[pt] Este trabalho tem por objetivo fazer uma avaliação das condições de contaminação, por hexaclorociclohexano (HCH), do subsolo da área da antiga fábrica de pesticidas, localizada na Cidade dos Meninos, Duque de Caxias. Pretende também caracterizar as condições hidrogeológicas básicas locais. Para isto foi feita amostragem de solo através de sondagens à percussão, utilizando-se um amostrador SPT adaptado, e instalados piezômetros para medições do nível d`água local, e realização de ensaios de permeabilidade. As amostras de solo foram analisadas através de cromatografia gasosa. / [en] The purpose of this work is to make an evaluation of the contamination by hexaclorociclohexane of the susbsoil, in a former pesticide factory area, sited in Cidade dos Meninos, Duque de Caxias. The basic hydrogeological conditions were also determined. The soil sampling was made by percussion drilling, using an adapted SPT sampler. Several piezometers were installed to make water level measurements and permeability tests. The soil samples were analised by gas chromatography.

Biotransformation and biodegradation rate constants were determined for naphthalene, lindane, and phenol in water samples from three different sources. Rate constants produced from monitoring disappearance of the parent chemical (biotransformation) were compared to those obtained from mineralization of the chemical (ultimate biodegradation) by ¹⁴CO₂ evolution as well as acidification of the residual ¹⁴C-labeled compound (primary biodegradation). Rate constants were statistically different for the three chemicals. The water source affected the rate constants. When biomass measurements of the waters were considered and second-order rate constants were derived, there was no statistical evidence that this parameter gave a reliable rate constant statistic that could be useful in predicting the fate of any of naphthalene, lindane, and phenol in these waters.

Environmental pollution represents one of the most pressing problems in developed countries and in recent years has raised concern and doubts also from the scientific perspective. In fact, an ever-growing number of epidemiologic-observational studies, carried out on population at risk, correlated the exposure to environmental chemicals with the incidence of several pathological conditions, ranging from metabolic to cardiological and reproductive diseases, until the development of cancers. These evidences have made more urgent the need for further investigations on the biological mechanism at the basis of pollutants toxicity. In particular, significant attention has been paid to evaluating the impact of organochlorine pesticides (OCPs) on human health. OCPs belong to a large class of organic compounds that the Stockholm Convention catalogued as “POPs” (Persistent Organic Pollutants). The list of banned chemicals includes dioxins and their derivatives, hexachlorocyclohexane, polychlorinated biphenyls and aldrin, whereas many other similar substances are subjected to restrictions. OCPs are widely distributed in the biosphere and their hazardousness is mostly related to physicochemical properties such as lipophilia and energetic stability, that allow these molecules to be resistant to biodegradation and to bio-accumulate into the adipose tissue. Information about the molecular mechanisms of the most popular OCPs (i.e. dioxins, DDT) is already present in scientific literature and several studies indicated them as endocrine disrupting chemicals as well as oncogenes. On the other hand, not much is known about a dangerous and widely diffused compound: the hexachlorocyclohexane. Hexachlorocyclohexane (HCH) is a chlorinated cyclic saturated hydrocarbon that exists in four isomers: α, β, γ and δ hexachlorocyclohexane. The g-isomer of HCH, also known as lindane, is a broad-spectrum insecticide that has been extensively used for the control of agricultural pests and for health purposes. Among HCH isomers, which are by-products of lindane industrial synthesis, β-HCH is the most recalcitrant because of its higher energetic stability due to the equatorial position of all six chlorine atoms in the chair cyclohexane conformation; in addition, few reports are available about its metabolic breakdown. For this characteristic, it is usually the predominant isomer remaining in soils and in animal tissue and can still be detected at low background environmental levels. The improper disposal of huge amounts of β-HCH led to the generation of contaminated sites in several parts of the world (Italy, Turkey, Spain, Kazakhstan, Canada, India, China, Russia, Poland, Germany, Argentine): this classifies “lindane’s contamination” as one of the environmental catastrophe of global