Reproduction de : Thèse de doctorat : Dynamique et environnement sédimentaire : Lille 1 : 2001.

In order to understand the response of authigenic minerals to the gas hydrate geo-system, various authigenic pyrites were picked out under Zeiss Microscope and their S isotopes were analyzed later from 652 sediments samples at intervals of about 1.5m recovered from all 5 sites of Integrated Ocean Drilling Program (IODP) Expedition 311 on Cascadia Margin, northeastern Pacific. SEM photos of picked pyrites exhibit various aggregation features mainly in forms of strawberry, pillar/rod and dumbbell in sizes from 200 m to 1000m. Typical cubic pyrite crystals could be seen under smaller scale SEM photos. Most δ34S values in Site U1325 at the west deeper water location of IODP 311 show negative values low to -33.964‰ CDT, distinctly contrasted to the δ34S in Site U1329 at the east shallower location having much more positive values up to 28.29‰ CDT. At the cold venting position assigned as Site U1328 the δ34S values show strong negative values in the upper part of sediments column above 135 mbsf (meter below sea floor), increasing gradually with the depth from -35.83‰ CDT to -1.32‰ CDT, and then display many positive excursions up to 32.49‰ CDT below 135 mbsf, which is significantly distinguished from the values in nearby non-cold venting Site U1327 having much less positive excursions in the lower part of column below 110 mbsf. In all sites a general negative δ34S excursion occur in the upper part of sediments columns above 30~35 mbsf except in Site U1328 having more depth, indicating the potential current sulfate methane interface (SMI) activity zones. Distinct positive δ34S excursions up to the highest δ34S value 53.65‰ CDT from strawberry pyrites aggregations might indicate that sulfide products by AOM probably inherit completely the sulfate having high δ34S value and no sulfate was left after AOM at a high methane flux under gas hydrate geological background.

No description available.

The electronic spectra of sulfide minerals can be complex, and their features difficult to assign. Often, therefore, they are interpreted using electronic-structure models obtained from quantum-chemical calculations. The aim of this study is to provide such models for the minerals sphalerite, wurtzite, pyrite, marcasite, and chalcopyrite. All are important minerals within a mining context, either as a source for their component metals or as a gangue mineral. They are also semiconductors. Each is the structural archetype for a particular class of semiconductors, and so a knowledge of their electronic structures has wider applicability. / PhD Doctorate

Arbetets syfte är att undersöka svällande alunskiffer i Östersund, vad de senaste framstegen är för vad som orsakar svällning och hur den kan identifieras och hanteras. Enklare laborationsmoment utförs med provmaterial från jord-bergsondering i Östersund, men arbetet är främst en litteraturstudie. Alunskiffer har en varierande sammansättning av organiskt material, kalkrika mineraler och järnsulfider. Svällningen orsakas av oxidationen av järnsulfider vilket leder till bildning av gipskristaller. Omfattande krafter kan utvecklas i samband med svällningen vilket gör det till ett stort problem som kan orsaka deformationer av ovanliggande byggnader. Vårt förslag till hur svällskiffer kan identifieras är att utföra en övergripande kartläggning av alunskiffern i Östersund. Dess beskaffenhet bör undersökas kemiskt för att ta reda på halten svavelkis, magnetskis och andra mineral. Skifferns mekaniska egenskaper bör undersökas ytterligare. För att motverka svällningen föreslår vi att de metoder som tidigare prövats i Östersund och visat sig vara framgångsrika bör undersökas och utvecklas ytterligare. Inspiration kan också tas från gruvindustrin och hur de arbetar för att motverka surt avfall. De laborativa momenten visar att svällförloppet inte var tillräckligt snabbt för att ge ett resultat under testperioden på drygt två veckor. Smektittestet visar att det inte förekommer svällande lera, smektit, i borrkaxprovet från jord-bergsonderingen. / The purpose of the essay is to examine swelling alum shale in Östersund, what the state of the art concerning the cause of the swelling and how it may be identified and dealt with. Minor laboratory experiment is performed with test materials from soil-rock probing in Östersund, although the essay is mainly focused on studying literature. Alum shale has a varied composition of organic matter, calcareous minerals and iron sulphides. The swelling is caused by oxidation of the iron sulphides which forms gypsum. The extensive forces associated with the swelling can inflict deformations in the overlying buildings and is a major issue in Östersund. Our suggestions for how to identify the swelling shale is to make an extensive survey of the Östersund area. The survey would locate the alum shale and take samples to determine the chemical composition of the shale. We also suggest further analysis of the mechanical properties of the shale. Our suggestions for how to deal with the swelling would be to further examine the methods that proved to be successful at earlier attempts in Östersund. Inspiration can also be found in the mining industry and how they deal with acid mine drainage. The smectite test show that there is no swelling clay, also known as smectite, present in the drill cutting sample from the soil-rock probing. The swelling test show no signs of swelling caused by pyrite oxidation and the development of gypsum, during the test period of around two weeks.

