Chemostratigraphy of the lowermost iron-manganese cycle of the Hotazel Formation, and implications for its primary depositional environment
- Authors: Masoabi, Ntseka Thomas
- Date: 2022-10-14
- Subjects: Chemostratigraphy , Great Oxygenation Event , Manganese ores Geology South Africa Northern Cape , Banded iron formation
- Language: English
- Type: Academic theses , Master's theses , text
- Identifier: http://hdl.handle.net/10962/362938 , vital:65376
- Description: The giant Kalahari Manganese Field (KMF), located in the Northern Cape Province, South Africa, comprises approximately half of the world’s manganese resources, estimated at about eight billion tons at grades ranging from 20-48 wt%. The KMF is linked to a period in geological time when the Earth’s atmospheric and oceanic conditions underwent a major transition from oxygen-deficient to oxygen-enriched conditions – an event famously referred to as the Great Oxidation Event (GOE) that occurred around 2.4 Ga. The KMF deposits are hosted in Banded Iron Formation (BIF) of the Paleoproterozoic Hotazel Formation in the uppermost Transvaal Supergroup. The sedimentary Mn ores are interbedded with Hotazel BIF in the form of three alternating depositional cycles of BIF, transitional hematite lutite and laminated, carbonate-rich manganese ore. The lowermost and thickest of the three cycles is the most economically significant and has been mined for several decades on a large scale from the southernmost KMF. In this study, two drill cores from the southern KMF were inspected, logged and sampled at a high resolution of approximately half-meter interval per sample. The selected cores, namely G774, capturing the lower portion of the Hotazel Formation from the Mamatwan locality, and MP-56, capturing the corresponding portion from the Middleplaats locality, are geographically proximal to each other, with a horizontal distance of roughly 3 km separating the two of them. The G774 drill core is characterized by a conspicuously thick manganese layer covering a thickness of 50 m, with the overlying BIF reaching a total thickness of 11 m. The MP-56 drill core, on the other hand, has a relatively thinner corresponding manganese layer of 30 m in thickness, while the overlying BIF layer exhibits a thickness of 24 m. The extent of sampling up-section was constrained by an apparently coeval black shale layer which represents the chosen upper stratigraphic marker for the lower part of the Hotazel section in the broader area that is under investigation in this thesis. That way, a high resolution chemostratigraphic approach was employed to elucidate the potential factors contributing to the relative sedimentary lateral thickness variations seen across the southernmost KMF. High-resolution geochemical data were used to explore relationships and signals that might constrain relative precipitation rates for iron and manganese against detrital species, fluctuating redox conditions in the original environment of deposition, and chemostratigraphic correlation. All geochemical data (i.e., major oxides, minor and trace elements and carbonate carbon isotopes) were obtained respectively through employing X-ray Fluorescence (XRF), Laser Ablation Inductively Coupled Mass Spectrometry (ICP-MS), and Gas-source mass spectrometry. Comparative considerations made between the bulk geochemistry of the two sequences (i.e., Mamatwan and Middleplaats sections) reveal that periods of high-Mn deposition in the Hotazel Formation appear to be very Ca-carbonate rich (as indicated by high CaO, LOI and Sr concentrations). This, in turn, suggests that the Mn abundance is in the Hotazel ores is controlled mainly by the silicate phase braunite and is diluted by the deposition of Ca-carbonate through time. Bulk-rock concentration results for trace elements of the High Field Strength Element (HFSE) group (namely Zr, Hf, Y, Nb and Sc) were utilized to constrain the rates of either clastic and/or volcanic detrital inputs, as they traditionally represent refractory mineral particles of a common detrital/volcanic origin. The two chemosedimentary sequences preserve these elements in very low and thus quantitatively negligible concentrations – suggesting that the Hotazel depositional environment received very low and insignificant influx of a terrigeneous detrital component. A selection of these elements was therefore used to deduce, with caution, the relative as opposed to absolute precipitation rate of the major chemical constituents (i.e., Fe + Si vs Mn + carbonate), assuming a constant detrital flux through time. It was found that the relative abundances of Zr, Y and Nb is roughly 1.5 – 2 times as high in the BIF lithofacies relative to the Mn ones at both localities. This led to the inference that the Mn-enriched portion of the sediment must have been deposited at approximately twice the rate that the Fe-rich (BIF) portion was originally deposited. In terms of redox-sensitive elements, the elements Co and Mo seem to reveal the most valuable insights into the redox environment of primary chemical deposition. Cobalt displays a unique pattern in that its highest concentration is attained at the hematite lutite transitions (similarly with the REE in this regard), while very low and seemingly invariant concentration is exhibited within the core of the main orebodies. The same pattern seems to be reproduced to a degree by the corresponding bulk MgO component, whereby