proportions on the planetary scale. A detailed epidemiological study, ongoing since 2006, has found correlation between high blood levels of β-HCH and the occurrence of a wide range of diseases in a sample of 660 exposed patients living close the Valle del Sacco, south of Rome. The Valle del Sacco, in fact, is characterized by the presence of a large industrial conglomerate in which lindane production has been stopped in 70’s. Although the biomonitoring study highlighted a link between β-HCH contamination and the incidence of several pathological conditions, few data are currently available in the scientific literature regarding the molecular mechanism of β-HCH. For this reason, our laboratory is investigating since 2015 the intracellular effects of β-HCH with a particular focus on its impact on cancer cells. In a first published study, experiments were carried out on a panel of cells representing different human tumor types (i.e. liver, lungs, prostate, breast) associated with the expression and activation of specific receptors or kinases that are related to STAT3 activity. The experimental concentration of 10 µM for β-HCH was chosen averaging across all the plasma concentration values detected in patients under the biomonitoring study carried out in the Valle del Sacco, in order to reproduce the real exposure conditions. After evaluating the effects of β-HCH on cellular viability, different types of analysis were performed to identify the transduction cascades involved in the molecular responses to β-HCH. Obtained results established that β-HCH can activate cell-line specific pathways that all converge in STAT3 activation. Then, a special focus was placed on investigating the putative role of β-HCH in prostate cancer progression; in fact, literature data, together with our previous findings, suggest that β-HCH could have an endocrine disrupting activity by interfering with Androgen Receptor (AR) signaling. To confirm this hypothesis, LNCaP cells (hormone-sensitive prostate cancer cell line) were treated with β-HCH or testosterone in the presence or absence of the chemotherapeutic agent bicalutamide. The outcomes show that AR nuclear translocation occurs upon both β-HCH and testosterone treatment, whereas is inhibited in the presence of bicalutamide, as evidenced by immunoblotting analysis on nuclear extracts and immunofluorescence experiments. Subsequently, was verified whether β-HCH could affect the activity of AhR (Aryl Hydrocarbon Receptor), the xenobiotic sensor par excellence, in both hormone-dependent and independent tumor types. Immunofluorescence analysis evidenced the capability of β-HCH to induce AhR nuclear translocation. In addition, immunoblotting analysis were performed on cells treated with β-HCH in the presence or not of MG-132 (proteasome inhibitor) and CH223191 (AhR inhibitor) and obtained results clearly highlighted the influence of β-HCH on AhR signaling. Then, experiments were performed to investigate whether β-HCH, on par with other organochlorine pesticides, can induce oxidative stress. For this purpose, ROS production and GSSG/GSH ratio were measured, evidencing the impact of β-HCH on cellular redox homeostasis. In parallel, variations in cellular bioenergetic profile were monitored, demonstrating that β-HCH promote a metabolic shift toward aerobic glycolysis. In this altered context, β-HCH can also induce DNA damage through H2AX phosphorylation. Subsequently, the potential role of β-HCH as a contributor in tumor initiation was inspected. Experiments were carried out on a continuous normal bronchial epithelium cell line to investigate whether β-HCH could trigger cellular malignant transformation toward cancer development. For this reason, β-HCH impact was evaluated on cells viability and morphology and some markers for tumorigenesis, as Ki67 positive-cells and EGF secretion, were studied along with β-HCH activation pathways. Experimental outcomes strongly support the oncogenic potential of this molecule. Considering the capability of β-HCH to promote cell growth and tumor progression, the next question to answer is whether the exposure to β-HCH may lead to a loss of response to chemotherapeutic agents such as tyrosine kinases inhibitors. Experiments carried out on a HER2-positive lung cancer cell line revealed that β-HCH can counteract the inhibitory activity of lapatinib, leading to a higher cell proliferation rate via STAT3 activation. Further investigations were conducted using other chemotherapeutic agents (cisplatin, camptothecin and paclitaxel) and preliminar results seem to confirm the loss of sensitivity to drugs in the presence of β-HCH. From an environmental point of view, the persistence of β-HCH still represents an