O beneficiamento de carvão mineral para a utilização em termoelétricas gera grandes quantida-des de rejeitos, os quais contêm diversos minerais, entre eles a pirita (sulfeto de ferro - FeS2). A pirita, na presença de água e oxigênio se oxida, gerando a drenagem ácida de minas (DAM), principal fonte de contaminação dos aquíferos e do solo nas regiões carboníferas. Atualmente, a DAM é tratada pelo método de neutralização/precipitação de metais. Essa é uma técnica con-siderada “fim-de-tubo” com diversas desvantagens, entre elas o alto custo. Entretanto, através de técnicas preventivas, baseadas nos princípios da produção mais limpa, é possível, concomi-tantemente, minimizar a geração de DAM e agregar valor à parte ou totalidade dos rejeitos de carvão. Assim, o objetivo deste trabalho foi estudar a produção do coagulante sulfato férrico a partir da lixiviação de um concentrado de pirita oriundo de rejeitos de carvão via cristaliza-ção/solubilização de sulfato ferroso, comparando o processo para duas jazidas distintas de car-vão mineral. Amostras de concentrados de pirita foram obtidas de rejeitos de carvão das jazidas do Estado de Santa Catarina, minerados na cidade de Forquilhinha, e do Estado do Paraná, na cidade de Figueira A parte experimental foi realizada a partir de um reator de leito empacotado em planta-piloto e envolveu as seguintes etapas: produção de um lixiviado férrico, conversão do lixiviado férrico em ferroso, precipitação do Fe2+ e do sulfato na forma de cristais de sulfato ferroso heptahidratado com auxílio de etanol. Estudou-se, de forma detalhada, a proporção li-xiviado:etanol para o melhor rendimento do processo. Os cristais de sulfato ferroso produzidos a partir do concentrado de pirita catarinense apresentaram características semelhantes a um pa-drão analítico (menos de 1% de impurezas). Os cristais produzidos a partir da pirita paranaense apresentaram um índice levemente superior ao padrão estabelecido comercialmente (1,08%), além de apresentar alguns metais bastante perigosos à saúde, como arsênio. Também se estudou a produção do coagulante férrico via dissolução dos cristais de sulfato ferroso e oxidação do ferro pela adição de soluções aquosas com agentes ácidos e oxidantes. A melhor condição ob-tida foi a seguinte: 5 g de sulfato ferroso, 7,5 mL de água destilada, 1,5 mL de peróxido de hidrogênio e 5 gotas de ácido sulfúrico. Essa proporção proporcionou um coagulante com quase 12% de ferro, sendo que 97% deste ferro na forma férrica. O coagulante produzido foi utilizado no tratamento de água do corpo hídrico Guaíba, empregando-se como referência os padrões brasileiros de potabilidade (Portaria nº 2914 do Ministério da Saúde). Mostrando-se eficiente no tratamento de água para fins de abastecimento público. / The coal processing for use in power plants, generates amounts of residues, which contain var-ious minerals, such as pyrite (iron sulfide-FeS2). Pyrite, in the presence of water and oxygen, oxidizes, generating acid mine drainage (AMD), the main source of contamination of aquifers and soil in the carboniferous region of Santa Catarina. Currently, the AMD is treated by the method of neutralization/precipitation of metals. This is a technique considered "end-of-pipe" with many disadvantages, like the excessive cost. However, through preventive techniques, based on the principles of cleaner production, it is possible, at the same time, minimize the generation of AMD and to add value to a part or totality of coal waste. Thus, the objective of this work was to study the production of ferric sulphate coagulant from the leaching of a pyrite concentrate from coal tailings via crystallization / solubilization of ferrous sulphate, comparing the process to two distinct mineral coal deposits. Samples of pyrite concentrates were obtained from coal tailings from the State of Santa Catarina mines, mined in the city of Forquilhinha, and from the State of Paraná, in the city of Figueira The experimental part was carried out in a bed reactor packed in a pilot plant and involved the following steps: production of a ferric leachate, conversion of ferric leachate into ferrous, precipitation of Fe2 + and sulphate as crystals of ferrous sulphate heptahydrate. It was also studied, in detail, the proportion leached:ethanol for the best yield of the process. The ferrous sulphate crystals produced from the Santa Catarina pyrite concentrate showed characteristics similar to an analytical standard (less than 1% of im-purities). The crystals produced from the Paraná pyrite concentrate presented an index slightly higher than the commercially established standard (1.08%), besides presenting some metals very dangerous to health, such as arsenic. The production of ferric coagulant was also studied by dissolving the ferrous sulphate crystals and iron oxidation by adding aqueous solutions with acidic and oxidizing agents. The best condition obtained was as follows: 5 g of ferrous sulphate, 7.5 ml of distilled water, 1.5 ml of hydrogen peroxide and, 5 drops of sulfuric acid. This pro-portion provided a coagulant with almost 12% iron, with 97% of this iron in the ferric form. The coagulant produced was used in the water treatment of lake Guaíba, using as reference the Brazilian standards of potability. The coagulant produced showed to be efficient in the water treatment for public supply purposes.

