Contaminated land is a widespread, global issue affecting millions of people. Atrazine is a commonly used herbicide which often contaminates groundwater and drinking water supplies and is associated with adverse health outcomes. Biochar is the solid product of pyrolysis and is associated with several environmental benefits. It may be an effective remediation tool when used as a soil amendment. This thesis investigates the mechanisms through which biochar can immobilise atrazine, and the implications of the mechanisms for remediating contaminated land. Nine biochar samples were obtained from the United Kingdom Biochar Research Centre , which were produced from softwood pellets (SWP), wheat straw pellets (WSP), miscanthus straw pellets (MSP), rice husk (RH) and oil seed rape (OSR) each at pyrolysis temperatures of 550°C and 700°C (excluding OSR at 700°C). The sorption mechanisms controlling atrazine sorption to these biochars were determined through various characterisation methods and batch sorption experiments. The sorption tests showed that sorption to each of the standard biochars occurs via multiple simultaneously occurring mechanisms, which are each promoted under certain conditions. Studies investigating sorption kinetics, isotherms and interactions with humic acids showed that for all biochars in this study, pore filling was a significant process through which atrazine is transported to adsorption sites, although poor intraparticle diffusion for softwood and oil seed rape biochars can prevent efficient transport. Wheat straw and rice husk biochars showed effective pore diffusion, resulting in high sorption capacities. Partitioning was associated with poor remediation outcomes and was significant to softwood biochars, although adsorption dominated overall sorption for all other biochars. pH was shown to significantly influence the occurrence of various sorption mechanisms. At low pH values, most biochars showed evidence of electrostatic repulsion between positive atrazine species and the positively charged biochar surface. At intermediate pH values, all biochars showed strong hydrogen bonding between H+ groups on the surface of the biochar and atrazine. A meta-analysis of previous relevant studies provided further evidence for hydrogen bonding of atrazine to biochar and showed that hydrophobic effects likely play little role in adsorption after accounting for the effects of surface area. Varying contributions of π-π EDA interactions, hydrogen bonding involving biochar O- groups, and interactions with ash minerals resulted in different sorption profiles for each biochar at high pH values. In order to further determine the mechanisms controlling sorption at high pH, surface compositions of SWP550, RH700 and OSR550 biochars were modified using hydrofluoric acid. Modification with hydrofluoric acid successfully removed the ash contents of rice husk and oil seed rape biochars and reduced atrazine removal at high pH values. This suggested that the ash fraction increases atrazine removal at high pH through complexation or catalytic hydrolysis. The roles of the various mechanisms are related to remediation outcomes in a novel manner allowing for the improved design of biochar for environmental remediation.

Submitted by Angela Maria de Oliveira (amolivei@uepg.br) on 2018-07-31T12:30:12Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Tatiana Roselena de Oliveira Stremel.pdf: 2464228 bytes, checksum: 246fc4842a96b73dff9b3d790b4e16dc (MD5) / Made available in DSpace on 2018-07-31T12:30:12Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Tatiana Roselena de Oliveira Stremel.pdf: 2464228 bytes, checksum: 246fc4842a96b73dff9b3d790b4e16dc (MD5) Previous issue date: 2018-04-12 / A maior parte dos pesticidas organoclorados (OCPs) possuem comercialização controlada ou proibida a décadas, no entanto são ainda encontrados em todos os locais do planeta. A determinação destes compostos em matrizes complexas como tecido de peixe é alvo constante de pesquisas, especialmente com o objetivo de minimizar consumo de reagentes e tempo. Este estudo objetivou desenvolver e validar um método QuECheRS com ultrassom e d-SPE para determinação por CG/ECD/MS de p,p’-DDE, p,p’-DDT, α-endosulfan, β-endosulfan, Aldrin e Dieldrin em tecidos de peixe, aplicar em amostras de tecidos de peixe comercializadas