Marine sulfide – bearing sediments that oxidize when in contact with oxygen and leach outelements in high concentrations to small watercourses have been a problem for many years allover the world especially around the Bothnian Bay. The purpose of this study was to furtherinvestigate the sulfur mineralogy present in acid sulfate soils in the area of Luleå, Sweden. Asecondary aim was to see if elements leach out and accumulate in an acid sulfate soil closer tothe recipient. Samples were taken in two profiles (one oxidized and one waterlogged) fromfour sites (sites A-D) and were analyzed for whole rock geochemistry. Two sites were furtherinvestigated for mineralogy in polished samples with an optical microscope, Ramanspectroscopy and SEM-EDS. Each profile consisted of three layers: oxidation zone, transitionzone and reduced zone. The oxidation zone above the groundwater table was light grey withbrown iron hydroxide staining. Parts that lied under the water table were dark grey-black within general strong odor (“rotten eggs”) due to its sulfur content. It was usually straightforwardto distinguish and separate the layers from each other directly in the field, however in somecases pH was needed for confirmation.A general feature of investigated polished samples is the presence of abundant framboidalpyrites that are common in reduced marine sediments. The transition zone was formed in suboxicconditions and this feature is reflected by the mineralogy. Many morphologies of theframboidal pyrite were observed in this layer and signs of both dissolution and formationoccur. In the sample from site C one could observe elemental sulfur in form of large (up to 50μm) euhedral crystals. In the samples with pH<4, no sulfides occur as they have been replacedby jarosite (site B). Site C lacks these sulfur-bearing hydroxides which is thought to be due toa sulfur concentration of <0.2 %. Sulfur shows extensive leaching at most sites but at site B andD1, it accumulates in the transition zone. Elements like cobalt (Co), nickel (Ni) and zinc (Zn)are leached out or are accumulated further down in the profile. Elements that could have beentransported and have accumulated in the waterlogged profiles are Co, Ni, Zn and chromium(Cr) and in some profiles also copper (Cu) and vanadium (V). / Coastal watercourses in Bottenviken: Method development and ecological restoration- A cross-border Swedish-Finnish cooperation project

A presente pesquisa teve por objetivo a análise do comportamento de diferentes combinações de liners de um determinado solo com e sem cimentação, submetidos à percolação de líquidos ácidos, com o objetivo de simular o comportamento de campo de liners de aterros especiais, que recebem resíduos à base de pirita. Tal resíduo em contato com água e oxigênio forma solução de ácido sulfúrico. Assim sendo, as pretensões deste trabalho foram a análise do comportamento compressivo de liners formados por um dado tipo de solo compactado, com e sem a adição de cimento, através do emprego de um equipamento de adensamento modificado desenvolvido especialmente para esta pesquisa. Da mesma forma, procedeu-se o estudo dos fenômenos de transporte de contaminantes por meio do liner em estudo, basicamente daqueles que comandam o transporte (difusão, advecção, sorção, retardamento da frente de contaminação e grau de afinidade entre o contaminante e o liner). Ensaios isotrópicos a altas tensões de confinamento também foram realizados a fim de se estudar a possível desestruturação dos liners quando percolados por resíduos ácidos. Os resultados obtidos destacam a desestruturação de amostras naturais do solo estudado quando percolado por rejeitos ácidos, em todas as concentrações estudadas, tanto em ensaios triaxiais isotrópicos quanto em ensaios de carregamento axial com deformações laterais nulas. Conclui-se que as águas ácidas quando percoladas por meio de um solo com presença de finos, tende a proporcionar um efeito de carreamento de partículas, aumentando conseqüentemente a porosidade, fator este que poderia proporcionar a falha operacional de um liner. / The objective of this work is to analyse the behavior of a liner formatted by different combinations of soil and cement, percolated by low pH waters under different hydraulic gradients and concentration of acid in the percolant, aiming to simulate in laboratory what would happen in the field to liners in contact with pyrite wastes, from mineral coal mining. Pyrite wastes in contact with water and oxygen result in sulphuric acid, what makes the objective of this research the study of the compressive behavior of the liner submitted to the percolation of acid waters, by means of a special column equipment developed during this research, which allows applying an axial load to the sample under flux. Also, the variation of the transport of contaminants values were investigated, basically diffusion, advection, sorption, retardation coefficient, distribution coefficient, hydrodynamic dispersion, ground water velocity and hydraulic conductivity). Triaxial Isotropic tests were carried out under high confinant pressures in order to verify the volume changes of the samples due to the low-pH contamination. The results show that liners formatted only by soil had rearrange of their structure due to acid percolations, according to both column and isotropic tests. The value of the hydrodynamic dispersion was considerated being totally dependent on the diffusion, because the hydraulic conductivity of the differente combination was low. The results also show that low-pH percolations make a rearrange of the fine particles into the sample, because after a grain size distribution test, the fine particles from the top of the samples were detected on the bottom of the sample, what increase the porosity on the top of the samples, what could lead the liner to a failure.

