Beim Bergbau werden bestehende Ökosysteme in großem Maße beeinflusst. Im ehemaligen Uranbergwerk Königstein (Sachsen) wurde die Umwelt durch den Einsatz von chemischen Säuren zur Lösung des Urans aus dem Erz (Laugung) in Folge der Verschiebung des pH-Wertes zusätzlich belastet. Durch diesen Prozess entstand eine Umgebung, die einen niedrigen pH-Wert und hohe Konzentrationen an gelösten Schwermetall-Ionen aufweist. Die komplexe mikrobielle Lebensgemeinschaft verschob sich daraufhin, indem sich bevorzugt säuretolerante und Schwermetall-tolerante Mikroorganismen durchsetzten. Diese Mikroorganismen wurden durch die Flutung der unter Tage Schächte im Jahr 2010 in ihrer Zusammensetzung erneut beeinflusst. In dieser Arbeit wurde die mikrobielle Biozönose nach Flutung der unter Tage Schächte des ehemaligen Uranbergwerkes Königstein charakterisiert und mit den Ergebnissen der mikrobiellen Diversität vor dem Flutungsprozess verglichen. Hierfür kam ein breites Spektrum an Methoden zum Einsatz, das klassische mikrobiologische Methoden und molekularbiologische Techniken umfasste. Die Analysen erfolgten dabei über mehrere Jahre hinweg, um die Variabilität der mikrobiellen Population im Grubenwasser planktonisch und im Biofilm zu erfassen.

Acid mine drainage (AMD) typically involves waters with low pH (pH 2-4) and high concentrations of Fe, SO4 and potentially toxic trace metals. Adsorption onto iron oxyhydroxides is the dominant mechanism controlling the transport and toxicity of trace metals in water bodies impacted by AMD. The purpose of this study was to apply the Diffuse Layer Model (DLM) to describe the adsorption of trace metals by iron oxyhydroxides from these systems, using synthetic iron oxyhydroxide minerals, ferrihydrite, pure acicular goethite, SO4-rich goethite prepared from FeSO4 oxidation and a synthetic schwertmannite. The ferrihydrite adsorption of the trace metals Cu, Zn, Cd and Co from single sorbate systems was accurately described using the DLM with two surface site types (type-1 and type-2) having site densities of 0.005 and 0.2 mol (mol Fe)-1 respectively. The ferrihydrite adsorption of SO4 from single sorbate systems was accurately described using the DLM with adsorption on the type-2 sites. However, the enhanced adsorption of Cu, Zn, Cd and Co in the presence of SO4 was not predicted using adsorption constants derived from single sorbate systems. By including a neutral ternary complex with stoichiometry Fe(2)OHMeSO4 (where Fe(2)OH is a type-2 surface site and Me is the trace metal) the effect of SO4 on metal adsorption was accurately described for the range of Me, Fe and SO4 concentrations studied. The adsorption of Cu and Zn onto schwertmannite at total metal to iron ratios (MeT:Fe) up to 8 x 10-3 was almost identical to that predicted for ferrihydrite in the presence of 0.01 mol kg-1 SO4. To model the ferrihydrite adsorption of Pb from single sorbate systems a third higher affinity site (type-0) with a site density of 0.00035 mol (mol Fe)-1 was required. The effect of SO4 on Pb adsorption could only be modelled by including a neutral ternary complex on both the type 1 and type 2 sites in the case of Pb. Metal adsorption onto a pure acicular goethite could be accurately described by the DLM with two surface site types. The type 2 site density that provided the best fit to the goethite adsorption data was 0.027 mol (mol Fe)-1 corresponding to 2.3 nm-2. The type-1 site density that provided the best fit to goethite adsorption of Cu, Pb and Cd was 0.00028 mol (mol Fe)-1 corresponding to 0.024 nm-2. For Zn adsorption on goethite the type-1 site density was significantly larger at 0.0015 mol (mol Fe)-1 corresponding to 0.13 nm-2. In all cases studied the presence of SO4 caused an increase in the extent of metal adsorption by goethite. This increased adsorption of metals in the presence of SO4 was accurately predicted by including ternary complex formation at both the high and low affinity adsorption sites. For both ferrihydrite and goethite the values of adsorption constants for ternary complex formation (logKxMeTC) were related to the adsorption constant for metal adsorption in the absence of SO4 (logKxMeINT). This was evident from a plot of logKxMeTC as a function of logKxMeINT for all metals, which showed a linear relationship with slope of 0.69 and intercept of 8.03. This relationship suggests that the enhancement of metal adsorption on both oxyhydroxides due to SO4 occurs by the same process. When comparing Cu, Zn and Cd adsorption onto ferrihydrite and acicular goethite the effect of the larger goethite adsorption constants are approximately compensated for by the lower goethite site densities. Therefore the Cu, Cd and Zn adsorption isotherms on ferrihydrite and acicular goethite are fairly similar at low adsorption densities. In the case of Pb, the site densities and adsorption constants are both larger on ferrihydrite and there is a large difference between the ferrihydrite and acicular goethite adsorption isotherms. Sulfate-rich goethite had considerably higher site densities, per mol of oxide, than the pure acicular goethite. Adsorption onto the sulfate-rich goethite could be modelled reasonably accurately using the parameters developed to model adsorption onto the pure acicular goethite but with a higher surface area and a higher ratio of type-1 to type 2 sites. In general, therefore, the parameters developed for pure goethite are apparently similar to those for the sulfate-rich goethite, but are not directly transferable. The difficulty in measuring the surface area of the highly aggregated sulfate-rich goethite makes comparisons between the two goethites more difficult. The adsorption of Cu, Zn and Cd onto the SO4-rich goethite exceeds that of ferrihydrite because the higher adsorption constants of goethite are combined with the considerably higher site densities of the SO4-rich goethite compared to the acicular goethite. In contrast the higher site densities of the SO4-rich goethite does not completely compensate for the low logKINT values of Pb adsorption on goethite. Therefore SO4-rich goethite adsorption of Pb is lower than that of ferrihydrite. When applied to literature data from AMD oxides the parameters derived in this thesis have significantly improved the ability of the DLM to predict trace metal adsorption in AMD systems, compared to using ferrihydrite as a proxy for all iron oxyhydroxides and adsorption data derived only from single sorbate systems.

