Au cours des dernières décennies, un contexte alarmant de déclin des paramètres du sperme etd’accroissement constant des pathologies génitales masculines a été décrit dans de nombreuxpays industrialisés.Notre travail évalue dans un premier temps l’évolution des paramètres spermatiques chez11 330 hommes ayant consulté pour infertilité conjugale au Centre de ProcréationMédicalement Assistée du CHU de Marseille entre 1988 et 2007. Les données ont étérecueillies de manière rétrospective et analysées par régression linéaire multi-variée afin detenir compte de l’effet lié à l’âge. Nous montrons une diminution significative des principauxparamètres du sperme: concentration en spermatozoïdes (-1.4% par an), numération totale enspermatozoïdes (-1.5% par an), mobilité progressive rapide (-5.6% par an) et morphologienormale (-1.9% par an). Les possibles biais de selection ont été discutés. L’effet del’environnement sur notre fonction de reproduction est l’une des hypothèses principalesévoquées pour expliquer ce phénomène.Nous montrons ensuite comment un modèle de culture de tubes séminifères de rat en chambrebicamérale, couplé à des techniques d’étude de la méiose en immunocytochimie peut êtreutilisé comme nouvel outil de reprotoxicologie. Nous décrivons tout d’abord avec l’anticorpsanti-SCP3 la prophase de première division méiotique chez le rat in-vivo et nous validons lemodèle de culture par comparaison entre les résultats des cellules obtenues in vivo et ceux descellules obtenues ex-vivo. Nous montrons ensuite grâce à ce système l’impact du ChromeHexavalent et du Cadmium sur la méiose du rat. Ces 2 métaux lourds, largement présent dansnotre environnement, peuvent être responsables d’atteintes importantes des cellulesméiotiques, y compris à de faibles doses pouvant correspondre à celles retrouvées chez desindividus exposés dans leur vie quotidienne et/ou professionnelle. / In recent decades, an alarming decline of sperm parameters and a constant increase in malegenital diseases has been described in many industrialized countries.In a first time, our study evaluates the evolution of sperm parameters in 11 330 menconsulting for infertility of their couple in the Reproduction Biology Laboratory of anUniversity Hospital in Marseilles between 1988 and 2007. Data were collected retrospectivelyand analyzed by multivariate linear regression to take into account the effect related to age.We show a significant decrease of the main sperm parameters: sperm concentration (-1.4%per year), total sperm count (-1.5% per year), rapid progressive motility (-5.6% per year) andnormal morphology (-1.9 % per year). Possible selection bias were discussed. The effect ofenvironment on our reproductive function is one of the main hypothesis to explain thisphenomenon.Secondly, we show how a rat seminiferous tubule culture in a bicameral chamber system,coupled with study of meiosis by immunocytochemistry can be used as a new tool ofreprotoxicology. We first describe with an anti-SCP3 antibody the first prophase of ratmeiosis and we validate the model of culture by comparing the results obtained on cellsobtained after in vivo spermatogenesis and those of cells obtained ex-vivo. Then, we showusing this system, the impact of hexavalent chromium and cadmium on rat meiosis. These twoheavy metals, widely present in our environment, may cause substantial impairment ofmeiotic cells, including low doses which can fit with those found in individuals exposed intheir personnal life and / or occupational training.

A intensificação da degradação ambiental impulsionada pelas atividades antrópicas tem comprometido a qualidade da água. A presença de metais potencialmente tóxicos no ambiente provoca diversos impactos na fauna e flora, como, por exemplo, o processo de magnificação trófica. Assim, é fundamental que estudos de adsorção desses contaminantes sejam realizados, a fim de buscar novos métodos que permitam a remoção dos mesmos no meio aquático. O metal crômio está nos efluentes de diversos processos industriais, como curtumes, refino de petróleo, galvanoplastia, soldagem e cromagem. Esse metal na forma hexavalente possuí efeito tóxico a biota e riscos à saúde humana, indicando a necessidade da realização de estudos para sua remoção de efluentes industriais e corpos d\'água. O biopolímero quitosana tem sido reportado em diversos estudos como bioadsorvente de alto potencial de retenção de metais, por conta da presença de amino-grupos em sua estrutura. Além disso, a quitosana possui propriedades singulares e é obtida da quitina, um dos biopolímeros mais abundantes na natureza. Com a finalidade de avaliar a capacidade de adsorção de Cr (VI) pelo biopolímero quitosana em forma de pérolas (P-QTS), realizou-se ensaios de adsorção em processo contínuo com diferentes concentrações do metal cromo em coluna de leito fixo, preenchida pelo material adsorvente (P-QTS). Além disso, realizou-se testes de toxicidade com os organismos Daphnia magna, Allonais inaequalis e Chironomus xanthus no afluente e efluente da coluna de adsorção, buscando avaliar a toxicidade dessas amostras para os organismos e a consequente eficácia do tratamento da solução de dicromato de potássio na coluna de leito fixo com as P-QTS. As curvas de ruptura indicaram que para as maiores concentrações de K2Cr2O7 houve intensificação da saturação da CALF (coluna de adsorção de leito fixo), e, consequentemente, a zona de transferência de massa (ZTM) se deslocou no sentido descendente do leito fixo da coluna de adsorção. A razão C/Co (concentração efluente/concentração afluente) aumentou de maneira significativa no decorrer do ensaio para as maiores concentrações afluentes (25 e 28,5 mg L-1) de K2Cr2O7 alcançando valores de até 0,4, e, isso demonstra a saturação de parte das P-QTS na coluna de leito fixo. De maneira geral, a remoção de Cr VI foi alta (superior a 50% e atingindo a máxima de 98%) para os tempos estudados na presente pesquisa, sendo maior nos menores tempos (60 e 120 min) do ensaio, estado em que os sítios ativos para adsorção das P-QTS provavelmente estavam livres. Da extração do cromo das P-QTS obteve-se valor máximo de 8,18 mg g-1 e mínimo de 0,42 mg g-1 de massa adsorvida por massa de adsorvente, o que indica variação de acordo com a concentração da solução de K2Cr2O7 afluente a CALF, ou seja, para as maiores concentrações, maior a quantidade adsorvida de Cr VI por massa de adsorvente (P-QTS). Alguns pesquisadores obtiveram relação de 2,6 mg de crômio (III) /g de quitosana indicando que as P-QTS na coluna de leito fixo possuem boa capacidade de adsorção. Os testes de toxicidade mostraram diferentes sensibilidades dos organismos-teste às soluções de dicromato de potássio, sendo na ordem decrescente: Chironomus xanthus < Allonais inaequalis < Daphnia magna. A coluna de adsorção de leito fixo diminuiu, de modo geral, a mortalidade dos organismos-teste comparando o afluente e efluente, principalmente das amostras efluentes de menor tempo (60 e 120 min) de ensaio de adsorção. A média de comprimento das larvas de C. xanthus reduziu (10,07 mm > 8,34 mm > 4,59 mm), de modo geral, a medida que o tempo de ensaio (60, 120 e 180 min) aumentou, indicando aumento da concentração de Cr VI nos efluentes. / The intensification of environmental degradation driven by anthropic activities has led to a decrease in water quality. The presence of potentially toxic metals in the environment causes several impacts on fauna and flora, such as the trophic magnification process. Thus, it is fundamental that adsorption studies of these contaminants are carried out in order to search for new methods that allow their removal in the aquatic environment. Chromium metal is in the effluents of various industrial processes, such as tanning, petroleum refining, electroplating, welding and chrome plating. The chromium in the hexavalent form has a toxic effect on biota and risks to human health, indicating the need to carry out studies to your removal of industrial effluents and water bodies. The biopolymer chitosan has been reported in several studies as bioadsorbent with high potential for metal retention, due to the presence of amino groups in its structure. In addition, chitosan has unique properties and is obtained from chitin, one of the most abundant biopolymers in nature. In order to evaluate the Cr (VI) adsorption capacity of the chitosan biopolymer in the form of beads (P-QTS), adsorption tests were carried out in continuous process with different concentrations of the chromium metal in a fixed bed column, filled by adsorbent material (P-QTS). Besides that, toxicity tests were carried out with the organisms Daphnia magna, Allonais inaequalis and Chironomus xanthus on the affluent and effluent of the adsorption column, seeking to evaluate the toxicity of these samples to the organisms and the consequent effectiveness of the treatment of potassium dichromate solution in the fixed bed column with the P-QTS. The breakthrough curves indicated that for the higher concentrations of K2Cr2O7 there was an increase in the saturation of the CALF (fixed bed adsorption column), and consequently the mass transfer zone (ZTM) moved downwards from the fixed bed of the column of adsorption. The C/Co (affluent concentration/effluent concentration) ratio increased significantly during the test for the highest affluent concentrations, reaching values of up to 0.4 for the affluent concentrations of 25 and 28.5 mg L-1 of K2Cr2O7, and this demonstrates the saturation of part of the P-QTS in the fixed bed column. The removal of Cr VI was high (higher than 50% and reaching a maximum of 98%) for the times studied in the present study, but it was higher in the lower times (60 and 120 min) of the test, in which the active sites for adsorption of P-QTS probably were free. From the extraction of chromium from P-QTS, a maximum value of 8.18 mg g-1 and a minimum of 0.42 mg g-1 was obtained, which indicates variation according to the concentration of the K2Cr2O7 solution affluent to CALF, i.e the adsorbed amount of Cr VI per adsorbent mass (P-QTS) is higher at higher concentrations. Some authors have obtained a ratio of 2.6 mg of chromium (III) / g of chitosan indicating that the P-QTS in the fixed bed column have good adsorption capacity. The toxicity tests showed different sensitivities of the test organisms to the solutions of potassium dichromate, being in descending order: Chironomus xanthus < Allonais inaequalis < Daphnia magna. The fixed-bed adsorption column decreased the mortality of the test organisms by comparing the affluent and the effluent, mainly from the effluent samples with the shortest adsorption test time (60 and 120 min). The mean length of the C. xanthus larvae decreased (10.07 mm> 8.34 mm> 4.59 mm), generally as the test time (60, 120 and 180 min) increased, indicating rise in Cr VI concentration in the effluents.

