Dans de nombreux gisements métalliques, notamment en contexte sédimentaire et en particulier dans le cas des shales noirs, des relations spatiales voire génétiques sont décrites entre la matière organique et les métaux. Une série de shales/schistes noirs affectés par des conditions thermo barométriques croissantes a été sélectionnée afin d'étudier le comportement et le devenir de l'uranium de la sédimentation au métamorphisme. Dans les Alum Shales cambro ordoviciens (Suède) faiblement enfouis, l'uranium reste dispersé et n'apparaît sous aucune forme minéralogique identifiable. Le passage des Alum Shales dans la fenêtre pétrolière et la génération d'hydrocarbures n'a pas provoqué de remobilisation identifiable de la concentration primaire, les hydrocarbures migrés ne transportant pas l'uranium. En revanche, le métamorphisme de faciès schiste vert associé à l'orogénèse calédonienne a entraîné une réexpression de la minéralisation uranifère sous la forme d'uraninite, d'urano titanates et/ou de phospho silicates à U, Ti, Zr, Y. Dans le cas des schistes noirs paléoprotérozoïques de Talvivaara (Finlande), le métamorphisme de faciès amphibolite a provoqué la remobilisation de l'uranium synsédimentaire et la cristallisation synmétamorphique, pendant l'orogénèse svécofennienne à 1880 1870 Ma, de cristaux d'uraninite fréquemment inclus dans des nodules carbonés. Cette étude montre que l'uranium, préconcentré au moment de la sédimentation, reste immobile pendant les premiers stades d'enfouissement mais est remobilisé dans les conditions P T croissantes et cristallise sous forme d'oxydes d'uranium pouvant évoluer vers des (phospho-)silicates d'uranium / In many metallic deposits, especially in sedimentary context and particularly in black shales, spatial or genetic relationships are described between organic matter and metals. Several black shales/schists affected by increasing thermo barometric conditions were selected to study the behavior and fate of uranium from sedimentation to high grade metamorphism. In shallow buried cambro ordovician Alum Shales (Sweden), uranium is dispersed and is not detectable as a particular mineralogical expression. Thermal maturation of the Alum Shales and hydrocarbon generation did not cause any identifiable remobilization of primary concentration, since migrated hydrocarbons did not carry uranium. In contrast, greenschist facies metamorphism associated with the Caledonian orogeny resulted in a re expression of uranium mineralization as uraninite or urano titanate crystals, which may evolve into U Ti Zr Y phospho silicates. In the case of Talvivaara, amphibolite facies metamorphism caused remobilization of synsedimentary uranium and synmetamorphic crystallization, during Svecofennian orogeny at 1880 1870 Ma, of uraninite crystals that are frequently included in carbonaceous nodules. This study shows that uranium, which is preconcentrated during sedimentation, remains immobile in the early stages of burial but is remobilized with increasing PT conditions and crystallizes as uranium oxides and/or uranium (phospho-)silicates

Thesis (M.Phil.)--Chinese University of Hong Kong, 1996. / Includes bibliographical references (leaves 113-120). / Abstract --- p.i / Acknowledgement --- p.iii / Table of Contents --- p.iv / List of Tables --- p.viii / List of Figures --- p.xii / Chapter CHAPTER 1. --- INTRODUCTION --- p.1 / Chapter 1.1 --- Previous Heavy Metal Studies of Hong Kong Marine Waters and Sediments --- p.4 / Chapter 1.2 --- Speciation of Metals in Aquatic Environment --- p.6 / Chapter 1.2.1 --- Speciation of Metals in Water --- p.7 / Chapter 1.2.2 --- Speciation of Metals in Bottom Sediments --- p.7 / Chapter 1.3 --- AVS in Marine Sediments --- p.10 / Chapter 1.3.1 --- Formation of AVS --- p.10 / Chapter 1.3.2 --- Seasonal and Spatial Variation of AVS --- p.11 / Chapter 1.3.3 --- AVS as Mediator of Metal Toxicity --- p.13 / Chapter 1.3.4 --- Chemical Basis for AVS Sediment Normalization --- p.15 / Chapter 1.3.5 --- Analysis of Pore Water Metals --- p.17 / Chapter 1.4 --- Significance of the Research --- p.18 / Chapter 1.4.1 --- Importance of Metal Bioavailability Study in Hong Kong --- p.18 / Chapter 1.4.2 --- Importance of AVS Study in Hong Kong --- p.19 / Chapter 1.4.3 --- Approach of the Present Study --- p.21 / Chapter 1.5 --- Organization of the Thesis --- p.22 / Chapter CHAPTER 2. --- METHODOLOGY --- p.23 / Chapter 2.1 --- Study Area --- p.24 / Chapter 2.2 --- Sampling Strategy --- p.25 / Chapter 2.2.1 --- Sampling Locations --- p.25 / Chapter 2.2.2 --- Sampling Dates --- p.28 / Chapter 2.2.3 --- Sample Collection and Handling --- p.28 / Chapter 2.3 --- Sample Analysis --- p.32 / Chapter 2.3.1 --- Sediment Analysis --- p.32 / Chapter 2.3.2 --- Pore Water and Overlying Water Analysis --- p.34 / Chapter 2.3.3 --- Limitations --- p.36 / Chapter 2.4 --- Statistical Analysis --- p.39 / Chapter CHAPTER 3. --- METALS IN WATER AND BOTTOM SEDIMENTS --- p.40 / Chapter 3.1 --- Metals in the Water --- p.40 / Chapter 3.1.1 --- Variation of Metal Concentrations --- p.41 / Chapter 3.1.2 --- Metal Pollution Level of the Overlying Water --- p.42 / Chapter 3.2 --- Metals in Bottom Sediments --- p.44 / Chapter 3.2.1 --- Spatial Distribution Pattern of Heavy Metals --- p.44 / Chapter 3.2.2 --- Temporal Variation of Metal Content in the Bottom Sediments --- p.48 / Chapter 3.2.3 --- Metal Pollution Level of the Bottom Sediments --- p.49 / Chapter 3.3 --- Conclusion --- p.50 / Chapter CHAPTER 4. --- SPECIATION OF METALS IN THE OVERLYING WATER AND BOTTOM SEDIMENTS --- p.51 / Chapter 4.1 --- Speciation of Metals in the Overlying Water --- p.51 / Chapter 4.1.1 --- Concentration of Labile Metals in the Overlying Water --- p.52 / Chapter 4.1.2 --- Seasonal and Spatial Variation in the Concentration of Labile Metals in the Overlying Water --- p.54 / Chapter 4.1.3 --- Percentage of Labile Fraction in Total Metals --- p.55 / Chapter 4.2 --- Speciation of Metals in the Bottom Sediments --- p.59 / Chapter 4.2.1 --- Proportion of Various Metal Species in the Sediments --- p.60 / Chapter 4.2.2 --- Variation of the Overlying Water Properties --- p.63 / Chapter 4.2.2.1 --- Chemical Properties of the Water in the Study Area --- p.63 / Chapter 4.2.2.2 --- Seasonal Variation of Water Properties --- p.67 / Chapter 4.2.2.3 --- Stratification of the Water Column --- p.69 / Chapter 4.2.3 --- Implication of the Changes of Water Quality on Metal Remobilization --- p.73 / Chapter CHAPTER 5. --- VARIATION OF AVS AND ITS ROLE IN METAL TOXICITY MEDIATION --- p.77 / Chapter 5.1 --- Variation of AVS in the Study Area --- p.78 / Chapter 5.1.1 --- Spatial Variation of AVS --- p.78 / Chapter 5.1.2 --- Seasonal Variation of AVS --- p.81 / Chapter 5.1.3 --- Vertical Variation of AVS --- p.85 / Chapter 5.1.4 --- Effects of AVS Variation on Metal Bioavailability --- p.88 / Chapter 5.2 --- Role of AVS in Metal Toxicity Mediation --- p.91 / Chapter 5.2.1 --- SEM/AVS Molar Ratio --- p.91 / Chapter 5.2.2 --- Fraction of SEM in Total Metals of the Sediments --- p.94 / Chapter 5.2.3 --- Labile Metals in Pore Water --- p.96 / Chapter 5.2.4 --- Dissolved Sulfides in the Pore Water and Overlying Water --- p.99 / Chapter 5.3 --- Conclusion --- p.100 / Chapter CHAPTER 6. --- CONCLUSION --- p.102 / Chapter 6.1 --- Introduction --- p.102 / Chapter 6.2 --- Major Findings --- p.103 / Chapter 6.3 --- Practical Implication of the Findings --- p.108 / Chapter 6.4 --- Suggestion for Further Studies --- p.110 / Bibliography --- p.113 / Appendix A. AVS Extraction and Detection Method --- p.121 / Appendix B. Sequential Extraction Method for Metals Speciation Analysis --- p.123 / Appendix C. Instrument List for the Experiments --- p.125 / Appendix