Acid mine drainage (AMD) typically involves waters with low pH (pH 2-4) and high concentrations of Fe, SO4 and potentially toxic trace metals. Adsorption onto iron oxyhydroxides is the dominant mechanism controlling the transport and toxicity of trace metals in water bodies impacted by AMD. The purpose of this study was to apply the Diffuse Layer Model (DLM) to describe the adsorption of trace metals by iron oxyhydroxides from these systems, using synthetic iron oxyhydroxide minerals, ferrihydrite, pure acicular goethite, SO4-rich goethite prepared from FeSO4 oxidation and a synthetic schwertmannite. The ferrihydrite adsorption of the trace metals Cu, Zn, Cd and Co from single sorbate systems was accurately described using the DLM with two surface site types (type-1 and type-2) having site densities of 0.005 and 0.2 mol (mol Fe)-1 respectively. The ferrihydrite adsorption of SO4 from single sorbate systems was accurately described using the DLM with adsorption on the type-2 sites. However, the enhanced adsorption of Cu, Zn, Cd and Co in the presence of SO4 was not predicted using adsorption constants derived from single sorbate systems. By including a neutral ternary complex with stoichiometry Fe(2)OHMeSO4 (where Fe(2)OH is a type-2 surface site and Me is the trace metal) the effect of SO4 on metal adsorption was accurately described for the range of Me, Fe and SO4 concentrations studied. The adsorption of Cu and Zn onto schwertmannite at total metal to iron ratios (MeT:Fe) up to 8 x 10-3 was almost identical to that predicted for ferrihydrite in the presence of 0.01 mol kg-1 SO4. To model the ferrihydrite adsorption of Pb from single sorbate systems a third higher affinity site (type-0) with a site density of 0.00035 mol (mol Fe)-1 was required. The effect of SO4 on Pb adsorption could only be modelled by including a neutral ternary complex on both the type 1 and type 2 sites in the case of Pb. Metal adsorption onto a pure acicular goethite could be accurately described by the DLM with two surface site types. The type 2 site density that provided the best fit to the goethite adsorption data was 0.027 mol (mol Fe)-1 corresponding to 2.3 nm-2. The type-1 site density that provided the best fit to goethite adsorption of Cu, Pb and Cd was 0.00028 mol (mol Fe)-1 corresponding to 0.024 nm-2. For Zn adsorption on goethite the type-1 site density was significantly larger at 0.0015 mol (mol Fe)-1 corresponding to 0.13 nm-2. In all cases studied the presence of SO4 caused an increase in the extent of metal adsorption by goethite. This increased adsorption of metals in the presence of SO4 was accurately predicted by including ternary complex formation at both the high and low affinity adsorption sites. For both ferrihydrite and goethite the values of adsorption constants for ternary complex formation (logKxMeTC) were related to the adsorption constant for metal adsorption in the absence of SO4 (logKxMeINT). This was evident from a plot of logKxMeTC as a function of logKxMeINT for all metals, which showed a linear relationship with slope of 0.69 and intercept of 8.03. This relationship suggests that the enhancement of metal adsorption on both oxyhydroxides due to SO4 occurs by the same process. When comparing Cu, Zn and Cd adsorption onto ferrihydrite and acicular goethite the effect of the larger goethite adsorption constants are approximately compensated for by the lower goethite site densities. Therefore the Cu, Cd and Zn adsorption isotherms on ferrihydrite and acicular goethite are fairly similar at low adsorption densities. In the case of Pb, the site densities and adsorption constants are both larger on ferrihydrite and there is a large difference between the ferrihydrite and acicular goethite adsorption isotherms. Sulfate-rich goethite had considerably higher site densities, per mol of oxide, than the pure acicular goethite. Adsorption onto the sulfate-rich goethite could be modelled reasonably accurately using the parameters developed to model adsorption onto the pure acicular goethite but with a higher surface area and a higher ratio of type-1 to type 2 sites. In general, therefore, the parameters developed for pure goethite are apparently similar to those for the sulfate-rich goethite, but are not directly transferable. The difficulty in measuring the surface area of the highly aggregated sulfate-rich goethite makes comparisons between the two goethites more difficult. The adsorption of Cu, Zn and Cd onto the SO4-rich goethite exceeds that of ferrihydrite because the higher adsorption constants of goethite are combined with the considerably higher site densities of the SO4-rich goethite compared to the acicular goethite. In contrast the higher site densities of the SO4-rich goethite does not completely compensate for the low logKINT values of Pb adsorption on goethite. Therefore SO4-rich goethite adsorption of Pb is lower than that of ferrihydrite. When applied to literature data from AMD oxides the parameters derived in this thesis have significantly improved the ability of the DLM to predict trace metal adsorption in AMD systems, compared to using ferrihydrite as a proxy for all iron oxyhydroxides and adsorption data derived only from single sorbate systems.