A intensificação da degradação ambiental impulsionada pelas atividades antrópicas tem comprometido a qualidade da água. A presença de metais potencialmente tóxicos no ambiente provoca diversos impactos na fauna e flora, como, por exemplo, o processo de magnificação trófica. Assim, é fundamental que estudos de adsorção desses contaminantes sejam realizados, a fim de buscar novos métodos que permitam a remoção dos mesmos no meio aquático. O metal crômio está nos efluentes de diversos processos industriais, como curtumes, refino de petróleo, galvanoplastia, soldagem e cromagem. Esse metal na forma hexavalente possuí efeito tóxico a biota e riscos à saúde humana, indicando a necessidade da realização de estudos para sua remoção de efluentes industriais e corpos d\'água. O biopolímero quitosana tem sido reportado em diversos estudos como bioadsorvente de alto potencial de retenção de metais, por conta da presença de amino-grupos em sua estrutura. Além disso, a quitosana possui propriedades singulares e é obtida da quitina, um dos biopolímeros mais abundantes na natureza. Com a finalidade de avaliar a capacidade de adsorção de Cr (VI) pelo biopolímero quitosana em forma de pérolas (P-QTS), realizou-se ensaios de adsorção em processo contínuo com diferentes concentrações do metal cromo em coluna de leito fixo, preenchida pelo material adsorvente (P-QTS). Além disso, realizou-se testes de toxicidade com os organismos Daphnia magna, Allonais inaequalis e Chironomus xanthus no afluente e efluente da coluna de adsorção, buscando avaliar a toxicidade dessas amostras para os organismos e a consequente eficácia do tratamento da solução de dicromato de potássio na coluna de leito fixo com as P-QTS. As curvas de ruptura indicaram que para as maiores concentrações de K2Cr2O7 houve intensificação da saturação da CALF (coluna de adsorção de leito fixo), e, consequentemente, a zona de transferência de massa (ZTM) se deslocou no sentido descendente do leito fixo da coluna de adsorção. A razão C/Co (concentração efluente/concentração afluente) aumentou de maneira significativa no decorrer do ensaio para as maiores concentrações afluentes (25 e 28,5 mg L-1) de K2Cr2O7 alcançando valores de até 0,4, e, isso demonstra a saturação de parte das P-QTS na coluna de leito fixo. De maneira geral, a remoção de Cr VI foi alta (superior a 50% e atingindo a máxima de 98%) para os tempos estudados na presente pesquisa, sendo maior nos menores tempos (60 e 120 min) do ensaio, estado em que os sítios ativos para adsorção das P-QTS provavelmente estavam livres. Da extração do cromo das P-QTS obteve-se valor máximo de 8,18 mg g-1 e mínimo de 0,42 mg g-1 de massa adsorvida por massa de adsorvente, o que indica variação de acordo com a concentração da solução de K2Cr2O7 afluente a CALF, ou seja, para as maiores concentrações, maior a quantidade adsorvida de Cr VI por massa de adsorvente (P-QTS). Alguns pesquisadores obtiveram relação de 2,6 mg de crômio (III) /g de quitosana indicando que as P-QTS na coluna de leito fixo possuem boa capacidade de adsorção. Os testes de toxicidade mostraram diferentes sensibilidades dos organismos-teste às soluções de dicromato de potássio, sendo na ordem decrescente: Chironomus xanthus < Allonais inaequalis < Daphnia magna. A coluna de adsorção de leito fixo diminuiu, de modo geral, a mortalidade dos organismos-teste comparando o afluente e efluente, principalmente das amostras efluentes de menor tempo (60 e 120 min) de ensaio de adsorção. A média de comprimento das larvas de C. xanthus reduziu (10,07 mm > 8,34 mm > 4,59 mm), de modo geral, a medida que o tempo de ensaio (60, 120 e 180 min) aumentou, indicando aumento da concentração de Cr VI nos efluentes. / The intensification of environmental degradation driven by anthropic activities has led to a decrease in water quality. The presence of potentially toxic metals in the environment causes several impacts on fauna and flora, such as the trophic magnification process. Thus, it is fundamental that adsorption studies of these contaminants are carried out in order to search for new methods that allow their removal in the aquatic environment. Chromium metal is in the effluents of various industrial processes, such as tanning, petroleum refining, electroplating, welding and chrome plating. The chromium in the hexavalent form has a toxic effect on biota and risks to human health, indicating the need to carry out studies to your removal of industrial effluents and water bodies. The biopolymer chitosan has been reported in several studies as bioadsorbent with high potential for metal retention, due to the presence of amino groups in its structure. In addition, chitosan has unique properties and is obtained from chitin, one of the most abundant biopolymers in nature. In order to evaluate the Cr (VI) adsorption capacity of the chitosan biopolymer in the form of beads (P-QTS), adsorption tests were carried out in continuous process with different concentrations of the chromium metal in a fixed bed column, filled by adsorbent material (P-QTS). Besides that, toxicity tests were carried out with the organisms Daphnia magna, Allonais inaequalis and Chironomus xanthus on the affluent and effluent of the adsorption column, seeking to evaluate the toxicity of these samples to the organisms and the consequent effectiveness of the treatment of potassium dichromate solution in the fixed bed column with the P-QTS. The breakthrough curves indicated that for the higher concentrations of K2Cr2O7 there was an increase in the saturation of the CALF (fixed bed adsorption column), and consequently the mass transfer zone (ZTM) moved downwards from the fixed bed of the column of adsorption. The C/Co (affluent concentration/effluent concentration) ratio