No description available.

Thallium is a highly toxic element that humans are exposed to mainly by consumption of drinking water and vegetables grown in soil with high thallium content but also through inhalation of particles in the air. Thallium is also present in fossil fuels, alloys, and in electronic utilities. The increasing use of the element and emissions from notably energy production has lead to a higher load on the surface of the Earth. This study aims at increasing the knowledge about the behaviour of thallium in aquatic environments. Focus has been on the redox chemistry of thallium in relation to its mobility, which is of great importance because Tl(I) and Tl(III) have very different properties in this respect. The relationship between Tl(I) and Tl(III) in surface waters from contaminated and uncontaminated environments was examined by ion chromatography connected on line to ICP-MS (inductively coupled plasma mass spectrometry). It was found in controlled systems that even though Tl(III) is thermodynamically unstable under fresh water conditions Tl(I) was oxidised in the presence of light and iron(III). This was also confirmed in field studies. When lake water samples were exposed to light, Tl(I) was oxidised and thallium was lost from the solution. The most likely explanation for this was adsorption of thallium to particle surfaces. The concentration of thallium in Swedish lakes and soil were measured. In unpolluted lakes the concentration ranges between 4.5-12 ng/l, the sediment concentration was 0.07-1.46 mg/kg. The anthropogenic load was found to have increased since the end of the Second World War although concentrations above background were found since the early industrialisation. In contaminated areas the concentration in soil ranges from 0.64-88 mg/kg, high concentrations were found in systems with alum shale and in soil exposed to runoff from a lead and zinc enrichment plant. The mobilisation of thallium from solid phases in contaminated areas was dependent on pH and about 50% of the leachable content was mobilised already at pH 5-6. Once it had been released to water it was highly mobile. These conditions suggest that in a large part of the Swedish environment a high mobility of thallium can be expected.

Waste rocks (WRs) from coal mining and fly ash (FA) from coal combustion were studied to determine the potential of the WRs to generate AMD, FAs to neutralise it and estimate their impacts on environment. The ultimate goal was to develop a methodology based on co-disposal to mitigate the environmental problems associated to both wastes. Two methods for co-disposal were tested: i) Mixing WRs and FAs and ii) covering WRs with FAs. WRs were sampled from the Lakhra coal mines in Pakistan (PK), which has an estimated coal reserves of 1.3 Btonne, varying from lignite to sub-bituminous quality. The FA was sampled from a power plant utilising coal from Lakhra coal mines and is situated in close vicinity (15km) of the mine site. For comparative purposes a bituminous FA from Finland (FI) and biomass FA from Sweden (SE) were also characterised. The WRs and FA samples were characterised by mineralogical and geochemical methods. Besides organic material (coal traces), quartz, pyrite, kaolinite, hematite, gypsum and traces of calcite, lime, malladerite, spangolite, franklinite and birnessite were identified in WRs by XRD. The major elements Si, Al, Ca and Fe were in the range (wt. %) of 8 – 12, 6 – 9, 0.3 – 3 and 1 – 10, respectively, with high S concentrations (1.94 – 11.33 wt. %) in WRs. The AMD potential of WRs ranged from -70 to -492 kg CaCO3 tonne-1. All FAs contained quartz, with iron oxide, anhydrite and magnesioferrite in PK, mullite and lime in FI and calcite and anorthite in SE. The Ca content in SE was 6 and 8 times higher compared to PK and FI, respectively. FAs were enriched in As, Cd, Co, Cr, Cu, Hg, Ni, Pb and Zn compared to continental crust. The acid neutralising potential of PK was equivalent to 20 kg CaCO3 tonne-1 compared to 275 kg CaCO3 tonne-1 (SE) and 25 kg CaCO3 tonne-1 (FI). During the period of 192 days in weathering cell experiments (WCE), the pH of leachates from most acidic WRs was maintained from 1 to 2.5, whereas, the less acidic WRs produced leachates of mildly acidic (2.7) to neutral (7.3) pH. The leachates from very acidic WRs ranged in the concentrations of Fe, SO24− and Al from mg L-1 to g L-1. The samples were subjected to column leaching experiments (CLE) in which mixture (FA:WR; 1:3) and cover (FA:WR; 1:5) cases were mimicked (with 10mm particle size) and effects of particle size (2, 5 and 10mm) on element leaching were studied. Despite having the lowest acid-neutralisation