Acid mine drainage (AMD) typically involves waters with low pH (pH 2-4) and high concentrations of Fe, SO4 and potentially toxic trace metals. Adsorption onto iron oxyhydroxides is the dominant mechanism controlling the transport and toxicity of trace metals in water bodies impacted by AMD. The purpose of this study was to apply the Diffuse Layer Model (DLM) to describe the adsorption of trace metals by iron oxyhydroxides from these systems, using synthetic iron oxyhydroxide minerals, ferrihydrite, pure acicular goethite, SO4-rich goethite prepared from FeSO4 oxidation and a synthetic schwertmannite. The ferrihydrite adsorption of the trace metals Cu, Zn, Cd and Co from single sorbate systems was accurately described using the DLM with two surface site types (type-1 and type-2) having site densities of 0.005 and 0.2 mol (mol Fe)-1 respectively. The ferrihydrite adsorption of SO4 from single sorbate systems was accurately described using the DLM with adsorption on the type-2 sites. However, the enhanced adsorption of Cu, Zn, Cd and Co in the presence of SO4 was not predicted using adsorption constants derived from single sorbate systems. By including a neutral ternary complex with stoichiometry Fe(2)OHMeSO4 (where Fe(2)OH is a type-2 surface site and Me is the trace metal) the effect of SO4 on metal adsorption was accurately described for the range of Me, Fe and SO4 concentrations studied. The adsorption of Cu and Zn onto schwertmannite at total metal to iron ratios (MeT:Fe) up to 8 x 10-3 was almost identical to that predicted for ferrihydrite in the presence of 0.01 mol kg-1 SO4. To model the ferrihydrite adsorption of Pb from single sorbate systems a third higher affinity site (type-0) with a site density of 0.00035 mol (mol Fe)-1 was required. The effect of SO4 on Pb adsorption could only be modelled by including a neutral ternary complex on both the type 1 and type 2 sites in the case of Pb. Metal adsorption onto a pure acicular goethite could be accurately described by the DLM with two surface site types. The type 2 site density that provided the best fit to the goethite adsorption data was 0.027 mol (mol Fe)-1 corresponding to 2.3 nm-2. The type-1 site density that provided the best fit to goethite adsorption of Cu, Pb and Cd was 0.00028 mol (mol Fe)-1 corresponding to 0.024 nm-2. For Zn adsorption on goethite the type-1 site density was significantly larger at 0.0015 mol (mol Fe)-1 corresponding to 0.13 nm-2. In all cases studied the presence of SO4 caused an increase in the extent of metal adsorption by goethite. This increased adsorption of metals in the presence of SO4 was accurately predicted by including ternary complex formation at both the high and low affinity adsorption sites. For both ferrihydrite and goethite the values of adsorption constants for ternary complex formation (logKxMeTC) were related to the adsorption constant for metal adsorption in the absence of SO4 (logKxMeINT). This was evident from a plot of logKxMeTC as a function of logKxMeINT for all metals, which showed a linear relationship with slope of 0.69 and intercept of 8.03. This relationship suggests that the enhancement of metal adsorption on both oxyhydroxides due to SO4 occurs by the same process. When comparing Cu, Zn and Cd adsorption onto ferrihydrite and acicular goethite the effect of the larger goethite adsorption constants are approximately compensated for by the lower goethite site densities. Therefore the Cu, Cd and Zn adsorption isotherms on ferrihydrite and acicular goethite are fairly similar at low adsorption densities. In the case of Pb, the site densities and adsorption constants are both larger on ferrihydrite and there is a large difference between the ferrihydrite and acicular goethite adsorption isotherms. Sulfate-rich goethite had considerably higher site densities, per mol of oxide, than the pure acicular goethite. Adsorption onto the sulfate-rich goethite could be modelled reasonably accurately using the parameters developed to model adsorption onto the pure acicular goethite but with a higher surface area and a higher ratio of type-1 to type 2 sites. In general, therefore, the parameters developed for pure goethite are apparently similar to those for the sulfate-rich goethite, but are not directly transferable. The difficulty in measuring the surface area of the highly aggregated sulfate-rich goethite makes comparisons between the two goethites more difficult. The adsorption of Cu, Zn and Cd onto the SO4-rich goethite exceeds that of ferrihydrite because the higher adsorption constants of goethite are combined with the considerably higher site densities of the SO4-rich goethite compared to the acicular goethite. In contrast the higher site densities of the SO4-rich goethite does not completely compensate for the low logKINT values of Pb adsorption on goethite. Therefore SO4-rich goethite adsorption of Pb is lower than that of ferrihydrite. When applied to literature data from AMD oxides the parameters derived in this thesis have significantly improved the ability of the DLM to predict trace metal adsorption in AMD systems, compared to using ferrihydrite as a proxy for all iron oxyhydroxides and adsorption data derived only from single sorbate systems.