increased significantly during the test for the highest affluent concentrations, reaching values of up to 0.4 for the affluent concentrations of 25 and 28.5 mg L-1 of K2Cr2O7, and this demonstrates the saturation of part of the P-QTS in the fixed bed column. The removal of Cr VI was high (higher than 50% and reaching a maximum of 98%) for the times studied in the present study, but it was higher in the lower times (60 and 120 min) of the test, in which the active sites for adsorption of P-QTS probably were free. From the extraction of chromium from P-QTS, a maximum value of 8.18 mg g-1 and a minimum of 0.42 mg g-1 was obtained, which indicates variation according to the concentration of the K2Cr2O7 solution affluent to CALF, i.e the adsorbed amount of Cr VI per adsorbent mass (P-QTS) is higher at higher concentrations. Some authors have obtained a ratio of 2.6 mg of chromium (III) / g of chitosan indicating that the P-QTS in the fixed bed column have good adsorption capacity. The toxicity tests showed different sensitivities of the test organisms to the solutions of potassium dichromate, being in descending order: Chironomus xanthus < Allonais inaequalis < Daphnia magna. The fixed-bed adsorption column decreased the mortality of the test organisms by comparing the affluent and the effluent, mainly from the effluent samples with the shortest adsorption test time (60 and 120 min). The mean length of the C. xanthus larvae decreased (10.07 mm> 8.34 mm> 4.59 mm), generally as the test time (60, 120 and 180 min) increased, indicating rise in Cr VI concentration in the effluents.

The growth of anthropogenic actions, especially industrial development and urbanization, has increased the release of heavy metals in the environment, including hexavalent chromium, Cr (VI), requiring, as a matter of urgency, new processes for pollutants removal, among which are the adsorption processes, which are the focus of this work. Biosorption is an efficient, economical, high selectivity and low energy consumption technique. The main objective of this work was the production of a biosorbent from the crop residues of Cocos nucifera, enhancing it with superparamagnetic properties, as a viable technical and economical alternative, able to adsorb hexavalent chromium ions, Cr (VI), applicable to the treatment of industrial wastewater, expanding pollution control strategies and minimizing environmental impacts. Thus, low concentration coprecipitation routes for the synthesis of nanoparticle (NPs) were proposed, conveying magnetic property to the Cocos nucifera biomass. During the biosorption of hexavalent chromium ions, Cr (VI), the saturation conditions (equilibrium) and the kinetic parameters were evaluated to determine the maximum removal capacity and equilibrium time for the biosorption, besides the optimum conditions for pH, initial concentration, biosorbent content, particle size (grain size), stirring velocity and temperature, providing the fitting of equilibrium models and kinetic constants determination. The biosorbents were characterized by scanning electron microscopy techniques with dispersive energy spectroscopy (SEM/EDS), Fourier transform infrared spectrometry (FT-IR), X-ray diffraction (EDX), X-ray fluorescence with dispersive energy (FR-X/WD), thermogravimetric analysis (TGA), magnetization measurements, zero load point analysis (pCZ), and specific surface analysis through the Brunauer, Emmet and Teller (BET) method. The leachate effluent obtained in the production of the magnetized fibers was characterized through the parameters biochemical oxygen demand (BOD), chemical oxygen demand (COD), total organic carbon (TOC) and pH. The characterization of biosorbents and the determination of kinetic and equilibrium parameters provided the main mechanisms of the biosorption process, giving arise to a possible application on an industrial scale, helping to solve serious environmental problems. / O crescimento das atividades antrópicas, sobretudo o desenvolvimento industrial e o crescimento das cidades têm como consequência o aumento do descarte de metais pesados no ambiente com destaque para o cromo hexavalente, Cr(VI), demandando, urgentemente, novos processos para remoção destes poluentes, dentre os quais os processos adsortivos, que são o foco do presente trabalho. A biossorção tem se destacado como uma técnica eficaz, econômica, de alta seletividade e baixo consumo energético. O objetivo principal desse trabalho é a produção de um biossorvente a partir de rejeitos agrícolas de fibra de Cocos nucifera com propriedades superparamagnética, capaz de adsorver íons de cromo hexavalente, Cr(VI), facilmente aplicável as indústrias, como uma alternativa técnica e econômica viável, ampliando as estratégias de controle de poluentes e minimizando os impactos ambientais. Com essa finalidade foram propostas rotas de síntese de coprecipitação de nanoparticulas (NPs) de magnetita, em baixas concentrações, promovendo propriedade magnética à biomassa das fibras do Cocos nucifera. No processo de biossorção dos íons cromo hexavalente, Cr(VI), foram avaliadas as condições de saturação (equilíbrio) e os parâmetros cinéticos para determinar a capacidade máxima de remoção e o tempo de equilíbrio da biossorção, além das condições ótimas de pH, concentração inicial e carga dos biossorventes, tamanho das partículas (granulometria), velocidade de agitação e temperatura, definindo os modelos de equilíbrio e as constantes cinéticas. Os biossorventes foram caracterizados pelas técnicas de microscopia eletrônica de varredura com espectroscopia de energia dispersiva (MEV/EDS), espectrometria de infravermelho por transformada de Fourier (FT-IR), difratometria de raios-X (EDX), fluorescência de raios-X por energia dispersiva (FR-X/WD), análise termogravimétrica (TGA), medidas de magnetização, análise do ponto de carga zero (pCZ) e análise superficial especifica pelo método de Brunauer, Emmet e Teller (B.E.T). O lixiviado, efluente obtido na produção das fibras magnetizadas, foi caracterizado pelas determinações da demanda bioquímica de oxigênio (DBO), demanda química de oxigênio (DQO), carbono orgânico total (COT) e pH. Como resultado da caracterização dos biossorventes e dos cálculos dos parâmetros cinéticos e de equilíbrio, foi possível sugerir os principais mecanismos do processo de biossorção, facilitando uma possível aplicação em escala industrial, remediando sérios problemas ambientais.