open question for the presence of massive illegal repositories all around the world. For this reason, β-HCH degradation through a copper-based Fenton-like method was explored by setting up a HPLC protocol under different experimental conditions. The process focused on the quantitative degradation of the parental β-HCH, since the detection of its breakdown products or transformed molecules would need a mass-spectrometry for their qualitative characterization. In parallel with the β-HCH research topic, the role of the protein STAT3 in prostate cancer was further deepened. STAT3 (Signal Transducer and Activator of Transcription 3) is a converging point for many signaling cascades and has been reported constitutively activated in a wide range of solid tumors and hematological malignancies. STAT3 is a latent cytosolic transcription factor and upregulates the expression of genes involved in cell survival and proliferation upon a wide variety of stimuli, including cytokines, oncogenes, growth factors or cytosolic kinases. The dynamic biological behavior of STAT3 can explain the higher proliferation rate triggered by β-HCH through the activation of STAT3-mediated pathways. STAT3 fulfils its multifaceted molecular functions through two different intracellular mechanisms, generally referred as canonical and non-canonical pathways. The canonical activation of STAT3 is strictly dependent on its phosphorylation at the tyrosine residue 705; upon phosphorylation at Y705, induced by the binding of a ligand to its receptor, STAT3 undergoes homodimerization to form an active dimer that can translocate to nucleus and mediates its transcriptional activity. Besides its well-described canonical signaling, STAT3 can be subjected to alternative post-translational modifications. In addition, recent studies assessed the involvement of STAT3, by means of both its canonical and non-canonical pathway, in the metabolic shift toward aerobic glycolysis known as Warburg Effect, which is typical of the more aggressive tumor phenotypes. On the basis of these premises, the existence of a link between PTMs and specific STAT3-mediated pathways was investigated in LNCaP (less aggressive PCa form) and DU-145 (more aggressive) cells performing experiments that simulated inflammatory and oxidative-stress conditions. Cells were treated with IL-6 to induce an inflammatory response, whereas tert-butyl hydroperoxide (t-BHP) was used to simulate oxidative stress. Obtained results on cellular models confirmed the relationship between STAT3 PTMs and cellular conditions, thereby reinforcing the hypothesis that PTMs can drive intracellular responses through STAT3-mediated signaling pathways. Thus, it is possible to identify STAT3 PTMs and STAT3 modulators as suitable markers or targets for PCa prevention, diagnosis and therapy. Then the role of STAT3 in prostate cancer energy metabolism was further investigated, with particular focus on the protein SHMT2 (Serine-Hydroxymethyltransferase). Results indicate that SHMT2 is an active player in STAT3 signaling and that its expression is upregulated by the JAK2/STAT3 canonical pathway upon IL-6 stimulation. Experiments were carried out on two different prostate cancer cell lines, LNCaP (less aggressive) and DU145 (more aggressive). The observation was extended to PCa formalin-fixed paraffin-embedded (FFPE) tissue sections obtained from total prostatectomies: collected specimens are characterized by a different Gleason score, ranging from 6 (less aggressive) to 9 (more aggressive). In both cell lines, STAT3 activation mode, the amount and distribution of PKM2, SHMT2, and HIF-1a proteins, as well as the cellular metabolic conditions, were evaluated in the presence or absence of IL-6-induced inflammation. Expression levels of PKM2, SHMT2, and HIF-1a, together with interleukin-6, were also analyzed utilizing normal and tumor FFPE tissues. / Doctorat en Sciences agronomiques et ingénierie biologique / info:eu-repo/semantics/nonPublished

Bluegill were exposed to 3 and 30 pg/L lindane and 20 and 200 pg/L naphthalene to determine uptake rate constants, K1 depuration rate constants, K2, and bioconcentration factors, BCF. Correlations were determined between lipid normalized and non-lipid normalized BCFs, and between observed Kl, K2 and BCFs and predicted values. The K1 values for both chemicals and concentrations were similar. The K2 values were different (1.04 day~1, 0.46 day 1). Naphthalene was more rapid. BCFs for lindane (315) and naphthalene (98) were different. Lipid normalized BCFs for naphthalene were more variable than non-lipid normalized BCFs. The reverse was observed for lindane BCFs. Predicted K1, K2 , and BCFs were in agreement with observed values.

