals (Al, Cd, Cr, Fe, Mn, Ni, and Zn) but did increase the recovery of Cu and Pb with nonionic surfactant and cyclodextrin. When coupled with PCB removal by hexane back-extraction and precipitation of the HMs (mediated by hydrolysis of zero-valent magnesium (Mg0)}, aqueous washing suspension was regenerated and recycled twice to mobilize more contaminants from the soil. Three sonication-washes with the same charge of reagent mobilized appreciable quantities of PCBs (68 - 83%) and virtually all of the available Cd, Cu, Mn, and Pb and lesser amounts of the Zn (56%), Ni (59%), and Cr (50%) but only small quantities of Al (28%) and Fe (30%). / The release of EDTA from heavy metals complexes was efficient for most metals (99%) but was influenced by the nature of surfactant. EDTA recovery (62-65%) post three cycles of soil washing, hexane back-extraction, and Mg 0 treatment was similar for all reagent combinations. Among surfactants and cyclodextrin, only anionic surfactants suffered losses to Mg0 treatment.

<p>Single-walled carbon nanotubes (SWNT) are highly ordered filamentous nanocarbon structures. As their commercial and industrial use becomes more widespread, it is anticipated that SWNT will enter the environment through waste streams and product degradation. Because of their highly hydrophobic nature, SWNT aggregate and settle out of aqueous environments, especially in saline environments such as estuaries. Therefore, sediments are a likely environmental sink for SWNT once released. It is important to understand how these materials will impact benthic estuarine systems since they are the probable target area for SWNT exposure in addition to containing many lower trophic level organisms whose survvial and contaminant body burdens can have a large impact on the overall ecosystem. Disruptions in lower trophic level organism survival can have negative consequences for higher trophic levels, impacting the overall health of the ecosystem. It is also important to consider contaminant bioaccumulation, trophic transfer and biomagnification. If SWNT are taken up by benthic invertebrates, there is the possibility for trophic transfer, increasing the exposure of SWNT to higher trophic level organisms that otherwise would not have been exposed. If this type of transfer occurs in environmentally important species, the potential for human exposure may increase. My research aims to determine the magnitude of the toxicity and bioaccumulation of SWNT in benthic estuarine systems, as well as determine how they interact with other contaminants in the environment. This research will contribute to the knowledge base necessary for performing environmental risk assessments by providing information on the effects of SWNT to benthic estuarine systems. </p><p> Before investigating the environmental effects of SWNT, it is imperative that a measurement method is established to detect and quantify SWNT once they enter the environment. This research utilized pristine, semiconducting SWNT to develop extraction and measurement methods to detect and quantify these specific materials in environmental media using near infrared fluorescence (NIRF) spectroscopy. Semiconducting SWNT fluoresce in the near infrared (NIR) spectrum when excited with visible&ndashNIR light. This unique optical property can be used to selectively measure SWNT in complex media. </p><p> The fate, bioavailability, bioaccumulation and toxicity of SWNT have not been extensively studied to date. Pristine SWNT are highly hydrophobic and have been shown to strongly associate with natural particulate matter in aquatic environments. In light of this, I have focused my research to examine the influence of sediment and food exposure routes on bioavailability, bioaccumulation, and toxicity of structurally diverse SWNT in several ecologically-important marine invertebrate species. No significant mortality was observed in any organism at concentrations up to 1000 mg/kg. Evidence of biouptake after ingestion was observed for pristine semiconducting SWNT using NIRF spectroscopy and for oxidized <super>14</super>C&ndashSWNT using liquid scintillation counting. After a 24 hour depuration period, the pristine semiconducting SWNT were eliminated from organisms to below the method detection limit (5 &mug/mL), and the <super>14</super>C&ndashSWNT body burden was decreased by an order of magnitude to a bioaccumulation factor (BAF) of <0.01. Neither pristine SWNT nor oxidized <super>14</super>C&ndashSWNT caused environmentally relevant toxicity or bioaccumulation in benthic invertebrates. Overall, the SWNT were not bioavailable and appear to associate with the sediment.