A contaminação da antiga Zona de Uso Predominantemente Industrial 131 (ZUPI 131) em Jurubatuba, São Paulo, levou ao estabelecimento de uma zona de restrição de uso da água subterrânea pelo Poder Público, sendo classificada posteriormente como uma área contaminada crítica. A falta de uma ferramenta que integre os dados ambientais dificulta o trabalho de gerenciamento do problema na escala de trabalho. O desenvolvimento desta ferramenta em SIG, objeto deste trabalho, contribui para a solução dessa demanda e apresenta um modelo conceitual da contaminação da ZUPI 131. O método de trabalho se mostrou adequado para superar as dificuldades de sistematização dos dados e a ferramenta apresentou bom desempenho. Contudo, não foram esgotadas todas as possibilidades de avaliação e processamento de dados, tampouco sua interpretação. A ferramenta possui caráter dinâmico, pode receber maior quantidade de dados e possibilitar novas interpretações e avanços na caracterização da contaminação. As operações espaciais realizadas permitiram identificar áreas prioritárias para futuras investigações; constatar a ausência de registros de informações pretéritas em metade dos empreendimentos; caracterizar rios e córregos como principais zonas de descarga dos aquíferos de porosidade intergranular (sedimentos e saprólito); caracterizar os principais locais de ocorrência de concentrações mais elevadas de solventes clorados; e identificar a existência de concentrações elevadas em alguns poços de abastecimento próximos às áreas que manipularam solventes clorados no passado. Todos esses achados contribuem para a gestão integrada da antiga ZUPI 131. / The contamination of the former industrial area 131 (ZUPI 131) at the Jurubatuba area, Sao Paulo, leaded to the demarcation of a groundwater restriction zone by the government authorities which classified the areas as critically contaminated. The lack of a Geographic Information System (GIS) to manage all the data poses many challenges to the problem in the work scale. The development of GIS tool brings new light to the former ZUPI 131 integrated management and its application resulted in a conceptual model of the contamination. The adopted method has proved to be able to deal with the data systematization issues and the tool had good performance, however the data evaluation and processing had just began as well as its interpretation. The tool is dynamic and more data can be imported enabling new interpretations and advances in the cha racterization of the contamination. Spatial operations have identified priority areas for future investigations such as; verify that half of the sites lack records of past land use; characterize the rivers and the streams as main discharge zones of the porous aquifers (sediments and saprolite); characterize the main hot spots of chlorinated solvents contamination; and identify the existence of high concentrations in some of the supply wells close to sites that manipulated chlorinated solvents in the past. All these findings contribute to the integrated management of the former ZUPI 131.

L’objectif général de ce travail était d’étudier la relation entre exposition professionnelle maternelle aux solvants organiques et malformations congénitales.Ce projet s’est appuyé sur les données de la cohorte PELAGIE. Il s’agit d’une cohorte mère enfant avec inclusion de 3 421 femmes en début de grossesse en population générale en Bretagne. L’exposition aux solvants était définie par différentes méthodes (expositions déclarées, matrices emplois-expositions, dosages urinaires de métabolites de solvants chlorés et d’éthers de glycol).Nous avons mis en évidence une relation entre l’exposition aux solvants mesurée par des méthodes indirectes et les malformations congénitales. Puis, pour un échantillon aléatoire de451 femmes, nous avons étudié les déterminants de la détection urinaire des métabolites de solvants. Enfin, dans le cadre d’une étude cas-témoins dans la cohorte, la relation entre métabolites urinaires de solvants et malformations congénitales a été étudiée. / The aim of this project was to study the relation between maternal occupational exposure to solvents and congenital malformations.This project used data from the PELAGIE study. This is a mother child cohort which had included 3 421 women from the general population at the beginning of their pregnancy in Britany. Occupational exposure to solvents was assessed by different methods (self-report, job exposure matrix, and urinary determination of glycol ethers and chlorinated solvents metabolites).We have shown an association between solvent exposure using indirect method of assessment and congenital malformations. Using a randomized sample of 451 women, we have studied the occupational and non occupational determinants of urinary detection of glycol ethers and chlorinated solvents metabolites. Finally, we have studied in a nested case-control study, the relation between urinary solvent metabolites and congenital malformations.

