Devido à alta toxicidade, a produção e comercialização dos PCBs (Polychlorinated Biphenyls - Bifenilas Policloradas) estão proibidas no mundo todo. Esses compostos foram utilizados principalmente como base de misturas comerciais em óleos dielétricos para transformadores e capacitores. Hoje existem diversas áreas contaminadas com essas substâncias que são de difícil degradação ocasionada pela sua elevada estabilidade térmica e química. Há diversos estudos sobre diferentes técnicas de tratamento de áreas contaminadas por PCBs. A técnica proposta nesse trabalho foi a de oxidação química através do reagente de Fenton. Para isso, foi simulado em laboratório experimentos de tratamento de solo contaminados artificialmente por ascarel (mistura comercial de PCBs). A oxidação foi realizada segundo a técnica do planejamento experimental fatorial de dois níveis e duas variáveis. Manteve-se constante a concentração do contaminante - em torno de 6000 mg de PCB/ kg de solo - e variou-se a concentração de Fe2+ (0,04 a 0,1 mol/L) e H2O2 (2,07 a 4,15 mol/L). Os ensaios foram realizados ainda nos seguintes tempos de reação: 0, 5, 24 e 48 horas. A análise dos dados foi realizada através de cromatografia gasosa acoplada a um espectrômetro de massa - GC/MS. Dos resultados, concluiu-se que o experimento cuja concentração do reagente de Fenton era 4,15 mol/L de H2O2 e 0,04 mol/L de Fe2+, apresentou melhor percentual de remoção, em torno de 76% para o pentaclorobifenila, 67% para o hexaclorobifenila e 72% para o heptaclorobifenila. Além disso, observou-se que, dentro da região experimental estudada, o efeito da concentração de íons ferrosos foi mais significativo do que o causado pela concentração de peróxido de hidrogênio e que o mesmo tem um efeito negativo pois aumentando a concentração dos íons ferrosos diminui-se a remoção dos contaminantes. / Production and trading of polychlorinated biphenyls (PCBs) are prohibited at whole world due to their high toxicity. They were used mainly as dielectric oils for transformers and capacitors. Recently there are many contaminated areas with these compounds. The high thermic and chemistry stability of PCBs are responsible for their hard degradation. Many studies have been conducted about several techniques of soil remediation. The main purpose of this research is to study chemical oxidation using Fenton\'s reagent to soils treatment. It was simulated in laboratory experiments of soil treatment which was artificially contaminated with Ascarel (PCBs commercial mixture). Process oxidation was made according to factorial experimental planning technique of two levels and two variables (22). The contaminant concentration was constant - 6000 mg PCB/ kg soil - and it was varied the Fe2+ concentration (0,04 mol/L to 0,10 mol/L) and H2O2 concentration (2,07 mol/L to 4,15 mol/L). The times reaction of experiments were: 0, 5, 24 and 48 hours. It was used gas chromatography coupled with mass spectrometer - GC/MS. The better result shown removal rate of 76% to pentachlorobiphenyl, 67% to hexachlorobiphenyl and 72% to heptachlorobiphenyl, experimental conditions were Fe2+ concentration of 0,04 mol/L and H2O2 concentration of 4,15 mol/L. Besides it was observed that studied region the concentration effect of ferrous ions was more significant than concentration effect of hydrogen peroxide. The concentration effect of ferrous ions was negative on system because removal rate of contaminants decreases when [Fe2+] increases.