Acid mine drainage (AMD) typically involves waters with low pH (pH 2-4) and high concentrations of Fe, SO4 and potentially toxic trace metals. Adsorption onto iron oxyhydroxides is the dominant mechanism controlling the transport and toxicity of trace metals in water bodies impacted by AMD. The purpose of this study was to apply the Diffuse Layer Model (DLM) to describe the adsorption of trace metals by iron oxyhydroxides from these systems, using synthetic iron oxyhydroxide minerals, ferrihydrite, pure acicular goethite, SO4-rich goethite prepared from FeSO4 oxidation and a synthetic schwertmannite. The ferrihydrite adsorption of the trace metals Cu, Zn, Cd and Co from single sorbate systems was accurately described using the DLM with two surface site types (type-1 and type-2) having site densities of 0.005 and 0.2 mol (mol Fe)-1 respectively. The ferrihydrite adsorption of SO4 from single sorbate systems was accurately described using the DLM with adsorption on the type-2 sites. However, the enhanced adsorption of Cu, Zn, Cd and Co in the presence of SO4 was not predicted using adsorption constants derived from single sorbate systems. By including a neutral ternary complex with stoichiometry Fe(2)OHMeSO4 (where Fe(2)OH is a type-2 surface site and Me is the trace metal) the effect of SO4 on metal adsorption was accurately described for the range of Me, Fe and SO4 concentrations studied. The adsorption of Cu and Zn onto schwertmannite at total metal to iron ratios (MeT:Fe) up to 8 x 10-3 was almost identical to that predicted for ferrihydrite in the presence of 0.01 mol kg-1 SO4. To model the ferrihydrite adsorption of Pb from single sorbate systems a third higher affinity site (type-0) with a site density of 0.00035 mol (mol Fe)-1 was required. The effect of SO4 on Pb adsorption could only be modelled by including a neutral ternary complex on both the type 1 and type 2 sites in the case of Pb. Metal adsorption onto a pure acicular goethite could be accurately described by the DLM with two surface site types. The type 2 site density that provided the best fit to the goethite adsorption data was 0.027 mol (mol Fe)-1 corresponding to 2.3 nm-2. The type-1 site density that provided the best fit to goethite adsorption of Cu, Pb and Cd was 0.00028 mol (mol Fe)-1 corresponding to 0.024 nm-2. For Zn adsorption on goethite the type-1 site density was significantly larger at 0.0015 mol (mol Fe)-1 corresponding to 0.13 nm-2. In all cases studied the presence of SO4 caused an increase in the extent of metal adsorption by goethite. This increased adsorption of metals in the presence of SO4 was accurately predicted by including ternary complex formation at both the high and low affinity adsorption sites. For both ferrihydrite and goethite the values of adsorption constants for ternary complex formation (logKxMeTC) were related to the adsorption constant for metal adsorption in the absence of SO4 (logKxMeINT). This was evident from a plot of logKxMeTC as a function of logKxMeINT for all metals, which showed a linear relationship with slope of 0.69 and intercept of 8.03. This relationship suggests that the enhancement of metal adsorption on both oxyhydroxides due to SO4 occurs by the same process. When comparing Cu, Zn and Cd adsorption onto ferrihydrite and acicular goethite the effect of the larger goethite adsorption constants are approximately compensated for by the lower goethite site densities. Therefore the Cu, Cd and Zn adsorption isotherms on ferrihydrite and acicular goethite are fairly similar at low adsorption densities. In the case of Pb, the site densities and adsorption constants are both larger on ferrihydrite and there is a large difference between the ferrihydrite and acicular goethite adsorption isotherms. Sulfate-rich goethite had considerably higher site densities, per mol of oxide, than the pure acicular goethite. Adsorption onto the sulfate-rich goethite could be modelled reasonably accurately using the parameters developed to model adsorption onto the pure acicular goethite but with a higher surface area and a higher ratio of type-1 to type 2 sites. In general, therefore, the parameters developed for pure goethite are apparently similar to those for the sulfate-rich goethite, but are not directly transferable. The difficulty in measuring the surface area of the highly aggregated sulfate-rich goethite makes comparisons between the two goethites more difficult. The adsorption of Cu, Zn and Cd onto the SO4-rich goethite exceeds that of ferrihydrite because the higher adsorption constants of goethite are combined with the considerably higher site densities of the SO4-rich goethite compared to the acicular goethite. In contrast the higher site densities of the SO4-rich goethite does not completely compensate for the low logKINT values of Pb adsorption on goethite. Therefore SO4-rich goethite adsorption of Pb is lower than that of ferrihydrite. When applied to literature data from AMD oxides the parameters derived in this thesis have significantly improved the ability of the DLM to predict trace metal adsorption in AMD systems, compared to using ferrihydrite as a proxy for all iron oxyhydroxides and adsorption data derived only from single sorbate systems.