D. Monthly Total Rainfall and Mean Temperature of1995 --- p.127 / Appendix E. Analytical Results of the Overlying Water --- p.128 / Appendix F. Analytical Results of the Bottom Sediments --- p.132 / Appendix G. Analytical Results of the Pore Water --- p.136 / Appendix H. Concentration (μg/g) and Fraction (%) of Pbin Sediments --- p.140 / Appendix I. Concentration (μg/g) and Fraction (%) of Cuin Sediments --- p.142 / Appendix J. Concentration (μg/g) and Fraction (%) of Cdin Sediments --- p.144 / Appendix K. Concentration (μg/g) and Fraction (%) of Znin Sediments --- p.146 / Appendix L. Concentration (μg/g) and Fraction (%) of Niin Sediments --- p.148 / Appendix M. Fraction of Different Speciations of Metals in the Sediments --- p.150 / Appendix N. Vertical Profile of Dissolved Oxygen in the Overlying Water --- p.155 / Appendix O. Vertical Profile of Salinity in the Overlying Water --- p.159 / Appendix P. Vertical Profile of Temperature in the Overlying Water --- p.163 / Appendix Q. Vertical Profile of pH in the Overlying Water --- p.167

The Fäboliden gold deposit is an ore body in northern Sweden’s Bothnian Basin and has been the subject of studies and test mining since the early 2000s when the Gold Line, an area of anomalously high-Au glacial till in Northern Sweden, became a center of economic interest. The deposit is a hypozonal orogenic gold deposit that displays many characteristic features of ore bodies of this type, including the presence of compound sulfide grains composed of a core of löllingite surrounded by a rim of arsenopyrite, and an abundance of pyrrhotite throughout the deposit and surrounding alteration zone. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to first map the distribution of trace elements in several of the arsenpyrite-löllingite grains, then to perform spot analyses of pyrrhotite grains in samples from across the distal and proximal alteration zones of the deposit. The maps of the trace elements in the compound löllingite-arsenopyrite grains show that: As and Au are found in greater abundance in the löllingite than in the arsenopyrite; Cu, Fe, S, and Ti are found in greater abundance in the arsenopyrite than in the löllingite; and Ag, Au, Bi, La, Mn, Pb, Sr, Ti and Tl are found in zones of secondary enrichment along fractures within the grains. Uranium and V may also be enriched along fractures, although this isn’t clear on all of the maps. Gold is an element of particular interest, because its distribution throughout the sulfide phases can be used to constrain the mechanism and relative timing of mineralization within the deposit. The presence of invisible gold within the löllingite, but not within the arsenopyrite, shows that gold is not incorporated into arsenopyrite at high temperatures and will instead be concentrated in the löllingite core of the composite grain and at the margin between the two sulfide phases as the löllingite is altered to arsenopyrite. Previous research on the Fäboliden gold deposit, including geothermometric analysis of vein-hosted graphite within fluid inclusions and garnet-biotite geothermometry as well as structural evidence provided by regional deformation, indicate that mineralization occurred post-peak metamorphism. The textures seen are therefore not conclusive of mineralization occurring syn- or pre-peak metamorphism, as has previously been proposed based on research of orogenic gold deposits in Western Australia. The spot analysis of pyrrhotite samples from across the deposit shows a distinct decrease in Ni and Co content in the proximal alteration zone, suggesting uptake of these elements by other minerals such as the löllingite and arsenopyrite. Multiple analyses performed on single grains show local variation, but are insufficient to establish the presence or determine the character of growth zonation within pyrrhotite.