potential compared to FI and SE, co-disposal of PKFA as mixture readily provides acid buffering minerals, resulting in better start-up pH conditions and leachate quality. However, acidity produced by secondary mineralisation contributes towards the acidification of the system, causing stabilisation of pH at around 4.5−5. Secondary mineralisation (especially Fe- and Al-mineral precipitation) also removes toxic elements such as As, Pb, Cu, Zn, Cd, Co, Ni and Mn, and these secondary minerals can also buffer acidity when the pH tends to be acidic. In contrast, the pH of the leachates from the PKFA cover scenario gradually increased from strongly acidic to mildly acidic and circumneutral along with decrease in EC and elemental leaching in different WRs. Gradually increasing pH can be attributed to the cover effect, which reduces oxygen ingress, thus sulphide oxidation, causing pH to elevate. Due to the fact that pH~4–5 is sufficient for secondary Fe- and Al-mineral precipitation which also removes toxic elements (such as Cd, Co, Cu, Zn and Ni) by adsorption and/or co-precipitation, the FA cover performs well enough to achieve that pH until the conclusion of the CLE. However, due to the slower reactivity of the buffering system (additional to the initial flush-out), leaching in the beginning could not be restricted. The co-disposal of FA as cover and/or mixture possesses potential for neutralisation of AMD and improving leachate quality significantly. Particle size of the WRs affected the leaching of the sulphide related elements (such as Fe, S, Zn, Co, Cr, Cu, Mn and Ni) in CLE and WCE. Experiments with ≤1mm particle size constantly produced acidic and metal laden leachates. Co-disposal of FA and WRs as cover and mixture need to be investigated on pilot-scales before full-scale application.

No description available.

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.

Na região do Vale do Ribeira, os resíduos provenientes do beneficiamento e fundição do minério de chumbo (Pb) foram lançados por décadas no rio Ribeira de Iguape ou depositados diretamente na superfície do solo, sem qualquer proteção, constituindo fontes de contaminação do solo e das águas por metais potencialmente tóxicos. O uso do solo local na construção de barreira selante para impermeabilização e retenção dos contaminantes representa uma alternativa para o controle desse tipo de contaminação. Por isso é importante estudar os solos da região, sua capacidade de retenção de metais potencialmente tóxicos, e alternativas de baixo custo para melhorar suas propriedades físicas e químicas. A adição de matéria orgânica é um caminho para aumentar a retenção de cátions. Assim, a presente pesquisa visou verificar se um solo residual proveniente de Eldorado Paulista, no Vale do Ribeira, apresenta características favoráveis para o emprego como barreira selante na disposição de resíduos de mineração desta região; bem como analisar a melhoria da sua capacidade de adsorção de Pb e cádmio (Cd), quando misturado com turfa, um material orgânico com elevada capacidade de retenção de metais e de baixo custo, em proporções de 10 e 20% (m/m). Foram realizados ensaios de caracterização para determinação das propriedades físicas, químicas e mineralógicas do solo. Para avaliação da capacidade de adsorção de Pb e Cd pelo solo e pelas misturas solo-turfa, foram realizados ensaios de equilíbrio em lote. O solo estudado é um solo residual argiloso, cuja fração argilosa é predominantemente composta por caulinita. Ele apresenta alguns pontos favoráveis para que seja utilizado como barreira selante na retenção de cátions metálicos, como granulometria predominantemente fina (54,5% de argila), índice de plasticidade adequado (25,1%), meio oxidante (Eh = +333 mV), predomínio de cargas negativas na superfície dos coloides (ΔpH = -0,9 e PESN = 3,6) e baixa condutividade hidráulica quando compactado (na ordem de 10-9 m/s). Por outro lado, algumas características são menos interessantes para a retenção de metais, como baixa capacidade de troca catiônica (41,4 mmolc/dm3), baixo teor de matéria orgânica (9 g/kg) e pH ácido (4,6). A adição de turfa em proporções de 10 e 20% (m/m) ao solo aumentou o teor de matéria orgânica em 4,3 vezes e 6,4 vezes, respectivamente. A CTC também aumentou, variando de 41,4 mmolc/dm3 para o solo a 101,7 mmolc/dm3 para a mistura com 10% de turfa, e ainda a 143,1 mmolc/dm3 para a mistura com 20% de turfa. Não foram observadas mudanças de pH. Observou-se também a melhoria da capacidade de adsorção de Pb e Cd. O solo residual natural apresentou eficiência de remoção de Pb de 54% a 100% para concentrações iniciais de 22 a 232 mg/L deste metal. A mistura com maior teor de