This dissertation includes theoretical and applied components that address the effect of coatings on rates of mineral reactions that occur in acid mine drainage (AMD) environments. The two major projects investigated how diffusion-limited transport of reactants through pore spaces in coatings on mineral grains affects the reaction rate of the underlying mineral. The first project considered the growth of gypsum coatings on the surface of dissolving limestone in anoxic limestone drains (ALD), which reduces the neutralization rate of the dissolving limestone and the subsequent effectiveness of this treatment. The second project investigated the conditions where iron oxyhydroxide coatings form on oxidizing pyrite and the potential strategies to prevent "runaway" AMD by reducing the rate of acid production to the point that the acid can be neutralized by the surrounding rocks. In both studies, experiments were conducted to measure reaction rates for the underlying minerals, as coatings grew thicker. These experimental data were fit to a diffusion model to estimate diffusion coefficients of reactants through pore spaces in coatings. These models are extrapolated to longer times to predict the behavior of the coated grains under field conditions. The experimental results indicate that management practices can be improved for ALDs and mine waste piles. For example, supersaturation with respect to gypsum, leading to coating formation, can be avoided by diluting the ALD feed solution or by replacing limestone with dolomite. AMD can be prevented if the rate of alkalinity addition to mine waste piles is faster than acid is produced by pyrite oxidation. The diffusion model developed in this study predicts when iron oxyhydroxide coatings will become thick enough that alkalinity from the surroundings is sufficient to neutralize acid produced by coated pyrite oxidation and additional alkalinity is no longer required. / Ph. D.

This thesis examines sulfide oxidation in 4 physically and mineralogically diverse acid sulfate soil (ASS) materials collected from coastal floodplain sites in north-eastern New South Wales. The aim of this study is to gain further understanding of the process of sulfide oxidation in ASS materials, which will allow improved and more effective management strategies to be applied to these materials. The process of sulfide oxidation was examined using laboratory incubation experiments. The oxidation of pyrite was the primary cause of initial acidification of the ASS materials studied. Although the acid volatile sulfur fraction increased in concentration by an order of magnitude over the initial 8 days of incubation, the subsequent oxidation of this fraction did not result in substantial acidification. Sulfate (SO42-) was the dominant sulfur species produced from sulfide oxidation, however, water-soluble SO42- was a poor indicator of the extent of sulfide oxidation. The sulfoxyanion intermediates thiosulfate (S2O32-) and tetrathionate(S4O62-) were only detected in the early stages of incubation, and their relative abundance appeared to be pH dependent. The diminishing presence of these 2 sulfur species as oxidation progressed was indicative that ferric iron (Fe3+) and bacterial catalysis were driving the oxidation processes. The rate of sulfide oxidation, and consequent rate of acidification, was highly dependent on the soil pH and oxygen availability. Accelerated sulfide oxidation was only observed at low pH (i.e. pH < 4.0) when oxygen availability was not limited. The application of sub-optimal amounts of neutralising agents prevented severe soil acidification in the short-term (i.e. up to 2 months), but had little effect on decreasing the rate of sulfide oxidation and acidification in the long-term. Sub-optimal amounts of CaCO3 accelerated sulfide oxidation and acidification of the peaty marcasitic ASS material resulting in elevated soluble Fe and Al concentrations. For some of the ASS materials, sub-optimal applications of seawater-neutralised bauxite refinery residue (SNBRR) also resulted in elevated soluble Al concentrations. The response of partially-oxidised ASS materials to the exclusion of oxygen was variable. The rate of sulfide oxidation, acidification and the production of soluble oxidation products generally decreased markedly when subjected to anoxia. However, especially in highly acidic ASS materials (i.e. pH < 3.5), sulfide oxidation and acidification generally occurred (albeit at much slower rates), most probably due to oxidation by Fe3+. Rapid sulfide re-formation occurred in the peat ASS material that had been oxidised for 63 days, with 0.47% reduced inorganic sulfur (SCR) formed over 60 days of anoxia. Biogeochemical sulfide formation consumes acidity, however, sulfide re-formation was ineffective in reversing acidification under the conditions of this experiment. The peroxide oxidation methods examined were method dependent and substantially underestimated peroxide oxidisable sulfur, sulfidic acidity and net acidity. The precipitation of jarosite during peroxide oxidation was a major factor contributing to the underestimation in these ASS materials. Clay mineral dissolution may contribute towards the underestimation of both sulfidic and net acidity using peroxide oxidation methods. The atmospheric loss of sulfur and acidity was also identified as a possible additional interference. This study has shown that the initial pH of an ASS material is a useful indicator (additional to those already used) of the potential environmental hazard of an ASS material when oxygen is expected to be non-limiting, such as when ASS materials are excavated and stockpiled. The recommended action criteria need to be reassessed as the data indicate that the current criteria are conservative for alkaline and neutral ASS materials, but should be lowered for all acidic ASS materials (i.e. pH < 5.5) to 0.03% sulfide regardless of texture. Alternative strategies are necessary for the management of ASS materials that are subject to oxidation when the addition of optimal rates of neutralising materials cannot be ensured. The treatment of sites containing actual ASS materials by management strategies that rely on oxygen exclusion need to be accompanied by strategies that include either acid neutralisation or containment in order to reduce acid export from the site. The peroxide oxidation methods examined were subject to substantial interferences, and consequently are unable to reliably provide accurate measurements of the reduced inorganic sulfur fraction, sulfidic acidity, and net acidity in ASS materials.