MgO abundance maxima are associated with the basal hematite lutite and the hematitic flanks of the Mn-ore zone, while the core of the Mn-rich layer attains relatively low and essentially invariant MgO concentrations. This implicates a close and direct association of Co with the hematite fraction of the rocks and a concurrent enrichment in Mn-rich carbonate (dolomite). On the other hand, Mo seems to have a direct and clear association with peak MnO2 content of the rocks, which in turn presents a high possibility of Mo having adsorbed onto primary Mn-oxyhydroxides in the water column, thus providing evidence that Mn-oxide must have acted as an important Mo sink, at least locally. Finally, the carbonate-carbon isotope results provide a useful tool that brings the two stratigraphic sections “together“, in conjunction with other correlatable chemostratigraphic parameters (e.g. Co, Mg). The results demonstrate that bulk carbon fluxes and isotopic signals in the sediments must reflect primary processes of deposition, and that correlation across two apparently disparate lithostratigraphic sections can be effected. The key finding is that, at times, manganese deposition in one part of a vii stratified basin was evidently accompanied by simultaneous BIF deposition at another, thus painting a very complex picture of massive primary chemical precipitation of Fe and Mn at the dawn of the GOE. , Thesis (MSc) -- Faculty of Science, Geology, 2022
- Full Text:
- Date Issued: 2022-10-14
- Authors: Masoabi, Ntseka Thomas
- Date: 2022-10-14
- Subjects: Chemostratigraphy , Great Oxygenation Event , Manganese ores Geology South Africa Northern Cape , Banded iron formation
- Language: English
- Type: Academic theses , Master's theses , text
- Identifier: http://hdl.handle.net/10962/362938 , vital:65376
- Description: The giant Kalahari Manganese Field (KMF), located in the Northern Cape Province, South Africa, comprises approximately half of the world’s manganese resources, estimated at about eight billion tons at grades ranging from 20-48 wt%. The KMF is linked to a period in geological time when the Earth’s atmospheric and oceanic conditions underwent a major transition from oxygen-deficient to oxygen-enriched conditions – an event famously referred to as the Great Oxidation Event (GOE) that occurred around 2.4 Ga. The KMF deposits are hosted in Banded Iron Formation (BIF) of the Paleoproterozoic Hotazel Formation in the uppermost Transvaal Supergroup. The sedimentary Mn ores are interbedded with Hotazel BIF in the form of three alternating depositional cycles of BIF, transitional hematite lutite and laminated, carbonate-rich manganese ore. The lowermost and thickest of the three cycles is the most economically significant and has been mined for several decades on a large scale from the southernmost KMF. In this study, two drill cores from the southern KMF were inspected, logged and sampled at a high resolution of approximately half-meter interval per sample. The selected cores, namely G774, capturing the lower portion of the Hotazel Formation from the Mamatwan locality, and MP-56, capturing the corresponding portion from the Middleplaats locality, are geographically proximal to each other, with a horizontal distance of roughly 3 km separating the two of them. The G774 drill core is characterized by a conspicuously thick manganese layer covering a thickness of 50 m, with the overlying BIF reaching a total thickness of 11 m. The MP-56 drill core, on the other hand, has a relatively thinner corresponding manganese layer of 30 m in thickness, while the overlying BIF layer exhibits a thickness of 24 m. The extent of sampling up-section was constrained by an apparently coeval black shale layer which represents the chosen upper stratigraphic marker for the lower part of the Hotazel section in the broader area that is under investigation in this thesis. That way, a high resolution chemostratigraphic approach was employed to elucidate the potential factors contributing to the relative sedimentary lateral thickness variations seen across the southernmost KMF. High-resolution geochemical data were used to explore relationships and signals that might constrain relative precipitation rates for iron and manganese against detrital species, fluctuating redox conditions in the original environment of deposition, and chemostratigraphic correlation. All geochemical data (i.e., major oxides, minor and trace elements and carbonate carbon isotopes) were obtained respectively through employing X-ray Fluorescence (XRF), Laser Ablation Inductively Coupled Mass Spectrometry (ICP-MS), and Gas-source mass spectrometry. Comparative considerations made between the bulk geochemistry of the two sequences (i.e., Mamatwan and Middleplaats sections) reveal that periods of high-Mn deposition in the Hotazel Formation appear to be very Ca-carbonate rich (as indicated by high CaO, LOI and Sr concentrations). This, in turn, suggests that the Mn abundance is in the Hotazel ores is controlled mainly by the silicate phase braunite and is diluted by the deposition of Ca-carbonate through time. Bulk-rock concentration results for trace elements of the High Field Strength Element (HFSE) group (namely Zr, Hf, Y, Nb and Sc) were utilized to constrain the rates of either clastic and/or volcanic detrital inputs, as they traditionally represent refractory mineral particles of a common detrital/volcanic origin. The