The Platreef has been the site of platinum mining since the 1920’s. The reef itself comprises a series of pyroxenites, gabbronorites and norites that contain xenoliths/rafts of footwall rocks. The Platreef is irregularly mineralised with PGE, Cu and Ni, and has a greater abundance of sulphides than the Merensky Reef. The main base metal sulphides within the Platreef are pyrrhotite, pyrite, pentlandite, and chalcopyrite. Extremely varied platinum group minerals occur as tellurides, bismuthotellurides, antimonides and arsenides. This study aimed to gain a clearer understanding of the formation of sulphides within the Platreef. In order to do this, cores from both the northern and southern sectors of the Platreef were sampled. A detailed study of the sulphides within these cores was conducted to identify different styles of mineralisation and their occurrences. Four different styles of mineralisation were identified: massive, net-textured, blebby and interstitial. In general, sulphides in the southern sector of the Platreef are concentrated in the lower portion of the package, whereas in the northern sector they are concentrated in the upper part although in both sectors the sulphide occurrences are associated with metasedimentary xenoliths. Conventional and multiple sulphur isotope analyses were undertaken on sulphides from cores from both the southern and the northern sectors. This was done in order to determine the source of the sulphur. These analyses were also conducted to examine sulphur isotope variations with changing footwall. Previous sulphur isotope data predominantly obtained from the central sector of the Platreef indicated a crustal contribution to the sulphur budget but did not provide much data on footwall sulphides so the nature of the crustal component was only implied. In this thesis sulphur from an external source was identified as having contributed to the formation of sulphides in both the southern and the northern sectors of the Platreef, especially for sulphides in proximity to metasedimentary xenoliths. In the southern sector of the Platreef this source was identified as most likely being pyritic shales of the Lower Duitschland Formation. In the northern sector, Malmani dolomites, which are suggested to have collapsed from the roof of the Platreef, are the most likely source of sulphur. Importantly, in the northern sector no sulphur is thought to have come from the Archaean granite footwall. Oxygen isotope analyses were conducted on samples from the southern sector of the Platreef to verify the presence of crustal contamination. Data collected indicated that there had been a crustal oxygen component involved in the formation of silicates that led to their partial recrystallisation. When compared to oxygen isotope data from the central sector of the Platreef it appears that there are variations along strike that most likely result due to the changing footwall. This data indicates a major contribution of oxygen-, sulphur- and other volatile-rich fluids to the Platreef. This led to the partial re-crystallisation of silicates, and in areas in close proximity to sulphur-bearing metasedimentary xenoliths aided in the formation of sulphides. These volatile-rich fluids most likely originated from metasedimentary xenoliths during metamorphism that then migrated through the Platreef package. When the observations from both the southern and northern sectors of the Platreef are compared and combined with pre-existing data for the central sector, several general observations can be made. 1. The entire length of the Platreef has been affected by contamination from crustal sulphur sources to some degree. This contamination is suggested to be from volatile-rich fluids which were released from metasedimentary crustal xenoliths and footwall during metamorphism. 2. The proximity between sulphide enrichment and sulphur-bearing sediments (as footwall or xenoliths) is important and indicates the source of the sulphur which led to sulphide formation. 3. Contamination occurred on a localised scale, depending on the composition of the sedimentary lithologies and the proximity of the contaminant to the magma. In the southern sector of the Platreef the source of the sulphur is almost certainly pyritic shales of the Lower Duitschland Formation. In the central sector, sulphur has most likely come from sulphur-rich dolomites and evaporites from the Malmani dolomites. In the northern sector, sulphur-rich fluids were released from Malmani dolomite rafts that collapsed from the roof into the magma during the emplacement of the Platreef. The Archaean footwall in this area has had little or no control on the formation of the sulphides within the Platreef.

No description available.