e em tecidos coletados em ambiente natural e realizar uma avaliação de risco das concentrações de OCPs detectadas nos tecidos. Três planejamentos fatoriais foram empregados para otimizar a etapa de preparo da amostra. O método desenvolvido foi validado para verificar seu desempenho e um possível efeito matriz, sendo posteriormente aplicado na extração de OCPs de músculo de Tilápia e Lambari comercializados em supermercados de Ponta Grossa e em músculo, ovas e vísceras de Lambari coletado da represa de Alagados, em Ponta Grossa. Ao final realizou-se uma avaliação de risco relacionando o consumo diário local, com massa corporal média da população e contaminação por OCPs nos tecidos analisados. Na validação o método apresentou recuperações entre 77,3% e 110,8%, com RSD inferior a 13% e os limites de detecção estiveram entre 0,24 μgkg-1 e 2,88μgkg-1, mostrando boa sensibilidade e precisão. Resíduos dos OCPs estudados foram detectados nos tecidos analisados em concentrações que variaram entre 3,4 μgkg-1 e 417,6 μgkg-1, verificando-se que os poluentes possuem uma tendência a bioacumular em maior proporção nas vísceras, do que em ovas e no músculo, a presença destes compostos nas ovas, demonstra que indivíduos da espécie analisada entram em contato com os OCPs desde a fase de embrião. Na avaliação de risco verificou-se que ao se consumir esses peixes, esses OCPs podem ao longo do tempo gerar efeitos adversos para a saúde dos consumidores. O método proposto mostrou-se efetivo na determinação de baixas concentrações de OCPs em tecidos de peixe, utilizando pequena massa de amostra (0,5 gramas), viabilizando a análise sem a necessidade de agrupamento (pool), ao mesmo tempo possibilitou a análise de tecidos, de peixe de pequena massa corporal total (Lambari), avaliando ainda a bioacumulação dos OCPs em diferentes tecidos. O método é aplicável para análise de OCPs aplicado à área toxicológica. / Most organochlorine pesticides (OCPs) are controlled or banned for decades, but they are still found everywhere in the world. The determination of these compounds in complex matrices such as fish tissue is a constant goal of research, especially with the aim of minimizing reagent consumption and time. The aim of this study was to develop and validate a Quechers method with ultrasound and d-SPE for determination of p, p'-DDE, p, p'-DDT, α-endosulfan, β-endosulfan, Aldrin and Dieldrin in fish tissues, apply on samples of commercially available fish tissues and on tissues collected in the natural environment and carry out a risk assessment of the concentrations of OCPs detected in the tissues. Three factorial designs were used to optimize the preparation stage of the sample. The method developed was validated through figures of merit and matrix effect, and it was later applied in the extraction of OCPs from Tilapia and Lambari muscle marketed in supermarkets in Ponta Grossa and Lambari muscle, eggs and viscera collected from the Alagados dam in Ponta Thick. At the end of the study, a risk assessment was performed relating local daily consumption, mean body mass of the population and OCP contamination in the tissues analyzed. In the validation, the method presented recoveries between 77.3% and 110.8%, with RSD lower than 13% and detection limits between 0.24 μg kg -1 and 2.88 μg kg -1, showing good sensitivity and precision. Residues of the OCPs studied were detected in the tissues analyzed at concentrations ranging from 3.4 μgkg-1 to 417.6 μgkg-1, with pollutants having a tendency to bioaccumulate more in the viscera than in roe and in muscle, the presence of these compounds in the eggs, demonstrates that individuals of the analyzed species come into contact with OCPs from the embryo stage. In the risk assessment it was found that there is a risk when consuming these fish, these OCPs may over time generate adverse effects on the health of consumers. The proposed method was effective in the determination of low concentrations of OCPs in fish tissues, using a small sample mass (0.5 grams), making the analysis possible without the necessity of pooling, at the same time making possible the analysis of tissues, of fish of small total body mass (Lambari), also evaluating the bioaccumulation of OCPs in different tissues. The method is promising for OCP analysis applied to the toxicological area.