turfa (20%) removeu 95,3% a 100% do Pb para concentrações iniciais de 31 a 267 mg/L. O coeficiente de distribuição Kd aumentou de 4,57 cm3/g (para o solo natural) até 58,57 cm3/g (para a mistura com 20% de turfa). O Kf aumentou de 75,75 a 508,86 cm3/g e o KL aumentou de 0,0276 a 0,4118 cm3/g, devido a adição de turfa em 20%. Em relação ao Cd, o solo natural apresentou eficiência de remoção de 30,5 a 72,1% para concentrações iniciais de 17 a 170 mg/L. A mistura com 20% de turfa aumentou a eficiência de 54,9 a 88,9% para concentrações iniciais de 20 a 150 mg/L de Cd. O coeficiente Kd foi de 1,56 cm3/g para o solo natural a 6,42 cm3/g para a mistura com maior proporção de turfa. O Kf foi de 30,06 a 63,88 cm3/g, e o KL foi de 0,0301 a 0,0483 cm3/g. Concluiu-se que a adição de turfa ao solo nas proporções de 10 e 20% contribuiu para a melhoria das propriedades associadas a retenção de cátions metálicos e favoreceu a melhor adsorção de Pb e Cd. / In the Ribeira Valley region, in Brazil, mining waste originated from lead ore beneficiation and smelting was launched for decades in the Ribeira de Iguape river or deposited directly on the soil surface near this river, without any protection. This created sources of soil and water contamination by potentially toxic metals. The use of local soil for construction of sealant barriers aiming to waterproof and retain the contaminants represents an alternative to control this type of contamination. It is important to study the region soils, their capacity of retention of potentially toxic metals, and low cost alternatives to improve their physical and chemical properties. The addition of organic matter to the soil is an alternative to increase cation retention. Therefore, the purpose of this research was to verify if a residual soil collected in the Eldorado Paulista municipality, in the Ribeira Valley, presents suitable characteristics to be used as a sealant barrier for mining waste disposal; and to assess the improvement of its adsorption capacity of lead and cadmium, when mixed with peat (an organic material with high metal retention capacity, and low cost), in proportions of 10 and 20% (w/w). Characterization tests were carried out to determine the physical, chemical and mineralogical properties of the soil. For the evaluation of the adsorption capacity of lead and cadmium by the soil and soil-peat mixtures, batch equilibrium tests were performed. The studied soil is a clayey residual soil. Its clayey fraction is predominantly composed of kaolinite. It presents some favorable characteristics to be used as a sealant barrier for retention of metallic cations, such as: predominance of fines (54.5% clay), suitable plasticity index (25.1%), oxidizing medium (Eh = +333 mV), predominance of negative charges on the surface of the colloidal particles (ΔpH = -0.9 and PZSE = 3.6) and low hydraulic conductivity when compacted, which reached the order of 10-9 m/s. However, some soil properties are less suitable for metal retention, such as low cation exchange capacity (41.4 mmolc/dm3), low organic matter content (9 g/kg) and low pH (4.6). The addition of peat to the soil in proportions of 10 and 20% (w/w) increased the organic matter content by 4.3 times and 6.4 times, respectively. CTC also increased. It ranged from 41.4 mmolc/dm3 (natural soil) to 107.7 mmolc/dm3 (mixture with 10% peat) and to 143.1 mmolc/dm3 (mixture with 20% of peat). No changes in pH were observed. It was also noticed the improvement of the adsorption capacity of lead and cadmium. The lead removal efficiency of the natural residual soil was from 54% to 100% at initial concentrations from 22 to 232 mg/L of this metal. The mixture with higher peat content (20%) removed 95.3% to 100% of the lead at initial concentrations from 31 to 267 mg/L. The distribution coefficient Kd increased from 4.57 cm3/g (for the natural soil) to 58.57 cm3/g (for the mixture with 20% of peat). The Kf increased from 75.75 to 508.86 cm3/g and the KL increased from 0.0276 to 0.4118 cm3/g, due to the addition of peat in 20%. With regard to cadmium, the natural soil removed 30.5 to 72.1% of this metal for initial concentrations of 17 to 170 mg/L. The mixture with 20% of peat increased the Cd removal efficiency to 54.9 to 88.9% at initial concentrations from 20 to 150 mg/L. Kd was 1.56 cm3/g for the natural soil and increased to 6.42 cm3/g for the mixture with the highest content of peat. Kf increased from 30.06 to 63.88 cm3/g, and the KL increased from 0.0301 to 0.0483 cm3/g. It was concluded that the addition of peat to the soil in proportions of 10 and 20% caused improvement of properties related with metalic cation retention and favored Pb and Cd adsorption.