A mineração de carvão gera grandes volumes de rejeitos que podem ser responsáveis por graves danos ambientais. A oxidação da pirita (FeS2), na presença de ar e água, promove a formação da drenagem ácida de mina (DAM), uma solução aquosa fortemente ácida e rica em sulfato e ferro (nas formas Fe²+ e Fe³+), além de outros metais associados. Atualmente, poucos estudos têm considerado a possibilidade da produção de materiais de valor econômico agregado a partir da água de percolação em rejeitos de carvão. Neste trabalho, o objetivo foi o desenvolvimento de uma rota hidrometalúrgica para a produção de sulfato ferroso (FeSO4). O trabalho experimental consistiu inicialmente na coleta de amostra de rejeitos de carvão rico em pirita e a sua caracterização. Realizou-se, em laboratório, a lixiviação do material em colunas de percolação em ambiente oxidante, adequado para proporcionar a oxidação da pirita em meio aquoso. A recirculação da lixívia permitiu a obtenção de um extrato rico em ferro. A seguir, procedeu-se a conversão do Fe³+ em Fe²+ para obtenção do sulfato ferroso, utilizandose radiação ultravioleta. O lixiviado, rico em Fe+², foi evaporado para cristalização do sulfato ferroso e purificado com álcool etílico. Os cristais foram caracterizados por análise química elementar, difração de raios X e microscopia eletrônica de varredura. A recuperação de Fe na forma melanterita (FeSO4.7H2O) em relação ao Fe pirítico existente na coluna (0,30 kg de Fe pirítico por kg de rejeito de carvão) variou de 7,5 a 9,0 %. Os resultados demonstraram que é possível produzir sulfato ferroso n-hidratado tendo como matéria-prima o rejeito rico em pirita resultante da mineração de carvão mineral. / The coal mining generates large volumes of tailings that may be responsible for serious environmental damages. The oxidation of pyrite (FeS2), in the presence of air and water, promotes the formation of acid mine drainage (AMD), an aqueous and highly acid solution rich in sulfate and iron (in the form Fe³+ and Fe²+), along with other associated metals. Currently, few studies have considered the possibility of production of materials with agregated economic value from the percolation of water in coal mining tailings. In this study, the objective was the development of a hydrometallurgical route for its production. The experimental work consisted initially in the collection of samples of coal waste rich in pyrite and its characterization. In the laboratory was performed the leaching of the material in percolation collums in an oxidizing environment, appropriate to provide the pyrite oxidation in aqueous medium. The recirculation of liquor allowed to obtain an extract rich in the iron. Then, the conversion of Fe³+ to Fe²+ for obtaining ferrous sulfate was performed using ultraviolet irradiation. The leached liquor, rich in Fe+², was evaporated for ferrous sulphate crystallization and purified with ethanol. The ferrous sulphate crystals were characterized by x ray diffraction and scanning electron microscopy. The recovery of Fe in the form melanterite (FeSO4.7H2O ) on pyrite Fe existing in the column (0,30 kg of Fe per kg of pyrite tailings and coal) ranged from 7,5 to 9,0 %. The results demonstrated that it is possible to produce nhydrated iron sulfate having as a raw material the waste rich in pyrite produced from the coal mining.