A cause d’une anthropisation toujours plus forte des écosystèmes, de plus en plus de menaces pèsent sur la biodiversité. Parmi celles-ci, l’exposition aux contaminants est particulièrement problématique pour les organismes vivants. Emis et utilisés dans les pays industrialisés, ces contaminants hautement persistants dans l’environnement vont gagner les régions polaires puis se bio-accumuler dans les organismes vivants au cours du temps et se bio-amplifier le long du réseau trophique. Ainsi, les oiseaux marins, longévifs et situés dans les maillons supérieurs de la chaine alimentaire, sont particulièrement exposés et vulnérables à une exposition chronique à ces contaminants. A travers une perturbation endocrinienne, ces contaminants vont pouvoir impacter certains mécanismes physiologiques et traits comportementaux, entrainant in fine des conséquences à long-terme sur la fitness des individus et populations. Ma thèse s’articule autour de trois grandes familles de contaminants : i) les composés perfluoroalkylés (PFASs), encore largement utilisés dans plusieurs secteurs industriels et agricoles et en augmentation dans l’environnement ; (ii) les composés organochlorés dits « d’héritage » (OCs), interdits depuis des années mais entrainants toujours des effets délétères sur la biodiversité et (iii) le mercure (Hg), métal lourd non-essentiel ayant une origine à la fois anthropique et naturelle. Basé sur une approche corrélative in natura, je me suis intéressé aux conséquences physiologiques et comportementales d’une exposition chronique à ces trois grandes familles de contaminants présents chez la mouette tridactyle (Rissa tridactyla) de l’Arctique Norvégien (Svalbard) au cours de son cycle reproducteur (depuis l’accouplement jusqu’à l’élevage des poussins). Spécifiquement, j’ai étudié les relations entre ces contaminants et la fertilité (morphologie et motilité des spermatozoïdes), l’expression des signaux sexuels (visuel : coloration des téguments, olfactif : signature chimique), les comportements de soins parentaux (température d’incubation et rotation de l’œuf), le vieillissement cellulaire (longueur des télomères) et la dépense énergétique (métabolisme de base). Je me suis également penché sur de potentiels mécanismes sous-jacents permettant d’expliquer ces relations. Puisque ces mécanismes physiologiques et comportementaux sont fortement impliqués dans la valeur sélective des individus, les possibles conséquences à long terme de cette exposition sur la reproduction et survie des individus sont discutées. Ce travail permet de souligner la forte toxicité de certains composés organochlorés « historiques » (en particulier les chlordanes) et d’apporter de toutes nouvelles connaissances sur la toxicité très mal connue des PFASs chez la faune sauvage. Fait important, ce travail de thèse révèle que les PFASs et les OCs pourraient agir de manière contrastée sur plusieurs mécanismes physiologiques et traits comportementaux. Spécifiquement, une forte exposition à l’oxychlordane, un métabolite du chlordane, pesticide interdit depuis des décennies, est associée à des télomères plus courts, une réduction du métabolisme de base et à une moindre capacité à incuber les œufs. A l’inverse, on observe une élongation des télomères, une augmentation du métabolisme de base et une rotation des œufs accrue chez les individus les plus exposés aux PFASs. Le Hg, au moins en ce qui concerne les paramètres étudiés, ne semble pas jouer un rôle majeur. Cette étude souligne l'importance de tenir compte de plusieurs groupes de contaminants lorsqu'on étudie les conséquences de l'exposition aux contaminants environnementaux chez la faune sauvage. / Due to increasing human activities, a growing number of threats are challenging the fate of biodiversity. Among them, environmental contamination is particularly concerning for living organisms. Used and released in industrialized countries, these highly persistent contaminants can reach remote areas such as the Arctic ecosystem and will biomagnify though food webs and bioaccumulate in organisms. Long-lived seabirds are located in the upper levels of the food chains and thus particularly exposed and sensitive to a chronic contaminants exposure. Through endocrine disruption, these contaminants can impact physiological mechanisms and behavioural traits, inducing in fine, long-term fitness consequences on individuals and populations. My thesis focuses on three groups of contaminants: (i) poly- and perfluoroalkyl substances (PFASs), still broadly used in a vast array of industrial processes and increasing in the Arctic; (ii) “legacy” organochlorine contaminants (OCs, pesticides and industrial compounds), banned from use but still well present in the Arctic and (iii) mercury (Hg), a non-essential metal coming of both natural and anthropic origins. Based on a correlative approach conducted in natura, I investigated the physiological and behavioural consequences of exposure to these contaminants during the whole breeding cycle (from pre-laying to chick-rearing period) in an Arctic seabird, the black-legged kittiwake (Rissa tridactyla) from Svalbard, Norwegian Arctic. Specifically, I examined the relationships between several PFASs, OCs, Hg and fertility (sperm morphology and motility), sexual signaling (visual: integument coloration and olfactory: chemical signature), parental care behaviors (incubation temperature and egg-turning), ageing (telomere length) and energy expenditure (basal metabolic rate). In addition, some potential underlying mechanisms were also studied to better understand the way through which contaminants can be detrimental for kittiwakes. Furthermore, since physiological mechanisms and behavioral traits investigated here are tightly involved in self maintenance and reproduction, possible effects on fitness are then discussed. This PhD work underlines the major role of certain legacy chlorinated organic compounds (e.g. chlordanes) and significantly contributes at documenting the poorly known toxicological consequences of PFASs exposure in wildlife. Importantly, this PhD shows that PFASs and OCs could impact ageing, energy expenditure and some parental care behaviors in a contrasted manner. Specifically, oxychlordane, a metabolite of a banned organochlorine pesticide was associated with decreased telomere length, lowered metabolic rate and reduced ability to incubate the eggs. Conversely, elongated telomere, increased BMR and enhanced egg rotation were observed in birds bearing the highest concentrations of PFASs. Finally, at least for the considered endpoints, Hg appears as a coming minor threat for kittiwakes. This study highlights the importance of considering several groups of contaminants when investigating the consequences of environmental contaminants exposure in wildlife.