Introdução: Dioxinas, furanos e bifenilas policloradas são poluentes tóxicos para a saúde humana incluindo riscos de incidência de cânceres, efeitos de neurodesenvolvimento, lesões dérmicas, cloroacne. Estes compostos são poluentes orgânicos persistentes (POPs) que podem ser transportados de longas distâncias da fonte de emissão e se bioacumular em ecossistemas. A atmosfera poluída foi recentemente classificada como carcinogênica para os seres humanos pela Organização Mundial da Saúde, mostrando a importância de sua caracterização, principalmente para compostos tóxicos. Entretanto, técnica de coleta ativa tem custo elevado para POPs, e existem poucos estudos de calibração que validem a substituição. Objetivos: Avaliar a toxicidade equivalente da atmosfera por dioxinas, furanos e bifenilas cloradas, utilizando técnicas de coleta ativa e passiva, e verificar gradiente de concentração nos ambientes urbano, urbano/industrial e de background. Método: Amostras de ar foram coletadas, utilizando coletores ativos e passivos, durante dois períodos consecutivos de quatro meses: de setembro a dezembro de 2014 (período 1) e de maio a agosto de 2015 (período 2) em três cidades de São Paulo, SP, em ambientes urbano, urbano/industrial e de background. Todas as amostras foram extraídas com solução de tolueno:acetona (9:1) em Soxhlet por 24 h e padrões marcados (13C12-PCDD/Fs e 13C12-PCBs) foram adicionados em cada amostra antes do processo de extração. Os extratos foram purificados em coluna de sílica mista (40 por cento H2SO4 e 10 por cento AgNO3) seguida por coluna de alumina. O procedimento analítico foi realizado utilizando HRGC/HRMS (High Resolution Gas Chromatograph/High Resolution Mass Spectrometer) operando em ionização de impacto de elétrons com energia de 35 eV no modo SIM (Select Ion Monitoring) e resolução de 10.000. Resultados mostraram que: (1) existe variação sazonal para concentrações de PCDD/Fs no ar entre os períodos 1 e 2 (p=0,03), enquanto as concentrações de dl-PCBs não foram estatisticamente diferentes nestes períodos (p=0,52); (2) existe gradiente de concentração de PCDD/Fs e dl- PCBs que aumenta na seguinte ordem: background<urbano<urbano/industrial, porém não foi encontrada diferença significante entre as concentrações dos locais urbano e urbano/industrial para as amostras da coleta ativa; (3) as concentrações de PCDD/Fs e dl-PCBs das amostras do coletor ativo variaram de 9,34 a 221 fg TEQ/m³ no período 1, e entre 7,76 a 453 fg TEQ/m³ no período 2; nas amostras dos coletores passivos estas concentrações variaram de 6,11 a 32,2 fg TEQ/m³ no período 1, e entre 48,6 e 298 fg TEQ/m³ no período 2; (4) a estimativa da taxa de coleta utilizando duas abordagens diferentes mostrou discrepâncias. Conclusões: Os resultados dos coletores ativos e passivos estão em boa concordância em termos de tendências espacial e temporal, assim como os perfis de congêneres e grupos homólogos, a coleta passiva com disco de PUF mostrou-se como uma técnica adequada para determinação de PCDD/Fs e dl-PCBs / Introduction: Dioxins, furans and polychlorinated biphenyls are toxic pollutants for human health including risks of cancer incidence, neurodevelopmental effects, dermal lesions, chloracne. These compounds are persistent organic pollutants (POPs) that can be transported to long distances from the emission source and they are bioaccumulated in ecosystems. Recently, the outdoor air pollution were classified as carcinogenic to humans by the World Health Organization, showing the importance of its characterization for toxic compounds. However, active air monitoring has a high cost for POPs, and there is a few calibration studies which support that substitution. Objective: To assess the equivalent toxicity of the atmosphere regarding the measurement of dioxins, furans and polychlorinated biphenyls, using active and passive air samplers, and to evatuate the contrasting concentrations at urban, urban/industrial and background sites. Method: Air samples were collected, using active and passive samplers, over two consecutive periods of four months: from September to December 2014 (period 1) and from May to August 2015 (period 2) at three cities in São Paulo, SP, covering urban, urban/industrial and background sites. All samples were extracted with toluene:acetone (9:1) in a Soxhlet apparatus for 24 hours and surrogate standards (13C12-PCDD/F and 13C12-PCBs) were spiked on each sample media prior to extraction procedure. The extracts were purified on an silica column (40 per cent H2SO4 and 10 per cent AgNO3) followed by an alumina column. The analytical procedure was carried out using HRGC/HRMS (High Resolution Gas Chromatograph/High Resolution Mass Spectrometer) operating in electron impact ionization with an energy of 35 eV in SIM (selected ion monitoring) mode and 10.000 resolution power. Results show that (1) there are seasonal variations for PCDD/F concentrations in air between period 1 and 2 (p=0.03), whereas dl-PCB levels were not statistically different (p=0.52) in those periods. (2) PCDD/F and dl-PCB air levels are in the following order: background <urban <urban/industrial for both active and passive samplers; (3) PCDD/F and dl-PCB concentrations in active air samples ranged from 9.34 to 221 fg TEQ/m³ in period 1, and between 7.76 and 453 fg TEQ/m³ in period 2; in the passive air samples, these concentrations ranged from 6.11 to 32.2 fg TEQ/m³ in period 1, and between 48.6 and 298 fg TEQ/m³ in period 2; (4) the estimation of sampling rate using two approachs for PCDD/Fs showed differences. Conclusions: Passive and active air sampling results are in good agreement in spatial terms and temporal trends, as are the congener and homologue profiles, showing that passive air sampling of PUF disk is a powerful sampler for PCDD/F and dl-PCB measurements