Die vorliegende Arbeit wurde im Rahmen des BMBF-geförderten Projektes "Luft- und bodengestützte spektrometrische Untersuchungen zur Differenzierung reaktiv veränderter Braunkohlentagebaugebiete in Mitteldeutschland" (Vorhaben 02 WB 9667/5) als Kooperation zwischen dem GeoForschungsZentrum Potsdam (GFZ), dem Deutschen Zentrum für Luft- und Raumfahrt (DLR), der Gesellschaft für Angewandte Fernerkundung (GAF) und dem Umweltforschungszentrum Leipzig/Halle GmbH (UFZ) angefertigt. Grundidee des Projektes war es, die durch spektrometrische Erfassungsmethoden der Fernerkundung erhaltenen Überfliegungsdaten mittels konventioneller petrographischer, mineralogischer und geochemischer Analytik zu kalibrieren. Der Schwerpunkt dieser Arbeit lag dabei in der Charakterisierung der hydro- und geochemischen Veränderungen in den Kippensedimenten des im mitteldeutschen Raum südlich von Leipzig aufgeschlossenen Braunkohlentagebaus Zwenkau. Zu diesem Zweck wurden die Kippensedimente in Abhängigkeit des Schüttungsalters und der Lagerung untersucht sowie die spezifischen Merkmale der Kippenwässer und Bodengase erfaßt, um die im Kippenkörper ablaufenden chemischen, petrographischen und gefügemäßigen Veränderungen sowie die Wechselwirkungen zwischen den Sedimenten, Wässern und Bodengasen zu beschreiben. Schließlich wird ein Modell zur zeitlichen Entwicklung der Abraumförderbrückenkippe, beginnend bei ihrer Verkippung bis hin zu einem Alter von etwa 20 Jahren, vorgestellt, welches die beobachteten Erscheinungen bezüglich der auftretenden endogenen und exogenen Wechselwirkungsfaktoren gut erklärt. / This thesis was prepared in cooperation with the GeoForschungsZentrum Potsdam (GFZ), the Deutsches Zentrum für Luft- und Raumfahrt (DLR), the Gesellschaft für Angewandte Fernerkundung (GAF), and the Umweltforschungszentrum Leipzig/Halle (UFZ) in frame of the project "Airborne and laboratory spectroscopic studies for differentiation of reactively alterated lignite mining pits in Central Germany" (No. 02 WB 9667/5) which was gratefully supported by the Bundesministerium für Bildung, Wissenschaft, Forschung und Technologie (BMBF). The major idea of the project was to achieve a calibration of the spectroscopic data acquired by the remote sensing though the results obtained from conventionally petrographical, mineralogical and geochemical analyses. The main goal of this thesis was the characterization of the hydro- and geochemical alterations in the conveyor bridge dump of the open lignite mining pit Zwenkau which is located in the Central Germany District southern of Leipzig. Therefore, dependent on their ages in terms of dumping and their surface-near locations the dump sediments were investigated and the specific properties of the different types of dump water and soil gases were acquired as well in order to describe the ongoing chemical, petrographical and structural alterations and interactions between the sediments, the water and the soil gases in the conveyor bridge. Finally, a model of the chronological development of the overburden sediments starting from their spilling up to an age of about 20 years is proposed which well explains the observed phenomena regarding the appearing endogenous and exogenous interaction factors.

