The study was done to understand the direction in which South Africa’s mining model is developed and the changes required for South Africa to take its rightful place in the mainstream spheres of economic and commercial affairs. The huge demand for African commodities is creating new opportunities for African governments to realise the hopes of their people for a better life. The objective of this study is to analyse the South African mining model to determine the sustainability of mining in South Africa. It was done by analysing Chrome, Coal and Platinum as selected minerals and metals. A literature study was conducted and the focus was on the reserves and resources that South Africa has in these minerals and metals, the current supply and demand factors and estimates were done on the future demand. The last part was to determine the state of and planned expansions of infrastructure like Electricity supply, Shipping Ports, Rail transport, Road transport and Water supply that mining operations require. Following the literature study, a survey was conducted in order to support the findings of the literature study and to determine the most important factors that can influence investment decisions in the mining sector by evaluating the investor’s acceptability of South Africa’s mineral and resource industry. It was concluded that the South Africa mining module is well developed with the required skills and knowledge for sustainable mining in the future. It was determined that there would be a future market to maintain a sustainable mining module. The major risk for the sustainable mining module is the reliance on infrastructures required in the mining environment, which is under governmental management. Survey results concluded that South Africa is not an investor-friendly country mainly because of its ineffective administration processes to perform mining. Investors are also seeking for independence of regulatory institutions. A recommendation for future research would be to determine the optimum South African Governmental needs of the investment in infrastructure capital to ensure that the country’s economy will be able to grow.The study was done to understand the direction in which South Africa’s mining model is developed and the changes required for South Africa to take its rightful place in the mainstream spheres of economic and commercial affairs. The huge demand for African commodities is creating new opportunities for African governments to realise the hopes of their people for a better life. The objective of this study is to analyse the South African mining model to determine the sustainability of mining in South Africa. It was done by analysing Chrome, Coal and Platinum as selected minerals and metals. A literature study was conducted and the focus was on the reserves and resources that South Africa has in these minerals and metals, the current supply and demand factors and estimates were done on the future demand. The last part was to determine the state of and planned expansions of infrastructure like Electricity supply, Shipping Ports, Rail transport, Road transport and Water supply that mining operations require. Following the literature study, a survey was conducted in order to support the findings of the literature study and to determine the most important factors that can influence investment decisions in the mining sector by evaluating the investor’s acceptability of South Africa’s mineral and resource industry. It was concluded that the South Africa mining module is well developed with the required skills and knowledge for sustainable mining in the future. It was determined that there would be a future market to maintain a sustainable mining module. The major risk for the sustainable mining module is the reliance on infrastructures required in the mining environment, which is under governmental management. Survey results concluded that South Africa is not an investor-friendly country mainly because of its ineffective administration processes to perform mining. Investors are also seeking for independence of regulatory institutions. A recommendation for future research would be to determine the optimum South African Governmental needs of the investment in infrastructure capital to ensure that the country’s economy will be able to grow. / Thesis (M.B.A.)--North-West University, Potchefstroom Campus, 2012

Thesis (MSc(Geography and Environmental Studies))--University of Stellenbosch, 2011. / ENGLISH ABSTRACT: In an area where mining activities dominate, there are likely to problems that need effective environmental management approaches, which can be facilitated through legislation and environmental management systems (EMS). The Great Dyke in Zimbabwe is a strategic economic resource with significant quantities of chrome and platinum. Chrome mining occurs across the whole length of the Great Dyke with most of the operations under Zimasco claims. Zimasco mining operations fall into two categories: the organization‟s own claims operated in its own right and claims that are leased out to a second party forming a tribute system from which tributor miners produce chromite ore exclusively for Zimasco. This study examines the environmental management approaches used by Zimasco operations, in particular the National Occupational Safety Association (NOSA) Integrated Five Start System, in order to identify the usefulness of EMS in the mining industry. Firstly, the