Foram realizados estudos do comportamento eletroquímico de eletrodos de pinta, pirrotita e arsenopirita em meio ácido. A investigação incluiu tanto a dissolução dos minerais (isolados ou combinados dois a dois) como o estudo da deposição de íons prata sobre eles, levando em consideração as propriedades semicondutoras de cada um. Com base nos dados obtidos, empregando voltametria cíclica, medidas de capacitância, medidas fotoeletroquímicas e microscopia eletrônica de varredura, foram propostos mecanismos de dissolução para cada mineral. A oxidação dos três minerais em função dos produtos obtidos foi avaliada a partir das quantidades relativas de SO42-, S e Fe(OH)3 e constatou-se que a quantidade relativa de sulfato produzida pela pirita é maior que a quantidade obtida do eletrodo de pirrotita. A arsenopirita apresenta comportamento intermediário. O hidróxido de ferro produzido pela pirrotita é maior que o obtido da pirita e da arsenopirita. A presença do As2S3 na superfície do eletrodo de arsenopirita dificulta a redução do enxofre. Os dados obtidos com os eletrodos mistos mostram que, em potenciais próximos de Eca, as reações que produzem enxofre e Fe(III) predominam. Acima de 0,8 V, tem início a oxidação de S e/ou S2O32- gerando sulfato para os três eletrodos, além da oxidação do As2S3 nos eletrodos que contém arsenopirita. A presença da pirita na mistura dos minerais, em quantidade maior que 60%, pode abaixar o pH local favorecendo a decomposição do tiossulfato. Os valores dos potenciais de bandas planas foram estimados com base nos modelos de Gärtner e Mott-Shottky e o valor da energia de banda proibida, de cada mineral e dos eletrodos mistos, foi avaliado. Foi estabelecido que, em meio de solução tampão de ácido acético/acetato de sódio, pH = 4,5, o nível de Fermi dos minerais está vinculado ao potencial de óxido redução do eletrólito. O potencial de circuito aberto é determinado pela presença de óxidos/hidróxidos de ferro na superfície dos eletrodos. Sob iluminação todos os eletrodos apresentaram fotoefeitos. Com o aumento da porcentagem de pirrotita ocorre uma diminuição na fotocorrente registrada. Já a adição de arsenopirita, provoca um aumento nos fotoefeitos observados. A adição de pirrotita faz diminuir a eficiência quântica dos eletrodos enquanto que a adição de arsenopirita favorece a resposta fotoeletroquímica das superfícies. O aumento da quantidade de pirrotita na superfície faz com que a energia de banda proibida diminua. A mistura pirita/pirrotita para qualquer composição deve favorecer a produção de enxofre em detrimento da de sulfato. Quando se utilizam eletrodos de pirita/arsenopirita não se observam variações a circuito aberto. A investigação sobre a deposição de íons prata sobre os eletrodos mostrou que o contato com os íons metálicos em solução não produz modificações morfológicas significativas na superfície dos eletrodos. A prata metálica e os sulfetos de prata formados são incorporados em pequenos núcleos espalhados pela superfície. Ficou demonstrado que sulfeto de prata e prata elementar podem ser identificados pela análise dos voltamogramas. Nos eletrodos construídos com combinações de minerais as interações com os íons prata ocorrem, preferencialmente, nos grãos de pirrotita ou arsenopirita para todas as composições. A interação mineral/prata ocorre mediante a competição de vários sítios da superfície pelos íons em solução. A quantidade de íons prata em solução tem um papel importante no aumento da velocidade de dissolução dos sulfetos. O consumo de H2S e de S2O32- deve causar o aumento na velocidade de dissolução dos minerais. De uma maneira geral, pode-se concluir que as combinações pirita-pirrotita otimizam as interações com os íons Ag+, tanto por oferecer maior quantidade de sítios de enxofre/intermediários para as interações químicas como por apresentar maior quantidade de elétrons na superfície a circuito aberto. Por outro lado, a presença de arsenopirita prejudica as interações com a prata já que causa uma diminuição na concentração efetiva de elétrons na superfície. Além disto, a formação de sulfetos de arsênio limita a quantidade de enxofre disponível para as interações químicas com os íons em solução. / The electrochemical behavior of iron sulfides, pyrite, pyrrhotite and arsenopyrite was studied in acetic acid/sodium acetate buffer, pH = 4.5. The investigations