A study has been conducted for the qualitative and Quantitative analysis of chlorinated organic compounds in water. The study included the adaptation of Amberlite XAD macroreticular resin techniques for the concentration of municipal wastewater samples, followed by GC/MS analysis. A new analytical method was developed for the determination of volatile halogenated organics using liquid-liquid extraction and electron capture gas chromatography. And, a computer program was written which searches raw GC/MS computer files for halogen-containing organic compounds.

O presente trabalho foi desenvolvido com o objetivo de verificar a eficiência de um reator anaeróbio híbrido (RAH) alimentado com uma mistura de ácidos orgânicos acético, propiônico, butírico, e láctico, bem como do álcool metanol, perfazendo uma DQO de 6,88 g/L, e avaliar nessas condições, a degradação do pentaclorofenol (PCP) na faixa de 2,0 a 21,0 mg/L. O RAH apresentou adequada performance na ausência de PCP, tendo sido inoculado com um lodo com AME cerca de 0,57 g DQO-CH4/g SV.d. Durante os 21 meses de operação do RAH na ausência de PCP verificou-se uma remoção média de DQO de 93% produção média de metano de 84%. Através de testes de toxicidade realizadas em batelada com o lodo granulado do RAH, antes da adição de PCP no reator, calculou-se o IC50, cujos valores foram 10, 12 e 13,69 mg/L. Na presença de PCP na faixa de 2,0 a 2,1 mg/L, o RAH apresentou remoção média de DQO de 96,7%, produção média de metano de 85,5% e remoção dos ácidos voláteis próxima a 74% do acético, 93% do butírico e 64% do propiônico. Individualmente, na presença da maior concentração de PCP adicionada, ocorreu decréscimo na remoção dos ácidos voláteis, principalmente do ácido propiônico e na taxa de conversão DQO/biogás. O PCP foi removido do sistema na ordem de 99% pela ação do lodo granulado com predominância do grupo das Archaea metanogênicas, verificada por exames microscópicos e hibridação \"in situ\". Valores da ordem de grandeza microbiana para os microrganismos metanogênicos nos períodos anteriores e posteriores a adição de PCP permaneceram na faixa de 105 e 106 céls./mL, quando cultivados em metanol e lactato mais sulfato, respectivamente. Os resultados sugerem que as Archaea metanogênicas podem estar envolvidas na degradação do PCP. A velocidade de remoção do organoclorado foi igual a 1,07 mg PCP/g SV.d quando a maior concentração de PCP foi estudada (21,0 mg/L). / The present research aimed to verify the efficiency of an Anaerobic Hybrid Reactor (AHR) supplied with a mixture of fatty acids, acetic, propionic, butyric and lactic and methanol as well. The total amount of COD was 6.88 g/L. The performance of the reactor was remarkably stable and efficient during PCP additions at range from 2.0 to 21.0 mg/L. The AHR showed a great performance in the PCP absence, inoculated with sludge with an specific methanogenic (SMA) activity of 0,057 g.COD-CH4/g. VS.d. During the 21 months of operation without PCP, the reduction of COD was around 93% and methane was up to 84% in the biogas. Before PCP addiction, two toxicity batch tests conducted with the granular sludge presented IC50 values around 10.12 mg/L and 13.69 mg/L. In the presence of PCP, at the range of 2.0 to 21.0 mg/L, the efficiency of volatile fatty acids breakdown was 93%, 64% and 74% respectively for butyric, propionic and acetic acids. Individually, at the presence of the higher PCP concentration studied, a decrease in the conversion of COD to biogas and organic acids removal occurred, mainly with propionic acid. PCP total removal of more than 99% was reached by granular sludge activities formed by the total time of reactor operation with a prevalence of methanogenic Archaea, verified under direct microscopy exams and in situ hybridization. Methanogenic cells predominance was noticed with 105 to 106 cells/mL during enumeration on methanol and lactate plus sulfate culture media, respectively. The results suggest that methanogenic Archaea can be involved in PCP degradation. The organochlorine removal rate was 1.07 mg PCP.g-1 VS.d-1 during the highest PCP (21.0 mg/L) concentration addition.