Este trabalho apresenta a caracterização geoambiental de solos de uma área contaminada, localizada no município de Santo André, Estado de São Paulo, Brasil. O objetivo foi determinar parâmetros experimentais para permitir o estudo de alguns aspectos do transporte do pesticida organoclorado Hexaclorociclohexano (HCH). A área de estudo contém células com cerca de 30.000 toneladas de um material contendo HCH em elevadas concentrações. As investigações de campo demonstram que há concentrações de HCH na água subterrânea. Em 2011, foram coletadas amostras deformadas e indeformadas de solo em quatro diferentes pontos superficiais da área contaminada, e posteriormente uma amostra composta da camada de solo de alteração de rocha (SAR), a fim de responder a questionamentos quanto à mobilidade do contaminante na área. A caracterização geoambiental, baseada em ensaios laboratoriais, foi realizada por meio das seguintes análises: análise granulométrica, limites de Atterberg, densidade específica, porosidade, umidade do solo, curva de retenção de água no solo, condutividade hidráulica, ensaio de adsorção, pH, condutividade elétrica, capacidade de troca catiônica (CTC), teor de matéria orgânica e teor de voláteis. O solo superficial da área é heterogêneo e a capacidade de adsorção dos solos analisados foi menor do que o esperado. Esta caracterização subsidiou o estudo de fluxo e transporte do HCH, por meio de simulação numérica, utilizando o programa Hydrus 1D. As simulações tiveram dois objetivos diferentes: no primeiro foi avaliado os resultados da simulação em comparação à situação atual no campo; no segundo foi avaliada a sensibilidade do transporte em função da alteração dos parâmetros obtidos experimentalmente Ks; Kd; s e (Van Genuchten); e dos parâmetros obtidos na literatura. Os resultados permitiram concluir que o modelo Hydrus 1D consegue representar a contaminação do HCH no solo. O parâmetro de degradação na água foi essencial para chegar em ordens de grandeza de concentrações próximas das identificadas em campo. Os parâmetros de degradação, difusividade, dispersividade e condutividade hidráulica são os que mais afetam os resultados finais de concentração do HCH na água subterrânea e, portanto, merecem atenção maior durante as futuras investigações. / This paper presents the geoenvironmental characterization of soils from a contaminated site, located in Santo André, São Paulo State, Brazil. The objective was to determine experimental parameters to allow the study of some aspects of transport of the organochlorine pesticide hexachlorocyclohexane (HCH). The study site contains trenches with about 30,000 tons of a material containing high concentrations of HCH. The site investigations show that there are HCH concentrations in groundwater. In 2011, disturbed and undisturbed soil samples were collected at four different surface points of the contaminated site, and then a sample of soil from rock alteration layer (SAR) was also composed for characterization in order to answer questions concerning the mobility of contaminant in the site. The environmental characterization based on laboratory tests, was performed by the following analyzes: grain size distribution, Atterberg limits, specific gravity, porosity, moisture content, water retention curve, hydraulic conductivity, pH, electrical conductivity, cation exchange capacity (CEC), organic matter content and volatile content. The surface soil of the area is heterogeneous and the adsorption capacity of the soils analyzed were lower than expected. This characterization allowed the study of flow and transport of HCH through numerical simulation using the Hydrus 1D software. The simulations had two different goals, the first was evaluated the simulation results compared to the current situation in the field. In a second step the sensitivity of transport due to the change of the parameters obtained experimentally Ks; Kd; s and (Van Genuchten); and parameters obtained from the literature. The results showed that the Hydrus 1D model simulates HCH contamination in soil. Water degradation parameter was essential to get orders of magnitude similar to those identified in field concentrations. The degradation, diffusivity, hydraulic conductivity and dispersivity parameters are those that most affect the final results of concentration of HCH in groundwater and therefore deserve more attention in future investigations.