current environmental impacts associated with the mining activities were identified and problem areas highlighted, after which environmental management approaches linked to national legislation were examined in terms of their contribution towards sound environmental management. A legal compliance checklist was carried out on the existing mines to assess levels of compliance to standards stipulated in the Environmental Management Act Chapter 20:27. This was followed by questionnaire surveys used for impact identification and the data was analysed using the aspect and impact analysis matrix. Underground mines with effluent discharges were assessed by means of an effluent analysis as a way of determining the effectiveness of the approaches on the mines. Recommendations for changes were made following a Strength Weaknesses Opportunities and Threats (SWOT) analysis of the approaches and system. Major environmental problems highlighted included unattended waste rock dump and pits as well as dissolved substances in effluent discharge. Although evidence of compliance to environmental legislation for the mining operations was found at administrative level, this was often not executed in operation. Limited hazards were observed in effluent discharge from mines under full implementation of the EMS. It is recommended that all mining operations need to be covered by an EMS system for improved environmental management and sustainable development. Effective implementation of legislation and EMS on the ground provides a better platform for sound environmental management. / AFRIKAANSE OPSOMMING: In 'n area waar grootskaalse mynbou aktiwiteite die omgewing kan affekteer word effektiewe omgewingsbestuur benodig. Die Groot Dyk in Zimbabwe is 'n strategiese ekonomiese hulpbron met groot hoeveelhede chroom en platinum. Chroom word grotendeels onder Zimasco kleims langs die Groot Dyk ontgin. Zimasco mynbedrywighede val in twee kategorieë: eerstens eie kleims wat direk deur Zimasco bedryf word, en tweedens kleims wat aan 'n tweede party verhuur en bewerk word en chroom eksklusief aan Zimasco lewer. Die omgewingsbestuursbenadering wat deur die Zimasco mynbedrywighede gebruik word, veral die NOSA Geïntegreerde Vyfster Stelsel, is bestudeer om vas te stel of omgewingsbestuurstelsels (OBS) effektief kan wees in die mynbedryf. Eerstens is die huidige omgewingsimpte veroorsaak deur mynbedrywighede geïdentifiseer en probleemareas uitgelig. Verder is die omgewingsbestuursbenadering in die lig van nasionale wetgewing bestudeer om die bydrae tot gesonde omgewingsbestuur toe te lig. 'n Lys is opgestel waarin die mate waartoe geselekteerde myne aan bestaande wetgewing voldoen bepaal is. Vraelyste is ook gebruik om die omgewingsimpak te identifiseer en data is met behulp van die aspek en impak analise matriks geanaliseer. 'n Afvoeranalise is op ondergrondse myne gedoen ten einde die effektiwiteit van omgewingsbestuursbenadering op die myn te bepaal, terwyl 'n SWOT analise van beide die benadering en die NOSA Vyfster Stelsel uitgevoer is met die oog op aanbevelings. Die belangrikste omgewingsimpakte langs die Groot Dyk sluit in: afvalrotshope, kuipe en slote vanaf oppervlakbedrywighede asook opgeloste afval in afloop vanaf ondergrondse myne. Bewyse van voldoening aan omgewingswetgewing is wel gevind in myndokumentasie, maar nie altyd in die praktyk nie. Laer vlakke van toksiese uitvloeisel vanaf myne waar OBS geïmplementeer is, is bewys van die suksesvolle gebruik van „n geïntegreerde OBS. Alle mynaktiwiteite moet ingesluit word in „n OBS stelsel om beter omgewingsbestuur en volhoubare ontwikkeling te verseker. Effektiewe implementering van wetgewing en OBS op die laagste vlak in mynaktiwiteite bied 'n beter platform vir gesonde omgewingsbestuur in die mynbedryf.

L’écotoxicité des éléments traces vis-à-vis du vivant est contrôlée par leur bioaccessibilité, leur biodisponibilité et leurs interactions avec le(s) site(s) d’action à l’intérieur des organismes. Dans le cas des certains éléments, l’existence dans le milieu naturel de plusieurs formes redox ayant des propriétés différentes doit aussi être prise en considération. Dans le cas spécifique du Cr, le consensus général considère le Cr(III) comme moins écotoxique que le Cr(VI). Toutefois, plusieurs études récentes soulignent que ce consensus devrait être réexaminé. Plus particulièrement, une connaissance insuffisante de la spéciation du Cr(III) pendant les tests en laboratoire pourrait avoir conduit à une sous-estimation de sa biodisponibilité et écotoxicité. Ce travail de thèse s’intéresse donc aux relations entre spéciation, biodisponibilité et bioaccumulation du Cr(III) et Cr(VI) dans différents modèles biologiques pour mieux appréhender leur potentiel écotoxique ainsi que leurs mécanismes d’interaction avec le vivant. Des études ont été menées chez les algues Pseudokirchneriella subcapitata et Chlamydomonas reinhardtii, le bivalve Corbicula fluminea et des cultures de cellules d’ovaire d’hamster chinois (CHO). L’ensemble des résultats de ce travail suggère que la validité du paradigme ‘le Cr(VI) est plus écotoxique que le Cr(III)’ serait dépendante des conditions d’exposition et du modèle biologique utilisé. Ce paradigme, accepté tant par la communauté scientifique que par les gestionnaires environnementaux, nécessite donc un réexamen afin d’assurer une meilleure gestion des risques liés au Cr / The ecotoxicity of the trace elements to the living