A contaminação bacteriana por espécies dos gêneros Lactobacillus, Bacillus e Leuconostoc entre outras bactérias lácticas é um dos principais fatores que afetam o rendimento da fermentação alcoólica. A formação de biofilmes acaba protegendo as bactérias e é uma fonte permanente de contaminação. Objetivando caracterizar tais contaminações em (1) biofilmes de centrífuga, dorna, trocador de calor e tubulação de água e (2) melaço, mosto, levedo, levedo tratado (com H2SO4) e vinho, amostras foram coletadas em diferentes períodos de um sistema fermentativo de alto teor alcoólico (16%). As enzimas de restrição AluI, BstUI, HaeIII, HinfI, MseI e MspI utilizadas nas análises de T-RFLP foram definidas por análises in silico com sequências do gene 16S rRNA de contaminantes freqüentes. Essas enzimas geram uma maior quantidade de T-RFs únicos entre 30 e 650 pb. Os DNAs extraídos das amostras foram submetidos às análises de T-RFLP para obtenção do perfil molecular das comunidades microbianas dos pontos de coleta. Os índices de diversidade de Shannon foram calculados com base no número dos T-RFs. Foram realizadas as análises dos componentes principais (PCA) e a inferência filogenética dos contaminantes com base nos perfis dos T-RFs. A quantificação dos principais táxons contaminantes foi feita por qPCR utilizando primers específicos delineados neste estudo e considerando a média de cópias do gene 16S rRNA presentes no genoma de cada táxon bacteriano. Na primeira coleta o biofilme de água apresentou maior índice de diversidade microbiana e na segunda, melaço e mosto. PCA sugere que os biofilmes (e não as fontes externas) são os principais contaminantes desse processo fermentativo devido as suas semelhanças com a composição das outras comunidades analisadas. Espécies de Lactobacillus e Bacillus predominaram entre as amostras da primeira coleta. Halomonas, Streptococcus, Lactococcus e Pseudomonas foram detectados em amostras de biofilme e em amostras líquidas, sendo os principais contaminantes provindos de biofilme no momento da primeira coleta. Na segunda coleta Bacillus foi o principal contaminante e novamente gêneros produtores de ácido lático como Streptococcus, Lactobacillus e Staphylococcus foram os mais freqüentes. Os resultados concordam com o reportado na literatura sobre sistemas fermentativos convencionais. Apenas os primers desenhados para amplificação do gene 16S rRNA de Burkholderia, Pseudomonas e Weissella apresentaram especificidade em testes com isolados. Halomonas sp. foi encontrada em biofilme de dorna através do sequenciamento utilizando primers para esse gênero. Halomonas pode produzir levânio podendo haver o consumo da sacarose disponível para fermentação. Biofilme da centrífuga teve a maior quantidade de micro-organismos nos dois momentos de coleta (1,93E+06 UFC.mg-1 e 2,14E+07 UFC.mg-1, respectivamente) assim como as amostra de levedo entre as amostras líquidas (1,03E+08 UFC.ml-1 e 2,96E+06 UFC.ml-1, na primeira e segunda coleta, respectivamente), indicando níveis consideráveis de contaminantes. Burkholderia e Pseudomonas foram os mais abundantes entre as amostras de biofilmes da primeira e segunda coleta. Nas amostras líquidas Burkholderia apresentou-se em maior quantidade na maioria das amostras da primeira coleta; enquanto Pseudomonas e Weissella em geral predominaram equivalentemente entre as amostras da segunda coleta / Bacterial contamination by Lactobacillus, Bacillus and Leuconostoc and other lactic acid bacteria is one of the main factors that affects the yield in alcoholic fermentation process. Biofilm formation protects the bacteria community and it is a permanent source of contamination. For characterization of these contaminations in (1) biofilms from centrifuge, tank fermentation, heat exchanger and water pipe and (2) molasses, must, yeast, yeast treated (with H2SO4) and wine, samples were taken at two different periods from fermentation system characterized by high alcohol yields (16%). Restriction enzymes AluI, BstUI, HaeIII, HinfI, MseI and MspI used in T-RFLP analysis were defined by 16S rRNA gene sequences analysis in silico from common contaminants. These enzymes generate high number of unique T-RFs between 30 and 650 bp. DNA from samples were used as template in T-RFLP reactions in order to obtain molecular profiles of microbial communities present at each sample. Shannon diversity index was calculated based on T-RFs numbers. Principal component analysis (PCA) and phylogenetic inference of contaminants were performed based on T-RFs profiles. The main contaminant bacterial taxa were quantified by qPCR using specific primers designed in this study and considering the average of 16S rRNA gene copies previously counted into the genome of each bacterial taxon. Water pipe biofilm showed the highest rate of bacterial diversity in the samples collected in the first sampling period. For the samples collected in the second sampling, the highest rate of bacterial diversity was revealed for molasses and must. PCA suggested that biofilms (but not external sources) are the main contaminants