A utilização de pesticidas organoclorados é motivo de preocupação das entidades ligadas à área de saúde em todo o mundo. Apesar de as formas de contaminação serem bem conhecidas, não há um controle eficaz na fiscalização do seu uso no Brasil. Sabe-se que altos níveis séricos destes compostos nos organismos de seres humanos e animais acarretam sérios problemas de saúde. Tendo em vista essa realidade, foi realizado, em 2009, o Projeto Piloto do I Inquérito Nacional de Populações Expostas a Substâncias Químicas, cujo subprojeto \"doadores de sangue\" teve como objetivo mensurar as concentrações de substâncias químicas no sangue de 547 residentes da região metropolitana de São Paulo, dentre elas os pesticidas organoclorados. Este trabalho teve como objetivos avaliar as concentrações dos pesticidas hexaclorobenzeno (HCB), alfa-HCH, ?-HCH, beta-HCH, beta-HCH, heptacloro, heptacloro epóxido, dieldrin, mirex, o,p\'-DDT, p,p\'-DDT, o,p\'-DDE, p,p\'-DDE, o,p\'-DDD e p,p\'-DDD nesta população e compará-las com as encontradas em outros países e determinar fatores associados aos níveis mais elevados destas substâncias. O método analítico utilizado foi de cromatografia a gás. Os resultados deste estudo indicam que a população adulta de São Paulo não está exposta a níveis preocupantes de pesticidas organoclorados, pois dentre os compostos analisados, apenas o beta-HCH e o p,p\'-DDE tiveram um número significante de amostras acima do limite de quantificação, 10,7% e 31,2% das amostras respectivamente. Quando utilizada a metade do limite de quantificação para substituir os valores abaixo do limite de quantificação do método, o valor médio encontrado para o beta-HCH foi de 0,028 ug/dL e para o p,p\'-DDE foi de 0,045 ug/dL. Este estudo propôs dois modelos multivariados para explicar os fatores associados aos compostos beta-HCH e p,p\'-DDE no sangue dos doadores. Segundo o modelo de Regressão Logística Ordinal Multivariado, os fatores associados a níveis mais altos de beta-HCH foram ter idade entre 26 e 45 anos e ser do sexo feminino. Para o p,p\'-DDE os fatores associados a níveis mais altos foram ter idade entre 26 e 45 anos, ser do sexo feminino e ter trabalhado com pesticidas, enquanto receber renda mensal de 3 a 5 salários mínimos e consumir derivados de origem animal uma ou mais vezes por semana foram associados a níveis mais baixos de p,p\'-DDE. Segundo o modelo de Regressão Linear Múltipla, os fatores associados a níveis mais altos de beta-HCH foram o sexo feminino, ter contato prévio com pesticidas na região agrícola, ter trabalhado com pesticidas em campanhas de saúde pública, ter trabalhado em empresas de capacitores ou transformadores, ter trabalhado em indústrias de solventes clorados, ter renda mensal de 3 a 5 salários mínimos, consumo de carnes uma ou duas vezes por semana e consumo de frutos do mar uma ou duas vezes por semana, enquanto consumo frequente de cerveja e ter renda mensal de 1 a 3 salários mínimos foram associado a níveis menores de beta-HCH. Já para o p,p\'-DDE, os fatores associados a níveis mais elevados foram ser do sexo feminino, ser não branco, ter trabalhado com pesticidas e consumir água de fontes que não sejam minerais ou de rede, enquanto o consumo frequente de bebidas alcoólicas foi associado a níveis mais baixos de p,p\'-DDE / The use of organochlorine pesticides is a cause of concern to the entities of the health field worldwide. Although the ways of contamination are well known, there is no effective surveillance of its use on Brazil. It\'s known that high levels of these compounds on human beings and animals entails serious health problems. Foreseeing this reality, a Pilot study of the 1st National Inquiry of Populations Exposed to Chemical Compounds was carried out in 2009, in a subproject called \"blood donors\" had the objective to measure the concentrations of chemical compounds on serum from 547 residents of the metropolitan area of São Paulo, among them, the organochlorine pesticides. This study had as objectives to evaluate the levels of the pesticides hexachlorobenzene (HCB), alfa-HCH, beta-HCH, beta-HCH, beta-HCH, heptachlor, heptachlor epoxide, dieldrin, mirex, o,p\'-DDT, p,p\'-DDT, o,p\'-DDE, p,p\'-DDE, o,p\'-DDD e p,p\'-DDD on blood donors and compare these with the ones found on other countries and to find out factors associated with higher levels of those compounds in the population. The analytical method used was gas chromatography. The results of this study indicate that, overall, the population in São Paulo is not exposed to high levels of these compounds because of all compounds analyzed, only beta-HCH and p,p\'-DDE had a significative number of samples above the quantification limit, 10,7% and 31,2% of the samples respectively. Using the half of the quantification limit to substitute the values below the quantification limit, the beta-HCH mean level was 0.028 ug/dL and p,p\'-DDE mean level was 0.045 ug/dL. This study proposed two multivariate models to explain the factors associated with beta-HCH and p,p\'-DDE blood levels. According to the Multivariable Ordinal Logistic Regression model, the factors associated with higher levels of beta-HCH were age between 26 and 45 years and female gender. For the p,p\'-DDE, the associated factors with higher levels were age between 26 to 45 years, female gender and previous work with pesticides while having income