organisms is controlled by their bioaccessibility, their bioavailability and their interactions with the site(s) of action inside the organisms. In the case of certain elements, the existence in the natural environment of several redox forms having different properties must also be taken into consideration. In the specific case of Cr, general consensus considers Cr(III) to be less ecotoxic than Cr(VI). However, several recent studies highlight that this consensus should be re-examined. In particular, insufficient knowledge of Cr(III) speciation during laboratory tests may have led to an underestimation of its bioavailability and ecotoxicity. This work focuses on the relationship between speciation, bioavailability and bioaccumulation of Cr(III) and Cr(VI) in different biological models in order to better understand their ecotoxic potential as well as their mechanisms of interaction with living organisms. Studies have been conducted on the algae Pseudokirchneriella subcapitata and Chlamydomonas reinhardtii, the bivalve Corbicula fluminea and cultures of Chinese hamster ovary cells (CHO). The results of this work suggest that the validity of the paradigm ‘Cr(VI) is more ecotoxic than Cr(III)’ would be dependent on the exposure conditions and the used biological model. This paradigm, accepted by both the scientific community and the environmental managers, requires a reassessment to ensure a better management of Cr risks

A presença de elevados teores de elementos metálicos nos resíduos industriais desperta o interesse no seu reaproveitamento. O setor coureiro-calçadista, por exemplo, importante no estado do Rio Grande do Sul, produz resíduos perigosos provenientes da etapa de curtimento do couro ao cromo. A possibilidade de utilização deste importante metal contido no resíduo se tornou realidade a partir da introdução, em nível piloto, de uma unidade de incineração. A cinza dos resíduos é utilizada, neste trabalho, como matéria-prima para a produção de uma liga ferro-cromo do tipo alto carbono (FeCrAC) – que tem amplo emprego na produção de aço-inoxidável; outros resíduos industriais do Estado também são utilizados neste processo extrativo. A cinza – denominada CIAC neste trabalho –, matéria-prima principal e fonte de cromo, contém ~50% Cr2O3. Outros resíduos empregados como insumos foram: finos de carvão vegetal da produção de carvão para a preparação de alimentos, sílica proveniente de operações de polimento de peças de ágata, carepa de produtos siderúrgicos e casca de ovos. O cálculo da carga foi realizado com a ajuda da termodinâmica computacional, pela simulação do processo de redução carbotérmica na temperatura de 1600 °C e pressão de 1 atm. A simulação utilizou algumas metas como diretrizes: i) obtenção de uma escória com a menor temperatura sólidus possível; (ii) obtenção de uma escória de baixa viscosidade; e, (iii) obtenção de teores apropriados de Cr e C na liga. Devido ao alto teor de P da CIAC, um procedimento experimental para a redução deste elemento foi estabelecido tendo por base (i) o uso de reagentes baratos e (ii) a sinergia que decorre da conjunção destes reagentes. Para a produção da liga ferro-cromo, seis tipos de experimentos foram realizados variando-se a composição da carga (fontes do cromo e ferro) e dois lotes diferentes da cinza. Os teores de Cr e C nas ligas FeCr obtidas nos experimentos variaram entre: 50 - 60 % Cr e 7 - 10% C, demonstrando a possibilidade de reutilização do cromo contido nas cinzas, para produção da liga FeCr. / The presence of high levels of metals in industrial waste arouses interest in its reuse. The leather-footwear industry, for example, important in the state of Rio Grande do Sul, produces hazardous Cr-containing waste from the leather tanning stage. The possibility for reuse of this important metal contained in the residue became a reality with the introduction, in a pilot project, of an incineration plant. The ash waste is used in this work as a raw material for the production of high carbon ferro-chrome type (FeCrAC) - which has wide use in the production of stainless steel; other industrial waste are also used in this extraction process. Ash - called CIAC thereafter - the main raw material and source of chromium, contains ~ 50% Cr2O3. Other residues employed as inputs were: coal fines from coal production plant for food preparation, silica from polishing operations from pieces of agate mill, scale from steel products and egg shell. The reactor load calculation was carried out with the help of computational thermodynamics, the simulation being of the carbothermic reduction process at a temperature of 1600 °C and 1 atm pressure. The simulation used as targets some guidelines: i) production of a slag with a lower solidus temperature as possible, (ii) or a low viscosity slag, and (iii) to provide suitable amounts of C and Cr in the alloy. Due to the high P content of CIAC, an experimental procedure for the reduction of this element was established based on (i) the use of inexpensive reagents, and (ii) the synergy arising from the combination of these reagents. For the production of ferro-chromium six types of experiments were performed varying the charge composition (sources of Cr and Fe) and two different lots of ash. The Cr and C contents in FeCr alloy in the experiments varied between 50 - 60% Cr and 7 - 10% C, demonstrating the possibility for reuse of Cr contained in the ashes for the production of FeCr alloy.