The isotopic ratios S33/S32, S34/S32 and S36/S32 of different forms of sulphur in a number of meteorites have been studied. The results obtained indicate that processes of chemical fractionation have occurred in some meteorites but that the isotopic composition of the total sulphur in a single meteorite is remarkably constant from meteorite to meteorite. The relationships between the S33, S34 and S36 isotope abundances indicate that variations in these abundances due to inhomogeneities in the processes of nucleo-synthesis are not detectable. Isotopic analysis of sulphur from the iron phase of the Clark County, Pinon and Tlacotepic meteorites has shown the presence of cosmic ray induced spallation S36 and S33. These spallation results are in reasonable agreement with predictions based on production rates of other nuclei. / Thesis / Doctor of Philosophy (PhD)

The isotopic fractionation of sulphur in the plant metabolism of sulphate by chlorella was investigated; and for this purpose an apparatus was devised for growing chlorella under sterile conditions. A green alga from the shores of Lake Erie, and mustard plants from the field were also investigated. No isotopic fractionation was found in the plant metabolism of sulphate either in the laboratory or in nature. A new method for the reduction of sulphate to hydrogen sulphide was also developed. / Thesis / Master of Science (MS)

No description available.

No description available.

Current mining operators in the Athabasca oil sands deposit of Alberta, Canada have made commitments to zero discharge of oil sands process-affected waste materials (OSPM) from the mine site and rehabilitation of mined lands to a pre-mining state. As part of aquatic reclamation efforts, experimental test sites that contain a range of OSPM (solid and liquid components) were constructed to monitor the evolution and viability of aquatic habitats used as disposal sinks for OSPM produced by mining activities. In the present study, stable isotopes of carbon, nitrogen and sulphur were used to gauge some of the potential effects of OSPM site construction methods on aquatic food webs. Carbon and nitrogen isotopic signatures of sediment, dissolved inorganic carbon, dissolved organic carbon, particulate organic matter, periphytic material, plants, plankton, aquatic invertebrates and fish were used to assess differences related to the naphthenic acid (NA) concentration in OSPM and reference sites. For statistical analyses, sites were grouped into low (0 to 4 mg/L), medium (4 to 15 mg/L) and high (> 15 mg/L) NA concentrations. There were no significant differences in food web area or food web length among the low, medium and high NA concentration sites. In most cases, sample carbon isotope analyses of low, medium and high NA concentration sites were not significantly different, suggesting food web carbon sources did not include significant contributions from OSPM materials at OSPM sites. Significant differences, however, were found in the sample nitrogen isotope signatures between low, medium and high NA concentration sites. Ammonia from OSPM is suggested to be the main contributor to &delta;¹⁵N enrichment. <br /><br /> To determine the potential effects of site construction and OSPM within experimental test sites, carbon and sulphur stable isotopes of water, plankton, aquatic invertebrates and fish were analyzed. With the exception of <em>Chaoborus</em> and <em>Haliplus</em>, all carbon isotope signatures were not significantly different in constructed and reference sites. Also with the exception of <em>Haliplus</em>, sulphur isotope values for aquatic organisms from constructed and reference sites were significantly different. Aquatic organisms and water samples from constructed sites built in, or close, to the boundary of Kcw clays typically had &delta;³⁴S < 0 ?. Coinciding with depleted &delta;³⁴S signatures found in these aquatic systems were elevated sulphate concentrations. The waters at experimental test sites are in direct contact with the soil materials that facilitate the accumulation of sulphates as a result of the oxidation of substrate sulphide minerals. In general the results of the study suggest that aquatic food web structure and function do not change with the introduction of OSPM. Shifts in isotopic signatures suggestive of changes in food web structure, however, do occur when site construction exposes Kcw clays in the substrate.