Les zones sources formées par les organochlorés dans les sols (DNAPL) peuvent contaminer les aquifères pour plusieurs siècles en alimentant un panache de composés dissous. Pour épuiser ces zones sources, pomper le DNAPL est la solution la plus simple, mais l’efficacité est limitée par le cheminement préférentiel de l'eau dans le sol et les forces capillaires qui piègent le DNAPL. Les stratégies plus agressives (dissolution, traitement thermique, dégradation chimique…) sont aussi plus coûteuses. Dans cette thèse, deux stratégies de traitement à base de mousse de surfactant ont été développées et évaluées au laboratoire en préparation d’un essai terrain. La première stratégie utilise l’injection de mousse en zone source pour mobiliser de façon contrôlée le DNAPL et le diriger vers des puits de pompage. Dans les meilleures conditions, la saturation en DNAPL après traitement a pu être abaissé en dessous de 1 % avec une consommation de surfactant inférieure à 10 g kg-1 de DNAPL éliminé. La seconde stratégie utilise la mousse comme vecteur de réactif (hydrogène) pour accélérer la biodégradation des composés dissous dans le panache. Sous forme de mousse, l’hydrogène a été délivré de façon ciblée et plus rémanente dans l’horizon à traiter. Les technologies développées se sont montrées très prometteuses à l’échelle du terrain et lors de l’évaluation technico-économique. De la recherche reste nécessaire pour rendre ces procédés plus prédictibles lors de leur mise en œuvre. / Source zones formed by chlorinated organic compounds in soils (DNAPL) can contaminate aquifers for several centuries by feeding a plume of dissolved compounds. To deplete those source zones, DNAPL pumping is the simplest option, but the efficacy is limited by preferential water flow in the soil and capillary forces that are trapping the DNAPL. More aggressive strategies (dissolution, thermal treatment, chemical degradation...) are also costlier. Within this thesis work, two treatment strategies using surfactant foam were developed and assessed at lab-scale to prepare field assessment. The first strategy relies on foam injection in the source zone to mobilize the DNAPL in a controlled fashion to drive it ahead to pumping wells. In the best conditions, DNAPL saturation was lowered below 1% after treatment with a surfactant consumption below 10 g kg-1 of DNAPL removed. The second strategy uses foam as a reagent (hydrogen) carrier to accelerate the biodegradation of dissolved compounds in the plume. When injected as a foam, hydrogen was delivered in a targeted and more persistent manner in the strata to be treated. Developed technologies showed to be promising at field-scale and when the technico-economic assessment was conducted. Research still remains to be done to make those techniques more predictable during their implementation.

abstract: This dissertation critically evaluated methodologies and devices for assessing and protecting the health of human populations, with particular emphasis on groundwater remediation and the use of wastewater-based epidemiology (WBE) to inform population health. A meta-analysis and assessment of laboratory-scale treatability studies for removing chlorinated solvents from groundwater found that sediment microcosms operated as continuous-flow columns are preferable to batch bottles when seeking to emulate with high fidelity the complex conditions prevailing in the subsurface in contaminated aquifers (Chapter 2). Compared to monitoring at the field-scale, use of column microcosms also showed (i) improved chemical speciation, and (ii) qualitative predictability of field parameters (Chapter 3). Monitoring of glucocorticoid hormones in wastewater of a university campus showed (i) elevated stress levels particularly at the start of the semester, (ii) on weekdays relative to weekend days (p = 0.05) (161 ± 42 μg d-1 per person, 122 ± 54 μg d-1 per person; p ≤ 0.05), and (iii) a positive association between levels of stress hormones and nicotine (rs: 0.49) and caffeine (0.63) consumption in this student population (Chapter 4). Also, (i) alcohol consumption determined by WBE was in line with literature estimates for this young sub-population (11.3 ± 7.5 g d-1 per person vs. 10.1 ± 0.8 g d-1 per person), whereas caffeine and nicotine uses were below (114 ± 49 g d-1 per person, 178 ± 19 g d-1 per person; 627 ± 219 g d-1 per person, 927 ± 243 g d-1 per person). The introduction of a novel continuous in situ sampler to WBE brought noted benefits relative to traditional time-integrated sampling, including (i) a higher sample coverage (93% vs. 3%), (ii) an ability to captured short-term analyte pulses (e.g., heroin, fentanyl, norbuprenorphine, and methadone), and (iii) an overall higher mass capture for drugs of abuse like morphine, fentanyl, methamphetamine, amphetamine, and the opioid antagonist metabolite norbuprenorphine (p ≤ 0.01). Methods and devices developed in this work are poised to find applications in the remediation sector and in human health assessments. / Dissertation/Thesis / Doctoral Dissertation Civil, Environmental and Sustainable Engineering 2018