Devido à necessidade de obtenção de uma superfície resistente ao desgaste e a oxidação, os cilindros hidráulicos são tradicionalmente revestidos com cromo duro eletrodepositado. Todavia, este tipo de revestimento apresenta uma redução gradual do coeficiente de atrito, interferindo diretamente na lubrificação da haste, ocasionando danos aos elementos de vedação e promovendo consequentes vazamentos. Outro apelo contrário à utilização do processo de revestimento com cromo é a presença, em elevados níveis, de cromo hexavalente Cr+6, apresentando alto poder cancerígeno e de contaminação ambiental. Atualmente, o processo de aspersão térmica em alta velocidade (HVOF - High Velocity Oxi-Fuel) se caracteriza como uma técnica de revestimento alternativa ao cromo duro, utilizando materiais compósitos (metal-cerâmico), os quais propiciam baixas taxas de desgaste. Este trabalho tem como objetivo avaliar o desempenho de revestimentos aplicados em hastes de cilindros hidráulicos revestidas com WC-CoCr pelo processo HVOF, em comparação ao revestimento de cromo duro eletrodepositado. As técnicas de caracterização empregadas foram divididas em duas etapas, sendo que a primeira foi: análise microestrutural, ensaios de dureza e desgaste, medições de rugosidade e perfilometria, em corpos de prova planos e, na segunda etapa, a análise dos revestimentos adquiridos através de uma bancada de testes de hastes de cilindros hidráulicos, onde a caracterização foi obtida através de, medições específicas dos principais parâmetros de rugosidades aplicadas a superfícies de vedação, como Rz, Rmáx e Rmr, desgaste visuais das hastes e vedações e medições de vazamento de óleo. Ao final, os resultados mostram que o revestimento aspergido, indica características competitivas em relação à eletrodeposição de cromo, podendo ser aplicado em hastes de cilindros hidráulicos com algumas vantagens, como por exemplo, maior resistência ao desgaste, menor coeficiente de atrito, menores taxas de vazamento e melhores condições finais de superfícies. / To obtain a surface that is resistant to wear and oxidation, hydraulic cylinders are typically coated with in hard chromium through the process of electroplating process. However, this type of coating displays a gradual reduction of the friction coefficient as the lubrication directly interferes with the shaft mechanism, which in turn causes damage to the sealing elements and promotes subsequent leakage. Another disadvantage in using the electroplated hard chromium process is the presence of high level hexavalent chromium Cr+6 which is not only carcinogenic, but also extremely contaminating to the environment. Currently, the alternative process of high-speed thermal spraying (HVOF - High Velocity Oxy-Fuel), as opposed to hard chrome coating, uses composite materials (metalceramic) possessing low wear rates. This study aims to evaluate and compare the performance of hydraulic cylinder rods coated with WC-CoCr in the HVOF process, and those coated with electroplated hard chromium. The characterization techniques employed were divided into two steps, the first of which was: microstructural analysis, testing the hardness, wear, roughness and profilometry and on specimens plans and, in the second step, analysis of the coating obtained through a bench test rods of hydraulic cylinders, where the characterization was through achieved , specific measurement of the main parameters of roughness applied to sealing surfaces, as Rz, Rmáx and Rmr, wear visual of the rods and seals and measurements of oil leakage. At the end, the results show that the sprayed coating, indicate competitive characteristics in relation to the electrodeposition of chromium, which can be applied in rods of hydraulic cylinders with some advantages, such as improved wear resistance, coefficient friction low, lower rates of leakage and condition final better surface.