Current mining operators in the Athabasca oil sands deposit of Alberta, Canada have made commitments to zero discharge of oil sands process-affected waste materials (OSPM) from the mine site and rehabilitation of mined lands to a pre-mining state. As part of aquatic reclamation efforts, experimental test sites that contain a range of OSPM (solid and liquid components) were constructed to monitor the evolution and viability of aquatic habitats used as disposal sinks for OSPM produced by mining activities. In the present study, stable isotopes of carbon, nitrogen and sulphur were used to gauge some of the potential effects of OSPM site construction methods on aquatic food webs. Carbon and nitrogen isotopic signatures of sediment, dissolved inorganic carbon, dissolved organic carbon, particulate organic matter, periphytic material, plants, plankton, aquatic invertebrates and fish were used to assess differences related to the naphthenic acid (NA) concentration in OSPM and reference sites. For statistical analyses, sites were grouped into low (0 to 4 mg/L), medium (4 to 15 mg/L) and high (> 15 mg/L) NA concentrations. There were no significant differences in food web area or food web length among the low, medium and high NA concentration sites. In most cases, sample carbon isotope analyses of low, medium and high NA concentration sites were not significantly different, suggesting food web carbon sources did not include significant contributions from OSPM materials at OSPM sites. Significant differences, however, were found in the sample nitrogen isotope signatures between low, medium and high NA concentration sites. Ammonia from OSPM is suggested to be the main contributor to &delta;¹⁵N enrichment. <br /><br /> To determine the potential effects of site construction and OSPM within experimental test sites, carbon and sulphur stable isotopes of water, plankton, aquatic invertebrates and fish were analyzed. With the exception of <em>Chaoborus</em> and <em>Haliplus</em>, all carbon isotope signatures were not significantly different in constructed and reference sites. Also with the exception of <em>Haliplus</em>, sulphur isotope values for aquatic organisms from constructed and reference sites were significantly different. Aquatic organisms and water samples from constructed sites built in, or close, to the boundary of Kcw clays typically had &delta;³⁴S < 0 ?. Coinciding with depleted &delta;³⁴S signatures found in these aquatic systems were elevated sulphate concentrations. The waters at experimental test sites are in direct contact with the soil materials that facilitate the accumulation of sulphates as a result of the oxidation of substrate sulphide minerals. In general the results of the study suggest that aquatic food web structure and function do not change with the introduction of OSPM. Shifts in isotopic signatures suggestive of changes in food web structure, however, do occur when site construction exposes Kcw clays in the substrate.

<p>The transport of elements by streams from headwater regions to the sea is influenced by landscape characteristics. This thesis focuses on the influence of landscape characteristics (e.g. proportion of wetland/forest coverage) on temporal and spatial variations of Fe, Mn, S and trace elements (As, Co, Pb) in streams located in northern Sweden, a boreal region characterized by coniferous forests and peat wetlands.</p><p>Water samples from a network of 15 streams revealed a different hydrogeochemistry in forested catchments compared to wetland catchments. The temporal variation was dominated by spring flood, when concentrations of Fe, Mn and trace elements increased in forested headwaters. However, in streams of wetland catchments concentrations decreased, but Pb concentrations were higher in comparison to other streams. Both Fe and Pb showed positive correlations with wetland area, while Co correlated with forest coverage. The anthropogenic contribution of As and Pb appear to be larger than the supply from natural sources.</p><p>During spring flood SO₄^2- decreased in most streams, although concentrations increased in streams of wetland catchments. Concentrations of SO₄^2-were higher in streams of forested catchments than in wetland dominated streams, the former being net exporters of S and the latter net accumulators. Isotope values of stream water SO₄^2- (δ³⁴S_SO4) were close to that of precipitation during spring flood, indicating that the major source of S is from deposition. The results show that, although emissions of anthropogenic S have been reduced, there is still a strong influence of past and current S deposition on runoff in this region.</p><p>In conclusion, wetlands are key areas for the hydrogeochemistry in this boreal landscape. The findings emphasize the importance of understanding stream water chemistry and element cycling from a landscape perspective. This may be important for predicting how boreal regions respond to environmental disturbances such as climate change.</p>