of 3 to 5 minimum wages and consumption of derivates of animal origin at least once per week were associated to lower levels of p,p\'-DDE. According to the Multiple Linear Regression model, the factors associated with higher levels of beta-HCH were female gender, previous contact with pesticides on agricultural region, working with pesticides on campaigns of public health, in companies of capacitators or transformers, in companies of chlorinated solvents, having income of 3 to 5 minimum wages, consumption of meat once or twice per week, and consumption of seafood once or twice per week, while frequent consumption of beer and income of 1 to 3 minimum wages lead to lower levels of beta-HCH. Factors associated with higher levels of p,p\'-DDE were female gender, being non-white, previous work with pesticides and consumption of water from sources that not mineral or mains, while frequent consumption of alcohol were associated with lower levels of p,p\'-DDE

Este trabalho apresenta a caracterização geoambiental de solos de uma área contaminada, localizada no município de Santo André, Estado de São Paulo, Brasil. O objetivo foi determinar parâmetros experimentais para permitir o estudo de alguns aspectos do transporte do pesticida organoclorado Hexaclorociclohexano (HCH). A área de estudo contém células com cerca de 30.000 toneladas de um material contendo HCH em elevadas concentrações. As investigações de campo demonstram que há concentrações de HCH na água subterrânea. Em 2011, foram coletadas amostras deformadas e indeformadas de solo em quatro diferentes pontos superficiais da área contaminada, e posteriormente uma amostra composta da camada de solo de alteração de rocha (SAR), a fim de responder a questionamentos quanto à mobilidade do contaminante na área. A caracterização geoambiental, baseada em ensaios laboratoriais, foi realizada por meio das seguintes análises: análise granulométrica, limites de Atterberg, densidade específica, porosidade, umidade do solo, curva de retenção de água no solo, condutividade hidráulica, ensaio de adsorção, pH, condutividade elétrica, capacidade de troca catiônica (CTC), teor de matéria orgânica e teor de voláteis. O solo superficial da área é heterogêneo e a capacidade de adsorção dos solos analisados foi menor do que o esperado. Esta caracterização subsidiou o estudo de fluxo e transporte do HCH, por meio de simulação numérica, utilizando o programa Hydrus 1D. As simulações tiveram dois objetivos diferentes: no primeiro foi avaliado os resultados da simulação em comparação à situação atual no campo; no segundo foi avaliada a sensibilidade do transporte em função da alteração dos parâmetros obtidos experimentalmente Ks; Kd; s e (Van Genuchten); e dos parâmetros obtidos na literatura. Os resultados permitiram concluir que o modelo Hydrus 1D consegue representar a contaminação do HCH no solo. O parâmetro de degradação na água foi essencial para chegar em ordens de grandeza de concentrações próximas das identificadas em campo. Os parâmetros de degradação, difusividade, dispersividade e condutividade hidráulica são os que mais afetam os resultados finais de concentração do HCH na água subterrânea e, portanto, merecem atenção maior durante as futuras investigações. / This paper presents the geoenvironmental characterization of soils from a contaminated site, located in Santo André, São Paulo State, Brazil. The objective was to determine experimental parameters to allow the study of some aspects of transport of the organochlorine pesticide hexachlorocyclohexane (HCH). The study site contains trenches with about 30,000 tons of a material containing high concentrations of HCH. The site investigations show that there are HCH concentrations in groundwater. In 2011, disturbed and undisturbed soil samples were collected at four different surface points of the contaminated site, and then a sample of soil from rock alteration layer (SAR) was also composed for characterization in order to answer questions concerning the mobility of contaminant in the site. The environmental characterization based on laboratory tests, was performed by the following analyzes: grain size distribution, Atterberg limits, specific gravity, porosity, moisture content, water retention curve, hydraulic conductivity, pH, electrical conductivity, cation exchange capacity (CEC), organic matter content and volatile content. The surface soil of the area is heterogeneous and the adsorption capacity of the soils analyzed were lower than expected. This characterization allowed the study of flow and transport of HCH through numerical simulation using the Hydrus 1D software. The simulations had two different goals, the first was evaluated the simulation results compared to the current situation in the field. In a second step the sensitivity of transport due to the change of the parameters obtained experimentally Ks; Kd; s and (Van Genuchten); and parameters obtained from the literature. The results showed that the Hydrus 1D model simulates HCH contamination in soil. Water degradation parameter was essential to get orders of magnitude similar to those identified in field concentrations. The degradation, diffusivity, hydraulic conductivity and dispersivity parameters are those that most affect the final results of concentration of HCH in groundwater and therefore deserve more attention in future investigations.