PUMPS mimics natural geothermal vents as a conceptual model designed for the remediation of acid mine water (AMW) in voids of abandoned gold mines of the Witwatersrand Basin in South Africa. In this system, a reaction chamber containing Desulfotomaculum kuznetsovii sulfate reducing bacteria will be set at the bottom of a 3-4 km deep mine that will be flooded. A geothermal system with at least one (1) doublet will be drilled from the bottom of the mine to the depth of 8km, where the temperatures are sufficient for geothermal energy harvesting. AMW, used as a geothermal fluid, will be pumped down the injection well and circulate through hot rock. The hot water is then used to generate electricity and then channelled into the reaction chamber to undergo bio-remediation. Following treatment, the water flows back into the mine voids where it will improve the quality of untreated AMW through dilution. Eventually, the mine will be flooded with clean water that can be stored underground and/or pumped up to surface for social and ecosystem services. Following an introduction and proof of concept for the PUMPS, the research builds further on the technical and economic evaluation of the PUMPS in order to assert its viability and sustainability. The technical viability includes testing the ability for Desulfotomaculum kuznetsovii to survive in high pressure condition; quantifying the amount of energy that can be drawn from the geothermal reservoir; determining the placement and scheme of the geothermal wells; and, finally, developing a robust economic model of the system. Experiments show that Desulfotomaculum Kuznetsovii can tolerate high pressure conditions in of at least 100bar at their ideal sulfate reducing temperature of 63°C. Geochemical modelling shows that AMW can be used effectively as a geothermal fluid for PUMPS. To achieve highest efficiency and minimal fluid loss, the geothermal wells should be placed along the SSE-NNW direction, based on the known stress field across the Witwatersrand Basin. With a flow rate of 30l/s the energy drawn from the geothermal reservoir is sufficient to drive PUMPS and the surplus energy is determined by the volume of AMW treated per day. All results indicate that the PUMPS is technically and economically viable. The economic model shows that the value and viability of the PUMPS is best reflected with a comprehensive inclusion of potential revenue (for example from chemical solution mining of deep seated gold) and financial/environmental incentives.

A concentração de Fe, Ni, Cd, Mn, Zn, Cr e Pb, determinada por TXRF, foi investigada em matrizes de água, sedimento e fígados de peixes, amostrados em rios da região mineradora de carvão de Criciúma - SC/Brasil - afetadas por descargas de drenagem ácida de mina (DAM). A relação destes metais com a toxicidade para o bioindicador Daphnia magna (24 e 48 h) foi avaliada, sendo estabelecida correlação entre [Fe]solúvel e toxicidade à D. magna nas amostras de água. Para os sedimentos, há indícios de correlação dos teores de Fe e toxicidade, e nos fígados suspeita-se de níveis de Zn alterados. Efluentes da mineração, incluindo a DAM, após o tratamento por floculação e/ou decantação e/ou flotação e alcalinização mantiveram toxicidade mesmo com os metais reduzidos para concentrações não tóxicas à D. magna. Creditou-se a toxicidade remanescente a hidrocarbonetos policíclicos aromáticos (HPAs, determinada por CG/MS). Foram testados três adsorventes de baixo custo na retenção de metais (Fe, Ni, Cd, Mn, Zn, Cr e Pb) em soluções ácidas multimetais: casca de arroz (CA), carvão de casca de arroz (CCA) e turfa e carvão ativado comercial (CAC – adsorvente de confronto). As quantidades máximas adsorvidas dos metais (mg) por massa de sorbente (g) - qm, somatório dos metais, foram: CA 75,46 mg g-1; CAC 78,2 mg g-1; turfa 111,3 mg g-1 e CCA 137,49 mg g-1, (Langmuir e Freundlich - não linear). A toxicidade dos metais para D. magna destes eluatos foi reduzida. Foram preparados compósitos a partir de casca de arroz com deposição in situ de TiO2 (CCT – carbon covered with titanium), e testados como catalisador em Processos Oxidativos Avançados (POA). Os catalisadores TiO2 (P25 Degussa) e CCTs (25 e 50% de TiO2) em POA mostraram remoção dos HPAs e da toxicidade (D. magna e Scenedesmus subspicatus) nos efluentes de mineração, adequando os níveis de toxicidade à legislação ambiental vigente (Portaria FATMA 017/02) com resultados superiores do CCT. Assim, a presente tese alega que o uso de adsorventes à base de carvão de casca de arroz é capaz de reter os metais tipicamente presentes em efluentes ácidos (mineração de carvão), e que a toxicidade remanescente nestes efluentes, devida aos HPAs, pode ser reduzida pelo uso de POA, com incremento de eficiência quando o compósito CCT aqui desenvolvido é utilizado. / The concentration of Fe, Ni, Cd, Mn, Zn, Cr and Pb, determined by TXRF, was investigated