This thesis examines sulfide oxidation in 4 physically and mineralogically diverse acid sulfate soil (ASS) materials collected from coastal floodplain sites in north-eastern New South Wales. The aim of this study is to gain further understanding of the process of sulfide oxidation in ASS materials, which will allow improved and more effective management strategies to be applied to these materials. The process of sulfide oxidation was examined using laboratory incubation experiments. The oxidation of pyrite was the primary cause of initial acidification of the ASS materials studied. Although the acid volatile sulfur fraction increased in concentration by an order of magnitude over the initial 8 days of incubation, the subsequent oxidation of this fraction did not result in substantial acidification. Sulfate (SO42-) was the dominant sulfur species produced from sulfide oxidation, however, water-soluble SO42- was a poor indicator of the extent of sulfide oxidation. The sulfoxyanion intermediates thiosulfate (S2O32-) and tetrathionate(S4O62-) were only detected in the early stages of incubation, and their relative abundance appeared to be pH dependent. The diminishing presence of these 2 sulfur species as oxidation progressed was indicative that ferric iron (Fe3+) and bacterial catalysis were driving the oxidation processes. The rate of sulfide oxidation, and consequent rate of acidification, was highly dependent on the soil pH and oxygen availability. Accelerated sulfide oxidation was only observed at low pH (i.e. pH < 4.0) when oxygen availability was not limited. The application of sub-optimal amounts of neutralising agents prevented severe soil acidification in the short-term (i.e. up to 2 months), but had little effect on decreasing the rate of sulfide oxidation and acidification in the long-term. Sub-optimal amounts of CaCO3 accelerated sulfide oxidation and acidification of the peaty marcasitic ASS material resulting in elevated soluble Fe and Al concentrations. For some of the ASS materials, sub-optimal applications of seawater-neutralised bauxite refinery residue (SNBRR) also resulted in elevated soluble Al concentrations. The response of partially-oxidised ASS materials to the exclusion of oxygen was variable. The rate of sulfide oxidation, acidification and the production of soluble oxidation products generally decreased markedly when subjected to anoxia. However, especially in highly acidic ASS materials (i.e. pH < 3.5), sulfide oxidation and acidification generally occurred (albeit at much slower rates), most probably due to oxidation by Fe3+. Rapid sulfide re-formation occurred in the peat ASS material that had been oxidised for 63 days, with 0.47% reduced inorganic sulfur (SCR) formed over 60 days of anoxia. Biogeochemical sulfide formation consumes acidity, however, sulfide re-formation was ineffective in reversing acidification under the conditions of this experiment. The peroxide oxidation methods examined were method dependent and substantially underestimated peroxide oxidisable sulfur, sulfidic acidity and net acidity. The precipitation of jarosite during peroxide oxidation was a major factor contributing to the underestimation in these ASS materials. Clay mineral dissolution may contribute towards the underestimation of both sulfidic and net acidity using peroxide oxidation methods. The atmospheric loss of sulfur and acidity was also identified as a possible additional interference. This study has shown that the initial pH of an ASS material is a useful indicator (additional to those already used) of the potential environmental hazard of an ASS material when oxygen is expected to be non-limiting, such as when ASS materials are excavated and stockpiled. The recommended action criteria need to be reassessed as the data indicate that the current criteria are conservative for alkaline and neutral ASS materials, but should be lowered for all acidic ASS materials (i.e. pH < 5.5) to 0.03% sulfide regardless of texture. Alternative strategies are necessary for the management of ASS materials that are subject to oxidation when the addition of optimal rates of neutralising materials cannot be ensured. The treatment of sites containing actual ASS materials by management strategies that rely on oxygen exclusion need to be accompanied by strategies that include either acid neutralisation or containment in order to reduce acid export from the site. The peroxide oxidation methods examined were subject to substantial interferences, and consequently are unable to reliably provide accurate measurements of the reduced inorganic sulfur fraction, sulfidic acidity, and net acidity in ASS materials.

No description available.