A utilização de pesticidas organoclorados é motivo de preocupação das entidades ligadas à área de saúde em todo o mundo. Apesar de as formas de contaminação serem bem conhecidas, não há um controle eficaz na fiscalização do seu uso no Brasil. Sabe-se que altos níveis séricos destes compostos nos organismos de seres humanos e animais acarretam sérios problemas de saúde. Tendo em vista essa realidade, foi realizado, em 2009, o Projeto Piloto do I Inquérito Nacional de Populações Expostas a Substâncias Químicas, cujo subprojeto \"doadores de sangue\" teve como objetivo mensurar as concentrações de substâncias químicas no sangue de 547 residentes da região metropolitana de São Paulo, dentre elas os pesticidas organoclorados. Este trabalho teve como objetivos avaliar as concentrações dos pesticidas hexaclorobenzeno (HCB), alfa-HCH, ?-HCH, beta-HCH, beta-HCH, heptacloro, heptacloro epóxido, dieldrin, mirex, o,p\'-DDT, p,p\'-DDT, o,p\'-DDE, p,p\'-DDE, o,p\'-DDD e p,p\'-DDD nesta população e compará-las com as encontradas em outros países e determinar fatores associados aos níveis mais elevados destas substâncias. O método analítico utilizado foi de cromatografia a gás. Os resultados deste estudo indicam que a população adulta de São Paulo não está exposta a níveis preocupantes de pesticidas organoclorados, pois dentre os compostos analisados, apenas o beta-HCH e o p,p\'-DDE tiveram um número significante de amostras acima do limite de quantificação, 10,7% e 31,2% das amostras respectivamente. Quando utilizada a metade do limite de quantificação para substituir os valores abaixo do limite de quantificação do método, o valor médio encontrado para o beta-HCH foi de 0,028 ug/dL e para o p,p\'-DDE foi de 0,045 ug/dL. Este estudo propôs dois modelos multivariados para explicar os fatores associados aos compostos beta-HCH e p,p\'-DDE no sangue dos doadores. Segundo o modelo de Regressão Logística Ordinal Multivariado, os fatores associados a níveis mais altos de beta-HCH foram ter idade entre 26 e 45 anos e ser do sexo feminino. Para o p,p\'-DDE os fatores associados a níveis mais altos foram ter idade entre 26 e 45 anos, ser do sexo feminino e ter trabalhado com pesticidas, enquanto receber renda mensal de 3 a 5 salários mínimos e consumir derivados de origem animal uma ou mais vezes por semana foram associados a níveis mais baixos de p,p\'-DDE. Segundo o modelo de Regressão Linear Múltipla, os fatores associados a níveis mais altos de beta-HCH foram o sexo feminino, ter contato prévio com pesticidas na região agrícola, ter trabalhado com pesticidas em campanhas de saúde pública, ter trabalhado em empresas de capacitores ou transformadores, ter trabalhado em indústrias de solventes clorados, ter renda mensal de 3 a 5 salários mínimos, consumo de carnes uma ou duas vezes por semana e consumo de frutos do mar uma ou duas vezes por semana, enquanto consumo frequente de cerveja e ter renda mensal de 1 a 3 salários mínimos foram associado a níveis menores de beta-HCH. Já para o p,p\'-DDE, os fatores associados a níveis mais elevados foram ser do sexo feminino, ser não branco, ter trabalhado com pesticidas e consumir água de fontes que não sejam minerais ou de rede, enquanto o consumo frequente de bebidas alcoólicas foi associado a níveis mais baixos de p,p\'-DDE / The use of organochlorine pesticides is a cause of concern to the entities of the health field worldwide. Although the ways of contamination are well known, there is no effective surveillance of its use on Brazil. It\'s known that high levels of these compounds on human beings and animals entails serious health problems. Foreseeing this reality, a Pilot study of the 1st National Inquiry of Populations Exposed to Chemical Compounds was carried out in 2009, in a subproject called \"blood donors\" had the objective to measure the concentrations of chemical compounds on serum from 547 residents of the metropolitan area of São Paulo, among them, the organochlorine pesticides. This study had as objectives to evaluate the levels of the pesticides hexachlorobenzene (HCB), alfa-HCH, beta-HCH, beta-HCH, beta-HCH, heptachlor, heptachlor epoxide, dieldrin, mirex, o,p\'-DDT, p,p\'-DDT, o,p\'-DDE, p,p\'-DDE, o,p\'-DDD e p,p\'-DDD on blood donors and compare these with the ones found on other countries and to find out factors associated with higher levels of those compounds in the population. The analytical method used was gas chromatography. The results of this study indicate that, overall, the population in São Paulo is not exposed to high levels