Magister Scientiae - MSc (Earth Science) / The city of Randfontein, in the Witwatersrand, hosts several slimes and tailings storage facilities which pose potential threat to the environment in the form of acid mine drainage (AMD). The latter, readily scavenges toxic metals, contaminating surrounding soils and water resources, thereby potentially compromising the overall environmental- and public health of the area. To this end, three slimes sections (section T001, T002 and T003) from the Gold One Millsite Slimes Complex were investigated, with the aim of understanding metal release from the slimes dam into the Randfontein area. To achieve this, the mineralogical and geochemical factors controlling metal release were investigated using combined core log analysis, cluster and discriminant analysis, x-ray diffraction analysis, bulk geochemical analysis, acid base accounting methods and selective sequential extraction procedures.

Oxidation of pyrite can significantly affect properties and the behavior of soil and rock in civil construction. Problems with pyritic rock and soil extend globally and across many disciplines. Consequences of pyrite oxidation include heave, concrete degradation, steel corrosion, environmental damage, acid mine drainage, and accelerated weathering of rock with concomitant effects on strength and stability. Affected disciplines include soil science, mining, engineering geology, geochemistry, environmental engineering, and geotechnical engineering. While pyrite problems may be well known in their respective disciplines, there has been to date relatively little cross-disciplinary communication regarding problems with pyritic geomaterials. Thus, there is a need to establish an inter-disciplinary and inter-regional awareness regarding the effects of pyrite oxidation and their prevention or mitigation. This engineering research is a compilation of information about geotechnical problems and engineering behavior of pyritic rock and soil, the underlying physicochemical processes, site investigation strategies, and known problematic formations. Several case histories documenting consequences of pyrite oxidation are provided. The results of chemical analyses performed on pyritic shale samples from a formation with acknowledged heave problems are presented. Digital data and ESRI's ArcGIS digital mapping program were used to create maps showing results of sampling and testing performed during this study. Appendices include mitigation options, results of a practitioner survey, chemical test procedures, a glossary, a visual identification key for sulfidic geomaterials, and a summary table of the literature review for this research. / Master of Science

La déshydratation, l’oxydation et la fracturation sont les trois principaux processus couplés subis par l’argilite callovo-oxfordienne recoupée par les galeries du Laboratoire Souterrain de Meuse/Haute-Marne de l'Andra lors de l'excavation de galeries. Une série de forages à différents temps après l'ouverture de la galerie a permis d'étudier l'évolution des perturbations en fonction du temps, jusqu'à 18 mois. Les profils de teneur en eau et les analyses isotopiques montrent une déshydratation en surface des parois d'environ 50%. Le front de déshydratation est rapidement sub-stationnaire car il résulte d'un équilibre entre la recharge par l'eau de la formation et l'évaporation imposée par la pression partielle de l'eau dans l'air de la galerie. La zone perturbée affecte principalement les premiers 70 cm, et ne se fait plus sentir à partir de 1 m 50. L’oxydation des pyrites provoque la formation de fluides sulfatés acides qui dissolvent les minéraux environnants, libèrent dans la solution des ions Ca2+, K+ et Na+ puis lors de la déshydratation de l’argilite, l'évaporation de l'eau porale induit la précipitation de minéraux sulfatés principalement. La dégradation de la matière organique dans les conditions des galeries montre une dégradation limitée, due soit à une oxydation très discrète, soit à une dégradation lente non détectable aux temps courts. Une série d'expérience de mise en équilibre d'eau avec une roche plus ou moins oxydée a permis d'évaluer l'impact de la présence des phases minérales néoformées sur les caractéristiques chimiques des eaux de réhydratation. Cette approche expérimentale a été confrontée aux résultats de modélisation géochimique. Les résultats obtenus permettent de mieux préciser les caractéristiques géométriques, minéralogiques et physico-chimiques de cette zone perturbée qui est susceptible d'évoluer par la suite en condition de réhydratation et d'élévation de température lors du stockage / Dehydration, oxidation, and fracturing are the three main and coupled processes underwent by Callovian-Oxfordian argillite cut by the galleries of the Laboratoire Souterrain of Meuse / Haute-Marne of Andra during the excavation. Several boreholes drilled at different times after the opening of the gallery were used to study the evolution of disturbances with time up to 18 months. Profiles of water content and isotopic analysis show dehydration at the surface of the walls of about 50%. The area of dehydration is rapidly sub-stationary because it results from a balance between the suction by the pore water and the evaporation imposed by the partial pressure of water in the air of the gallery. The disturbed area mainly affects the first 70 cm, and not exceeds 1 m 50. The oxidation of pyrite causes the formation of acid sulphate fluids which dissolve the surrounding minerals in the solution, release Ca2+, K+ and Na+ in the pore water then during the dehydration of argillite, the evaporation of the pore water leads to the precipitation of sulphate minerals mainly. The degradation of organic matter in the galleries shows a limited deterioration due to a very moderate oxidation or the slow degradation is not detectable at short times. Several experiments of equilibration between more or less oxidized samples and water were used to evaluate the impact of the presence of new-formed mineral phases (sulphates) on the chemical composition of the rehydration water. This experimental approach has been compared to results of geochemical modelling. The results obtained allow us to define geometrical, mineralogical and physico-chemical properties of the disturbed zone which could evolve thereafter during rehydration and temperature rise in storage condition

No description available.