Ensaios cronogalvanométricos, análises por difração de raios -X, microscopia eletrônica de varredura (MEV) e curvas de polarização potenciostáticas foram usadas com o propósito de caracterizar os filmes formados sobre o aço API T95 em soluções alcalinas de sulfeto de sódio (Na2S 0,02M). As características destes filmes foram analisadas em função do pH da solução. O pH usado em cada caso (entre 8 e 11) foi obtido através da injeção de gás sulfídrico (H2S) na solução previamente desarejada. As curvas de polarização potenciostáticas mostram o aparecimento de uma região passiva ou pseudo-passiva para os pHs mais elevados (1 O e 11 ). As curvas cronogalvanométricas permitiram verificar uma queda de densidade de corrente nestes mesmos pHs, evidenciando a melhor proteção contra a corrosão dos filmes de sulfeto formados nestas condições. / Chronogalvanometric electrochemical essays, X - ray diffraction analysis, scanning electron microscopy (SEM) and potentiostatic curves were used with the pourpose of characterizing the sulfide films formed on API T95 steel in alkaline sodium sulfide (Na2S 0,02M) environments. The characterization of these films were followed by pH measurements and the potential at witch they were formed. The pH of the used environments was varied between 8 and 11 through hydrogen sulfide (H2S) injection in the previously deaerated solution. Potentiostatic polarization curves indicate a pseudopassive or passive area in the highest pH values (1 O and 11 ). The chronogalvanometric curves show a decrease of current density, at the same pH, characterizing a better corrosion protection of the films formed in these conditions.

La présente étude porte sur les problématiques d’entreposage de colis de déchets nucléaires. En France, via le projet Cigéo, il est envisagé d’entreposer les déchets radioactifs de moyenne et haute activité à vie longue à 500 mètres de profondeur dans un conteneur en acier API 5L X65 (chemisage) déposé dans des galeries creusées au sein d’une formation argileuse (argilites). Une température maximum de 90°C est attendue à la surface de l’acier en raison de l’intense radioactivité. Finalement, un coulis cimentaire (matériau de remplissage) sera injecté entre le chemisage et les argilites. La synthèse de couches de produits de corrosion susceptibles d’être rencontrées à la surface de l’acier dans les conditions de stockage a constitué le premier objectif de ce travail. Les conditions pour l’obtention de sidérite (FeCO3), de mackinawite (FeS) et de magnétite (Fe3O4) ont été déterminées. Par la suite, des essais de couplage impliquant deux électrodes recouvertes de produits différents ont été réalisés dans le but de simuler le comportement d’une surface d’acier recouverte d’une couche hétérogène de produits de corrosion. Il est apparu que l’acier recouvert d’une couche de mackinawite se comportait dans chaque cas comme une cathode. Ce phénomène est associé au caractère plutôt protecteur de la couche de mackinawite. Parallèlement, les essais de formation de la mackinawite par polarisation anodique ont montré que la formation d’une couche de produits de corrosion composée de magnétite/mackinawite était associée à un phénomène de corrosion localisée. Le comportement de l’acier au contact du matériau de remplissage envisagé pour combler l’espace entre le chemisage et les argilites a ensuite été étudié. Ce deuxième volet de l’étude a montré que