of these compounds because of all compounds analyzed, only beta-HCH and p,p\'-DDE had a significative number of samples above the quantification limit, 10,7% and 31,2% of the samples respectively. Using the half of the quantification limit to substitute the values below the quantification limit, the beta-HCH mean level was 0.028 ug/dL and p,p\'-DDE mean level was 0.045 ug/dL. This study proposed two multivariate models to explain the factors associated with beta-HCH and p,p\'-DDE blood levels. According to the Multivariable Ordinal Logistic Regression model, the factors associated with higher levels of beta-HCH were age between 26 and 45 years and female gender. For the p,p\'-DDE, the associated factors with higher levels were age between 26 to 45 years, female gender and previous work with pesticides while having income of 3 to 5 minimum wages and consumption of derivates of animal origin at least once per week were associated to lower levels of p,p\'-DDE. According to the Multiple Linear Regression model, the factors associated with higher levels of beta-HCH were female gender, previous contact with pesticides on agricultural region, working with pesticides on campaigns of public health, in companies of capacitators or transformers, in companies of chlorinated solvents, having income of 3 to 5 minimum wages, consumption of meat once or twice per week, and consumption of seafood once or twice per week, while frequent consumption of beer and income of 1 to 3 minimum wages lead to lower levels of beta-HCH. Factors associated with higher levels of p,p\'-DDE were female gender, being non-white, previous work with pesticides and consumption of water from sources that not mineral or mains, while frequent consumption of alcohol were associated with lower levels of p,p\'-DDE

In the studies underlying this thesis, various source tracing techniques were applied to environmental samples from the Baltic region. Comprehensive sampling and analysis of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in surface sediments in Swedish coastal and offshore areas resulted in a unique data set for this region. Nearly 150 samples of surface sediments were analyzed for all tetra- to octa-chlorinated PCDD/Fs. The levels showed large spatial variability with hotspots in several coastal regions. Neither Sweden nor the EU has introduced guideline values for PCDD/Fs in sediment, but comparisons to available guidelines and quality standards from other countries indicate that large areas of primarily coastal sediments may constitute a risk to marine organisms. Multivariate pattern analysis techniques and receptor models, such as Principal Component Analysis (PCA) and Positive Matrix Factorization (PMF), were used to trace sources. These analyses suggested that three to six source types can explain most of the observed pattern variations found in the sediment samples. Atmospheric deposition was suggested as the most important source to offshore areas, thus confirming earlier estimates. However, spatial differences indicated a larger fraction of local/regional atmospheric sources, characterized by PCDFs, in the south. This was indicated by the identification of several patterns of atmospheric origin. In coastal areas, the influence of direct emission sources was larger, and among these, chlorophenol used for wood preservation and emissions from pulp/paper production and other wood related industry appeared to be most important. The historic emissions connected to processes involving chemical reactions with chlorine (e.g. pulp bleaching) were found to be of less importance except at some coastal sites. The analysis of PCDD/Fs in Baltic herring also revealed spatial variations in the levels and pollution patterns along the coast. The geographical match against areas with elevated sediment levels indicated that transfer from sediments via water to organisms was one possible explanation. Fugacity, a concept used to predict the net transport direction between environmental matrices, was used to explore the gas exchange of hexachlorocyclohexanes (HCHs) and polychlorinated biphenyls (PCBs) between air and water. These estimates suggested that, in the Kattegat Sea, the gaseous exchange of HCHs primarily resulted in net deposition while PCBs were net volatilized under certain environmental conditions. The study also indicated that, while the air concentrations of both PCBs and γ-HCH are mostly dependent upon the origin of the air mass, the fluctuations in α-HCH were primarily influenced by seasonal changes.