Pressure oxidation of refractory gold ores containing carbonate minerals is conducted under neutral/alkaline conditions in order to promote fast kinetics, reduced reagent consumption and suppressing the formation of elemental sulphur and CO2 (which reduces the effectiveness of the process). In this work, both the addition of sodium carbonate and the presence of silica were investigated during the pressure oxidation of pyrite in the presence of calcium carbonate. It was found that the shift to an alkaline leaching environment favours the formation of soluble sulphate products over anhydrite (an industrial scale), but that the increase in kinetics is likely due to an increase in pH and carbonate/bicarbonate concentrations. The presence of silica in the autoclave induces the formation of an in situ iron oxyhydroxide silicate coating and a significant reduction in pyrite oxidation, which was minimized by addition of sodium carbonate.

Pressure oxidation of refractory gold ores containing carbonate minerals is conducted under neutral/alkaline conditions in order to promote fast kinetics, reduced reagent consumption and suppressing the formation of elemental sulphur and CO2 (which reduces the effectiveness of the process). In this work, both the addition of sodium carbonate and the presence of silica were investigated during the pressure oxidation of pyrite in the presence of calcium carbonate. It was found that the shift to an alkaline leaching environment favours the formation of soluble sulphate products over anhydrite (an industrial scale), but that the increase in kinetics is likely due to an increase in pH and carbonate/bicarbonate concentrations. The presence of silica in the autoclave induces the formation of an in situ iron oxyhydroxide silicate coating and a significant reduction in pyrite oxidation, which was minimized by addition of sodium carbonate.

[Truncated abstract] The influence of environmental conditions and properties of pyritic shale in the mining waste from Mt. Whaleback in Western Australia, in particular the inclusions and encapsulation of pyrite on the oxidation of pyritic shale and its subsequent acid mine drainage, was studied by employing an isothermal batch reactor system and QEMSCAN technique. The experimental technique was validated by comparing the experimental results obtained in this study with the literature data. It was found that the presence of water significantly accelerates the rate of shale oxidation. Weathering of the shale samples was found to influence the O2 consumption rate. It was also found that shale properties have a major effect on the oxidation rate and thereby affect the acid generation. Static test methods (Sobek and Lawrence) were employed to test the Neutralisation Potential (NP) of more than 100 actual and composite samples including pyritic shale samples, rock samples, mineral samples, various pyrite-mineral, pyrite-shale, and pseudo-shale blends. The influence of sample properties (bulk elemental composition, and mineralogy), test technique (Sobek and Lawrence) and associated variables (acid strength and volume) on the acid neutralisation potential of the samples was studied. It was found that the Sobek method produced consistently higher NP results under comparable acid conditions to those obtained with the Lawrence method. The theoretical NP values of individual minerals were calculated based on the mineral composition combined with the acid neutralising equations and ideal chemical formula. ... To experimentally model the major mineral phases, 11 minerals were used to produce pyrite-mineral blends and pseudo-shales, whose compositions mimic those of the actual shales studied. Mineral blends were employed to evaluate and contrast their individual acid generation or neutralisation behaviour with binary and higher order interactions. Blends of pyrite with some selected shales were also employed in this study. It was found that interactions can occur between the multiple mineral components which can enhance the rate of acid generation beyond that of the individual behaviour. It was found that the products from the pre-oxidation of shales, the properties and morphology of a sample such as the surface area, encapsulation, the mineralogy and pH all play a significant role in the acid generation and neutralisation rates. However, the absolute rate of acid generation appears to be most sensitive to the components such as Fe3+, which contribute to its reaction mechanisms. This investigation has provided a scientific insight into the acid generation and neutralisation behaviour of pyritic shale in relation to its mineralogy. It was found that the relative instantaneous rates of acid generation and consumption for individual minerals can be significantly different to that of their total potentials for acid generation and neutralisation. The significantly different behaviour of the actual and pseudo shales suggests that at low pH, there may be other mechanisms underlying the net capacity and rates of shales to generate or consume acid than bulk mineralogy. These findings have significant implications to the mining industry operating in reactive grounds.

No description available.