Polychlorinated biphenyls (PCBs) are synthetic organic chemicals that persist in the environment and are known to be carcinogenic to humans. Virtually all of the deleterious effects of PCB 126, the most potent dioxin-like PCB, are mediated by the aryl hydrocarbon receptor (AhR). By means of the common cofactor ARNT, the AhR signaling pathway can crosstalk with the hypoxia signaling pathway. Regulated by hypoxia-inducible factors (HIFs), the hypoxia pathway mediates responses to environments of reduced oxygen availability (hypoxia). This dissertation specifically examines the crosstalk and interference between these two pathways in the context of PCB 126 exposure. The results of this dissertation show that the antagonistic relationship between the AhR and hypoxia signaling pathways affects the function and responses of both AhR and HIF-1Α. We provide substantial evidence that ARNT is indeed a crucial factor in both the AhR and HIF-1Α signaling pathways. Furthermore, this dissertation examines regulatory mechanisms involved in AhR-mediated gene expression and identifies epigenetic regulation as a critical factor in AhR target gene expression. In summary, this dissertation helped to improve the understanding of mechanisms of PCB 126 toxicity. Understanding the detrimental biological effects of these ubiquitous environmental pollutants might ultimately have significant implications for human health.

Our understanding about the presence, behavior, and toxicities of atmospheric persistent organic pollutants is limited by our ability to accurately measure them. This dissertation details the development and characterization of a model for the determination of an accurate sampling rate (Rs), and effective sampling volume (Veff), for polyurethane equipped passive air samplers (PUF-PAS), and the subsequent application of PUF-PAS sampling methods towards novel applications studying polychlorinated biphenyls (PCBs). The user friendly mathematical model resulting from this work, published as a Matlab script, predicts Rs and Veff as a function of local hourly meteorology and the physical-chemical properties of the target analytes. The model was first developed using active sampling methods in urban Chicago, where good agreement was found between the PUF-PAS and high volume active samplers: Active/Passive = 1.1 ± 1.2. The model was then expanded and calibrated globally using the dataset from the Global Atmospheric Passive Sampling (GAPS) network. After this global calibration we found acceptable agreement between modelled and depuration-determined sampling rates for an independent dataset, with several compounds having near zero mean percent bias (±6%). The globally applicable model is the best alternative for locations experiencing low average wind speeds or cold temperatures, and is particularly useful for the interpretation of samples with long deployments, deployments conducted under warming conditions, and compounds with high volatility. An interactive web-based graphical user interface for the sampling rate model was developed. Users input sampler locations, deployment dates, and target chemicals, in the web-interface and are provided with a sample and compound specific Rs and Veff. The sampling rate model was examined for use in the indoor environment and it was found that both the experimentally calibrated (1.10 ± 0.23 m3 d-1) and modeled (1.08 ± 0.04 m3 d-1) Rs agreed with literature reports. Correlating sample specific wind speeds with uptake rates, it was determined that variability of wind speeds throughout the room significantly (p-value < 0.001) affected uptake rates. Despite this, the PUF-PAS concentration measurements using modelled Rs values were within 27% of the active sampling determined concentration measurements. Using PUF-PAS samplers, PCBs 47, 51, and 68 were found to account for up to 50% of measured indoor sum PCB concentration (2700 pg m-3). Direct surface measurements were conducted to identify finished cabinetry to be a major source, as a result of the decomposition of 2,4-dichlorobenzoyl peroxide used as an initiator in free-radical polymerization of polyester resins. While this phenomenon has been detected at trace levels in other polymer products, it has never been shown to be a significant environment source of PCBs. PUF-PAS samplers were similarly used to study the presence of airborne hydroxylated polychlorinated biphenyls (OH-PCBs) and PCBs in the metropolitan Chicago area. While OH-PCBs have been hypothesized to be an important removal mechanism for atmospheric PCBs, they were not directly measured in the air until recently. The two most frequently detect OH-PCB congeners in this study, 2OH-PCB2 and 6OH-PCB2, were detected at levels comparable to a previous report of atmospheric OH-PCBs utilizing active sampling methods, suggesting the viability of PUF-PAS methods to study atmospheric OH-PCBs. One sampling site detected as many as 50 OH-PCBs but uncertainties with sampling and laboratory methods prevent any strong conclusions from being drawn.

