Thesis (M.S.)--Ohio State University, 1965. / Available online via OhioLINK's ETD Center

Bibliography: leaves 192-193. / ix, 214, ix leaves : ill. ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / The focus of the thesis is to investigate the fundamental kinetics of the pyrite-nitric acid system. Particular attention is paid to the formation and oxidation of elemental sulfur. The study aims to elucidate the chemistry of the sulfide oxidation and of elemental sulfur formation and oxidation. / Thesis (Ph.D.)--University of Adelaide, Dept. of Chemical Engineering, 1997?

The major objective of this work was to investigate the initial oxidation behavior of pyrite in order to better understand how mine wastes containing pyrite generate acid water. It was found that a unique potential exists at which a fresh surface of pyrite undergoes neither oxidation nor reduction. This potential is pH dependent and is referred to as the "stable" potential. The stable potential was found to be 0 V at pH 4.6 and -0.3 V at pH 9.2. Fresh, unoxidized pyrite surfaces were obtained by fracturing under the electrolyte while holding at the stable potentials. The initial oxidation behavior of pure pyrite was investigated using cyclic voltammetry technique by beginning potential sweeps from the stable potential and sweeping in the positive-going or negative-going direction. The effects of semiconducting properties of pyrite on its electrochemical behavior were studied by photocurrent measurement. The results indicate that pyrite samples from Peru and Spain are all highly n-type. A spontaneous depletion layer is formed on the fresh surfaces of n-type pyrite. The depletion layer is attributed to an intrinsic, acceptor-like surface state. Charge storage in this surface state pins the band edge over a wide potential range, accounting for the metallic-like electrochemical behavior that has been reported for pyrite. Electrochemical and photocurrent measurements were also conducted on galena for comparison with pyrite. The results indicate that galena samples from the same cluster have varying semiconducting properties, ranging from nearly intrinsic to highly n-type. Abrasion introduces defects in the surface of pyrite and galena, which strongly decrease the magnitude of photocurrent. / Master of Science

[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.

Thesis (Master of Engineering in Chemical Engineering)--Cape Peninsula University of Technology, 2018. / Acid rock drainage (ARD) is one of the most severe environmental challenges currently faced by the mining industry worldwide. ARD is formed from the oxidation of sulphide-bearing minerals, particularly pyrite, in the presence of water and oxygen. ARD generation is accelerated by the presence of naturally occurring iron and sulphur-oxidizing micro-organisms, which regenerate leaching agents that facilitate sulphide mineral oxidation. ARD pollution is characterized by a high concentration of metals and sulphates in solution, low pH and a high salt content (salinity) in the environment, contaminating soil and groundwater. In South Africa, ARD is a major challenge in the gold and coal mining industries, where millions of tons of sulphide waste rock and overburden are generated and discarded. Characterization of these waste materials is required to develop an appropriate disposal strategy to minimise the risk of pollution and the generation of ARD. Potential ARD generation prediction from waste rock depends on the precise characterization of ARD potential using Biokinetic tests. Commonly used ARD prediction methods are static and long-term kinetic tests. Static tests provide data for a worst-case scenario focussing on strong acid chemical leaching potential to give an overall acid forming potential of a sample. Such kinetic tests provide data illustrating the rate of the net acid generation capacity of mine waste. However, these tests are capital intensive and time-consuming and fail to provide adequate information on the effect of micro-organisms on the overall net acid generation capacity of mine waste. The Biokinetic test reported herein and developed at the University of Cape Town, focusses on addressing a worst case scenario provided by static tests in a cost-effective manner and reduced time frames provided for by conventional kinetic tests. This test primarily provides relative rates of ARD generation in the presence of micro-organisms within 90 days. However, the Biokinetic test is at the developmental stage and thus far, has not been consistently used for different waste ores to determine a standardised approach. Therefore, the aim of this study was to investigate the effects of microbial consortia and to develop a standardisation approach for the test for ARD formation potential using gold-bearing and copper-bearing waste rock. Additionally, to refine the Semi-continuous Biokinetic test simulation, a flow-through system where there is minimal seepage in the waste deposit, was also developed. The sulphur content of the gold and copper-bearing samples used in this study was between 2.3 and 3.15%, respectively. These waste rock samples were found to be potentially acid- forming. In the Biokinetic test, finely milled waste rock samples were slurrified, inoculated with consortia and cultured under standard bioleaching conditions. Leaching and acidification rates were monitored.