included the dissolution of minerals (isolated and mixed in pairs) and the studies of the deposition of silver ions on the electrode surfaces, taking into account the semiconducting properties of each one. Based on the data obtained using cyclic voltammetry, capacitance and photoelectrochemical measurements and scanning electron microscopy, mechanisms of dissolution for each mineral were proposed. The dissolution of the three minerals was evaluated taking into account the relative amounts of SO42-, S and Fe(OH)3 obtained and evidenced that the relative amount of sulfate formed from pyrite is greater that from pyrrhotite. Arsenopyrite presents intermediate behavior. The quantity of iron hydroxide produced by pyrrhotite is greater that produced by pyrite and arsenopyrite. The presence of the As2S3 in the surface of the arsenopyrite electrode inhibits the reduction of sulfur. The results obtained with the electrodes constructed with two minerals show that, in potentials next to Eoc, the reactions producing sulfur and Fe(III) predominate. Above 0.8 V, the oxidation of S and/or S2O32- occurs, generating sulfate for all electrodes. On the electrodes, containing arsenopyrite, the oxidation of As2S3 also takes place. The presence of pyrite in the mixture of minerals (more than 40% in weight) causes a decrease of the local pH, favoring the thiosulfate decomposition. The values of the flat band potentials have been estimated based on Gartner\'s and Mott-Shottky \'s models. The value of the band gap energy, of each mineral and of the mixed electrodes, was evaluated. It was established that, in the working solution, the Fermi level of the minerals coincided with the redox potential of the electrolyte. The open circuit potential is determined by the presence of oxides/hydroxides on the electrode surface. The pyrrhotite addition reduces the quantum efficiency while the presence of arsenopyrite favors the photoelectrochemical yield of the electrodes. An increase of the amount of pyrrhotite produces a decrease in the value of the bandgap energy of the electrodes. The pyrite/pyrrhotite mixture, for any composition, favors the sulfur production in detriment of the sulfate one. At open circuit conditions, the mixture pyrite/arsenopyrite does not present any variation. The study of the deposition of silver ions showed that the contact with the metallic ions in solution does not produce significant morphologic modifications on the electrode surfaces. The metallic silver and the silver sulfide formed are incorporated in small grains spread along the surface. It was demonstrated that silver sulfide and elemental silver might be identified by the inspection of the voltammograms. In the electrodes constructed with mineral combinations the interactions with silver ions occur, specially, in the grains of pyrrhotite or arsenopyrite for all compositions. The silver concentration in solution plays an important role increasing the dissolution rate of the sulfides. The S2O32- and H2S consumption may intensify the dissolution rate of the minerals. The mixture pyrite-pyrrhotite improves the interactions with Ag+ ions, at open circuit, by producing more S2O32-/S for the chemical interactions and by increasing the electron concentration at the surface. On the other hand, the presence of arsenopyrite disfavors the interactions with silver as it reduces the number of charge carriers on the electrode surface. Moreover, the formation of arsenic sulfides limits the reduction of sulfur and the chemical interactions with ions in solution.

A presença da pirita (FeS2) em depósitos de rejeitos de carvão mineral pode causar danos ambientais. A pirita oxida e proporciona a geração da drenagem ácida de minas (DAM). Uma possível maneira de se evitar tal problema é separando a pirita e empregando-a para algum fim. Assim, o objetivo do presente trabalho foi desenvolver uma rota para sintetizar óxidos magnéticos a partir de um concentrado de pirita oriundo de rejeito de carvão. Experimentalmente, utilizou-se 300 kg de um concentrado com 73,2% de pirita em escala piloto. Realizou-se uma etapa de lixiviação aeróbica com água, em circuito fechado, com o intuito de se obter um extrato aquoso rico em íons férricos. A seguir, procederam-se mudanças no sistema de forma a estabelecer uma condição anaeróbia e redutora ao meio para obterem-se íons ferrosos. O