La faible masse volumique et les bonnes propriétés mécaniques des alliages d’aluminium en font des matériaux de structure de choix dans l’industrie aéronautique. Ils présentent une microstructure polyphasée qui crée des discontinuités électrochimiques et une sensibilité accrue à la corrosion. Un système de revêtements protecteurs composé de chromate Cr(+VI) est traditionnellement formé à la surface de ces alliages. Néanmoins, les directives environnementales REACH imposent leur remplacement en raison de la cancérogénicité des chromates. L'objectif des travaux a été le développement d'un nouveau traitement constitué d’une Oxydation Anodique Sulfurique (OAS) et d’un colmatage aux sels de sulfate de chrome et de fluorozirconate (Cr3+ / ZrF62-). L’étude du procédé électrochimique d’OAS a permis de faire le lien entre la microstructure des alliages et la morphologie poreuse de la couche anodique développée à leur surface. Le traitement de colmatage Cr3+ / ZrF62- est réalisé par simple immersion dans la solution. Il est démontré que le colmatage est le fait d’une alcalinisation locale de la surface de la couche anodique qui mène à la précipitation des sels de Cr3+ et ZrF62-. Ces derniers forment un film de colmatage de 300 nm d’épaisseur très recouvrant des pores nanométriques. Le colmatage des couches anodiques permet d’améliorer considérablement la tenue à la corrosion des alliages anodisés en formant une barrière supplémentaire contre les agents corrosifs et en cicatrisant les départs de corrosion. Le traitement développé permet à la fois d’atteindre les performances des traitements aux Cr(+VI) sur une large gamme d’alliages et de satisfaire aux exigences environnementales / Aluminium alloys are very used in the aircraft industry as structural materials because of their low density and their good mechanical properties. They have a polyphase microstructure that is causing electrochemical discontinuities and increasing sensitivity to corrosion. A system of protective coatings containing chromate Cr(+VI) is traditionally formed at the surface of these alloys. However, the REACH environmental guidelines impose Cr(+VI) surface treatments replacement because of chromate carcinogenicity. The aim of the thesis work has been the development of a new surface treatment constituted of a sulfuric acid anodizing (SAA) and a sulfate chromium and fluorozirconate salts sealing (Cr3+/ ZrF62-). The study of the SAA electrochemical process linked the alloys microstructure and the anodic layer porous morphology developed at their surface. The Cr3+ / ZrF62- sealing treatment is realized by a simple immersion of the anodized alloy in the solution. It is demonstrated that the sealing is caused by a local alkalinization of the anodized coating surface that leads to the precipitation of the Cr3+ and ZrF62- salts. These ones are forming a sealing film of about 300 nm thick, very covering of the nanometric pores. The anodic layers sealing greatly improves the corrosion resistance of the anodized alloys by forming an additional barrier against corrosive agents and by healing the corrosion initiation. The developed treatment allows both to achieve Cr(+VI) treatments performance over a wide range of alloys and to satisfy the environmental requirements.

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No. of bitstreams: 1 lopes_em_dr_jabo.pdf: 4795462 bytes, checksum: a765e5c29ecbc64ad68f0f7cc83e9aff (MD5) Previous issue date: 2016-01-29 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Os impactos ambientais causados por sucessivas extrações de minérios e compostos gerados dos resíduos tóxicos dessa atividade têm sido foco de preocupação dos ambientalistas, neste contexto há um grande esforço gerado para o desenvolvimento de metodologias eficientes e de baixo custo para remoção de metais pesados de solos e águas contaminadas. Os métodos biológicos surgem como uma alternativa aos métodos convencionais para o solo, um dos ecossistemas terrestre que apresentam uma infinidade de recursos naturais além da grande diversidade de microrganismos interagindo entre si. O mesmo constitui fonte de investimento para o isolamento de microrganismos e análises metagenômicas para prospecção de genes envolvidos em processos importantes para o equilíbrio metabólico e ecológico, pois, tanto de maneira isolada, como em interações, estes organismos desempenham papel importante no que diz respeito à produção de enzimas na biorremoção de metais e contaminantes do solo. Este trabalho teve como objetivo isolar, caracterizar e avaliar a biossorção e bioacumulação de metais por microrganismos originados de solos de ecossistemas de Sabará, uma região de mineradora desativada Minas Gerais. Adicionalmente buscou-se avaliar a diversidade metabólica funcional, para uma comparação da microbiota de, Sabará e Brumadinho, combinada com busca de genes que conferem resistência a cromo (crhA), cobre (copA, copB, cueO) e níquel (nixA). Os isolados obtidos foram classificados em gêneros como Burkolderia, Serratia, Bacillus, Stenotrophomonas e Artrobacter, que apresentam potencial para biorremediação de metais do solo e água. Entretanto, seis dos 32 isolados apresentaram resistência aos metais cobre, cromo e níquel, na concentração de 500 mgL-1. Destes isolados, dois deles, do gênero Burkolderia e Arthrobacter (CP15 e CR11) apresentaram capacidade metabólica de biossorver e interiorizar metais pesados em diferentes fases do desenvolvimento. Quanto a atividade metabólica, a comunidade microbiana dos solos do perímetro do quadrilátero ferrífero (MG) tem alta atividade na degradação de fontes de carbono