Thesis (MSc)--Stellenbosch University, 1997. / ENGLISH ABSTRACT: The activity of iron-oxidizing bacteria, for example, Thiobacillut. ferrooxidans, in the outer layers of coal waste dumps results in the oxidation of pyrite with the formation of large volumes of acid mine drainage. The process requires atmospheric oxygen and moisture. Acid mine drainage may possibly be controlled by creating unfavourable environmental conditions in dumps for the iron-oxidizing bacteria. The present research investigated the possibility of inhibiting these bacteria and consequently acid formation in coal waste dumps by means of different dump construction techniques. Physical and chemical conditions, acid formation and populations of four groups of bacteria which might produce acid were studied in the outer layers of ten differently constructed pilot scale coal waste dumps at the Kilbarchan Mine near Newcastle, Kwazulu-Natal, from September 1993 to July 1995. Dump covers consisting of a 30-cm or 70-cm layer of Estcourt soil of low permeability covered with 70 cm or 30 cm, respectively, of more permeable Avalon soil produced anaerobic conditions in the dumps throughout most of the 22 months of the test period, as did a cover of 70 cm compacted plus 30 cm uncompacted Avalon soil alone. An uncoMpacted 30-cm or compacted 50- cm Avalon soil cover proved ineffective in causing prolonged anaerobic conditions. Uncovered dumps showed only slight reduction of oxygen in the coal waste after heavy rains. Pockets of acidity were detected on several occasions in the coal waste below the 50-cm Avalon soil layer from the time of construction and progressively increasing acidity in the uncovered dumps and the waste below the 30-cm Avalon soil cover. Iron-oxidizing bacterial populations of the T. ferrooxidans type have tended to be higher in the uncovered dumps and Avalon soil-covered dumps showing acidification than in the non-acidified dumps covered with 1 m of Avalon soil or Avalon and Estcourt soil. Associated populations of iron-oxidizing bacteria of the Metallogenium type, acidophilic and non-acidophilic thiosulphate-oxidizing bacteria were generally low in the coal waste of the dumps. Thus, five of the soil covers, all with a thickness of 1 m, but not covers with a thickness of 0.5 m or less, proved effective for almost 2 years in inhibiting the diffusion of oxygen to the underlying coal waste in the pilot scale dumps and also appeared to suppress the populations of iron-oxidizing bacteria believed to be implicated in acid formation in the coal waste. These results suggest that coal waste dumps in South Africa should be covered with soil layers of 0.5-1.0 m thick to prevent the generation of acid mine drainage. / AFRIKAANSE OPSOMMING: Die aktiwiteit van ysteroksiderende bakteriee soos Thiobacillus ferrooxidans, in die buitenste lae van steenkoolafvalhope, veroorsaak die oksidasie van piriet met die gevolg dat groot volumes suur mynafloopwater gevorm word. Hierdie proses benodig suurstof en vog. Suur mynafloopwater kan moontlik beheer word deur 'n situasie te skep waar die toestande in die hope ongunstig is vir die ysteroksiderende bakteriee. Die huidige navorsing het die moontlikheid ondersoek om hierdie bakteriee te inhibeer deur verskillende afvalhoopontwerpe op die proef te stel en sodoende suurvorming in steenkoolmynhope te beperk. Die fisiese en chemies kondisies, suurvorming en populasies van vier verskillende bakterie-groepe wat dalk by suurvorming betrokke is, is vanaf September 1993 tot Julie 1995 bestudeer in die buitenste lae van tien verskillend gekonstrueerde loodsskaalafvalhope by die Kilbarchan myn naby Newcastle in KwaZulu-Natal. Afvalhoopbedekkings bestaande uit 'n 30-cm of 70-cm Estcourt grond met 'n lae permeabiliteit bedek met'n 70-cm of 30-cm laag van meer deurlaatbare Avalon grond het anaerobe kondisies veroorsaak. Ongekompakteerde 30-cm en gekompakteerde 50-cm Avalon grondlae het egter nie bestendige anaerobe kondisies in die hope veroorsaak nie. Die onbedekte hope het aerobics gebly met slegs effense dalings van suurstofkonsentrasies gedurende en na swaar reens. Geisoleerde monsters uit die steenkoolafval onder die 50-cm Avalon grondlaag het vanaf die begin