Die vorliegende Arbeit wurde im Rahmen des BMBF-geförderten Projektes "Luft- und bodengestützte spektrometrische Untersuchungen zur Differenzierung reaktiv veränderter Braunkohlentagebaugebiete in Mitteldeutschland" (Vorhaben 02 WB 9667/5) als Kooperation zwischen dem GeoForschungsZentrum Potsdam (GFZ), dem Deutschen Zentrum für Luft- und Raumfahrt (DLR), der Gesellschaft für Angewandte Fernerkundung (GAF) und dem Umweltforschungszentrum Leipzig/Halle GmbH (UFZ) angefertigt. Grundidee des Projektes war es, die durch spektrometrische Erfassungsmethoden der Fernerkundung erhaltenen Überfliegungsdaten mittels konventioneller petrographischer, mineralogischer und geochemischer Analytik zu kalibrieren. Der Schwerpunkt dieser Arbeit lag dabei in der Charakterisierung der hydro- und geochemischen Veränderungen in den Kippensedimenten des im mitteldeutschen Raum südlich von Leipzig aufgeschlossenen Braunkohlentagebaus Zwenkau. Zu diesem Zweck wurden die Kippensedimente in Abhängigkeit des Schüttungsalters und der Lagerung untersucht sowie die spezifischen Merkmale der Kippenwässer und Bodengase erfaßt, um die im Kippenkörper ablaufenden chemischen, petrographischen und gefügemäßigen Veränderungen sowie die Wechselwirkungen zwischen den Sedimenten, Wässern und Bodengasen zu beschreiben. Schließlich wird ein Modell zur zeitlichen Entwicklung der Abraumförderbrückenkippe, beginnend bei ihrer Verkippung bis hin zu einem Alter von etwa 20 Jahren, vorgestellt, welches die beobachteten Erscheinungen bezüglich der auftretenden endogenen und exogenen Wechselwirkungsfaktoren gut erklärt. / This thesis was prepared in cooperation with the GeoForschungsZentrum Potsdam (GFZ), the Deutsches Zentrum für Luft- und Raumfahrt (DLR), the Gesellschaft für Angewandte Fernerkundung (GAF), and the Umweltforschungszentrum Leipzig/Halle (UFZ) in frame of the project "Airborne and laboratory spectroscopic studies for differentiation of reactively alterated lignite mining pits in Central Germany" (No. 02 WB 9667/5) which was gratefully supported by the Bundesministerium für Bildung, Wissenschaft, Forschung und Technologie (BMBF). The major idea of the project was to achieve a calibration of the spectroscopic data acquired by the remote sensing though the results obtained from conventionally petrographical, mineralogical and geochemical analyses. The main goal of this thesis was the characterization of the hydro- and geochemical alterations in the conveyor bridge dump of the open lignite mining pit Zwenkau which is located in the Central Germany District southern of Leipzig. Therefore, dependent on their ages in terms of dumping and their surface-near locations the dump sediments were investigated and the specific properties of the different types of dump water and soil gases were acquired as well in order to describe the ongoing chemical, petrographical and structural alterations and interactions between the sediments, the water and the soil gases in the conveyor bridge. Finally, a model of the chronological development of the overburden sediments starting from their spilling up to an age of about 20 years is proposed which well explains the observed phenomena regarding the appearing endogenous and exogenous interaction factors.

Tesis por compendio / [ES] Esta investigación se centra en la caliza de Prada, una formación del Cretácico inferior ubicada en la zona sur pirenaica de Cataluña (España). Se tomaron muestras de roca de sondeos perforados durante la etapa de diseño del túnel de Tres Ponts. El trabajo aquí presentado explora diferentes aspectos relacionados con el comportamiento térmi-co de la caliza de Prada y las consecuencias derivadas en el túnel de Tres Ponts. En primer lugar, este trabajo describe la variación en las propiedades texturales, físicas y mecánicas de la caliza de Prada después de ser sometida a temperaturas de entre 105 y 600 ºC, y luego enfriada a un ritmo lento o mediante templado, y determina las tem-peraturas clave y los métodos de enfriamiento que afectan más la estabilidad en caso de incendio en el túnel de Tres Ponts. En segundo lugar, esta investigación se centra en las causas y mecanismos implicados en el comportamiento explosivo y la liberación de gas sulfuroso observado en una fracción gris oscuro de muestras de caliza de Prada. Las implicaciones de tales muestras de color gris oscuro son críticas en infraestructuras subterráneas y en minería, ya que el potencial explosivo de esas muestras conlleva el riesgo de fracturación masiva y de disminución brusca en la resistencia. Además, el gas sulfuroso liberado tiene efectos nocivos sobre la salud de las personas y el poten-cial de formar compuestos ácidos que corroen los materiales, acortando su durabilidad y aumentando los costes de mantenimiento. Posteriormente, este trabajo determina si el tratamiento térmico sobre la caliza de Prada tiene un efecto significativo en facilitar su perforabilidad. Comprender la variación en el rendimiento de perforación de la caliza de Prada tratada térmicamente ayudaría a mejorar la eficiencia de los medios mecánicos de excavación. Finalmente, se proponen algunas correlaciones para deter-minar indirectamente las características de resistencia, deformación y perforabilidad de la caliza de Prada tras ser tratada térmicamente, a partir de pruebas simples, rápidas y no destructivas. / [CA] Aquesta investigació es centra en la calcària de Prada, una formació del Cretaci inferior situada a la zona sud pirinenca de Catalunya (Espanya). Es van prendre mostres de