Large Igneous Provinces (LIPs) form during short-lived pulses of extensive magmatic activity. LIPs are known for their ability to affect global climate as well as for their Ni-Cu-PGE ore potential. A key factor that controls the intensity of the climate impact of a LIP and its ore potential is the assimilation of volatile-rich sedimentary host rocks. Magmas of the High Arctic Large Igneous Province (HALIP), exposed in the Arctic, intruded volatile-rich black shales, carbonates and evaporites in the Canadian Arctic Islands, offering a great opportunity for studying magma-sediment interaction. The purpose of this study is to test whether assimilation of sedimentary sulphide can promote sulphide immiscibility in magma and thus aid formation of Ni-Cu-PGE ore bodies. This is done by analysing sulphur isotopes in pyrite grains hosted in a HALIP dolerite sill, which was emplaced into black shale, by using Secondary Ion Mass Spectrometry (SIMS). Four dolerite samples are analysed; two coming from the lower contact margin of the sill, one from 60 cm into the sill and one sample from a basaltic vein at the upper contact margin of the sill. A total of 14 pyrite grains (n = 246 individual SIMS spot analyses) were analysed for their sulphur isotope ratios. The results of the SIMS analyses show that all analysed sulphides have highly negative δ34S values ranging from -19.5 to -5.7‰ (average δ34S = -8.2 ± 0.83‰, 2SD), which therefore differ largely from that of the primitive mantle (0 ± 1.8‰). In order to put our four analysed dolerite samples into a broader context, δ34S data of our sulphides are compared with whole-rock δ34S and δ18O data from Hare Fiord shale and dolerite samples. The δ34S values of the sulphide samples from the sill typically trend toward the negative sulphur isotope composition of the sulphides in the surrounding shale, and the shale surrounding the sill experiences a loss of 32S near the contact of the sill. This indicates that sedimentary light sulphur (32S) has been locally incorporated into the sill by the surrounding shale, resulting in negative δ34S values in the magmatic sulphides. Since sulphide immiscibility in the Hare Fiord sill was triggered by assimilation of sulphur from host rock shale, the igneous rocks of the HALIP may be prospective for Ni-Cu-PGE mineralization, though more studies are needed. Furthermore, our results suggest that incorporation of crustal sulphur increased the volatile budget of HALIP magmas, which therefore could have contributed to a deterioration of the environmental conditions during the emplacement of the HALIP. / Stora magmatiska provinser (på engelska Large Igneous Provinces, LIPs) är vulkaniska event då enorma mängder magma avsätts över en väldigt stor yta under ett, i ett geologiskt perspektiv, kort tidsspann. Dessa stora vulkaniska utbrott har väckt stort intresse då de är samtida med flera av de största massutdöendena i jordens historia, men också för att en viss typ av sulfidmalm rik på nickel, koppar och platinametaller (Ni-Cu-PGE malmer) ofta förekommer i provinsernas magmagångar och magmakammare. En viktig faktor som till stor del avgör en magmatisk provins påverkan på klimatet och potentiella malmförekomster är inkorporering av sedimentära bergarter till magman som, när de hettas upp, kan frigöra gaser rika på svavel och kol. I Kanadas arktiska öar trängde magma tillhörande den högarktiska magmatiska provinsen (HALIP) in i svart skiffer, karbonater och evaporiter, som är sedimentära bergarter rika på flyktiga ämnen. Denna magmatiska provins erbjuder därför stora möjligheter till att studera interaktionen mellan magma och sedimentära bergarter. Syftet med denna studie är att testa om inkorporering av sedimentärt svavel kan främja bildandet av sulfidsmälta i magma och därigenom bidra till bildandet av sulfidmalmer. Detta görs genom att analysera svavelisotoper i sulfidmineral i prover från en magmagång, som trängde in i en skifferformation, tillhörande den högarktiska magmatiska provinsen i norra Kanada. Genom att analysera svavelisotopkvoten (δ34S) i sulfidmineral kan man få information om huruvida svavlet i mineralen är av sedimentärt ursprung (där skiffer generellt har negativa δ34S värden) eller om svavlet har δ34S värden liknande de från manteln (som har δ34S värden runt 0‰), vilket i så fall skulle innebära att magman inte har inkorporerat sedimentärt svavel. Genom att använda masspektrometri av typen SIMS analyseras totalt 14 sulfidmineralkorn (n = 246 individuella SIMS punkter) för deras svavelisotopkvoter. Resultatet av studien visar att alla analyserade sulfidmineral har mycket negativa δ34S värden mellan -19.5 och -5.7‰ (med ett δ34S medelvärde på -8.2 ± 0.83‰, två standardavvikelser). Genom att jämföra våra δ34S värden med δ34S och δ18O värden för andra prover från både magmagången och den omgivande skiffern kunde vi se att δ34S värdena för sulfidmineralen i de yttre delarna av magmagången har liknande negativa värden som den omgivande skiffern, och att δ34S värdena för skiffern närmast magmagången är mer positiva. Detta tyder på att sedimentärt svavel i kontakten mellan magmagången och skiffern har blivit inkorporerat i magman från den omgivande skiffern. Våra resultat tyder därför på att sulfidmineralen i våra prover från magmagången bildades genom assimilering av svavel från den omgivande skiffern. Detta innebär i sin tur att den kanadensiska högarktiska magma provinsen potentiellt kan vara en källa för sulfidmalm, även om ytterligare studier behövs. Dessutom visar våra resultat att inkorporering av sedimentärt svavel förmodligen ökade de vulkaniska gaserna i magman, vilket kan ha bidragit till klimatförändringar relaterade till den vulkaniska aktiviteten av den högarktiska magmatiska provinsen.