<p>Soil bottles and soil slurry experiments were conducted to investigate the effect of some additives on the aerobic and anaerobic biodegradation of chlorinated aliphatic hydrocarbons; tetrachloroethylene (PCE), trichloroethylene (TCE) and dichloroethylene (DCE) in a contaminated soil from Startvätten AB Linköping Sweden. For the aerobic degradation study the soil sample was divided into two groups, one was fertilised. The two groups of soil in the experimental bottles were treated to varying amount of methane in pairs. DCE and TCE were added to all samples while PCE was found in the contaminated soil. Both aerobic and anaerobic experiments were conducted. For aerobic study air was added to all bottles to serve as electron acceptor (oxygen). It was observed that all the samples showed a very small amount of methane consumption while the fertilised soil samples showed more oxygen consumption. For the chlorinated compounds the expected degradation could not be ascertained since the control and experimental set up were more or less the same.</p><p>For the anaerobic biodegradation study soil slurry was made with different media i.e. basic mineral medium (BM), BM and an organic compound (lactate), water and sulphide, phosphate buffer and sulphide and phosphate buffer, sulphide and ammonia. To assure anaerobic conditions, the headspace in the experimental bottles was changed to N2/CO2. As for the aerobic study all the samples were added DCE and TCE while PCE was found in the contaminated soil. The sample without the soil i.e. the control was also given PCE. It was observed that there was no clear decrease in the GC peak area of the pollutants in the different media. The decrease in GC peak area of the pollutants could not be seen, this may be so because more susceptible microorganisms are required, stringent addition of nutrients and to lower the risk of the high concentration of PCE and petroleum products in the soil from Startvätten AB.</p>

The long-term performance of stabilized polyolefins in different environments was studied with focus on antioxidant consumption and migration. Plaques of linear polyethylene (LPE) and branched polyethylene (BPE) were stabilized with Santonox® R (4,4'-Thiobis(6-tert-butyl-3-methylphenol)), Irganox® 1081 (2,2’-Thiobis(4-methyl-6-tertbutylphenol)), or Lowinox® 22M46 (2,2’-Methylenebis(6-tert-butyl-4-methylphenol)). The samples were aged in water and nitrogen at 75, 90 and 95°C. Antioxidant concentration profiles were obtained by oxidation induction time (OIT) measurements using differential scanning calorimetry (DSC). The very flat antioxidant concentration profiles of the plaques exposed to non-aqueous media indicated that the migration of antioxidant to the surrounding medium was controlled by the low evaporation rate at the sample boundary. The samples of BPE and Santonox R were also exposed to air and water saturated with air. The similarity of the antioxidant concentration profiles of Santonox R obtained after ageing in air and nitrogen suggested that the fraction of antioxidant oxidized is negligible in comparison with the loss of antioxidant by migration to the surrounding media. The loss of Santonox R in samples exposed to water saturated with air was faster than for the samples exposed to oxygen-free water. This was due to increased mass transport of the antioxidant from the polymer phase boundary to the water phase when oxygen was present. An unexpected higher migration rate from LPE than from BPE was proposed to be due to the low boundary loss rate in BPE, caused by the presence of a thin liquid-like (oligomeric) surface layer developed during ageing. A quantitative relationship was found between the boundary loss rate to water and the polarity of antioxidants. The antioxidant diffusivities were approximately equal in LPE and BPE, indicating that the constraining effect of the crystals on the non-crystalline fraction did not affect the antioxidant molecules. Results obtained by liquid chromatography of extracts confirmed that the gradual decrease in OIT with increasing ageing time was due to migration of antioxidant to the surrounding medium. Pipes of high-density polyethylene stabilized with hindered phenols and phosphites were exposed to chlorinated water at elevated temperatures. OIT showed that the stabilizing system was rapidly chemically consumed by the action of chlorinated water. Size exclusion chromatography and DSC showed extensive polymer degradation strictly confined to the immediate surface of the unprotected inner wall material and to the amorphous phase of the semicrystalline polymer. The rate of growth of the layer of highly degraded polymer was constant. Pipes of isotactic polybutene-1 were pressure-tested in chlorinated water at a controlled pH, and the lifetime was assessed as a function of temperature and chlorine content. The lifetime shortening in chlorinated water was significant even at relatively low chlorine contents, 0.5 ppm. A further increase of chlorine content led to only a moderate shortening of the lifetime. The temperature dependence of the lifetime data obeyed the Arrhenius law. The decrease of the antioxidant concentration was independent of the chlorine concentration in the range of 0.5-1.5 ppm. The time to reach depletion of the antioxidant system could be predicted by linear extrapolation. / QC 20101020