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In Brazil, the SMP buffer has been used since the 60's as the main method to estimate the potential acidity and/or the soil lime requirement. However, SMP contains pnitrophenol and potassium chromate, substances with high potential for environmental contamination and able to promote the development of methemoglobin and carcinomas in lab handlers as a result of continued exposure. This work aimed to develop a buffer solution free of hazardous substances which can mimic the acid-base characteristics of the SMP buffer, with the composition used in the states of RS and SC (SMP-RS/SC), in response to the acidity of Brazilian soils. To develop the new buffer, imidazole and 2-(Nmorpholino) ethanessulfonic acid monohydrate (MES) were used as substitutes for pnitrophenol and potassium chromate, respectively. The titration of the buffer SMP-RS/SC with HCl was carried out and these data were used as the starting point for the new buffer reproduce the potentiometric behavior of SMP-RS/SC buffer. To achieve this, multiparametric regression analysis was used, taking as adjustable parameters the pKa values and the concentrations of the components of the new buffer. The final composition for the new buffer, called Santa Maria buffer (TSM) was obtained with: 37.5 mM of triethanolamine; 17.3 mM of imidazole; 30.7 mM of MES; 20.7 mM of calcium acetate and 721 mM of calcium chloride; with initial pH adjusted to 7.5. For comparison between TSM and SMP-RS/SC, we utilized 42 soil samples collected in different physiographic regions of Brazil. Linear regression was performed with pH-SMP and pHTSM values, and also, between the lime requirement by SMP and TSM, reaching determination coefficient (R2) greater than 0.99 in both cases. The TSM had equivalent sensitivity to the SMP-RS/SC in differentiating the acidity degree of soils, and can be used replacing this, without the need for change in routine laboratory and interpretations already developed to estimate the potential acidity or need limestone of soil. At temperature from 22 to 27 °C, the TSM has a long shelf life and can be stored in plasticpolypropylene or glass containers protected from light, for a period of 120 to 150 days. The replacement of SMP-RS/SC buffer by TSM is a viable alternative for soil testing laboratories to avoid the generation of hazardous wastes and to reducing the health risks for the lab handlers. / No Brasil, o tampão SMP vem sendo utilizado desde a década de 60 como o principal método para a estimativa da acidez potencial e/ou da necessidade de calcário do solo. No entanto, em sua composição, a solução SMP apresenta p-nitrofenol e cromato de potássio, substâncias essas com elevado potencial de contaminação ambiental e capazes de promover o desenvolvimento de metahemoglobina e carcinomas aos seus manipuladores, como conseqüência da exposição continuada. Este trabalho teve como objetivo principal desenvolver uma solução tampão livre de substâncias tóxicas, capaz de mimetizar as características ácido-base do tampão SMP, na composição utilizada nos estados do RS e SC (SMP-RS/SC), em resposta à acidez de solos brasileiros. Para o desenvolvimento do novo tampão, utilizaram-se como substitutos ao p-nitrofenol e ao cromato de potássio, o imidazol e o ácido 2-(N-morfolino) etanossulfônico monohidratado (MES), respectivamente. Realizou-se a titulação do tampão SMP-RS/SC com HCl e esses dados de titulação foram utilizados como ponto de partida para que o novo tampão reproduzisse o comportamento potenciométrico do tampão SMP-RS/SC. Para tanto, empregou-se análise de regressão multiparamétrica, considerando como variáveis os valores de pKa e as concentrações dos componentes do novo tampão. A composição final para o novo tampão, denominado Tampão Santa Maria (TSM), foi obtida com: 37,5 mM de trietanolamina; 17,3 mM de imidazol; 30,7 mM de MES; 20,7 mM de acetato de cálcio e 721 mM de cloreto de cálcio; com pH inicial ajustado a 7,5. Para comparação entre o TSM e o SMP-RS/SC, utilizaram-se 42 amostras de solo oriundas de diferentes regiões fisiográficas do Brasil. Ajustou-se regressão linear entre os valores de pH-TSM e pH-SMP, e também, entre a recomendação de calcário por TSM e por SMP, alcançando-se coeficiente de determinação (R2) superior a 0,99 em ambos os casos. O TSM apresentou sensibilidade equivalente ao SMP-RS/SC na diferenciação do grau de acidez dos solos estudados, podendo ser utilizado em substituição a esse, sem a necessidade de alteração da rotina e das interpretações laboratoriais já desenvolvidas para a estimativa da acidez potencial ou necessidade de calcário do solo. À temperatura de 22 a 27 ºC, o TSM apresenta uma longa vida útil, podendo ser armazenado em recipiente de plástico-polipropileno ou vidro protegido da luz, por um período de 120 a 150 dias. A substituição do tampão SMP-RS/SC pelo TSM é uma alternativa viável para os laboratórios de análise de solo evitarem a geração de resíduos perigosos e reduzirem os riscos à saúde dos técnicos manipuladores.