O presente trabalho teve como objetivo desenvolver um protótipo para a produção hidrometalúrgica de sulfato ferroso heptahidratado (FeSO4.7H2O – melanterita). A matéria prima foi um concentrado de pirita obtido a partir de rejeitos do beneficiamento de carvão mineral. Construiu-se, em escala piloto, uma planta de lixiviação com 300 kg de um concentrado com 73,2% de pirita. Nesta unidade, realizou-se uma etapa de lixiviação com água, em circuito fechado, sob condições aeróbias, com o intuito de se obter um extrato aquoso rico em íons férrico e sulfato. A seguir, procederam-se mudanças no sistema de forma a estabelecer uma condição anaeróbia ao meio, transformando os íons férricos em ferrosos. O lixiviado, rico em Fe2+, foi precipitado na forma de sulfato ferroso heptahidratado pela adição de etanol. Esse precipitado foi submetido a uma etapa de recristalização, obtendo-se cristais de melanterita de maior pureza. Ambos os produtos foram caracterizado por análise química elementar e difração de raios X. Os cristais de melanterita recristalizados apresentaram alta pureza, com qualidade para uso químico e farmacêutico. Assim, desenvolveu-se uma nova rota para produção de sulfato ferroso tendo como matéria-prima um concentrado de pirita da mineração de carvão (usualmente o sulfato ferroso é produzido como coproduto da produção de ilmenita e aço). A tecnologia apresenta uma elevada conversão do ferro lixiviado em melanterita e os insumos necessários são pirita, água e álcool etílico. A proposta abre uma nova possibilidade de uso dos rejeitos de carvão e a possibilidade de comercialização de outro produto na cadeia produtiva de carvão mineral. / The aim of this work was to develop a prototype for hydrometallurgical production of ferrous sulfate heptahydrate crystals (FeSO4.7H2O – melanterite). The raw material was a pyrite concentrate obtained from a coal tailing. The leaching system was assembled in pilot scale with 300 kg of a concentrate with 73.2% pyrite. Initially, it was carried out a leaching step in aerobic conditions with the purpose to obtain an aqueous solution rich in ferric ions and sulfate. Next, modifications were proceeded to establish an anaerobic condition in the reactor, converting the ferric to ferrous ions. Ethanol was added to the leaching solution to provide the precipitation of the Fe2+ and sulfate as ferrous sulfate heptahydrate. The ferrous sulfate precipitate was recrystallized, allowing producing melanterite crystals of higher purity. The crystals were characterized in terms of chemical and mineralogical composition. The process allowed producing crystals with a high purity attending chemical and pharmaceutical purposes. Thus, it was developed a process to produce ferrous sulfate from coal wastes (usually, ferrous sulfate crystals are produced as a co product from titanium dioxide and steel production). The technology presents a high conversion factor of soluble Fe2+ to melanterite and the necessary incomes are pyrite, water, and ethylic alcohol. The hydrometallurgical technique applied in this study allowed production of a commercial grade product from coal mining waste material.