in matrixes as water, sediment and fish liver, sampled at mining of coal region rivers from Criciúma - SC/Brazil – targets by acid mine drainage (ADM) discards. The relation of these metals with toxicity to Daphnia magna bioindicator (24 and 48 h) was evaluated, being established a correlation between [Fe]soluble and toxicity to D. magna in water samples. In sediments, correlation between Fe levels and toxicity was observed, and in liver Zn levels were altered. Mining effluents including AMD, after treatment by flocculation and/or decantation and/or flotation and alkalinization remain toxic even when metal concentrations had been reduced to levels which would be non toxic to D. magna. Residual toxicity was accounted to the presence of polycyclic aromatic hydrocarbons (PAHs, determined by GC/MS). Three low cost adsorbents were tested in metal retention (Fe, Ni, Cd, Mn, Zn, Cr and Pb) from multielemental acid solution: rice husk (RH), rice husk carbon (RHC), peat and commercial activated carbon (CAC – confront adsorbent). The maximum quantity of adsorbed metals (mg) by sorbent mass (g) - qm, as metals sum, were: CA 75.46 mg g-1; CAC 78.2 mg g-1; peat 111.3 mg g-1 and CCA 137.49 mg g-1, (Langmuir and Freundlich – non linear). The metal toxicity to D. magna of these eluates was reduced. Composites from rice husk with in situ deposition of TiO2 were synthesized (CCT – carbon covered with titanium), and tested as catalyst in advanced oxidative process (AOP). The catalysts TiO2 (P25 Degussa) and CCTs (25 e 50% de TiO2) in AOP showed PAHs and toxicity remotion (D. magna and Scenedesmus subspicatus) on mining effluents, adjusting toxicity levels to environmental legislation in force (FATMA 017/02), with best results to CCT. Then, the present thesis argues that rice husk carbon adsorbents is capable of retaining the metals typically presents in acid effluents (coal mining), and that remain toxicity in these effluents, from PAHs, can be reduced by AOP use, with efficient increasing when the composite here developed (CCT) is employed.

Ce travail de thèse a pour objectif de développer une méthodologie permettant de prédire l’impact environnemental des futurs projets miniers, dès l’étape d’exploration. Le drainage minier acide, connu comme le principal problème environnemental des gisements sulfurés, se produit lors de l’oxydation des sulfures par l’oxygène et l’eau. Des échantillons de sulfures et sulfosels ont été soumis à des tests géochimiques afin d’étudier leur taux de réactivité. Les minéraux ont été classés par ordre décroissant: gersdorffite > pyrrhotite > arsénopyrite > Ni-pyrite > Ni-pyrrhotite > Fe-sphalérite > pyrite > galène > chalcopyrite. L’influence des interactions galvaniques sur le taux de réactivité de la pyrite, la chalcopyrite et la sphalérite a été étudiée. La pyrite est protégée galvaniquement en présence de chalcopyrite mais n’est pas complètement protégée en présence de sphalérite. Des mélanges synthétiques de minéraux purs ont permis la modification du calcul de potentiel de génération d’acidité par l’ajout d’un facteur cinétique, basée sur les équations de Paktunc (1999) et Bouzahzah et al. (2013). Dix minerais polymétalliques et aurifères ont été caractérisés selon une méthodologie pluridisciplinaire. La caractérisation minéralogique des minerais a permis de connaître leur composition minéralogique quantitative et de détecter les éléments contaminants ainsi que leur spéciation. Une méthode automatisée de quantification minéralogique basée sur la microscopie optique multispectrale a été développée. Cette innovation vise à développer la microscopie optique pour des applications métallurgiques et environnementales de routine / This thesis proposes the implementation of a reliable methodology, based on the characterization of ores at the exploration stage. The main environmental issues for the mining industry are acid mine drainage and contaminated neutral drainage. Sulfides and sulfosalts, when in contact with water and oxygen, oxidize at different rates, resulting in the production of acid and release of various contaminants. Samples of pure sulfides were submitted to geochemical testing to determine their oxidation rates. The pure minerals can be ordered from the highest to the lowest reactivity as: gersdorffite > pyrrhotite > arsenopyrite > Ni-pyrite > Ni-pyrrhotite > Fe-sphalerite > pyrite > galena > chalcopyrite. Galvanic interactions between pyrite, chalcopyrite, and sphalerite were geochemically investigated. Pyrite was galvanically protected in presence of chalcopyrite, and partially protected in presence of sphalerite. Five synthetic tailings, simulating realistic tailings sulfides compositions, were prepared to compare geochemical behaviors and produce a better assessment of the acid-generation potential (AP). A new method is proposed by adding a kinetic factor. Ten polymetallic and gold sulfide ores were fully characterized with multidisciplinary techniques. Mineralogical investigations allowed for the mineralogical quantification of the ores, and for the knowledge of trace elements and their speciation. A method was developed to automatically quantify sulfides by multispectral optical microscopy. Detailed mineralogical work can save time and money and allows detecting the problems at the beginning of mining developments, improving mine waste management and mine closure planning