Löslighet och transport av sällsynta jordartsmetaller i Källfallsfältets gruvsandsmagasin Hugo de Campos Pereira Syftet med detta arbete har varit att kartlägga vilka mekanismer som styr lösligheten av sällsynta jordartsmetaller (eng. rare earth elements, REE) i sulfidhaltig anrikningssand vid den föredetta gruvan Källfallsfältet i Västmanland. För syftet har markvatten- och grundvattenprovtagning utförts, tillsammans med laktester och geokemisk modellering med Visual MINTEQ ver. 3.0. Resultaten visade att sulfidvittring är den främsta processen som styr pH i anrikningssanden, och därmed också indirekt REEs löslighet. Däremot är sulfidvittring ingen källa till REE i sig då ämnena inte föreligger sulfidbundna, något som oxiderat tillgänglighetstest NT ENVIR 006 visade. Istället går REE ut i lösning i anrikningssanden genom vittring av lättvittrade silikatmineral. Vanligtvis betraktas metall bunden i silikatform inte som geokemiskt aktiv. Jämförelser mellan laktester med olika jämviktstid visade att en kinetisk (tidsberoende) faktor föreligger, kopplad till nämnda silikatvittring, som påverkar pH och således också metallöslighet vid laktester på anrikningssanden. Vid jämförelse mellan laktester och halter i anrikningssandens mark- och grundvatten bör denna därmed vägas in. Det pH-statiska laktestet SIS-CEN/TS 14997 visade begränsad möjlighet att undersöka kinetik med anledning av att det utförs under förhållandevis kort tid, 48 timmar. REE- och Cu-halter vid syratitrering (de behandlingar med lägst syratillsatser) och enstegslakning (SIS-CEN ISO/TS 21268-2:2010) visade god, respektive förhållandevis god, överensstämmelse med uppmätta markvattenhalter. Detta visade att syratitrering och enstegslakning är laktest som är tillämpbara, respektive förhållandevis väl tillämpbara, för att uppskatta markvattenhalter i anrikningssanden. Specieringsmodellering med Visual MINTEQ ver. 3.0 visade att pH och DOC är de viktigaste parametrarna som styr REEs speciering i anrikningssandens mark-, grund och ytvatten. Samtliga REE bildar starka komplex med löst organiskt material, men koncentrationerna av DOC var generellt sett låga. I sura sulfatrika mark-, grund och ytvatten domineras specieringen av lösta sulfatkomplex, huvudsakligen (REE)SO4+, följt av fria hydratiserade joner som näst vanligaste förekomstform. Dessa resultat överensstämmer väl med tidigare modelleringsstudier av REEs speciering i sura sulfatrika vatten resulterande från gruvavfall. Med bakgrund av detta och av att REEs ekotoxicitet verkar överensstämma med den fria jon-modellen (eng. free ion model) förväntas REE uppvisa högre toxicitet vid låga pH-värden. / Solubility and transport of rare earth elements in the mine tailings of Källfallsfältet Hugo de Campos Pereira The mechanisms which govern the solubility of rare earth elements (REEs) in sulfide-containing tailings at the former mine site of Källfallsfältet (Västmanland, Sweden) were studied by the means of soil water and ground water sampling, leaching tests and geochemical modeling using Visual MINTEQ ver. 3.0. The results showed that weathering of sulfides is the primary process governing pH in the tailings, and thus also REE solubility. However, weathering of sulfides is no source for REE in itself since the elements are not bound in sulfides, which the oxidized availability test NT ENVIR 006 showed. Instead REE are released into solution by weathering of easily weathered silicates. Usually, metal bound in silicate form is not considered geochemically active. A kinetic (time dependent) factor, associated with the weathering of silicates, was found to affect pH and thus also metal solubility in leaching tests performed on the tailings. The standardized pH static leaching test (SIS-CEN/TS 14997) showed limitations in observing kinetic effects because of its relatively short equilibration time (48 h). Thus, in future studies with similar materials, leaching test kinetics should be taken into account when comparing leached concentrations with field measured concentrations. Acid titration and one step batch test (SIS-CEN ISO/TS 21268-2:2010) proved to be applicable and relatively well applicable to the tailings, respectively, in order to estimate soil solution concentrations. Speciation calculations using Visual MINTEQ ver. 3.0 showed that pH and DOC concentration are the most important factors which affect REE speciation in soil solution, ground water and surface water associated with the tailings. In acid sulfate rich solutions, low in DOC, speciation is dominated by sulfate complexes, mainly (REE)SO4+, followed by free dissolved ions as the second most common form. These results are in accordance with previous modeling studies of REE speciation in acid sulfate rich waters resulting from tailings. This, together with previous results showing that REE ecotoxicity seems to follow the free ion model, implies that the toxicity of the elements is expected to increase with decreasing pH value.