Industrial chemicals known as polychlorinated biphenyls (PCBs) were widely used for decades until their production was banned worldwide due to their persistence and toxicities to humans and other animals. Upon oxidative metabolism by cytochrome P450, hydroxylated metabolites of PCBs (OHPCBs) are formed. OHPCBs have been shown to competitively displace thyroxine from transthyretin, block normal hormonal activity, and inhibit phenol or family 1 sulfotransferases (SULTs) which catalyze sulfation of thyroid hormones and estrogens. Recently, three OHPCBs were shown to also interact with hydroxysteroid or family 2 sulfotransferases that play a role in the homeostasis of steroid hormones such as dehydroepiandrosterone (DHEA). The objectives of the studies presented in this thesis were to further examine the effects of selected OHPCBs on the activity of human hydroxysteroid sulfotransferase (hSULT2A1), to develop a three-dimensional quantitative structure activity relationship (3D-QSAR) model for OHPCBs as inhibitors of DHEA-sulfation catalyzed by this enzyme, and to investigate the mechanism of inhibition and binding of OHPCBs to hSULT2A1. All 15 OHPCBs examined inhibited the sulfation of 1 μ M [3H] DHEA, catalyzed by hSULT2A1 with IC50 values ranging from 0.6 to 96 μ M. The OHPCBs with a 3, 5-dichloro-4-hydroxy substitution were the most potent inhibitors of DHEA sulfation, and they were also shown to be substrates for hSULT2A1. Eight OHPCBs were substrates for hSULT2A1, and seven were solely inhibitors (i.e. they inhibited the sulfation of DHEA, yet they were not themselves sulfuryl-acceptors in hSULT2A1-catalyzed reactions). A 3D-QSAR model was developed utilizing comparative molecular field analysis (CoMFA). The model fit the data well and also had good predictability. The kinetics of inhibition showed that these OHPCBs were noncompetitive inhibitors of hSULT2A1. Binding studies utilizing the displacement of a fluorescent probe, 8-anilino-1-naphthalene sulfonic acid, revealed that several of the OHPCBs interact either at more than one binding site or with more than one enzyme conformation. Further exploration of this binding by molecular modeling showed that OHPCBs bind similarly to different conformations of the enzyme. This work has helped in our understanding of the roles of sulfotransferases in the metabolism and toxicities of OHPCBs, and it opens new avenues for future work.