A concentração de Fe, Ni, Cd, Mn, Zn, Cr e Pb, determinada por TXRF, foi investigada em matrizes de água, sedimento e fígados de peixes, amostrados em rios da região mineradora de carvão de Criciúma - SC/Brasil - afetadas por descargas de drenagem ácida de mina (DAM). A relação destes metais com a toxicidade para o bioindicador Daphnia magna (24 e 48 h) foi avaliada, sendo estabelecida correlação entre [Fe]solúvel e toxicidade à D. magna nas amostras de água. Para os sedimentos, há indícios de correlação dos teores de Fe e toxicidade, e nos fígados suspeita-se de níveis de Zn alterados. Efluentes da mineração, incluindo a DAM, após o tratamento por floculação e/ou decantação e/ou flotação e alcalinização mantiveram toxicidade mesmo com os metais reduzidos para concentrações não tóxicas à D. magna. Creditou-se a toxicidade remanescente a hidrocarbonetos policíclicos aromáticos (HPAs, determinada por CG/MS). Foram testados três adsorventes de baixo custo na retenção de metais (Fe, Ni, Cd, Mn, Zn, Cr e Pb) em soluções ácidas multimetais: casca de arroz (CA), carvão de casca de arroz (CCA) e turfa e carvão ativado comercial (CAC – adsorvente de confronto). As quantidades máximas adsorvidas dos metais (mg) por massa de sorbente (g) - qm, somatório dos metais, foram: CA 75,46 mg g-1; CAC 78,2 mg g-1; turfa 111,3 mg g-1 e CCA 137,49 mg g-1, (Langmuir e Freundlich - não linear). A toxicidade dos metais para D. magna destes eluatos foi reduzida. Foram preparados compósitos a partir de casca de arroz com deposição in situ de TiO2 (CCT – carbon covered with titanium), e testados como catalisador em Processos Oxidativos Avançados (POA). Os catalisadores TiO2 (P25 Degussa) e CCTs (25 e 50% de TiO2) em POA mostraram remoção dos HPAs e da toxicidade (D. magna e Scenedesmus subspicatus) nos efluentes de mineração, adequando os níveis de toxicidade à legislação ambiental vigente (Portaria FATMA 017/02) com resultados superiores do CCT. Assim, a presente tese alega que o uso de adsorventes à base de carvão de casca de arroz é capaz de reter os metais tipicamente presentes em efluentes ácidos (mineração de carvão), e que a toxicidade remanescente nestes efluentes, devida aos HPAs, pode ser reduzida pelo uso de POA, com incremento de eficiência quando o compósito CCT aqui desenvolvido é utilizado. / The concentration of Fe, Ni, Cd, Mn, Zn, Cr and Pb, determined by TXRF, was investigated in matrixes as water, sediment and fish liver, sampled at mining of coal region rivers from Criciúma - SC/Brazil – targets by acid mine drainage (ADM) discards. The relation of these metals with toxicity to Daphnia magna bioindicator (24 and 48 h) was evaluated, being established a correlation between [Fe]soluble and toxicity to D. magna in water samples. In sediments, correlation between Fe levels and toxicity was observed, and in liver Zn levels were altered. Mining effluents including AMD, after treatment by flocculation and/or decantation and/or flotation and alkalinization remain toxic even when metal concentrations had been reduced to levels which would be non toxic to D. magna. Residual toxicity was accounted to the presence of polycyclic aromatic hydrocarbons (PAHs, determined by GC/MS). Three low cost adsorbents were tested in metal retention (Fe, Ni, Cd, Mn, Zn, Cr and Pb) from multielemental acid solution: rice husk (RH), rice husk carbon (RHC), peat and commercial activated carbon (CAC – confront adsorbent). The maximum quantity of adsorbed metals (mg) by sorbent mass (g) - qm, as metals sum, were: CA 75.46 mg g-1; CAC 78.2 mg g-1; peat 111.3 mg g-1 and CCA 137.49 mg g-1, (Langmuir and Freundlich – non linear). The metal toxicity to D. magna of these eluates was reduced. Composites from rice husk with in situ deposition of TiO2 were synthesized (CCT – carbon covered with titanium), and tested as catalyst in advanced oxidative process (AOP). The catalysts TiO2 (P25 Degussa) and CCTs (25 e 50% de TiO2) in AOP showed PAHs and toxicity remotion (D. magna and Scenedesmus subspicatus) on mining effluents, adjusting toxicity levels to environmental legislation in force (FATMA 017/02), with best results to CCT. Then, the present thesis argues that rice husk carbon adsorbents is capable of retaining the metals typically presents in acid effluents (coal mining), and that remain toxicity in these effluents, from PAHs, can be reduced by AOP use, with efficient increasing when the composite here developed (CCT) is employed.