lixiviado, rico em íons Fe2+ e SO4 2-, foi misturado com etanol para a precipitação do ferro como melanterita. Duas rotas para a produção de óxidos ferromagnéticos foram avaliadas. Primeiro, para a síntese de ferritas, utilizou-se o direto ajuste de pH da solução lixiviada reduzida até 10,5 durante 4 dias e posterior precipitação do material magnético. Segundo, para a síntese da magnetita, os cristais de melanterita, obtidos pela precipitação com etanol, foram dissolvidos em água deionizada e procedeu-se o mesmo ajuste de pH e tempo reacional para a cristalização do ferro na forma de óxido. Os cristais foram separados por precipitação, lavados com água deionizada, secos e caracterizados em relação à composição elementar, cristalinidade, distribuição granulométrica, forma, termodecomposição e magnetização. Pode-se concluir que os procedimentos empregados resultaram na obtenção de ferritas e cristais de magnetita na faixa granulométrica entre 0,1 e 10,0 μm. As ferritas apresentaram medidas de magnetização de saturação e coercividade de 29 emu/g e 33,4 Oe e a magnetita de 86,6 emu/g e 75,2 Oe. Os rendimentos em relação ao Fe presentes no lixiviado reduzido (síntese da ferrita de zinco) e melanterita (síntese da magnetita) foram de 34,9% e 93,2%, respectivamente. A produção de reagentes e materiais com valor agregado a partir de concentrados de pirita, oriundo de um rejeito mineral é tecnologicamente viável. O custo estimado para a produção de nano e microgrãos de magnetita foi calculado em R$ 136,29/kg. O processo reduz o desperdício de materiais, minimiza impactos de descarte de resíduos ao meio ambiente e pode tornar-se uma fonte de recursos alternativa dentro da cadeia de produção de carvão. Deve-se ressaltar que os óxidos magnéticos encontram aplicações como pigmentos, em suspensões de meio denso, suporte magnético, agente de contraste em medicina e como material adsorvente. / The presence of pyrite (FeS2) in coal tailings deposits can cause environmental damage. Pyrite oxidizes and generates acid mine drainage (AMD). One possible way to avoid such a problem is by separating the pyrite and employing it for some purpose. Thus, the aim of the present work was to develop a route to synthesize magnetic oxides from a pyrite concentrated from coal rejects. Experimentally, it was carried out in a pilot leaching unit with 300 kg of a pyrite concentrate with of 73.2% FeS2. A step of aerobic leaching with closed circuit water was carried out in order to obtain an aqueous extract rich in ferric ions. Next, changes were made in order to establish an anaerobic and reductive condition in the medium to obtain ferrous ions. The leachate, rich in Fe2+ and SO4 2- ions, was mixtured with different proportions of ethanol to precipitate the iron as melanterite. Two procedures to produce ferromagnetic oxides were investigated. First, for ferrite synthesis, the reduced leachate had the pH adjusted to 10.5 and this condition was kept for a period of 4 days for crystallization of the magnetic material. Second, for magnetite synthesis, melanterite crystals obtained by the precipitation with ethanol (A.P) were dissolved in deionized water and the same pH adjustment and reaction time for the crystallization of the iron as ferrites was carried out. The crystals were separated by precipitation, washed with deionized water, dried, and characterized in relation to elemental composition, crystallinity, particles size distribution, shape, thermo-decomposition, and magnetization. The procedures applied resulted in ferrites and magnetite particles in particle size between 0.1 and 10.0 μm. Ferrite particles presented magnetization saturation and magnetization coercivity of 29 emu/g and 33,4 Oe and magnetite particles of 86.6 emu/g e 75.2 Oe. The yields, from the reduced leachate, were 34.9% for ferrites and 93.2% for magnetite. The production of reagent and materials with aggregate values from pyrite concentrates is viable. The estimated cost for nano and micro particles of magnetite synthesis was estimated in R$ 136.29/kg. The process reduces the waste of materials, minimize the discharge of wastes in the environment and could be source of resource in coal production chain. It should be noted that magnetic oxides find applications as pigments, in dense media suspensions, magnetic support, contrast agent in medicine, and as adsorbent material.