in the studied fermentation process. It is probably due their similarities with the composition of other analyzed communities. Lactobacillus and Bacillus species predominated in first sampling period. Halomonas, Streptococcus, Lactococcus and Pseudomonas were detected in biofilm and liquid samples. They were the main contaminants from biofilm at this time of sampling. In the second sampling period, Bacillus was the most common genera and other lactic acid bacteria such Streptococcus, Staphylococcus and Lactobacillus were also the most frequent contaminants. These results agree with other reported in the literature about conventional fermentation systems. Only the primers designed in this study to amplify the 16S rRNA gene of Burkholderia, Pseudomonas and Weissella showed specificity in tests with bacterial strains. Halomonas sp. was revealed in biofilms from tank fermentation by DNA sequencing using designed primers for genera. Halomonas can produce levan and may consume sucrose available for generation of alcohol. Centrifugal biofilm had the highest amount of bacteria in both sampling periods (1.93E+06 CFU.mg-1 and 2.14E+07 CFU.mg-1, respectively). In liquid samples, yeast had the highest amount of bacteria in both sampling periods (1.03E+08 CFU.ml-1 and 2.96E+06 CFU.ml-1, respectively); it shows significant levels of contaminants. Burkholderia and Pseudomonas were more abundant among biofilm samples of all samplings. Burkholderia was present in high quantities in the majority of liquid samples taken during the first sampling period; Pseudomonas and Weissella equivalently predominated among samples taken during the second sampling period

O lodo de esgoto, também denominado biossólido, depois de tratado adequadamente, constitui fonte de matéria orgânica, micro e macro-nutrientes para o crescimento das plantas. A aplicação do lodo de esgoto no solo pode trazer benefícios tais como: distribuição em áreas para produção agrícola, recuperação de solos perdidos por erosão, aplicação em áreas de reflorestamento. Os lodos de esgotos, entretanto, são resíduos que contem patógenos, metais pesados, e poluentes orgânicos, entre estes os compostos orgânicos voláteis (COVs). A resolução CONAMA nº 375 em vigor no Brasil, assim como as regulamentações de outros países, não exigem valores limites para alguns COVs considerados prioritários. Uma base de dados sobre COVs em lodos de esgoto é necessário para estabelecer valores limites nos lodos usados para fins agrícolas. O presente trabalho evidenciou a presença de COVs em concentrações significativas nas amostras de lodo coletadas nas Estações de Tratamento de Esgoto (ETE) na Região Metropolitana de São Paulo (RMSP), Jundiaí, Vinhedo e Americana. Na ETE da RMSP foram encontrados vários COVs em concentrações significativas. Dentre os COVs identificados, apenas 1,4-diclorobenzeno e naftaleno apresentam valores permitidos em solo agrícola (390 e 120 µmg/kg, respectivamente) e valores de concentrações muito acima desses limites foram encontrados para as amostras de lodo da ETE de RMSP (845 a 2037 e 901 a 5670 µmg/kg, respectivamente). Os resultados obtidos neste trabalho, embora não forneçam dados suficientes para uma imediata tomada de decisão, permitem fornecer subsídios técnicos para iniciar uma base de dados sobre COVs em lodo de esgoto que, futuramente, utilizando-se metodologias adequadas, será útil para se realizar uma revisão das regulamentações vigentes para lodo de esgoto com finalidade agrícola. / The sewage sludge also entitled biosolid, after adequate treatment, is source of organic matter, micro and macronutrients for plants growth. The application of sewage sludge in soil may provide some benefits like: distribution in areas for agricultural production, recovery of degraded soil by erosion, application in areas of reforestation. However, sewage sludges are residues that contain phatogens, heavy metals, organic pollutants, such as volatile organic compounds (VOCs). The current resolution in Brazil (CONAMA nº 375), as well as regulations from other countries do not establish acceptable levels for some priority VOCs. It is necessary to establish data a base related to VOCs in sewage sludge for agricultural use to be able to present acceptable levels of them. The present work reports the presence of VOCs at significant levels in sewage sludge samples collected at sewage treatment stations (ETE) in the Metropolitan Region of São Paulo city (RMSP), Jundiaí, Vinhedo and Americana. Among VOCs identified, only 1,4 dichlorobenzene and naphthalene are regulated for use in agricultural soil (390 and 120 µg/kg, respectively) and levels found for sewage sludge samples from RMSPETE were higher than those regulated limits (845 to 2037 and 901 to 5670 µg/kg, respectively). Although results obtained in this study do not provide enough data for an immediate decision, results will be useful to start a data base regarding to VOCs in iv sewage sludge for agricultural use that, using adequate methodologies, will permit a review of current regulations on VOCs for agricultural use.