Submitted thesis deal with estimation safeness of electroplating technologi with reference to occurrence hazardous substances falls on man and environment. To identification diversification was used quantitative risk assessment and chemical exposure index.

L’utilisation du chrome hexavalent pour le traitement de surface des matériaux de l’aéronautique est en passe d’être interdite par la réglementation REACH. Dans l’objectif de trouver une solution alternative, PROTEC industrie et le CEA travaillent en collaboration sur le développement d’une nouvelle solution sans-chrome permettant de remplacer les revêtements classiquement utilisés. Le travail de thèse présenté dans ce manuscrit s’inscrit dans le cadre du laboratoire commun MESTREL financé par le programme ANR Labcom, réunissant les deux entités citées ci-dessus. La solution proposée est basée sur le greffage d’un revêtement organique inspiré de la chimie des sels de diazoniums à la surface de l’Al2024-T3, alliage de référence du secteur aéronautique. Cette thèse vise initialement à déterminer les conditions pour lesquelles les propriétés du film greffé se rapprochent le plus de celles de son prédécesseur. Pour cela, des caractérisations spectroscopiques et électrochimiques des films greffés ont été réalisées. Les protocoles de microscopies électrochimiques développés ont notamment permis de sonder le niveau de passivation de la couche. La haute porosité du film greffé, nous a ainsi permis d’imaginer et de développer un système bicouche innovant combinant les propriétés anticorrosion des solutions actuelles aux hautes propriétés d’adhérence du film organique fonctionnalisé. En parallèle, une méthode de dépôt hors-cuve a été développée pour générer un gain économique important et faciliter le traitement de pièces de grandes dimensions. / The use of hexavalent chromium for anticorrosion surface treatments in aeronautics field will soon be banned by the REACH reglementation. Looking for an innovative solution, PROTEC industry and the CEA research center work in collaboration with the aim of developing a chromium free replacement treatment, which can substitute current solution and give competitive results both in adhesion and corrosion protection. The thesis project presented in this manuscript is part of a common laboratory named MESTREL, including the two entities. The proposed solution is based on the grafting of a polymeric film inspired by the diazonium chemistry on an Al2024-T3 surface, reference alloy in the aeronautic field. The principal objective of the thesis is to determinate the best conditions of grafting, -giving similar properties to chromium treatment. To this end, spectroscopic and electrochemical characterizations have been performed. Electrochemical Microscopy protocols are developed to assess the passivation properties of the film The high porosity of the film has allowed to develop a new innovative bilayer process combining anticorrosive properties of current solution and adhesion properties of the functionnal coating. At the same time, an out-of-tank deposition technique is developed. The goal is to enable economic benefits and facilitate treatment of very large aeronautic pieces.

[pt] Esta dissertação apresenta os resultados obtidos no processo de remediação de uma área contaminada por cromo hexavalente por meio da técnica de remediação química in situ (ISCR). A área de estudo localiza-se na cidade do Rio de Janeiro e foi ocupada por uma fábrica de vidros por cerca de quarenta anos e comprada para construção de condomínios residenciais. A área de estudo passou um processo de gerenciamento ambiental que contemplou diversos estudos ambientais para aquisição de dados e delimitar a contaminação, horizontal e verticalmente. O teste de bancada realizado com o reagente químico polissulfeto de cálcio demonstrou ser eficiente para reduzir as concentrações de cromo hexavalente em solo e água subterrânea. Com base nos dados adquiridos neste teste foi possível calcular a dose de injeção do polissulfeto de cálcio. Foram realizados setenta pontos de sondagem, pela técnica direct push, para injetar duzentos e cinquenta e dois mil e trinta litros de solução de polissulfeto de cálcio e água, sendo aproximadamente três mil e quinhentos litros por ponto de injeção. Os resultados após a injeção demonstraram que o polissulfeto de cálcio conseguiu remover o cromo hexavalente que estava adsorvido ao solo e reduziu a concentração de cromo hexavalente na água subterrânea entre quarenta e seis e sessenta e sete e noventa e nove e noventa e cinco por cento , após dezenove meses da injeção. Dessa forma, comprovou a eficiência deste reagente químico para remediação de áreas contaminadas por cromo hexavalente, assim como foi observado nos artigos técnicos de estudos de casos nos Estados Unidos e Europa. / [en] This dissertation presents the results obtained in the remediation process remediation of a contaminated area by hexavalent chromium applying the technology in situ chemical remediation (ISCR). The study area is located in the Rio de Janeiro city and was occupied by a glass factory for forty years and purchased for construction of residential condominiums. This dissertation presents the results obtained in the remediation process remediation of a contaminated area by hexavalent chromium applying the technology in situ chemical remediation (ISCR). The study area is located in the Rio de Janeiro city and was occupied by a glass factory for forty years and purchased for construction of residential condominiums. Chromium is an important metal for the industry and is used in various products and processes, such as electroplating, leather treatment, pulp, wood preservation, and refractory manufacturing. The trivalent chromium is essential from a nutritional point of view, non-toxic and poorly absorbed in the body, acting in the maintenance of some functions. Cr(III) is the most common being found and occurs naturally, since the element Cr(VI) can occur naturally, but in low concentrations, if the groundwater has geochemical conditions the Cr (III) can be