la couche de produits de corrosion se formant à la surface de l’acier était principalement composée de magnétite, associée à des sulfures de fer tels que la mackinawite. L’hétérogénéité du matériau de remplissage, la présence de sulfures en son sein et la présence d’oxygène dissous dans les solutions de test sont les principales causes de l’apparition d’un phénomène de corrosion localisée. Ce résultat traduit également le caractère imparfaitement protecteur des couches d’oxyde se formant sur l’acier au contact du matériau cimentaire. Enfin, la dernière partie de ce travail de recherche a porté sur l’étude d’éventuels effets galvaniques entre une zone recouverte d’argilites et une zone recouverte de matériau de remplissage impliquant la présence de magnétite et de mackinawite et pouvant faire office de cathode. De tels effets n’ont pas été mis en évidence, ce qui est attribué à l’absence d’un véritable état passif de l’acier en contact avec le matériau cimentaire. / The present study relates to the problem of long-term disposal of nuclear waste. In France, with the Cigéo project, it is envisaged to store high and intermediate level long lived radioactive waste at a depth of 500m inside a carbon steel (API 5L X65) casing in a deep geological disposal, drilled in a very stiff clay formation. A maximum temperature of 90°C is expected at the carbon steel surface, because of the intense radioactivity. Finally, a specific cement grout will be injected between the carbon steel casing and the argilites. The synthesis of corrosion product layers likely to form on the steel surface was the first objective of this work. The different parameters to obtain siderite (FeCO3), mackinawite (FeS) and magnetite (Fe3O4) have been determined. Subsequently, coupling tests were carried out with two steel electrodes covered with different corrosion products in order to simulate the behaviour of a steel surface covered with a heterogeneous corrosion product layer. It appeared that the steel electrode covered with mackinawite was in each case the cathode. This phenomenon is associated with the somewhat protective properties of the mackinawite layer. Besides, anodic polarization experiments conducted to prepare mackinawite layers showed that the formation of a corrosion product layer composed of magnetite/mackinawite was associated with localized corrosion. The behaviour of carbon steel in contact with cement grout envisaged to fill the gap between casing and argillites was studied next. This second part of the study showed that the corrosion product layer forming on the steel surface was mainly composed of magnetite, associated with iron sulphides such as mackinawite. Heterogeneity of the cement grout, presence of sulphide within it, and presence of dissolved oxygen in the test solutions are the main causes of the appearance of localized corrosion processes. This result also shows that the oxide layers forming on the steel surface in the specific cement grout only provides an imperfect protection. Finally, the last part of this research work focused on the study of possible galvanic effects between a zone covered with argilites, and a zone covered with cement grout implying the presence of magnetite and mackinawite and thus able to act as cathode. Such effects could not be evidenced which is attributed to the absence of a real passive state of the steel in contact with the cement grout.