Thesis (MSc. (Physics)) --University of Limpopo, 2009 / Calculations were carried out on transition-metal sulphides (TMS) and transitionmetal arsenides (TMA), in both pyrite- and marcasite-type structures, using planewave (PW) pseudopotential methods within density functional theory (DFT) in the local density approximation (LDA). The structural, electronic and optical properties for both pyrite- and marcasite-type structures (naturally occurring and converted) have been investigated. The equilibrium lattice parameters were investigated and are in good agreement with the experimental values. The heats of formation calculations predict that the naturally occurring pyrite- and marcasite-type structures are more stable than the converted ones. In particular, the calculated pyrite-type RuS2 compares well to the experimental value (with energy difference of 0.381 eV/atom). The bulk modulus and elastic properties were calculated. The predicted anisotropic ratio shows that the naturally occurring pyrite- and marcasite-type structures are more stable than the converted ones. Moreover, the electronic density of states and band structure calculations reveal that most compositions shows semiconducting behaviour except for the converted pyritetype structures, i.e OsAs2 and RuAs2 where a metallic behaviour was observed. The electronic charge density and charge density difference show charge accumulation on bonding atoms, predicting the charge gain/ loss and nature of bonding to be covalent/ weak ionic between the atoms. Lastly, optical properties are computed at equilibrium and predict that naturally occurring structures have lower absorption and reflectivity than the converted structures. At different pressures ranging from -10 GPa to 10 GPa, the absorption and reflectivity spectra show a shift from the 0 GPa spectrum for all the structures / National Research Foundation

In order to understand the mineralogical association and distribution of arsenic (As) in the Hawthorn Group in central Florida, I examined in detail the chemical and mineralogical composition of 361 samples that were collected from 16 cores. Geochemical analyses were performed by hydride generation - atomic fluorescence spectrometry (HG-AFS) and inductively coupled plasma optical emission spectrometry (ICP-OES). The identification of discrete minerals was aided by scanning electron microscopy (SEM) and chemical compositions were obtained by electron-probe microanalyses (EMPA). Arsenic concentrations for all Hawthorn samples vary from 0.1 to 69.0 ppm with a mean of 5.6 ppm. Average As concentrations for the individual units of the Hawthorn Group vary significantly from 9.0 ppm in the Peace River Formation to 3.0 ppm in the Tampa Member of the Arcadia Formation. This detailed mineralogical and geochemical study demonstrates that: (1) Arsenic in the Hawthorn Group varies from the formation to formation and is primarily concentrated in trace minerals, such as pyrite; (2) Concentrations of arsenic in pyrite crystals can vary drastically from a minimum of 0 ppm to a maximum of 8260 ppm; (3) Pyrite occurs in framboidal and euhedral forms and is unevenly distributed throughout the Hawthorn Group; (4) Hydrous ferric oxides can contain up to 540 ppm of arsenic; (5) Phosphate and organic material, and clays contain lower arsenic concentrations that pyrite and hydrous ferric oxides; and (6) Arsenic, sulfur, and iron have lognormal distribution throughout the Hawthorn Group. This study is important because phosphorous, arsenic and sulfur are chemically closely related, and thus they co-occur posing a potential problem for the phosphate industry. Information about the concentration, distribution and mineralogical association of naturally occurring arsenic is essential to forecast its behavior during anthropogenically induced physico-chemical changes in the aquifer. Recently, aquifer storage and recovery (ASR) facilities in west-central Florida reported arsenic concentrations in excess of 100 micro g/L (100 ppb) in recovered water. The ASR storage zone in this area is in the Suwannee Limestone, which directly underlies the Hawthorn sediments. It is crucial to the future of ASR in this area to understand the source, distribution, and cycling of arsenic in the overlying Hawthorn Group and the Florida Platform.

Ce travail a porté sur l'étude au laboratoire d'échantillons d'argilites, prélevés dans la couche d'argilites du Callovo-Oxfordien dans l'est du Bassin de Paris au droit du site du laboratoire souterrain de recherches in-situ. Ils ont été soumis à des sollicitations thermomécaniques en conditions humides avec un dispositif expérimental appelé microcellule CGI permettant de faire une observation visuelle de leur texture et de leur structure au cours des essais. D'autres moyens expérimentaux ont aussi été utilisés : essais pétrophysiques, rayons X, Microscope électronique à balayage. L'ensemble des résultats permettent de faire une distinction entre des échantillons prélevés à 445 m de profondeur, non loin du toit de la couche et des échantillons prélevés à 480 m de profondeur au milieu de la couche. Les argilites sont litées, leur densité est de l'ordre de 2,4. Elles contiennent environ 23% de carbonates, environ 1% de pyrite au toit et 1 à 2% au milieu. Les lames épaisses ont un comportement plutôt fragile. Celles du milieu sont plus déformables et sont plus sensibles à la température que celles du toit. L'initiation des fractures est liée aux hétérogénéités de la texture. L'altération des pyrites confère aux échantillons un comportement évolutif. Un modèle numérique simple (FLAC) permet d'en préciser certains aspects mécaniques. Ces résultats amènent à considérer que l'altération des pyrites doit être prise en compte comme une source supplémentaire d'endommagement susceptible de se développer dans le temps.