Polychlorinated biphenyls (PCBs) are a class of persistent organic pollutants that have been associated with a myriad of negative human health effects. These man-made compounds were used throughout most of the 20th century and although their intentional production has since been banned and their use limited to closed systems, their prevalence in the environment remains a factor in disease states for exposed populations. The worldwide levels of PCBs has been declining, however, there is evidence for renewed sources of these compounds. The presence of PCBs with lower numbers of chlorine atoms (LC-PCBs) have been verified as unintentional byproducts in paints and pigments, the decomposition of PCB waste, or the recycling or disposal attempts of PCB-laden materials. While exposure to the higher chlorinated congeners (HC-PCBs) is often attributed to the consumption of contaminated water or fatty animal meat, a significant route of exposure to the airborne LC-PCBs is through inhalation. These semi-volatile compounds have been detected in high quantities in both indoor and outdoor air in urban and rural communities, and their presence is pronounced in older buildings (e.g., homes and schools). When compared to HC-PCBs, LC-PCBs are more highly susceptible to metabolic transformations, and recently their sulfated metabolites have gained much interest. Although the sulfation of xenobiotics often is considered a route for their removal from the body, a previous study of Sprague-Dawley rats treated with 4-chlorobiphenyl (PCB 3) resulted in the substantial formation of sulfated metabolites (i.e., hydroxylation followed by sulfation of the LC-PCB). This metabolic route accounted for more than half of the treatment dose. Furthermore, LC-PCB sulfates have been shown to bind to the human serum protein, transthyretin, in vitro. Of the health effects associated with PCB exposure, neurotoxicity has been well established through various laboratory and epidemiological studies. It is proposed that the dopaminergic system lies at the core of the observed cognitive, motor, and intellectual dysfunction observed in exposed populations, especially in children exposed perinatally. Interestingly, PCB exposure has been linked to Parkinson's disease (PD) etiology, which is marked by a substantial loss of dopaminergic neurons. This thesis describes studies on the binding of selected LC-PCBs and their hydroxylated and sulfated metabolites to human serum albumin (HSA), the most abundant protein in human serum. The displacement of fluorescent probes, selective for the two major drug binding sites of HSA, indicates that LC-PCB sulfates generally bind to HSA with such affinity that is equal to or greater than that for the LC-PCBs or OH-LC-PCBs This work also included a study of the selective toxicity of these compounds to dopaminergic neuronal cells. The selective toxicity of these compounds was studied in a series of immortalized cell lines (i.e., two neuronal cell lines: the rat midbrain-derived N27 cell line, the human neuroblastoma-derived SH-SY5Y cell line, and the human liver-derived HepG2 cell line). The assessment of toxicity by MTT reduction and LDH release in these cellular models indicated that hydroxylated and sulfated metabolites of LC-PCBs exhibited toxicity that was selective to neuronal cells and, in most cases, selective for the dopaminergic neuronal cells. Furthermore, HPLC analysis of the distribution of the compounds from the extracellular medium into the cellular milieu indicated that the observed toxicity may be due in some cases to selective transport and further metabolism. This work contributes to understanding the neurotoxicity of LC-PCB hydroxylated and sulfated metabolites and the role that binding to serum proteins may play in it. Furthermore, it emphasizes the need for future studies on the effects that metabolism, particularly sulfation, may play in the disposition of LC-PCB congeners as it pertains to their metabolism, retention, and toxic effects.

No description available.

No description available.

The objective of this thesis is to improve the understanding of what processes and mechanism affects the distribution of polychlorinated biphenyls (PCBs) and organic carbon in coastal sediments. Because of the strong association of hydrophobic organic contaminants (HOCs) such as PCBs with organic matter in the aquatic environment, these two entities are naturally linked. The coastal environment is the most complex and dynamic part of the ocean when it comes to both cycling of organic matter and HOCs. This environment is characterised by the largest fluxes and most diverse sources of both entities. A wide array of methods was used to study these processes throughout this thesis. In the field sites in the Stockholm archipelago of the Baltic proper, bottom sediments and settling particulate matter were retrieved using sediment coring devices and sediment traps from morphometrically and seismically well-characterized locations. In the laboratory, the samples have been analysed for PCBs, stable carbon isotope ratios, carbon-nitrogen atom ratios as well as standard sediment properties. From the fieldwork in the Stockholm Archipelago and the following laboratory work it was concluded that the inner Stockholm archipelago has a low (≈ 4%) trapping efficiency for freshwater-derived organic carbon. The corollary is a large potential for long-range waterborne transport of OC and OC-associated nutrients and hydrophobic organic pollutants from urban Stockholm to more pristine offshore Baltic Sea ecosystems. Theoretical work has been carried out using Geographical Information Systems (GIS) and statistical methods on a database of 4214 individual sediment samples, each with reported individual PCB congener concentrations. From this work it was concluded that the continental shelf sediments are key global inventories and ultimate sinks of PCBs. Depending on congener, 10-80% of the cumulative historical emissions to the environment are accounted for in continental shelf sediments. Further it was concluded that the many infamous and highly contaminated surface sediments of urban harbours and estuaries of contaminated rivers cannot be of importance as a secondary source to sustain the concentrations observed in remote sediments. Of the global shelf PCB inventory &lt; 1% are in sediments near population centres while ≥ 90% is in remote areas (&gt; 10 km from any dwellings). The remote sub-basin of the North Atlantic Ocean contains approximately half of the global shelf sediment inventory for most of the PCBs studied.