Submitted by Rosina Valeria Lanzellotti Mattiussi Teixeira (rosina.teixeira@unisantos.br) on 2018-03-08T19:08:23Z No. of bitstreams: 1 Dennise Pimentel Claro.pdf: 637790 bytes, checksum: c4ed000204776db603ecf343f477a919 (MD5) / Made available in DSpace on 2018-03-08T19:08:23Z (GMT). No. of bitstreams: 1 Dennise Pimentel Claro.pdf: 637790 bytes, checksum: c4ed000204776db603ecf343f477a919 (MD5) Previous issue date: 2010-06-10 / Introduction - In 2001, it was reported the presence of toxic sources in areas located in the estuary of Santos and Sao Vicente, such as heavy metals, organochlorine, polychlorinated biphenyls, dioxins and furans. The exposure to these contaminants produces several adverse effects on the cardiovascular system of humans by damaging the endothelial cells of blood. To understand the impact of health conditions in these contaminated areas it is important to explore the risk of developing cardiovascular disease in the exposed population. Objective - To analyze the mortality of cardiovascular diseases in areas exposed to the referred environmental contaminants. Methods ¿ A cross-sectional study with analysis of historical series allowed an investigation of the mortality from cardiovascular disease, as provided by Fundação SEADE in five areas determined by a previous study entitled "Epidemiological Study in the Baixada Santista - Santos Estuary: Assessment of predictors of effects and exposure to environmental contaminants.", which investigated the health effects associated with exposure to environmental contaminants among residents of areas alongside Santos estuary. In this study the deaths of the five areas were subjected to descriptive analysis based on the period from 2003 through 2007 of the national census (IBGE) of 2000. The mortality rates were calculated by the direct method to standardize them with the population of São Paulo city. In addition to standardized mortality rates were estimated and the average mortality ratios. The resulting estimates allowed a comparison between the contaminated areas and the area that is contaminated free. The comparison between two proportion and Kruskal-Wallis tests was used with a significance level of 0.05. Results - observed the highest mortality coefficient in Area 1, with 24.66 per 1000 of male population, with statistically significant difference (p<0.005), but other areas with environmental contaminants their average coefficient ranged between 1.47 per 1000 to 3.96 per 1000 in both gender. Also, in both gender and all periods, there was significant statistical difference between the contaminated area 1 and Bertioga. The other areas sometimes presented lower coefficient ranged than the area without exposure to environmental contaminats (p<0.05).The mortality also showed high ratios in Area 1 (Pilões) compared to all other areas of the sample. And up to 32 times higher among females in 2003 compared with the control area (area 5, located in Bertioga). Conclusion ¿ for the analysis, higher mortality rates in Pilões and Água Fria was found, although it needs further studies to investigate a causal relationship between exposure and outcome studied. / Introdução - Em 2001 foi relatada a presença de fontes tóxicas em áreas localizadas na região estuarina de Santos e São Vicente, como os metais pesados, organoclorados, bifenilas policloradas, dioxinas e furanos. A exposição a esses contaminantes, a longo prazo, produzem diversos efeitos deletérios à saúde do ser humano, sendo uma delas o aparecimento de doenças cardiovasculares, através do dano nas células endoteliais dos vasos sanguíneos. Explorar o perfil das doenças cardiovasculares na população exposta permite entender o impacto das condições de saúde nestas áreas contaminadas. Objetivo ¿ analisar o perfil da mortalidade de doenças cardiovasculares nas áreas expostas a contaminantes ambientais. Casuística e Método ¿ estudo transversal com análise de séries históricas. Foram estudados os óbitos por doenças cardiovasculares, fornecidas pela Fundação SEADE, em 5 áreas determinadas por um estudo prévio intitulado ¿Estudo Epidemiológico na População Residente na Baixada Santista ¿ Estuário de Santos: Avaliação dos Indicadores de Efeito e de Exposição à Contaminantes Ambientais.