van die toetsperiode tekens van suurvorming getoon. Die onbedekte steenkoolafval en die van die sel met 'n 30-cm Avalon grondlaag het met verloop van tyd al hoe meer suur geword. Die ysteroksiderende bakterie-populasies van die T. ferrooxidans tipe het geblyk om in die onbedekte en Avalon grondbedekte hope wat tekens van suurvorming getoon het hoer te wees as in die hope wat met 'n 1-m laag Avalon grond of Avalon en Estcourt grond bedek is en geen tekens van suurvorming getoon het nie. Ysteroksiderende bakteriepopulasies van die Metallogenium tipe, nieasidofiele en asidofiele tiosulfaatoksiderende populasies was oor die algemeen laag in die steenkoolafvalhope. Vyf van die grondlae wat alma! 1 m dik was het dus geblyk om effektief te wees in die bekamping van die infiltrasie van suurstof na die onderliggende steenkoolafval in die loodskaalhope. Dit lyk asof daardie lae die ysteroksiderende populasies betrokke by suurvorming onderdruk het. Die 0.5-m grondbedekking het egter nie so 'n sterk onderdrukkende effek op die suurstofinfiltrasie of die bakteriepopulasie gehad nie. Na aanleiding van hierdie resultate blyk dit dat steenkoolafvalhope in Suid-Afrika met minstens 0.5 tot 1..0 m grond bedek moet word om effektief die probleem van suur mynafloopwater te bekamp.

Thesis (MSc)--Stellenbosch University, 1998. / One copy microfiche. / ENGLISH ABSTRACT: The biologically catalysed oxidation of pyrite in the outer layers of coal waste dumps leads to the formation of acid mine drainage. The oxidation of pyrite to ferric iron and sulphate is a complex process involving various abiotic and biologically catalysed reactions. Pyrite is abiotically oxidized by ferric iron, with the formation of thiosulphate and ferrous iron. Thiosulphate decomposes to form various inorganic sulphur compounds. Bacterial catalysis of pyrite oxidation is achieved by iron-oxidizing bacteria oxidizing ferrous iron to ferric iron. Bacteria that oxidize sulphur compounds assist the catalysis by oxidizing thiosulphate and its decomposition products. Heterotrophic organisms may play a role by consuming organic substances inhibitory to the lithotrophic bacteria. Abiotic ecological factors, acid formation and populations of iron-oxidizing bacterial groups were studied in 10 differently constructed pilot scale coal waste dumps, as the second phase of a study which started in September 1993. Gas samples were withdrawn weekly from coal waste through permanently buried stainless steel probes, for analysis in the field using a portable oxygen/carbon dioxide meter. Samples of coal waste were extracted by auger for analysis of moisture, pH and microbial populations. The analyses of oxygen and pH can be recommended for the routine monitoring of rehabilitated waste dumps. Covers of Avalon soil 0.3 or 0.5 m thick, were not adequate to prevent acidification. Coal waste covered with 0.7 m compacted beneath 0.3 m uncompacted Avalon soil, showed a slow pH decline, but reached approximately pH 3 in 1997. Covers of compacted Estcourt soil beneath tmcompacted Avalon soil to a cover depth of 1 m were effective in preventing acidification and generally kept the coal waste anaerobic. However, all covers developed cracks during drought conditions in 1995, allowing aeration. Low pH of some samples from these dumps during 1995/1996 may have indicated the start of acidification. Bacteria oxidizing high concentrations of ferrous iron and considered to be Thiobacillus ferrooxidans, were monitored routinely, but may not have been the dominant iron-oxidizer, as population counts using media with a lower ferrous iron concentration were higher. The majority of the latter organisms could also not oxidize sulphur, hence were not T. ferrooxidans. The populations of the high ferrous iron-oxidizing bacteria were affected by pH, tending to be high in acidified and low in non-acidified coal waste. Investigations of microbial populations forming iron-oxidizing consortia in enrichment cultures from coal waste and acid drainage samples showed the presence of T. ferrooxidans, the heterotrophic bacterial genus Acidiphilium, fungi of the genus Penicillium, unidentified filamentous fungi, including Cladophialophora-like morphological