MESMEG / Department of Mining and Environmental Geology / The Mushithe coal occurrence is situated approximately 16 km west of the Tshikondeni coal mine in the Tshipise-Pafuri sub-basin of the Soutpansberg coalfield in South Africa. The Soutpansberg Coalfield has received comparatively less attention compared to other more notable South African coalfields. There is as a consequence very limited information in the public domain applicable to the geology as well as quality of coal in this coalfield, as a result there is no known study focused exclusively on the Mushithe coal occurrence. The aim of the study was to conduct detailed geological mapping of the Mushithe Deposit so as to ascertain the geological environment and petrological characteristics of rocks within the area. Further work involved coal sampling and analysis in order to establish coal quality and its physical and chemical characteristics. Samples were collected using geological field mapping and channel sampling. Nine coal samples were collected from the coalbed and host rock, exposed along the Mbodi River, during geological field mapping using channel sampling. Furthermore, 92 rock samples were collected during geological field mapping of which 10 representative samples were selected for further analysis. X-ray fluorescence spectrometry was conducted on all selected samples. Proximate analysis and ultimate analyses, and calorimetry tests were undertaken on coal samples. Three samples were selected based on calorific value for maceral identification, mineral analyses and vitrinite reflectance using petrographic study. Detailed geological mapping of the area around the Mushithe coal occurrence showed the geological setting of coal in this area. The following lithologies were identified in the study area: sandstone, mudstone, ironstone, calcrete, shale, quartzite, quartz vein with a general strike direction to the north-east. The host rocks including coal were intruded by dolerite dykes and this resulted in the devolatilization of coal. The current study concluded that the Mushithe coal was formed in a wet swampy environment. This has been confirmed based on tissue preservation index (1.69) and gelification index (2.35). Coal rank ranged from bituminous Rank C- B according to United Nations Economic Commission for Europe Coal Classification (UNECE) and samples were characterised by high ash (27.90%), high moisture (10.47%) and low sulphur (0.24%). Furthermore, coal was graded below grade D based on classification for use by ESKOM which consider any calorific value below 24.5 MJ/kg to be in this category. The coal is vitrinite rich (77.75 vol%) and low in Inertinite (22.25 vol%) and devoid of Liptinite and pseudovitrinite, thus it is of good coking quality. Geochemical analysis revealed that the coal was enriched in TiO2 and Fe2O3 which was corroborated by the mineral matter which was mostly clay and pyrite. Comparatively, coal quality analysis revealed the calorific value of 14.26 MJ/kg and vitrinite reflectance between 0.94 %ROV to 1 %ROV which was less than that of the Tshikondeni Deposit but greater than that at Waterberg coalfield. The study recommends further detailed exploration of coal in the area, applying such techniques such as geophysical exploration and borehole drilling leading to resource evaluation. Further studies are recommended to provide a better interpretation of the depositional environment of coal at Mushithe as well as the effect of devolatilaziton by a dolerite dyke. / NRF

Thesis (M.Sc.(Chemistry)) -- University of Limpopo, 2022 / Water contamination caused by toxic elements has serious human health and ecological implications. The increasing quantity of toxic elements in surface and groundwater is currently an area of greater concern, especially since many industries are discharging their metal containing effluents into freshwater without any adequate treatment. The mineral dissolution in mining regions is highly enhanced by mining and smelting activities. The mine waste and drainage in areas surrounding mines have high levels of toxic element contamination above the permissible limits. Contamination of groundwater by toxic elements such as As, Fe, Mn, Al, Cr, Zn and Co due to operational