¿, financiado pelo CNPq, no qual investigou os efeitos à saúde associados à exposição aos contaminantes ambientais entre moradores da baixada Santista. No presente trabalho os óbitos das 5 áreas foram submetidos a uma análise descritiva, no período de 2003 a 2007, utilizando as estimativas populacionais do Instituto Brasileiro de Geografia e Estatística no ano 2000. Os cálculos dos coeficientes de mortalidade foram realizados pelo método direto, padronizando-os com a população do município de São Paulo. Além do coeficiente padronizado foram calculados os coeficientes médios e as razões entre os coeficientes de mortalidade por doenças cardiovasculares. Os resultados calculados permitiram uma comparação entre as áreas contaminadas e a área não contaminada, o município respectivo do local, e o município de São Paulo. Foi utilizado o teste de comparação entre duas proporções e o teste Kruskal-Wallis com teste Dunn positivo, adotando um nível de significância menor ou igual a 0,05. Resultados ¿ o coeficiente de mortalidade padronizados por doenças cardiovasculares mais elevado foi de 24,66/1000 habitantes na Área 1 (Pilões e Água Fria) no sexo masculino, com diferença estatisticamente significante com a área não contaminada (p<0,05), Nas outras áreas contaminadas os coeficientes médio de mortalidade variaram entre 1,47/1000 a 3,96/1000 em ambos os sexos, valores inferiores a area 1. Em todos os períodos, observou-se diferença estatisticamente significante entre a área 1 (Pilões) e a área contaminada (Bertioga), em ambos os sexos. Nas áreas 2 (Cubatão Centro), área 3 (São Vicente) e área 4 (Vicente de Carvalho) em alguns períodos da série histórica apresentaram coeficientes de mortalidade inferiores a área contaminada, sendo estatisticamente significante. As razões de mortalidade também se apresentaram elevadas na área 1 (Pilões) com todos os locais de comparação, chegando a 32 vezes maior no sexo feminino no ano de 2003, quando comparado com a área controle (área 5, localizada na região de Bertioga). Conclusão ¿ a análise da mortalidade, através dos coeficientes, revelou-se alta na área contaminada a poluentes ambientais, localizada em Pilões e Água Fria, porém há necessidade de novos estudos para investigar uma relação causal entre a exposição e o desfecho estudado.

Environmental impacts of mining at Calico, California, are poorly understood in comparison to the details of its history of silver production. Human health risks associated with arsenic from the lode rock, as well as mercury from the silver milling process, include central nervous system damage, organ failure, and death. To quantify the potential human health risk and manage remediation of this site, tailings from the Garfield Mill site were digitally mapped and chemically analyzed by portable x-ray fluorescence, which permitted volumetric estimates of total mill tailings and the arsenic and mercury budget, as well as identification of anomalies in the distribution of these elements within the tailings deposit. Final products include a high-resolution digital orthomosaic map showing the extent of the tailings deposit, giving contours of arsenic and mercury distribution and identifying areas of high concern for future remediation. The information gathered during this study will be of immense use to the city of Barstow, providing a basis for future public health studies and assessments of human health risks in the area.

Du fait du coût élevé de certains matériaux adsorbants d’intérêt pour le traitement de la micropollution organique, l’étude a porté sur la régénération de matériaux adsorbants de type zéolithes hydrophobes et monolithe de carbone dans le cas de l’adsorption du bisphénol A et du diclofénac comme micropolluants réfractaires. Des procédés d’oxydation avancée impliquant des espèces radicalaires HO• (réaction de Fenton, électro-Fenton) et SO₄• – (activation de persulfate par voie thermique) ont été utilisés pour assurer la régénération des matériaux par désorption et dégradation oxydative des polluants fixés. La production de radicaux HO• au sein de la phase aqueuse circulant au niveau de l’adsorbant n’est pas suffisamment efficace pour sa régénération. Il a donc été envisagé de générer les radicaux au plus près des molécules adsorbées. Au cours de ce travail, une méthode sensible d’analyse par polarographie de H₂O₂ a été développée et validée pour le suivi des expériences avec les procédés mettant en jeu la réaction de Fenton. Pour différentes zéolithes, le catalyseur de la réaction de Fenton à base de fer a été incorporé préalablement dans la zéolithe. Pour le monolithe de carbone, les propriétés de conduction du matériau ont été mises à profit en l’utilisant comme cathode pour l’application du procédé électro-Fenton permettant de produire les radicaux HO• directement au sein du matériau. Cela a conduit à améliorer les performances de la régénération avec toutefois une diminution de son efficacité au cours de cycles successifs adsorption/régénération. / The elimination of organic micropollutants often requires the use of adsorption processes among the water treatments. The aim of our study is to regenerate two expensive materials (hydrophobic zeolites and carbon monoliths) to increase their life expectancy and decrease their investing cost. Two organic contaminants were targeted : diclofenac and bisphenol A, which are refractory pollutants. Advanced oxidation processes involve radical species, HO• (Fenton and