This study investigated the concentrations of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in the particulate and dissolved phase, as well as concentrations of PAHs in the sediment in Kaohsiung Harbor lagoon. Sources of PAHs in the water column were determined by isomer ratios, hierarchical cluster analysis (HCA) and principal components analysis (PCA). The net and annual fluxes of PAHs were calculated after a lagoon-wide water sampling campaign and compared with those found in a previous study (Fang, 2007) in which data from only one water sampling station was used. ¡@¡@In rain season, total PAH concentrations ranged from 21.6 to 36.2 ng/L for water samples, with dissolved and particulate phase concentrations ranged from 15.5 to 27.2 ng/L and from 3.4 to 8.6 ng/L, respectively. In dry season, total PAH concentrations ranged from 13.2 to 31.5 ng/L for water samples, with dissolved and particulate phase concentrations ranged from 8.0 to 21.1 ng/L and from 5.3 to 10.5 ng/L, respectively. Total PAH concentrations were found higher in rain season than in dry season. The highest total PAH concentration in dry season was observed in Chianjen River estuary. Relatively high PAH concentrations were also observed in these southern stations of Kaohsiung Harbor because of their location near Dalin industrial park. Total PAH concentrations ranged from 81.7 to 2279 ng/g for sediment samples, with average of 895 ng/g. The correlations between PAH concentrations and organic carbons, water temperature, salinity and suspended particles were also examined in this study. PAH concentration in dissolved phase was negatively correlated with water temperature (p<0.05). PAH concentration in sediment was positively correlated with organic carbons (p<0.05), and negatively correlated with median diameter (p<0.01). The logKoc¡ÐlogKow relationship in rain and dry season was compared with literature. It was found that the logKoc values were higher than those reported in literature, suggesting that soot particles might play an important role in the transport and distribution of PAHs in the study area. In rain season, PAHs in dissolved phase were mainly from pyrogenic origins; while mainly from petrogenic origins in particulate phase. In contrast, in dry season, PAHs in dissolved phase were mainly from petrogenic origins; while mainly from pyrogenic origins in particulate phase. In addition, it was found, relatively, that petrogenic pollution was introduced maily from the northern area of the lagoon. In rain season, total PCB concentrations ranged from 1.1 to 2.7 ng/L for water samples, with dissolved and particulate phase concentrations ranged from 0.42 to 2.1 ng/L and from 0.24 to 1.4 ng/L, respectively. In dry season, total PCB concentrations ranged from 0.54 to 1.3 ng/L for water samples, with dissolved and particulate phase concentrations ranged from 0.20 to 0.74 ng/L and from 0.32 to 0.76 ng/L, respectively. The direction of net fluxes of PAHs in this study are from water to air (net volatilization) in summer. In winter, however, the absorptive PAH fluxes obtained for four to six-ring PAH, such as fluoranthrene, chrysene + triphenylene and benzo[a]anthracene, indicating that PAHs were absorbed into surface waters. According to our results, it was suggested that the results from previous study (Fang, 2007) might underestimate the net fluxes of Pyrene and total fluxes in dry season. The annual fluxes of PAHs estimated in this study were 212 mg/m2 /year and 5.7 kg of PAHs were emitted annually from the harbor lagoon surface waters to the ambient atmosphere.