activities of surrounding mines in the Sekhukhune district was reported by several researchers. Removal of toxic elements from contaminated water is a big challenge. The affected communities need to attain a safe water supply source for daily usage, hence there is an urgent need of technologies for the treatment of water supplies contaminated with these toxic elements to ensure the safety of potable water. The study was undertaken by modifying nitrogen-doped multi-walled carbon nanotubes (N-MWCNTs) and investigating the removal of chromium, nickel and lead from anthropogenic contaminated groundwater in the Sekhukhune area, in Limpopo. The as-prepared N-MWCNTs functionalised with metal oxide, thiol and amino functional groups are expected to increase the surface area of the nanocomposite, which can facilitate high adsorption of contaminants from water samples. The adsorption capabilities for the removal of these toxic elements by modified N MWCNTs nanocomposites were investigated in batch studies as a function of different parameters. The parameters studied included pH, contact time, adsorbent dosage, initial concentration, temperature, competing ions and reusability. The optimum condition was then acquired for removal of selected toxic elements from real water studies. The removal efficiencies of the as-prepared nanocomposites were pH dependent and the optimal pH values for adsorption was 5.5, 1.5, 11 and 6 at optimum contact time of 10, 80, 60 and 120 min and dosage of 0.30, 0.35, 0.05 and 0.6 g/L for Cr(III), Cr(VI), Ni(II) and Pb(II), respectively. The prepared nanocomposites were characterised using various techniques such as Fourier transform infrared (FTIR) spectroscopy, powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer-Emmet-Teller (BET) and thermogravimetric analysis (TGA). The FTIR analysis confirmed the presence of Fe3O4, -SH and -NH2 groups on the functionalised MWCNTs. The PXRD analysis further supported that the synthesized nanocomposites consisted of hexagonal graphite structure of MWCNTs. Furthermore, SEM and TEM results showed that the introduced functional groups were uniformly attached on the surface of the MWCNTs. The BET analysis indicated that the surface area of the modified MWCNTs nanocomposites increased significantly as compared to the acid treated MWCNTs. In addition, TGA showed that the M-MWCNTs (M = modified) nanocomposites possess high thermal stability. Raw N-MWCNTs showed higher stability as compared to oxidised N-MWCNTs, which decomposes at lower temperatures of 200 °C. No weight loss was observed below 800 °C for the hydrazine functionalised nanocomposites as compared to the triethylenetetramine (TETA)- substituted nanocomposites, which showed weight loss at 300 °C. Toxic elements in solutions before and after treatment were quantified using flame atomic absorption spectrometry (F-AAS). The adsorption isotherms of the as-prepared nanocomposites for chromium, nickel and lead removal fitted both the Langmuir and Freundlich model depending on the adsorbent used, which suggest that the adsorption process met both monolayer and heterogeneous adsorption. Thermodynamic analysis showed that the adsorption of Cr(III), Cr(VI), Ni(II) and Pb(II) ions are spontaneous and endothermic. The as-prepared nanocomposites showed an outstanding regeneration performance retaining over 50% toxic elements removal. Thus, the as prepared nanocomposites are promising for practical application in toxic element treatment. Analysis of the collected river and borehole water in Sekhukhune indicated that the concentration of total chromium, nickel and lead before treatment varied from (0.207 to 0.286 mg/L), (0.226 to 0.380 mg/L) and (3.301 to 8.017 mg/L), respectively which were above acceptable levels recommended by the South African National Standards (SANS), United States Environmental Protection Agency (USEPA) and World Health Organisation (WHO), i.e., 0.05 mg/L, 0.07 mg/L and 0.01 mg/L. After treatment, the nanocomposites were able to remove 100% of the metal ions from the water. TETA-functionalised nanocomposites showed greater removal efficiencies in comparison to the hydrazine-functionalised nanocomposites for all the studies done. / Water Research Commission (WRC)