electro-Fenton reactions) and SO₄• – (thermal activation of persulfate ion). These oxidants were used to decompose the adsorbed pollutants and thus regenerate the adsorbents. The HO• production, within the core of aqueous phase, did not reach satisfactory regeneration, and a loss of adsorption capacity was observed. Furthermore, during this study, a sensitive polarographic analytical method was developed and validated for the quantification of H₂O₂ in the aqueous phase. This method was used to follow in situ the Fenton reaction. The location of the catalyst in a closer vicinity of the adsorbed species was then optimized and the iron catalyst was impregnated in the host, prior to the adsorption, on different types of hydrophobic zeolites. Concerning carbon monolith, the electro-Fenton process was carried out using the material as the cathode thanks to its electrical conductivity. Consequently, HO• are produced in the porosity of monolith. This latter property enhanced the degradation of adsorbed solutes. The overall performances were increased compared to the homogeneous Fenton process. Nonetheless, a decrease of the adsorption capacities with adsorption-regeneration cycles was observed.

Lake restoration and management strategies focus on reducing the negative impacts of enriched or polluted inflows. These strategies become of paramount importance when lakes are used for recreational and/or drinking water purposes. Long term control of eutrophication and turbidity problems associated with large inflow loads is usually oriented to catchment management. Although it has been suggested that this is the correct long term approach, public concerns usually require a short term solution. In addition, due to political and economic costs related to changes in catchment management, in-lake restoration technologies have been emerging as a viable pretreatment option, complementary to water treatment plants, both reducing the operational costs of the water treatment plant and ameliorating the water residing in the lakes. This research investigates the effects of two in-lake technologies on the dynamics of inflowing rivers, where basin shape plays a significant role. The three lakes in this study suffer from eutrophication combined with a distinctive water quality problem: from turbidity in Silvan Reservoir (Australia), to heavy metal loads in Coeur d'Alene Lake (USA) and industrial wastes in Lake Como (Italy). Firstly, the influence of basin morphology, wind speed, and wind direction on the fate and transport of two rivers flowing into the L-shaped Coeur d'Alene Lake was examined, and it was shown that transport and mixing patterns in a lake can be greatly influenced by the shape of the lake, leading to important consequences for the plankton ecology in the lake. Secondly, in Silvan Reservoir we investigated the potential to modify the basin shape using vertical barriers, increasing the retention time and hence the barrier capacity to microbial pollution. A final in-lake technology was tested for Lake Como, using a downward pointing impeller to remove polluted water from the coastal margin. Lessons from these three examples indicate that there is significant potential for in-lake remediation at relatively low cost, over relatively short timescales.

Les crustacés décapodes marins sont des organismes macrobenthiques opportunistes, d'intérêt commercial, et susceptibles d'accumuler les contaminants. Dans un souci de sécurité du consommateur, une évaluation de la contamination de quatre espèces principales par les polychlorobiphényles (PCB), les polybromodiphényles éthers (PBDE) et les dioxines (PCDD/F) a été réalisée dans les eaux côtières de Bretagne et Normandie. Au regard des normes sanitaires actuelles, la consommation de chair de crustacés ne pose aucun problème de santé publique. Dans une seconde partie, les processus biologiques influant sur la bioaccumulation des polychlorobiphényles chez l'araignée de mer Maja brachydactyla ont été appréhendés. D'un point de vue quantitatif, l'organotropisme, le régime alimentaire et l'âge apparaissent comme les principaux facteurs d'influence. D'un point de vue qualitatif, les empreintes de contamination en PCB sont dépendantes du sexe, et dans une moindre mesure du comportement migratoire de l'espèce. L'analyse des isotopes stables du carbone (delta13C) et de l'azote (delta15N) dans la chaîne trophique de l'araignée de mer a confirmé le haut niveau de complexité des relations alimentaires dans le cas de prédateurs supérieurs omnivores. L'utilisation de la méthode isotopique stable en parallèle à l'analyse des contaminants a mis en évidence la bioamplification des congénères de PCB les plus persistants le long de la chaîne trophique de l'araignée de mer. A l'inverse, certains composés de structure chimique particulière sont métabolisés par les crustacés décapodes.