</p><p> In addition to investigating the toxicity and bioaccumulation of SWNT as an independent toxicant, it is important to consider how they will interact with other contaminants in the environment (i.e., increase or decrease toxicity and bioaccumulation of co&ndashcontaminants, alter the environmental transport of co&ndashcontaminants, induce degradation of co&ndashcontaminants, etc.). I wanted to investigate the effects of SWNT on a complex mixture of contaminants already present in a natural system. New Bedford Harbor (NBH) sediment, which is contaminated with polychlorinated biphenyls (PCBs), was amended with pristine SWNT to determine if the presence of SWNT would mitigate the toxicity and bioaccumulation of the PCBs in deposit-feeding invertebrates. A dilution series of the NBH sediment was created using uncontaminated Long Island Sound (LIS) sediment to test 25% NBH sediment, 50% NBH sediment, 75% NBH sediment, and 100% NBH sediment. The results of this work showed increased organism survival and decreased bioaccumulation of PCBs in treatments amended with SWNT, with the greatest reduction observed in the 25% NBH sediment treatment group amended with 10 mg SWNT/g dry sediment. Polyethylene (PE) passive samplers indicated a reduction of interstitial water (ITW) PCB concentration of greater than 90% in the 25% NBH sediment + 10 mg SWNT/g dry sediment amendment. The ITW concentration was reduced because PCBs were not desorbing from the SWNT. Lower bioavailability leads to reduced potential for toxic effects, supporting the observation of increased survival and decreased bioaccumulation. Once in the sediment, not only are SWNT not bioavailable, they act as a highly sorptive phase, such as black carbon (BC), into which hydrophobic organic contaminants (HOCs), such as PCBS and polycyclic aromatic hydrocarbons (PAHs), can partition, thereby reducing the toxicity and bioavailability of co-occurring HOCs.</p><p> To more fully understand the impact of SWNT in this environment, their biodegradability also needs to be investigated. Biodegradation of SWNT could lead to release and/or transformation of sorbed HOCs as well as a change in the inherent transport, toxicity, and bioaccumulation of SWNT in the estuarine environment. Because the persistence of SWNT will be a primary determinant of the fate of these materials in the environment, I conducted experiments to determine if the fungus <italic>Trametes versicolor</italic>, the natural bacterial communities present in NBH sediment, and municipal wastewater treatment plant sludge could degrade or mineralize oxidized <super>14</super>C&ndashSWNT. Over a six month time period, no significant degradation or mineralization was observed. In all treatments, approximately 99% of the 14C-SWNT remained associated with the solid phase, with only approximately 0.8% of added <super>14</super>C present as dissolved species and only 0.1% present as <super>14</super>CO₂. These small pools of non-SWNT <super>14</super>C were likely due to trace impurities, as no differences in production were observed between treatments and abiotic (killed) controls.</p> / Dissertation

Cardiovascular diseases are the number one cause of death in Western societies. Endothelial dysfunction is an early event in the pathology of atherosclerosis, which is an underlying cause in the majority of cardiovascular events. Exposure to persistent environmental pollutants, such as polychlorinated biphenyls (PCBs), is a risk factor for the development of atherosclerosis. First, we tested a hypothesis that coplanar PCBs, dioxin-like chemicals with affinity for aryl hydrocarbon receptor (AhR), can stimulate up-regulation of monocyte chemoattractant protein-1 (MCP-1), an endothelium-derived chemokine that attracts monocytes into sub-endothelial space in early stages of atherosclerosis. Coplanar PCBs 77 and 126 increased expression of MCP-1 in endothelial cells, and this effect was dependent on activation of AhR and increased levels of cytochrome P450 monoxygenases. Subsequent rise in the levels of reactive oxygen species (ROS) led to a downstream stimulation of redox-sensitive kinases and transcription factors. Lipid rafts, and particularly caveolae, are enriched in endothelial cells, and down-regulation of caveolin-1, a key structural protein of caveolae, decreases the progression of atherosclerosis. Studies using deletion of caveolin-1 in vitro and in vivo demonstrated that intact caveolae were required for up-regulation of MCP-1 and pro-inflammatory interleukin-6 (IL-6) by PCB77. Nutrition can modulate adverse outcomes of human exposure to environmental chemicals. Fish oil-derived long-chain omega-3 polyunsaturated fatty acids, such as docosahexaenoic acid (DHA, 22:6ω-3), can alleviate inflammatory responses and the risk of cardiovascular disease. Cyclopentenone metabolites produced by oxidation of DHA contribute to these protective effects. Endothelial cells were pre-treated with oxidized DHA (oxDHA), prepared by incubation of the fatty acid with a free radical generator. Subsequent up-regulation of MCP-1 by coplanar PCB77 was markedly reduced. DHA-derived cyclopentenones increased nuclear translocation and DNA binding of a transcription factor NF-E2-related factor-2 (Nrf2), as well as expression levels of its target, antioxidant enzyme NAD(P)H:quinone oxidoreductase (NQO1). This stimulation of antioxidant responses prevented ROS production and inflammatory responses induced by PCB77. These data support the concept that nutrition prevents toxicity caused by environmental pollutants; thus, nutrition and can be a sensible approach to alleviate chronic pathologies associated with these chemicals.