<p>Tailings are a fine-grained waste product produced during the metal recovery process. Tailings consist mostly of different silicates but also sulfides (e.g. pyrite), since 100 % metal recovery is not possible. Freshly processed tailings are deposited in large impoundments. If the mine tailings in the impoundments are exposed to water and oxygen, the sulfides will oxidize and release acidity and metals such as Fe, Cu, Zn, and Pb. The sulfide mineral oxidation reactions are catalyzed by sulfur and iron oxidizing bacteria (principally <i>Acidithiobacillus ferrooxidans</i>) that oxidize ferrous iron to ferric iron, which then oxidizes pyrite. When the leachate produced by this process discharges from the impoundment, it is called acid mine drainage, which may lead to the pollution of adjacent streams and lakes.</p><p>The intention with this thesis is to investigate and quantify mineral weathering processes and element release rates occurring in water-saturated and soil-covered sulfidic mine tailings. The study was performed in different batch and column experiments in room temperature and in the laboratory. The batch experiments were conducted for ca. three months and investigated: a) microbial and abiotic sulfide oxidation in freshly processed tailings under oxic conditions at pH 2-3 and pH 8, b) microbial oxidation of pure pyrite grains at pH 2-3 under different oxygen concentrations ranging from anoxic to oxic conditions. The column experiments, consisting of unoxidized tailings in water-saturated columns, were conducted for up to three years. In these experiments, an oxygen-saturated solution was continually pumped into the column inlet, and investigated: a) differences in oxidation rates between tailings of two different grain sizes, b) factors affecting element discharge rates, acid neutralization, and sulfide oxidation, c) the effect of ions released in a soil cover on release rates in the tailings.</p><p>Sulfide oxidation processes within the batch experiments were limited by surface kinetics. The microbial oxidation of pure pyrite at atmospheric conditions produced the most rapid rate, while the microbial oxidation of pure pyrite at anoxic conditions was slower by 1.8 orders of magnitude. Microbial and abiotic oxidation of pyrite in freshly-processed tailings resulted in pyrite oxidation rates that were intermediate between these two extremes. The results from the microbial experiments with pure pyrite indicated a positive correlation between the concentration of dissolved oxygen, ferric iron and bacterial cells (at a total cell concentration > 10⁶ cells/mL and a dissolved oxygen concentration ≥ 13.2 µM), which implies an interdependence of these factors. The results from these batch experiments support the indirect mechanism for microbial oxidation by the ferric oxidation pathway. Pyrite oxidation rates estimated from the batch experiments may be comparable with oxidation rates in the unsaturated zone and at the groundwater table in a tailings impoundment.</p><p>Acid neutralization reactions in the column experiments resulted in the release of base cations to the column leachate. Calcite was the most important neutralizing mineral despite that it was only present in minor amounts in the tailings. It was confirmed that acidity forced the calcite dissolution. Element release rates in the column experiments were controlled by the availability of dissolved oxygen, which was a function of the water flow rate into the column. These column experiments also showed that the results are comparable with results from field studies, justifying the use of column experiments to study processes within tailings impoundments.</p>

Tailings are a fine-grained waste product produced during the metal recovery process. Tailings consist mostly of different silicates but also sulfides (e.g. pyrite), since 100 % metal recovery is not possible. Freshly processed tailings are deposited in large impoundments. If the mine tailings in the impoundments are exposed to water and oxygen, the sulfides will oxidize and release acidity and metals such as Fe, Cu, Zn, and Pb. The sulfide mineral oxidation reactions are catalyzed by sulfur and iron oxidizing bacteria (principally Acidithiobacillus ferrooxidans) that oxidize ferrous iron to ferric iron, which then oxidizes pyrite. When the leachate produced by this process discharges from the impoundment, it is called acid mine drainage, which may lead to the pollution of adjacent streams and lakes. The intention with this thesis is to investigate and quantify mineral weathering processes and element release rates occurring in water-saturated and soil-covered sulfidic mine tailings. The study was performed in different batch and column experiments in room temperature and in the laboratory. The batch experiments were conducted for ca. three months and investigated: a) microbial and abiotic sulfide oxidation in freshly processed tailings under oxic conditions at pH 2-3 and pH 8, b) microbial oxidation of pure pyrite grains at pH 2-3 under different oxygen concentrations ranging from anoxic to oxic conditions. The column experiments, consisting of unoxidized tailings in water-saturated columns, were conducted for up to three years. In these experiments, an oxygen-saturated solution was continually pumped into the column inlet, and investigated: a) differences in oxidation rates between tailings of two different grain sizes, b) factors affecting element discharge rates, acid neutralization, and sulfide oxidation, c) the effect of ions released in a soil cover on release rates in the tailings. Sulfide oxidation processes within the batch experiments were limited by surface kinetics. The microbial oxidation of pure pyrite at atmospheric conditions produced the most rapid rate, while the microbial oxidation of pure pyrite at anoxic conditions was slower by 1.8 orders of magnitude. Microbial and abiotic oxidation of pyrite in freshly-processed tailings resulted in pyrite oxidation rates that were intermediate between these two extremes. The results from the microbial experiments with pure pyrite indicated a positive correlation between the concentration of dissolved oxygen, ferric iron and bacterial cells (at a total cell concentration &gt; 106 cells/mL and a dissolved oxygen concentration ≥ 13.2 µM), which implies an interdependence of these factors. The results from these batch experiments support the indirect mechanism for microbial oxidation by the ferric oxidation pathway. Pyrite oxidation rates estimated from the batch experiments may be comparable with oxidation rates in the unsaturated zone and at the groundwater table in a tailings impoundment. Acid neutralization reactions in the column experiments resulted in the release of base cations to the column leachate. Calcite was the most important neutralizing mineral despite that it was only present in minor amounts in the tailings. It was confirmed that acidity forced the calcite dissolution. Element release rates in the column experiments were controlled by the availability of dissolved oxygen, which was a function of the water flow rate into the column. These column experiments also showed that the results are comparable with results from field studies, justifying the use of column experiments to study processes within tailings impoundments.