<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>

In this work we have investigated the intercalation of electron-donors between NbS2 slabs in Nb-based layer sulfides. Two series of Sr substituted Nb-based misfit sulfides belonging to the 1.5Q/1H and 1Q/1H series of misfit layer compounds have been synthesised. For large lanthanides (Ln=La, Ce), only the 1Q/1H compounds formed whereas for smaller lanthanides and yttrium, both types of phases can be obtained. The crystal structure of misfit sulfide (Pr0.55Sr0.45S)1.15NbS2 has been refined using the composite approach. In the Q-slab, Pr-atoms are partly replaced by Sr with a random distribution over one cation position. The crystal structure of misfit sulfide [(Sm1/3Sr2/3S)1.5]1.15NbS2 belonging to the 1.5Q/1H series have also been determined. The obtained results suggest a preferred occupancy of the cation positions in the slab where Sr atoms mainly occupy positions on the exterior of the slab while Sm atoms are in the center of the slab. The (La1-xSrxS)1.15NbS2 solid solution (0.1&lt;x&lt;0.9) has also been studied. It was found that the maximum value of Sr substitution is 40-50% and therefore, the minimal value of charge transfer to stabilize this structure type is about 0.6ē per Nb atom. An attempt to synthesize SrxNbS2 (0.1≤x≤0.5) intercalates was made but single phases were not obtained and increasing the temperature from 1000оС to 1100оС leads to the decomposition of these intercalates. Single crystals of Sr0.22Nb1.05S2 and Sr0.23NbS2 were found and their structures were determined. The structures belong to two different types of packings with statistical distribution of Sr between layers. A new superconducting sulfide, "EuNb2S5", was investigated by ED and HREM and its structure model consisting of Nb7S14 and (Eu3S4)2 slabs alternating along the c-axis is suggested. An attempt to suggest a model for the structure of "SrNb2S5" by means of X-ray single crystal diffraction was made. The proposed structure consists of two types of slabs: a Nb7S14 and a [Sr6(NbS4)2S] slab with niobium in tetrahedral coordination. It is shown that "SrNb2S5" and "EuNb2S5" are have similar structures. For the first time, single crystals of the complex sulfide BaNb0.9S3 have also been studied by means of X-ray single crystal diffraction. The single crystal refinement and EDX analysis showed the existence of cation vacancies at the niobium position. BaNb0.9S3 has also been studied by ED and no superstructure was found which implies that and the vacancies are statistically distributed. No improvement of the magnetic properties of the studied compounds was observed in comparison to NbS2.

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.

One chemoautotrophic origin of life theory posits the abiotic formation of alkyl thiols as an initial step to forming biomolecules and eventually a simple chemoautotrophic cell. The premise of this theory is that a recurring reaction on the charged surfaces of pyrite served as a primordial metabolism analogous to the reductive acetyl-CoA pathway (Wächtershäuser 1988) that was later enveloped by a primitive cellular membrane. Alkyl thiols have not previously been identified in terrestrial hot springs as unequivocally abiogenic, but they have been produced in the laboratory under hydrothermal conditions in the presence of a catalyst. I analyzed the dissolved gas content of several hot springs and conducted sterile laboratory experiments in order to evaluate the abiogenic formation of methanethiol (CH3SH), the simplest of the alkyl thiols. Specifically of interest was Cinder Pool, an acid-sulfate-chloride hot spring in Yellowstone National Park. This spring is unusual in that it contains a subaqueous molten sulfur layer (~18 m depth) and thousands of iron- vii sulfur-spherules floating on the surface, which are created by gas bubbling through the molten floor of the spring. This material could potentially serve as a reactive and catalytic surface for abiogenic CH3SH formation in Cinder Pool. Gas samples were collected from Cinder Pool and an adjacent hydrothermal feature in fall of 2011 using the bubble strip method. Two samples contained measurable quantities of CH3SH and other organic sulfur gases, with concentrations of all gases generally higher at the bottom of the pool. Laboratory microcosm experiments were conducted to replicate these findings in a sterile environment. Analog Cinder Pool water was injected into serum bottles containing different iron-sulfur compounds, including cinders collected from the pool itself, as catalytic surfaces for the CH3SH generating reaction. The bottles were then charged with hydrogen (H2), carbon dioxide (CO2), and carbon disulfide (CS2) as reaction gases and incubated for a week at temperatures between 60 and 100oC. Bottles used either powdered FeS, FeS2 (pyrite) or cinder material as a catalytic surface, and all of these surfaces were capable of catalyzing CH3SH formation. In bottles without imposed CS2, however, cinder material was the only surface that produced any detectable CH3SH. While CH3SH is central to the autotroph-first theory and has been synthesized in the laboratory (e.g. Heinen and Lauwers 1996), it has not previously been observed to form abiotically in natural systems. I have identified CH3SH in a natural hydrothermal feature where it is unlikely to have formed secondary to microbial activity, and I have duplicated these field findings in sterile laboratory experiments using the cinders as a reactive surface for formation. / text

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