importantes nos ciclos biogeoquímico e biorremediação, justificando a grande quantidade de ORFs encontradas nas anotações do metagenoma sequenciado. Destaca-se os ecossistemas canga e floresta que apresentaram maior número de sequências identificadas para todos os genes envolvidos no processo de resistência, influxo e efluxo de metais, sendo eles genes de resistência a cobre, multicooper oxidase ATPase (copA, copB, cueO), multicopper ATPase like (copA, copB), cromo oxidase (chrA), cromo transporte (chrB) e níquel oxidase (nixA). Os solos da região de Sabará e Brumadinho alocados no, quadrilátero ferrífero, apresentam diversidade funcional para degradação de fontes de carbono como aminoácidos e compostos fenólicos, e genes funcionais de grande importância em processos metabólicos de remoção de metais pesados por microrganismos, além de microbiota com capacidade remover e interiorizar metais oriundos dos resíduos de mineração sendo um indicativo para a aplicação na biorremediação de metais em áreas afetadas pela mineração. / The environmental impacts caused by successive extractions of minerals and compounds generated toxic waste of this activity have been the focus of concern for environmentalists in this context there is a great effort generated for the development of efficient methodologies and cost-effective to remove heavy metals from soils and contaminated water. Biological methods appear as an alternative to conventional methods for the ground of the earth's ecosystems have a multitude of natural resources beyond the great diversity of microorganisms interacting. The same is investment source for the isolation of microorganisms and metagenomic analyzes to search for genes involved in important processes for metabolic and ecological balance, since both in isolation, as in interactions, these organisms play an important role as regards the production of enzymes in biorremoção metal and soil contaminants. This study aimed to isolate, characterize and evaluate the biosorption and bioaccumulation of metals by microorganisms originating from Sabara ecosystems soil, a mining region of Minas Gerais disabled. In addition we sought to evaluate the functional metabolic diversity, for a comparison of the microbiota of Sabara and Brumadinho, combined with search of genes that confer resistance to chromium (CRHA), copper (copA, CopB, cueO) and nickel (Nixa). The isolates were classified into genres such as Burkolderia, Serratia, Bacillus, Stenotrophomonas and Artrobacter, which have the potential for bioremediation of metals from soil and water. However, six of the 32 isolates were resistant to metals copper, chromium and nickel, at a concentration of 500 mg L-1. Of these isolates, two of them, the genus Arthrobacter and Burkolderia (CP15 and CR11) had metabolic capacity to internalize biossorver and heavy metals at different stages of development. As metabolic activity, the microbial community of the perimeter of iron quadrangle soils (MG) has high activity in the degradation of important carbon sources in biogeochemical cycles and bioremediation, which explains the large amount of ORFs found in the notes of sequenced metagenome. the yoke ecosystems and forest that had a greater number of sequences identified for all the genes involved in the resistance process is noteworthy, influx and efflux of metals, and they copper resistance genes, multicooper oxidase ATPase (copA, copB, cueO) multicopper ATPase like (copA, CopB), chrome oxidase (chrA), chrome transport (chrB) and nickel oxidase (nixA). The soils of Sabara and Brumadinho region allocated to, iron quadrangle, have functional diversity for degradation carbon sources such as amino acids and phenolic compounds, and functional genes of great importance for metabolic processes of removing heavy metals by microorganisms, and microorganisms with ability to remove and internalize metals coming from the waste mining being an indication for use in the bioremediation of metals in areas affected by mining. / FAPESP: 2012/20022-6

De par leurs propriétés mécaniques et anti-corrosion élevées, les revêtements métalliques de chrome sont utilisés dans de nombreux domaines tels que l’aéronautique, l’automobile, le ferroviaire, la défense,… Aujourd’hui le chromage dur industriel, réalisé à partir de chrome hexavalent, est fortement menacé par la directive européenne REACH qui prévoit l’interdiction d’utilisation de sels de chrome VI (classé CMR) à l’horizon 2017. Dans ce contexte le projet HCTC (Hard Chromium by Trivalent Chromium) regroupe 16 partenaires industriels et 2 partenaires académiques sous la coordination de l’Institut de Recherche Technologique Matériaux, Métallurgie, Procédés (IRT M2P) afin de développer une alternative à base de sel de chrome trivalent. Le développement d’un procédé de substitution à partir de sels de chrome trivalent nécessite de répondre aux interrogations liées notamment à la difficulté de réduire les ions Cr3+ formant en solution aqueuse un complexe hexa-aqua [Cr(H2O)6]3+ très stable et difficilement réductible. Afin de faciliter la réduction, l’ensemble des travaux recensés dans la littérature prône l’utilisation d’un agent complexant organique afin d’augmenter l’accessibilité du chrome. Une première partie de ce travail de thèse a été de caractériser les dépôts de chrome métallique réalisés à partir de la formulation de chrome III (EXDBA 1318) afin de mettre en évidence l’influence des paramètres de chromage (température du bain de traitement, densité de courant,…) sur les propriétés physico-chimiques des dépôts (Morphologie, cristallinité, composition chimique). Les