Most of the city of Uppsala rests on postglacial clay with a varying content of sulphur. The sulphur occurs naturally in the clay in reduced form as sulphide and the clay is for that reason usually called “sulphide clay”. Excavation during construction activities gives rise to large amounts of excavation material, of which the sulphide clay is a considerable part. When the clay is exposed to air and water, an oxidation of the sulphides occurs which may produce an acid leachate and the mobilisation of heavy metals bound in the clay or underlying material. The aim of the work has been to improve our understanding of the behaviour of sulphide clays and produce a basis for risk assessment in the future handling of excavation material with high sulphide content. After sampling had been carried out in two places, batch tests were performed to examine the long-term acidification potential of clays with different calcium carbonate content. The tests were performed with continuous air supply and during the experiment leachate water was analysed with respect to pH, alkalinity, dissolved sulphate and mobilised metals. The results from the laboratory study showed that a clay with a high calcium carbonate content and thus a high net neutralisation potential (NNP) will consume the generated acid and prevent against a lowering of the pH. In clay lacking calcium carbonate, the pH dropped significantly and caused a mobilisation of chiefly Cd, Mn, Co, Ni, Ca and As. Regardless of the changes in pH over time, a large production of sulphur was observed as a result of the sulphide oxidation. In a risk assessment, it is suggested that the NNP should be determined by methods agreed upon to facilitate future comparisons and because different methods may give different results. A clay with a NNP&lt;5 kg CaCO3/ton should be further analysed with respect to metal content to establish the leachate generation potential and estimate the future environmental influence of the excavation material. / Uppsala stad vilar till stor del på postglacial lera med varierande svavelhalt. Svavlet finns naturligt i leran i reducerad form som sulfid och leran kallas därför vanligtvis för ”sulfidlera”. Vid schaktningsarbete i samband med byggnation uppkommer stora mängder schaktmassor varav en betydande del är sulfidlera. Då leran exponeras för luft och nederbörd sker en oxidation av sulfiderna som kan ge upphov till surt lakvatten och läckage av tungmetaller bundna i leran eller underliggande material. Syftet med arbetet har varit att öka kunskaperna om hur sulfidleror beter sig och ta fram ett underlag för riskbedömning i samband med den framtida hanteringen av sulfidhaltiga schaktmassor i Uppsala. Efter genomförd provtagning på två platser utfördes skaktest för att undersöka den långsiktiga försurningspotentialen hos lera med varierande kalkinnehåll. Testerna utfördes med kontinuerlig tillförsel av luft och löpande under försökets gång togs lakvatten ut för analys avseende pH, alkalinitet, löst sulfat och utlakade metaller. Resultaten från den laborativa studien visade att en kalkhaltig lera med hög nettoneutralisationspotential (NNP) kan förbruka den bildade syran och därigenom genereras ingen pH-sänkning. I lera som saknar kalk sjönk pH kraftigt och föranledde läckage av framförallt Cd, Mn, Co, Ni, Ca och As. Oavsett utvecklingen av pH observerades en stor utlakning av svavel till följd av oxidationen av sulfider. I en riskbedömning föreslås att lerans NNP bestäms enligt överenskomna metoder för att underlätta framtida jämförelser och för att olika tekniker kan ge olika resultat. En lera med NNP-värde &lt; 5 kg CaCO3/ton bör analyseras vidare avseende metallinnehåll för att fastställa den potentiella utlakningen och bedöma schaktmassans framtida naturpåverkan.