oxidize to Cr (VI). The hexavalent chromium is the most dangerous valence state and, according to ATSDR (two thousand and twelve), have greater mobility in the groundwater, being carcinogenic by inhalation of high doses of soluble chromate salts. The mobility of hexavalent chromium is high in soil and groundwater because it is not adsorbed by the soil in that valence state, on the other hand when it is in trivalent form is strongly adsorbed by the soil, forming insoluble precipitates, having low mobility in soil and groundwater. The hexavalent chromium remediation by in situ chemical reduction using calcium polysulfide has been the subject of several field studies documented in the literature, both for soil and groundwater from the Chromite Ore Processing Residue (COPR) (Storch, et al., two thousand and two; Graham, et al., two thousand and six ; Charboneau, et al., two thousand and six ; Wazne, et al., two thousand seven a; Wazne, et al., two thousand seven b; Chrysochoou, et al., two thousand and ten ; Chrysochoou & Ting, two thousand and eleven ; Pakzadeh & Batista, two thousand and eleven ; Chrysochoou, et al., two thousand and twelve ). Calcium polysulfide is a fertilizer to soil and commercially available and has been used in some remediation studies cases for reducing hexavalent chromium in soil and groundwater. Being commercially available and used as fertilizer, it is a relatively cheap chemical reagent in comparison with other chemical compounds exclusively developed for this purpose. The stoichiometric demand and the chemical kinetics of the reduction of Cr (VI) by the calcium polysulfide in aqueous solution was studied by Graham et al. (two thousand and six) from the chromite ore processing residue (COPR). With this study it was reported that a molar ratio of a point sixty-six is required (close to the theoretical value of one point five) and a first-order kinetics with an initial concentration of twenty-six eight point mg/L and pH of the CPS solution around eleven point five, with the presence of oxygen. Thus, the hexavalent chromium is reduced to chromium hydroxide, slightly water soluble compound which is precipitated to the soil. The trivalent chromium has low solubility, toxicity, mobility, reactivity and is considered stable. There are various application techniques of chemical reagents in the underground environment, and choosing the most appropriate method for each area depends on the type of contaminant, geological environment, groundwater and surface interference, depth, thickness and size of the contaminated area. As described by Suthersan (mil novecentos ninety-six), the injection of chemical reagents has to achieve two objectives: (one) creating and maintaining an ideal redox environment and other parameters such as pH, presence or absence of dissolved oxygen, etc.; and (two) the delivery and distribution of the necessary reagents for a homogeneous way throughout the injection area, both horizontally and vertically. Thus, it is essential that the conceptual model of the study area is very detailed, so there is no doubt in the choice of chemical reagent application methodology. Although there are numerous laboratory studies on hexavalent chromium remediation using calcium polysulfide, there are few reports in the literature on the field application, especially case studies in Brazil, therefore, this case study becomes a demonstration applying calcium polysulfide as a remediation technique for hexavalent chrome, with geochemical data, which are important for monitoring chemical reduction. This case study shows the effectiveness, dosage and concentration of the study area, and may apply to other hexavalent chromium remediation projects. Materials and Methods A former glass factory (the Site ) operated in the North Zone of Rio de Janeiro / RJ, Brazil from the mid-thousand nine hundred and fifty s to two thousand and five. A portion of the facility was used to store raw material to produce glass, including arsenic oxide, and another portion of the Site was used to conduct industrial plating using hexavalent chromium (Cr(VI)) in the glass molds. In two thousand and nine, the Site was purchased for mixed use redevelopment, demanding an environmental assessment and subsequent remediation. Between two thousand and nine and two thousand and twelve several phases of site investigation was conducted. The results of the investigation indicated that Cr(VI) was present in soil at concentrations up to approximately twenty one mg/kg and in groundwater at concentrations up to approximately thirty mg/L. These concentrations exceeded regulatory criteria of three hundred mg/Kg for soil and zero point zero five mg/L for groundwater. A phased remedial approach was developed consisting of the following: (a) excavation and off-site disposal of two and four hundred ton of Cr(VI) impacted soil from the source area, performed in the unsaturated and saturated zone soils in the Cr(VI) source area; (b) post-excavation monitoring of the groundwater conditions; and (c) groundwater treatment following the excavation program. Hexavalent chromium concentrations in groundwater decreased significantly following the excavation, however, additional reduction of concentrations of Cr(VI) contaminant in groundwater was required. Then was designed and implemented a set of bench-scale treatability tests in order to evaluate groundwater remediation alternatives. Several proprietary and non-proprietary reductants for co-treatment of Cr(VI) were evaluated. Calcium polysulfide were selected to treat Cr(VI). To reduce residual Cr(VI) concentrations in the groundwater plume located downgradient of the former excavated source area, dois e seven hundred cubic meters were targeted for active treatment. The groundwater remediation approach consisted of the injection of thirty liters of CPS (twenty nine percent) diluted in two hundred and twenty liters of water, yielding a total of two hundred and fifty liters of solution injected using direct push technology into seventy two locations. Groundwater Monitoring As part of chemical reagent