résultats ont montré que la diminution de fissures tranversantes est généralement accompagnée d’une augmentation du taux de carbure de chrome qui dégrade l’état cristallin. La compréhension et l’optimisation du procédé a permis la réalisation de dépôts avec des propriétés physico-chimiques permettant de lancer les premiers essaies industriels dont les premiers retours sont très encourageants pour certaines applications (essentiellement automobile).Dans une deuxième partie plus fondamentale, des analyses par HPLC-ICP/AES ont mis en évidence la complexation du chrome par différents agents complexant. Les résultats obtenus ont montré que la complexation étaient d’autant plus importante que le pH est haut (pH=5) et le rapport molaire [Cr]/[Cplx] faible (1/10). Les mécanismes de réduction associés aux taux de complexation ont ensuite été déterminés par des mesures de voltammétrie cyclique en utilisant des électrodes sérigraphiées modifiées par de l’or. Les voltammogrammes obtenus montrent que la complexation du chrome par un agent complexant permet de passer d’un mécanisme de réduction en deux étape (Cr3+  Cr2+  Cr) en une seule (Cr3+  Cr).Une dernière partie du travail a été de définir l’influence de la chimie sur bain (pH et rapport molaire [Cr]/[Cplx]) sur les propriétés physico-chimiques des dépôts. Les résultats obtenus ont montré que pour des solutions faiblement complexées il est préférable de travailler à des pH bas et d’appliquer de faibles densités de courant (<15A/dm²) tandis qu’une augmentation du taux de complexation du chrome par l’agent complexant nécessite d’appliquer des densités de courant plus fortes. Ce travail a aussi permis de montrer l’existence d’une zone de pH optimale pour un rapport molaire [Cr]/[Cplx] donnée. L’existence de cette zone de pH révèle l’existence d’un domaine d’équilibre en solution, favorable à la réduction du chrome. L’ensemble de ces travaux plus fondamentaux ont permis d’améliorer les connaissances sur le procédé de chromage à partir d’un sel de chrome trivalent et ainsi de réfléchir à une nouvelle formulation pour des applications plus critiques où la solution actuelle a pu montrer quelques limites. / Due to their high mechanical and anti-corrosion properties, chromium metal coatings are used in many fields such as aeronautics, automotive, railway, defense, etc. Today industrial hard chromium coating, made from of hexavalent chromium, is strongly threatened by the European REACH Directive, which provides for the prohibition of the use of chromium VI salts (classified as CMR) by 2017. In this context, the HCTC project (Hard Chromium by Trivalent Chromium) groups together 16 industrial partners and 2 academic partners under the coordination of the Institute for Materials, Metallurgy and Process Technology Research (IRT M2P) to develop an alternative based on trivalent chromium salt. The development of a substitution process from trivalent chromium salts requires answering the questions related in particular to the difficulty of reducing the Cr3+ ions forming in aqueous solution a very stable hexa-aqua [Cr(H2O)6]3+ complex and hardly reducible. In order to facilitate the reduction, all the works listed in the literature advocate the use of an organic complexing agent in order to increase the accessibility of chromium.A first part of this thesis work was to characterize the chromium metal deposits made from the chromium III formulation (EXDBA 1318) in order to highlight the influence of chromium parameters (bath temperature, density of current, ...) on physico-chemicals properties of the deposits (Morphology, crystallinity, chemical composition). The results showed that the decrease of transverse cracks is generally accompanied by an increase in chromium carbide which degrades the crystalline state. The understanding and the optimization of the process allowed the realization of deposits with physico-chemical properties allowing to launch the first industrial tests whose first returns are very encouraging for certain applications (mainly automobile).In a second, more fundamental part, HPLC-ICP / AES analyzes have demonstrated the complexation of chromium by different complexing agents. The results obtained showed that the complexation was all the more important that the pH is high (pH = 5) and the molar ratio [Cr] / [Cplx] low (1/10). Reduction mechanisms associated with complexation rates were then determined by cyclic voltammetry measurements using gold-modified screen-printed electrodes. The voltammograms obtained show that the complexation of chromium by a complexing agent makes it possible to go from a reduction mechanism in two steps (Cr3+  Cr2+  Cr) to a single one (Cr3+  Cr).A final part of the work was to define the influence of bath chemistry (pH and [Cr]/[Cplx] molar ratio) on the physico-chemical properties of coatings. The results obtained showed that for weakly complexed solutions it is preferable to work at low pH and to apply low current densities (<15A / dm²) while an increase in the chromium complexation rate by the complexing agent requires the application of higher current densities. This work also showed the existence of an optimal pH zone for a given [Cr]/[Cplx] molar ratio. The existence of this zone of pH reveals the existence of a balance domain in solution, favorable to the reduction of chromium. All of these more fundamental works have made it possible to improve the knowledge on the chromium plating process from a trivalent chromium salt and thus to think about a new formulation for more critical applications where the current solution has been able to show some limits.