Made available in DSpace on 2016-12-08T15:50:05Z (GMT). No. of bitstreams: 1 PGCS15DA030.pdf: 2083078 bytes, checksum: 528b429a722bc87e38f8d6cc54d5dbbe (MD5) Previous issue date: 2015-04-24 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Catarinense Carboniferous Basin exploration of coal left deep marks degradation of the local ecosystem, restricting future use of areas affected by the activity. The process of mining and the improper disposal and uncontrolled waste (waste-pyritic and sterile) practiced in the past, led to the formation of any significance deposits in the open modifying the landscape. These tailings contain high concentrations of pyrite (FeS2), in the presence of air and water, it oxidizes, promoting the formation of acid mine drainage (AMD), a leading environmental impacts of the mining sector. The DAM is an aqueous solution, strongly acidic and rich in sulfate and iron, and other trace elements associated, which prevents water resources and soil extinct fauna and flora, causing social and economic impact. Thus, the study aimed to provide information about the chemical and the total content of trace elements (Cd, Pb, Ni, Zn) in waste and barren of 23 deposits of Carboniferous Basin Santa Catarina and to survey the species of ferns and lycophytes naturally occurring in these deposits, assessing its possible potential for colonization of areas degraded by mining coal. The study was conducted in 23 deposits of tailings and sterile in six municipalities, Criciuma, Forquilhinha, Lauro Müller, Siderópolis, Treviso and Urussanga. Tailings samples were collected and sterile and species of ferns and lycophytes at each location. It performed a characterization of chemical properties, pH in water and pH in KCl, Ca, Mg, P, K, Na, Mn, Fe, Al, clay and OM content and the determination of total content of trace elements Cd, Pb, Ni and Zn in the waste and barren. The collection of ferns and lycophytes was performed by means of traversal along the length of the deposits, being cataloged and incorporated them in the Herbarium LUSC UDESC / CAV and herbal CRI of UNESC. The mining tailings and sterile are chemically poor, probably due to the DAM process. The total concentration of trace elements Cd, Ni and Zn were below the values of prevention established by Resolution CONAMA 420/2006 and the total contents of Pb were above the value of prevention in deposits A7, A9, A18 and A2. 16 species of ferns and 1 kind of licófita, belonging to 14 genera and 11 botanical families were found. The preference for environments the predominant form was open spot. For the biological forms, hemicryptophytes ferns were more frequent while heliophytic stood out on environmental adaptations. The species of ferns and licófita, found in deposits of tailings and sterile demonstrate resistance to degraded environments, being an alternative to restoration projects and environmental monitoring in areas impacted by coal mining in the open / Na Bacia Carbonífera Catarinense a exploração do carvão mineral deixou marcas profundas de degradação no ecossistema local, restringindo o uso futuro das áreas atingidas pela atividade. O processo de mineração e a disposição inadequada e sem controle dos resíduos (rejeito-piritoso e estéreis) praticados no passado, culminou na formação de vultuosos depósitos a céu aberto modificando a paisagem. Esses rejeitos contém alta concentração de pirita (FeS2), que na presença de ar e água, oxida-se, promovendo a formação da drenagem ácida de mina (DAM), um dos maiores impactos ambientais do setor mineral. A DAM é uma solução aquosa, fortemente ácida e rica em sulfato e ferro, além de outros elementos-traço associados, que inviabiliza os recursos hídricos e o solo extinguindo a fauna e a flora, ocasionando impacto social e econômico. Diante disso, o trabalho teve como objetivo fornecer informações a respeito da caracterização química e do teor total de elementos traços (Cd, Pb, Ni, Zn) no rejeito e estéreis de 23 depósitos da Bacia Carbonífera Catarinense e realizar um levantamento das espécies de samambaias e licófitas que ocorrem naturalmente nesses depósitos, avaliando seu possível potencial na colonização das áreas degradadas pela mineração de carvão. O trabalho foi realizado em 23 depósitos de rejeito e estéreis distribuídos em seis municípios, Criciúma, Forquilhinha, Lauro Müller, Siderópolis, Treviso e Urussanga. Foram coletadas amostras de rejeito e estéril e das espécies de samambaias e licófitas existentes em cada local. Realizou-se uma caracterização dos atributos químicos, pH em água e pH em KCl, teores de Ca, Mg, P, K, Na, Mn, Fe, Al, argila e teores de M.O e a determinação dos teores totais dos elementos-traço Cd, Pb, Ni e Zn, no rejeito e estéreis. A coleta das samambaias e licófitas foi realizada por meio de caminhamento por toda a extensão dos depósitos, sendo as mesmas catalogadas e incorporadas no Herbário LUSC da UDESC/CAV e no herbário CRI da UNESC. O rejeito e os estéreis da mineração são pobres quimicamente, provavelmente devido ao processo de DAM. Os teores totais dos elementos-traço Cd, Ni e Zn ficaram abaixo dos valores de prevenção estabelecidos pela resolução do CONAMA 420/2006 e os teores totais de Pb ficaram acima do valor de prevenção nos depósitos A7, A9, A2 e A18. Foram encontradas 16 espécies de samambaias e 1 espécie de licófita, pertencentes a 14 gêneros e 11 famílias botânicas. Na preferência por ambientes a forma predominante foi local aberto. Para às formas biológicas, as samambaias hemicriptófitas foram mais frequentes enquanto as heliófitas sobressaíram-se quanto às adaptações ambientais. As espécies de samambaias e licófita, encontradas nos depósitos de rejeito e estéreis demostram resistência a ambientes degradados, sendo uma alternativa para projetos de recuperação e monitoramento ambiental, em áreas impactadas pela mineração de carvão a céu aberto