Pyrite (FeS2) is commonly present in complex sulphide ores in significant amounts. After the enrichment of such ores by flotation, pyrite is either produced as a separate concentrate and sold to acid manufactures or removed and disposed off as tailing. Due to lack of demand from manufacturers, most of pyrites is usually disposed off as tailing. Therefore, pyrite is usually a waste from complex sulphide ores. Yet, it may be a remediation additive for calcareous soils and calcareous- alkali soils deficient in Fe and other micronutrients such as Cu, Zn and Mn. Waste pyrite may be also an alternative amendment to gypsum because of the production of sulphuric acid which is effectively used in the reclamation of calcareous alkali soils. The effectiveness of adding waste pyrite and sulphuric acid produced from waste pyrite to calcareous-alkali soil (Sarayk&ouml / y-Ankara) and calcareous soil (Gaziantep) was studied under laboratory conditions. Pure gypsum was also used as an amendment for the comparison of the effectiveness of waste pyrite in the reclamation of alkali soils. Gypsum, powder waste pyrite and sulphuric acid were applied to the soil with reference to the gypsum requirement (GR) of the soils. Greenhouse pot tests were carried out with wheat as test plant to determine the effect of waste pyrite treatment on the plant yield (wheat) and on the amount of micronutrient (Fe, Cu, Zn, Mn) essential for plant growth. Hazard potential of pyritic tailings in terms of heavy metal contamination was also taken into account. The results showed that the soil pH and exchangeable sodium percentage (ESP), indicators of alkalization, decreased upon pyrite addition to calcareous- alkali soils of Sarayk&ouml / y-Ankara. It was also found that pyritic tailings were effective in the increasing level of essential micronutrients (Fe, Cu, Zn and Mn) for plant growth in both soils. This was ascertained by the dry matter yield of the plants in the green house pot tests. Heavy metal toxicity caused by pyrite which is a rightful concern remained well below the legal limits in the soils. Thus, it was concluded that the application of pyritic tailings promoted rapid amelioration of calcareous-alkali soil (Sarayk&ouml / y-Ankara) and calcareous soil (Gaziantep) with no deleterious heavy metal contamination.

On retrouve des contaminations d’aquifèr à l’arsenic dans touts les deltaï de l'Asie du Sud-Est, y compris dans le delta du Mékong, ce qui affecte la santé de millions de personnes. L’arsenic est très sensible aux fluctuations des conditions redox qui sont générés par les cycles alternés humides/secs pendant la saison de mousson. Une étude sur les caractéristiques géophysiques et chimiques du sol et des eaux souterraines dans le district de An Phu, dans le haut du delta du Mékong au Vietnam, suggère une forté contamination à l’As dans cette région. Les données chimiques et géophysiques indiquent une forte corrélation entre concentrations dans les eaux souterraines anoxiques et conductivité des sols. La liberation de l’arsenic est associée à la dissolution réductrice induih par des microorganisms des colloïdes et (oxyhydr)oxydes de fer dans des conditions d'oxydo-réduction oscillantes. La présence de bactéries sulforéductrices a le potentiel de stabiliser l’arsenic dans la phase solide et de l’atténuer dans la phase aqueuse par adsorption / désorption de l’arsenic sur les (oxyhydr)oxydes, et / ou sulfures de fer via la formation de complexes thiols. En raison de la teneur en pyrite élevée dans les sédiments, l'oxydation de la pyrite peut abaisser le pH et conduire à l'inhibition de la réduction microbienne du sulfate et aime empêcher la séquestration de l’arsenic dissous. Bien que le cycle biogéochimique de l’arsenic dans un système dynamique d’oxydoréduction soit une problématique complexe, il a été possible de renforcer notre compréhension de ce système / Aquifer arsenic (As) contamination is occuring throughout deltaic areas of Southeast Asia, including the Mekong Delta, and affects the health of millions of people. As is highly sensitive to fluctuations of redox conditions which are generated by the alternating wet-dry cycles during the monsoonal seasons. A survey of geophysical and chemical characteristics of soil and groundwater in the An Phu district, located in the vicinity of the Mekong Delta in Vietnam, shows the occurrence high As aqueous concentration in this region. Chemical and geophysical data indicate a strong positive correlation between As concentrations in the anoxic groundwater and conductivity of soils. In addition, mechanisms of As release are shown to be associated with colloidal and iron (oxyhydr)oxides which undergo microbial mediated reductive dissolution under redox oscilatting conditions. The presence of sulfate microbial reduction potentially stabilizes As in the solid phase and diminish As in the aqueous phase through the adsorption/desorption of As onto iron (oxyhydr)oxides and/ or sulfides with formation of thiols complexes in solid phase. Because of the high pyrite content in sediment, pyrite oxidation may drop in pH values, leads to inhibition of sulfate reducing bacteria and reduces sequestration of dissolved As. Although the biogeochemical cycling of redox sensitive species such as As in dynamic systems is challenging, it has been possible to strengthen our collective understanding of such system.