injection stage was performed the baseline monitoring with collection of soil and groundwater samples. The soil sampling was performed by direct push technique using PVC liner with two inches in diameter, to analyze the total and hexavalent chromium concentrations. Six months after the injection were installed sixteen monitoring wells, eight shallow wells (five meters) and eight deep wells (nine meters) spread upstream, side, middle and downstream of the injection area. Groundwater geochemical parameters (i.e., temperature, total solids dissolved, specific conductance, pH, oxidation-reduction potential, and temperature) were measured at the time groundwater samples were collected. Groundwater samples were collected and analyzed for total and dissolved chromium, hexavalent chromium, iron, arsenic, manganese, calcium, sulfate, and sulfide. Samples were field-filtered with disposable zero point forty-five μm polyethylene filter capsules prior to collecting samples for dissolved metals. Results and Discussion Dose calculations for the reduction of hexavalent chromium have been performed with the data obtained in the bench-scale treatability test and resulted in a stoichiometric demand of four mlCPS/kg soil to the treatment of the study area. Therefore thirty liters of solution was used containing twenty-nine percent calcium polysulfide and approximately two hundred and twenty two liters to perform their mixture, totaling two hundred and fifty-two thousand and thirty liters of solution. For solution injection were performed seventy two soil borings with eight point five meters deep, and the product was injected range between two point five and eightpoint five meters. The depth of injection was from two point five mbgl covered any change in water level due to seasonal variation. In each soil boring was injected chemical reagent solution comprised four hundred and seventeen liters of calcium polysulfide diluted in tree and eighty-three liters of water for a total volume of tree and a half liters of solution injected per point. The comparative analysis results of the third monitoring campaign ( eighteen months post-injection) with the baseline campaign (september/two thousand and twelve) indicated reduction of hexavalent chromium concentrations between forty-six point sixty-seven and ninety-nine and ninety-five percent. Regarding the second monitoring campaign (twelve months post-injection), the hexavalent chromium concentrations reduced between twenty-three point ninety-nine and ninety nine point seventy-nine percent in five of the fifteen monitoring wells that were sampled. In three of the fifteen monitoring wells the hexavalent chromium concentrations remained below the quantitation limit used by the analytical laboratory method. There was no increase in hexavalent chromium concentration, compared the results of the third and second monitoring campaign. The evaluation of the Eh and pH values measured in the monitoring campaigns showed that the pH value was in the acidic range (about four ) and after removal of contaminated soil with hexavalent chromium pH raised to between five and six, after the chemical reagent injection pH increased to the basic range (above seven point five). In the second and third campaign the pH reduced to acid range (below six point five), which can be regarded as the pH value of the area background. The Eh has inversely proportional behavior, increasing between the first and third campaign, and in the third campaign the measured values are in the ranges considered as moderately reducing (hundred to four hundred mV) and oxidizer (> four hundred mV). The pH variation also showed a relationship between increased concentrations of calcium, iron, manganese and sulfate (in some monitoring wells). There were also reductions in hexavalent chromium concentrations in monitoring wells. Conclusion This case study indicates that the use of different remediation techniques when applied together (excavation and chemical reduction), reducing the time required for remediation of a contaminated site without impacting the final cost of remediation. The chemical reduction of hexavalent chromium using calcium polysulfide was effective to reduce the concentration to less than the quantification limit of the analytical method used. Therefore, as presented it is necessary to carry out several studies to detail the hexavalent chromium concentration in the site, as well as understand the geochemistry of groundwater and performing bench-scale tests to evaluate the effectiveness of the chemical reagent in the site study hydrogeological environment and calculate the required dose. The treatability test with calcium polysulfide demonstrated the feasibility of using this chemical reagent by In Situ Chemical Reduction (ISCR) to reduce the hexavalent chrome concentration in soil and groundwater. The test resulted in a stoichiometric demand of four mlCPS /kg soil to the treatment of the study area. Soil samples collected six months after injection showed that the calcium polysulfide could desorb hexavalent chromium from the soil, since, contaminant concentrations were not detected in the samples. neteen months after the injection of the chemical reagent the groundwater concentrations of hexavalent chromium reduced from forty-six point sixty-seven to ninety-nine and ninety-five percent in relation to baseline campaign. And, of the fifteen monitoring wells in just three wells hexavalent chromium concentrations were detected. This demonstrates the effectiveness of using calcium polysulfide to remediate hexavalent chromium in soil and groundwater, confirming the studies by Storch et al. (two thousand and two), Graham et al (two thousand and six), Charboneau et al. ( two thousand and six), Wazne et al. (two thousand and seven a), Wazne et al. (two thousand and seven b), Chrysochoou et al. (two thousand and ten), Chrysochoou & Ting (two thousand and eleven), Pakzadeh & Batista (two thousand and eleven), Chrysochoou et al (2012) in several areas in United States and Europe.

No description available.

No description available.