types, and a yeast of the genus Dipodascus. In interaction studies, the Penicillium isolate had an inhibitory effect on T. ferrooxidans (subjected to organic compound stress), but the Cladophialophora-like fungi reduced inhibition by organics. Fungi have not previously been studied in detail as components of iron-oxidizing consortia, but the bacterial isolations agree with those elsewhere, indicating that appropriate conclusions from acid mine drainage research in other parts of the world can be applied in KwaZulu-Natal. / AFRIKAANSE OPSOMMING: Die biologies gekataliseerde oksidasie van piriet in die buitenste lae van steenkoolafvalhope lei tot die vorming van suur mynafloopwater. Die oksidasie van piriet tot ferri-yster en sulfaat is 'n komplekse proses wat abiotiese en biologies gekataliseerde reaksies insluit. Piriet word abioties deur ferri-yster geoksideer, met die vrystelling van tiosulfaat en ferro-yster. Tiosulfaat verval om verskeie anorganiese swawelverbindings te vorm. Bakteriese katalise van pirietoksidasie word deur ysteroksiderende bakteriee wat ferro-yster na ferri-yster oksideer, bewerkstellig. Bakteriee wat swawelverbindings oksideer maak 'n bydrae tot die katalise deur tiosulfaat en vervalprodukte daarvan te oksideer. Heterotrofe organismes mag ook 'n rol speel deur organiese verbindings wat die litotrofe bakteriee mag inhibeer, te verbruik. Abiotiese ekologiese faktore, suurvorming en bevolkings ysteroksiderende bakteriee is in 10 verskillend gekonstrueerde loodsskaal steenkoolafvalhope bestudeer, as die tweede fase van 'n studie wat in September 1993 begin het. Gas monsters is weekliks uit die steenkoolafval onttrek deur vlekvrye staal peilers wat permanent daarin begrawe is, en met behulp van 'n draagbare suurstoflkoolstofdioksiedanaliseerder in die veld ontleed. Monsters van die steenkoolafval is met behulp van 'n kleiboor vir die analise van vog, pH en mikrobepopulasies geneem. Die analise van suurstof en pH kan aanbeveel word vir die roetiene monitering van gerehabiliteerde afvalhope. Bedekkings van 0.3 of 0.5 m Avalongrond was nie voldoende om suurvorming te verhoed nie. Steenkoolafval wat met 0.7 m gekompakteerde en 0.3 m ongekompakteerde Avalongrond bedek is, het 'n stadige pH-daling getoon, maar het in 1997 ongeveer pH 3 bereik. Bedekkings van gekompakteerde Estcourtgrond onder ongekompakteerde A valongrond met 'n totale dikte van 1 m, was effektief in die voorkoming van suurvorming. Hulle het oor die algemeen die steenkoolafval anaerobies gehou, maar aile bedekings het tydens die droogte in 1995 krake ontwikkel, wat suurstof laat binnedring het. 'n Lae pH gedurende 1995/1996 by sommige monsters uit hierdie hope mag die begin van suurvorming aangedui het. Bakteriee wat hoe konsentrasies ferro-yster oksideer en wat as Thiobacillus ferrooxidans beskou is, was moontlik nie die dominante ysteroksideerder nie, aangesien bevolkingstellings waar 'n medium met 'n laer konsentrasie ferro-yster gebruik is, hoer bevolkings getoon het. Die meerderheid van laasgenoemde organismes kon ook nie swawel benut nie en dus nie T. ferrooxidans was nie. Die bevolkings van die hoe ferro-ysteroksiderende bakteriee is deur pH beInvloed, met 'n geneigdheid tot hoe bevolkings in suur en lae bevolkings in minder suur steenkoolafval. Ondersoeke na die rnilcrobebevollcings wat in ysteroksiderende konsortia in verryldngslculture vanaf steenkoolafval- en suur mynafloopwatermonsters voorgekom het, het die teenwoordigheid van 7'. ferrooxidans, die heterotrofe balcteriegenus Acidiphilium, fungi van die genus Penicillium, ongeIdentifiseerde fungi, insluitend Cladophialophora-agtige tipes en 'n gis van die genus Dipodascus aangetoon. By interaksiestudies het die Penicillium-isolaat 'n inhiberende effek op T ferrooxidans (onderworpe aan organiese verbindingstres) gehad, maar die Cladophialophora-agtige fungi het die inhibisie deur organiese verbindings verminder. Fungi is nog the in detail as komponente van ysteroksiderende konsortia bestudeer the, maar die isolasies van bakteried stem saam met die van elders wat aandui dat toepaslike gevolgtreldcings ten opsigte van suur mynafloopwatemavorsing vanaf ander dele van die wereld ook in KwaZulu-Natal toegepas kan word.