With the prospect of future construction on the Skutskär Pulp Mill property, Stora Enso Fine Paper has initiated an investigation of soil contaminants and a risk assessment of these contaminants. A soil and groundwater investigation has therefore been conducted on an open area of about 16 000 square meters, situated between the current wood room and digester house. To be able to integrate this study into an investigation for the whole industrial property, the study has been carried out as a phase 2 study according to the Swedish Environmental Protection Agency’s Methods of Inventories of Contaminated sites (MIFO). The site investigation has involved soil and groundwater sampling, together with the analysis of heavy metals and organic contaminants. The degree of hazard posed by the contaminants, the level of contamination, the potential for migration of the contaminants, as well as the degree to which protection of human health and the environment is required in the area, have been weighed together for an overall risk assessment of the area with regard to human health and the environment. The investigated area was built up by filling in the coastal waters. The fill material consists mainly of sand that becomes finer below the groundwater surface at the depth of about 2.3 m. Above the groundwater surface pyrite cinders was encountered. Underneath the cinders, lime sludge, bark and wood fiber were found at different depths. The deepest layer encountered consists of moraine. The results showed that most of the heavy metals in the soil originate from the pyrite cinders. The level of contamination was assessed as very high for Zn, Pb, Cu, Cd and Hg. In the groundwater, the level of contamination was assessed as high for Al and moderate for Pb and Cr. The level of organic contaminants was in general low. Heavy oils were encountered in shallow soil layers. Mercury was analysed due to risk of migration from an earlier factory that produced chlorine alkali. The metal was encountered in both the shallow and the deeper layers of soil. Only three of 56 soil samples exceeded the Swedish Environmental Protection Agency’s guideline value for less sensitive land use of 7 mg Hg/kg dry weight. The investigation indicates that the metals still are bound to the pyrite cinders and that most of the leachable parts were mobilized during the years when the ground was not covered with asphalt. Most of the contaminant migration is assumed to take place through groundwater advection. The groundwater flows in the direction of the dock and was calculated to about 3 m3 per day. The gradient in the area is about 0.5 %. The average linear groundwater velocity was computed to about 5 m per year. The transport of the pollutants might be slower due to adsorption and precipitation. Groundwater sampling indicates that the transport to the dock is up to 100 g Zn, 10 g Cr, 8 g Pb and 0.02 g Hg per year. The site was assigned to risk class 3, i.e. moderate risk regarding human health and environment and relatively low urgency concerning additional investigations. / Inför framtida ombyggnationer inom industrifastigheten vill Skutskärs Bruk, Stora Enso, kartlägga markföroreningar och utvärdera vilken spridningsrisk de utgör. En undersökning av mark- och grundvattenförhållanden har därför utförts på en ca 16 000 m2 stor yta, belägen mellan dagens renseri och kokeri. Undersökningen har utförts enligt Naturvårdsverkets Metodik för Inventering av Förorenade Områden (MIFO) för att i framtiden kunna integreras i en fas 2- undersökning för hela fastigheten. Arbetet har inneburit provtagning av mark- och grundvatten som analyserats med avseende på tungmetaller och organiska föroreningar. Föroreningarnas farlighet, föroreningsnivån, spridningsförutsättningarna samt objektets känslighet och skyddsvärde har vägts samman för att bedöma områdets risk för människors hälsa och miljö. Området utgörs av utfylld havsbotten. Massorna består främst av sand som blir siltigare under grundvattenytan på ca 2,3 m djup under markytan. Ovan grundvattenytan påträffades kisaska. Därefter hittades mesa, bark och träfiber på varierande djup. Fyllningen underlagras av morän. Resultatet visade att huvuddelen av tungmetallerna i marken härstammade från kisaskan. Föroreningsnivån bedömdes som mycket stor för Zn, Pb, Cu, Cd och Hg. I grundvattnet bedömdes föroreningsnivån som stor för Al och måttlig för Pb och Cr. Halten organiska föroreningar var generellt sett låg. Tyngre oljor påträffades i ytliga marklager. Kvicksilver har analyserats eftersom risk för spridning från en före detta kloralkalifabrik uppströms området förelåg. Ämnet påträffades både i ytnära marklager och på större djup. Endast tre av 56 markprover översteg Naturvårdsverkets gränsvärde för mindre känslig markanvändning på 7 mg/kg TS. Undersökningen tyder på att metallerna fortfarande är bundna till kisaskan och att stora delar av den lakbara delen transporterades bort under de år som ytan var oasfalterad. Huvuddelen av föroreningstransporten antas ske genom advektion. Grundvattnet flödar i riktning mot hamnbassängen och beräknas uppgå till ca 3 m3/dygn. Områdets gradient är ca 0,5 %. Vattenpartiklarnas hastighet beräknades till ca 5 m/år. Föroreningstransporten kan vara lägre på grund av adsorption och utfällning. Grundvattenprovtagningen tyder på att den årliga transporten till hamnbassängen skulle kunna uppgå till 100 g Zn, 10 g Cr, 8 g Pb och 0,02 g Hg. Objektet bedömdes tillhöra riskklass 3, det vill säga måttlig risk för människa och miljö samt relativt låg angelägenhet för vidare undersökningar.