abstract: The Web is one of the most exciting and dynamic areas of development in today’s technology. However, with such activity, innovation, and ubiquity have come a set of new challenges for digital forensic examiners, making their jobs even more difficult. For examiners to become as effective with evidence from the Web as they currently are with more traditional evidence, they need (1) methods that guide them to know how to approach this new type of evidence and (2) tools that accommodate web environments’ unique characteristics. In this dissertation, I present my research to alleviate the difficulties forensic examiners currently face with respect to evidence originating from web environments. First, I introduce a framework for web environment forensics, which elaborates on and addresses the key challenges examiners face and outlines a method for how to approach web-based evidence. Next, I describe my work to identify extensions installed on encrypted web thin clients using only a sound understanding of these systems’ inner workings and the metadata of the encrypted files. Finally, I discuss my approach to reconstructing the timeline of events on encrypted web thin clients by using service provider APIs as a proxy for directly analyzing the device. In each of these research areas, I also introduce structured formats that I customized to accommodate the unique features of the evidence sources while also facilitating tool interoperability and information sharing. / Dissertation/Thesis / Doctoral Dissertation Computer Science 2017

Devido à necessidade de obtenção de uma superfície resistente ao desgaste e a oxidação, os cilindros hidráulicos são tradicionalmente revestidos com cromo duro eletrodepositado. Todavia, este tipo de revestimento apresenta uma redução gradual do coeficiente de atrito, interferindo diretamente na lubrificação da haste, ocasionando danos aos elementos de vedação e promovendo consequentes vazamentos. Outro apelo contrário à utilização do processo de revestimento com cromo é a presença, em elevados níveis, de cromo hexavalente Cr+6, apresentando alto poder cancerígeno e de contaminação ambiental. Atualmente, o processo de aspersão térmica em alta velocidade (HVOF - High Velocity Oxi-Fuel) se caracteriza como uma técnica de revestimento alternativa ao cromo duro, utilizando materiais compósitos (metal-cerâmico), os quais propiciam baixas taxas de desgaste. Este trabalho tem como objetivo avaliar o desempenho de revestimentos aplicados em hastes de cilindros hidráulicos revestidas com WC-CoCr pelo processo HVOF, em comparação ao revestimento de cromo duro eletrodepositado. As técnicas de caracterização empregadas foram divididas em duas etapas, sendo que a primeira foi: análise microestrutural, ensaios de dureza e desgaste, medições de rugosidade e perfilometria, em corpos de prova planos e, na segunda etapa, a análise dos revestimentos adquiridos através de uma bancada de testes de hastes de cilindros hidráulicos, onde a caracterização foi obtida através de, medições específicas dos principais parâmetros de rugosidades aplicadas a superfícies de vedação, como Rz, Rmáx e Rmr, desgaste visuais das hastes e vedações e medições de vazamento de óleo. Ao final, os resultados mostram que o revestimento aspergido, indica características competitivas em relação à eletrodeposição de cromo, podendo ser aplicado em hastes de cilindros hidráulicos com algumas vantagens, como por exemplo, maior resistência ao desgaste, menor coeficiente de atrito, menores taxas de vazamento e melhores condições finais de superfícies. / To obtain a surface that is resistant to wear and oxidation, hydraulic cylinders are typically coated with in hard chromium through the process of electroplating process. However, this type of coating displays a gradual reduction of the friction coefficient as the lubrication directly interferes with the shaft mechanism, which in turn causes damage to the sealing elements and promotes subsequent leakage. Another disadvantage in using the electroplated hard chromium process is the presence of high level hexavalent chromium Cr+6 which is not only carcinogenic, but also extremely contaminating to the environment. Currently, the alternative process of high-speed thermal spraying (HVOF - High Velocity Oxy-Fuel), as opposed to hard chrome coating, uses composite materials (metalceramic) possessing low wear rates. This study aims to evaluate and compare the performance of hydraulic cylinder rods coated with WC-CoCr in the HVOF process, and those coated with electroplated hard chromium. The characterization techniques employed were divided into two steps, the first of which was: microstructural analysis, testing the hardness, wear, roughness and profilometry and on specimens plans and, in the second step, analysis of the coating obtained through a bench test rods of hydraulic cylinders, where the characterization was through achieved , specific measurement of the main parameters of roughness applied to sealing surfaces, as Rz, Rmáx and Rmr, wear visual of the rods and seals and measurements of oil leakage. At the end, the results show that the sprayed coating, indicate competitive characteristics in relation to the electrodeposition of chromium, which can be applied in rods of hydraulic cylinders with some advantages, such as improved wear resistance, coefficient friction low, lower rates of leakage and condition final better surface.