Soil bottles and soil slurry experiments were conducted to investigate the effect of some additives on the aerobic and anaerobic biodegradation of chlorinated aliphatic hydrocarbons; tetrachloroethylene (PCE), trichloroethylene (TCE) and dichloroethylene (DCE) in a contaminated soil from Startvätten AB Linköping Sweden. For the aerobic degradation study the soil sample was divided into two groups, one was fertilised. The two groups of soil in the experimental bottles were treated to varying amount of methane in pairs. DCE and TCE were added to all samples while PCE was found in the contaminated soil. Both aerobic and anaerobic experiments were conducted. For aerobic study air was added to all bottles to serve as electron acceptor (oxygen). It was observed that all the samples showed a very small amount of methane consumption while the fertilised soil samples showed more oxygen consumption. For the chlorinated compounds the expected degradation could not be ascertained since the control and experimental set up were more or less the same. For the anaerobic biodegradation study soil slurry was made with different media i.e. basic mineral medium (BM), BM and an organic compound (lactate), water and sulphide, phosphate buffer and sulphide and phosphate buffer, sulphide and ammonia. To assure anaerobic conditions, the headspace in the experimental bottles was changed to N2/CO2. As for the aerobic study all the samples were added DCE and TCE while PCE was found in the contaminated soil. The sample without the soil i.e. the control was also given PCE. It was observed that there was no clear decrease in the GC peak area of the pollutants in the different media. The decrease in GC peak area of the pollutants could not be seen, this may be so because more susceptible microorganisms are required, stringent addition of nutrients and to lower the risk of the high concentration of PCE and petroleum products in the soil from Startvätten AB.

Die elektrokinetische Bodensanierung nutzt Transporteffekte aus, die entstehen, wenn ein elektrisches Feld an einen Bodenkörper angelegt wird. Die Sanierungsmethode versagt bei immobilen Schadstoffen. Allerdings scheint unter bestimmten Bedingungen ein im Boden induzierter Abbau der Schadstoffe möglich. Dafür müssen so genannte &amp;quot;Mikroleiter&amp;quot; und Redox-Systeme im Boden vorhanden sein. Hierzu werden theoretische Modelle vorgestellt. An einem konkreten Beispiel (mit aliphatischen Chlorkohlenwasserstoffen kontaminierter Boden) wurde getestet, ob direkt im Boden ein Abbau der Schadstoffe mit der Technik der elektrochemischen Bodensanierung erzielt werden kann. Die Analyse der CKW wurde per GC-MS durchgeführt. Theoretisch ist ein reduktiver Abbau oder eine Dechlorierung durch Eliminierungsreaktionen möglich. Die Ergebnisse der Laborversuche (Einwaage 100-3.000 g) erbrachten unter Einhaltung bestimmter Faktoren einen erfolgreichen Abbau der CKW. Bei ständiger Bewässerung des Bodens und einer Feldstärke von mindestens 600 V/m konnte ein Abbau festgestellt werden. Die Erhöhung des Chlorid-Gehaltes im Abwasser zeigt die erfolgreiche Abbaureaktion an. Potentielle Abbauprodukte mit weniger Chlor-Atomen im Molekülaufbau konnten nachgewiesen werden. Diese Stoffe lassen sich mit den ursprünglichen Kontaminationssubstanzen verknüpfen. Da eine Migration der Schadstoffe im elektrischen Feld nicht beobachtet wurde, wird eine im Boden induzierte Abbaureaktion angenommen. In Bodenzonen mit hohem pH-Wert (Eliminierung) und in Kathodennähe (Reduktion) waren die stärksten Abbauraten zu verzeichnen. Bei Versuchen ohne ständige Bewässerung war der CKW-Abbau schwach. Die Widerstände stiegen stark an. Ein Versuch in einem Container (Einwaage Boden: ca. 2 t) erbrachte nur einen punktuellen Abbau der CKW. Die Struktur des Originalbodens verhinderte den Aufbau eines homogenen elektrischen Feldes. In einem Fassversuch (Einwaage Boden: ca. 33 kg) wurden die Versuchsbedingungen modifiziert. Anlagerungen an allen Elektroden verhinderten eine ausreichend hohe effektive Feldstärke im Bodenkörper. Sanierungseffekte fanden nur lokal begrenzt statt. Im Vergleich von Labor zu Großversuchen zeigte sich, dass die eingetragene Ladungsmenge eine entscheidende Rolle spielt.