roca de sondejos perforats durant l'etapa de disseny del túnel de Tres Ponts. El treball aquí presentat explora diferents aspectes relacionats amb el comportament tèrmic de la calcària de Prada i les conseqüències derivades al túnel de Tres Ponts. En primer lloc, aquest treball descriu la variació en les propietats texturals, físiques i mecàniques de la calcària de Prada després de ser tractada a temperatures d'entre 105 i 600 ºC, i després refredada a un ritme lent o ràpid, i determina les temperatures clau i els mètodes de refredament que afecten més l'estabilitat en cas d'incendi al túnel de Tres Ponts. En segon lloc, aquesta investigació es centra en les causes i mecanismes implicats en el comportament explosiu i l'alliberament de gas sulfurós observat en una fracció gris fosc de mostres de calcària de Prada. Les implicacions de tals mostres de color gris fosc són crítiques en infraestructures subterrànies i en mineria, ja que el potencial explosiu d'aquestes mostres comporta el risc de fracturació massiva i de disminució brusca en la resistència. A més, el gas sulfurós alliberat té efectes nocius sobre la salut de les persones i el potencial de formar compostos àcids que corroeixen els materials, retallant la seua durabilitat i augmentant els costos de manteniment. Posteriorment, aquest treball determina si el tractament tèrmic sobre la calcària de Prada té un efecte significatiu en facilitar la seua perforabilitat. Comprendre la variació en el rendiment de perforació de la calcària de Prada tractada tèrmicament ajudaria a millorar l'eficièn-cia dels mitjans mecànics d'excavació. Finalment, es proposen algunes correlacions per determinar indirectament les característiques de resistència, deformació i perforabilitat de la calcària de Prada després de ser tractada tèrmicament, a partir de proves simples, ràpides i no destructives. / [EN] This research is focused on Prada limestone, a lower Cretaceous formation located in the Catalan south Pyrenean zone (Spain). Rock samples were taken from boreholes drilled during the design stage of the Tres Ponts Tunnel. The work presented here explores different aspects related to the thermal behaviour of Prada limestone and the derived consequences on the Tres Ponts Tunnel. Firstly, this work reports the variation in the textural, physical, and mechanical properties of Prada limestone after being heated at temperatures of between 105 and 600 ºC and then cooled at a slow rate or by quenching and determines key temperatures and cooling methods that would most affect stability in case of a fire in the Tres Ponts Tunnel. Secondly, this research fo-cuses on the causes and mechanisms involved in the explosive behaviour and release of sulphurous gas observed on a dark grey fraction of samples from Prada limestone. Implications of such dark grey samples are critical in underground infrastructure and mining engineering works, as the explosive potential of that sample represents risk of mass fracturing and dramatic strength decay. Moreover, the sulphurous gas released has harmful health effects and may form acid compounds that corrode materials, shorten their durability, and increase maintenance costs. Later, this work determines if thermal treatment on Prada limestone has a significant effect on improving its drilla-bility. Understanding the variation in the drilling performance of the thermally treated Prada limestone would help improve the efficiency of mechanical excavation means. Finally, some correlations are proposed to indirectly determine the strength, deformational, and drillability features of Prada limestone after being thermally treated from simple, quick and non-destructive tests. / This research was partially supported by the Spanish Government [grant number RTI2018-099052-B-I00], also the Vice-Rectorate of Research and Knowledge Transfer at the University of Alicante through projects UAUSTI19-25 and UAUSTI20-20, and by the Departamento de Ingeniería del Terreno at the Universitat Politècnica de València. / Martínez Ibáñez, V. (2021). Effects of high temperatures in the physical, mechanical, and drilling features of Prada limestone [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/171023 / Compendio

Anthropogenic lakes constitute a significant part of the Czech countryside water component which has not been given sufficient attention so far. The presented thesis deals with the assessment of variability of physico-chemical properties of water in 30 selected pit lakes in order to identify specific features associated with quarrying of different mineral raw materials, basin morphometry and trophic level of the lakes affecting the quality of accumulated water. In the second part of the thesis the author deals with the comprehensive limnological study of the Hromnické Lake with extreme water chemism resulting from excavation of pyritic shales and focuses on the phenomenon of meromixis especially. The results are based on the evaluation of physical properties of water in the lake vertical profile (temperature, conductivity, dissolved oxygen, pH, transparency and colour) and chemical analyzes of water samples collected from the surface and bottom of the lakes during the four seasons in 2003-07 (determination of Ca, Mg, Na, K, Nammon., NO3 - , SO4 2- , Cl- and alkalinity), including determination of chlorophyll-a. In the case study of the Hromnické Lake conducted in 2010-11, the analysis of hydrological regime of the lake, determination of PO4 3- , TOC, selected metals (Fe, Mn, Al, Zn, Ni, Cu, Co,...