Os depósitos de carvão no Brasil possuem conteúdos relativamente baixos de matéria orgânica. Aproximadamente 65% do carvão ROM (Run-of-min) extraído de minas subterrâneas na região carbonífera de Santa Catarina são descartados como resíduo em depósitos de rejeitos. Esse rejeito contem minerais sulfetados, principalmente a pirita, que oxida e pode gerar drenagem ácida de minas, com diversos impactos ambientais e custos econômicos. Entretanto, com o processamento do rejeito de carvão para concentração da pirita, esta pode-se tornar matéria prima para diversos produtos, entre eles o ácido sulfúrico (insumo deficitário no país, utilizado em grandes quantidades na indústria de fertilizantes). O objetivo deste trabalho foi caracterizar o rejeito de carvão para concentração da pirita proveniente da camada Bonito, no estado de Santa Catarina, avaliando-se o seu potencial uso na produção de ácido sulfúrico e os ganhos ambientais com a dessulfurização do material remanescente. Para isso, foram construídas as curvas de separabilidade densimétrica de uma amostra de rejeito grosso e de uma amostra de rejeito fino. Definiram-se densidades de cortes, de forma a recuperar um material carbonoso remanescente (d<2,2), um material dessulfurizado (2,2<d<2,7) e um concentrado de pirita (d>2,7). Efetuou-se a caracterização das frações densimétricas através de imagens fotográficas e análises de cinzas, enxofre, umidade, poder calorífico, difração de raio-x (DRX), fluorescência de raio-x (FRX) e análise termogravimétrica. As análises ambientais realizadas foram: classificação de resíduos conforme NBR 10.004 e teste estático de predição de acidez pelo método de contabilização de ácidos e bases. Estimou-se a produção de ácido sulfúrico a partir do concentrado piritoso obtido com o processamento do rejeito de carvão das camadas Barro Branco e Bonito e avaliaram-se os ganhos ambientais. Os resultados demonstraram que o rejeito proveniente do circuito de grossos (87,2% do material descartado) possui teor de enxofre de 7,8% e 79,9% de cinzas, já os finos (12,8% do material) tem um teor de enxofre de 4,9% e 70,8% de cinzas. Com a separação densimétrica do rejeito em 2,2 e 2,7, obteve-se uma fração d<2,2 g/cm³ com recuperação mássica de 20,7% para os grossos e 45,2% para os finos que só possui aproveitamento energético em termoelétricas se misturado com carvão de baixo enxofre. O material dessulfurizado (2,2<d<2,7 g/cm³) corresponde a 66% em massa do rejeito para os grossos, possui 3,8% de enxofre e potencial de geração de acidez 60% inferior ao rejeito original. Já a fração pirítica (d>2,7 g/cm³) possui recuperação mássica de 13% para os grossos e teor de enxofre de 33,1%. Quando comparada com a camada Barro Branco, a camada Bonito apresenta níveis superiores de S na fração intermediária, com maior potencial de geração de acidez. De qualquer forma, os rejeitos de carvão grossos, tanto da Camada Barro Branco como Bonito, são passíveis de beneficiamento por processos gravimétricos para obtenção de concentrados com no mínimo 30% de enxofre. Caso houvesse um planejamento global de aproveitamento da pirita na região carbonífera de Santa Catarina para produção de ácido sulfúrico, um acréscimo de 14% da demanda brasileira deste insumo poderia ser realizado com os atuais níveis de produção de carvão, reduzindo em até 75% o enxofre disposto no ambiente e trazendo benefícios econômicos e ambientais à região carbonífera de Santa Catarina. / The grade of coal deposits in Brazil is relatively low, and approximately 65% of the run-of-mine (ROM) coal extracted from underground mines in the carboniferous region of Santa Catarina is discarded as waste in dump deposits. These waste discards contain sulfide minerals, particularly pyrite, which oxidize and give rise to acid rock drainage (ARD) with recognized environmental impacts and economic costs. However, the coal waste could be gravimetrically processed to produce a pyrite concentrate to be used as a raw material for sulfuric acid production (an income with deficient production in the country, largely used in fertilizer industry). The aim of this work was to study the coal waste from the Bonito seam in the state of Santa Catarina, Brazil, evaluating its use for the production of sulfuric acid and the environmental implications of remaining material after the desulfurizing step. Washability curves of coarse and fine waste material from a coal preparation plant working with the Bonito seam was performed. Three different density fractions were separated: a carbonaceous material (d<2.2 g/cm3), a desulfurized material (2.2 and 2.7 g/cm³), and a pyrite concentrate (d>2.7 g/cm³). Characterization studies were carried out by photographic images and ash, sulfur, moisture, calorific value, X-ray diffraction (XRD), X-ray fluorescence (XRF), and thermogravimetric analysis (TGA). Environmental classification of the waste was conducted in terms of NBR 10.004 and static acid prediction test by the acid-base accounting method. It was also estimated the production of sulfuric acid from Barro Branco and Bonito seams as well the environmental benefits of such desulfurization procedures. The results showed that the coarse fraction of coal tailing from Bonito seam (87.2% of the discarded mass) presents 7.8% sulfur and 79.9% ash. The fine waste fraction from the spirals circuit (12.8% of the discarded mass) showed 4.9% sulfur and 70.8% ash. Both materials were subjected to density separation. The fraction d<2.2 g/cm³, with a mass recovery of 20.7% for the coarse fraction and 45.2% for the fine fraction, could be only used for energy production if a moisture with low sulfur coal was provided. The intermediate density material (2.2<d<2.7 g/cm³), which corresponds to a 66% of the mass coarse mass fraction and presents 3.8% sulfur, have a 60% lower acid generation material than the raw waste. The pyrite concentrate (d>2,7) reached a 13% mass recovery with 33.1% sulfur. Comparing the Barro Branco and Bonito seams, the Bonito seam showed superior levels of sulfur in the 2.2<d<2.7 g/cm³ fraction, with a higher an acid generation potential. Nevertheless, the coarse fraction of both seams can be processed for pyrite concentration, reaching the minimum of 30% sulfur necessary for sulfuric acid production by roasting. Considering the levels of coal production in the carboniferous region of Santa Catarina, an input of 14% in the national demand of sulfuric acid would by supplied. This procedure will also reduce in 75% the pyrite disposed in landfills, bringing economic and environmental benefits to the local coal chain production.