two chemosedimentary sequences preserve these elements in very low and thus quantitatively negligible concentrations – suggesting that the Hotazel depositional environment received very low and insignificant influx of a terrigeneous detrital component. A selection of these elements was therefore used to deduce, with caution, the relative as opposed to absolute precipitation rate of the major chemical constituents (i.e., Fe + Si vs Mn + carbonate), assuming a constant detrital flux through time. It was found that the relative abundances of Zr, Y and Nb is roughly 1.5 – 2 times as high in the BIF lithofacies relative to the Mn ones at both localities. This led to the inference that the Mn-enriched portion of the sediment must have been deposited at approximately twice the rate that the Fe-rich (BIF) portion was originally deposited. In terms of redox-sensitive elements, the elements Co and Mo seem to reveal the most valuable insights into the redox environment of primary chemical deposition. Cobalt displays a unique pattern in that its highest concentration is attained at the hematite lutite transitions (similarly with the REE in this regard), while very low and seemingly invariant concentration is exhibited within the core of the main orebodies. The same pattern seems to be reproduced to a degree by the corresponding bulk MgO component, whereby MgO abundance maxima are associated with the basal hematite lutite and the hematitic flanks of the Mn-ore zone, while the core of the Mn-rich layer attains relatively low and essentially invariant MgO concentrations. This implicates a close and direct association of Co with the hematite fraction of the rocks and a concurrent enrichment in Mn-rich carbonate (dolomite). On the other hand, Mo seems to have a direct and clear association with peak MnO2 content of the rocks, which in turn presents a high possibility of Mo having adsorbed onto primary Mn-oxyhydroxides in the water column, thus providing evidence that Mn-oxide must have acted as an important Mo sink, at least locally. Finally, the carbonate-carbon isotope results provide a useful tool that brings the two stratigraphic sections “together“, in conjunction with other correlatable chemostratigraphic parameters (e.g. Co, Mg). The results demonstrate that bulk carbon fluxes and isotopic signals in the sediments must reflect primary processes of deposition, and that correlation across two apparently disparate lithostratigraphic sections can be effected. The key finding is that, at times, manganese deposition in one part of a vii stratified basin was evidently accompanied by simultaneous BIF deposition at another, thus painting a very complex picture of massive primary chemical precipitation of Fe and Mn at the dawn of the GOE. , Thesis (MSc) -- Faculty of Science, Geology, 2022
- Full Text:
- Date Issued: 2022-10-14
Mineralogical and geochemical constraints on the origin, alteration history and metallogenic significance of the Manganore iron-formation, Northern Cape Province, South Africa
- Authors: Papadopoulos, Vlassis
- Date: 2017
- Subjects: Banded iron formation , Transvaal Supergroup (South Africa) , Groups (Stratigraphy) South Africa , Lithostratigraphy , Petrology South Africa , Geochemistry South Africa
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/65189 , vital:28702
- Description: The Manganore iron-formation (MIF) of the Transvaal Supergroup is host to the most important high-grade iron ore bodies in South Africa. Prevailing models for ore genesis invoke supergene processes performing during a long period of erosion, oxidation and weathering under tropical lateritic conditions while the role of potential hydrothermal processes is not addressed. Lack of detailed petrographical and geochemical data necessitated reexamination of the MIF through new and existing drill core exploration material. Thorough petrographical investigation revealed a multi-event complex alteration history involving hydrothermal activity. Iron and silica mobility during alteration is demonstrated by a series of replacement, overprinting, crosscutting textures, extensive silicification and hematitization. Metasomatized textures such as pseudomorphs of primary magnetite, carbonate minerals and chert pods/lenses point to an alteration occurring in layer- controlled fronts and link stratigraphically the MIF to Kuruman and Griquatown iron- formations. Whole-rock geochemical data verify textural observations suggesting strong enrichment of iron or silica in meter-scale horizons, expressed by different generations of quartz and hematite. High-grade iron ore is highly enriched in TiO2 and Al2O3 compared to the protolith while both BIF and iron ore display highly increased concentrations of trace elements (transition metals and HFSE). Oxygen isotopes from different quartz textures reveal little to none isotopic exchangement during alteration whereas O isotopes from hematite are in concert to values from literature and suggest two different generations of hematite. A total of 20 minerals apart from quartz and hematite were documented. An earlier alkali/HFSE alteration event that is believed to have affected the overlying Gamagara shales is recorded in the BIF by the presence of muscovite, apatite, rutile, zircon and xenotime. A later and possibly ongoing event of succeeding hydrothermal pulses involves mainly sulphates (gypsum, baryte, celestine), pyrite, carbonates (siderite, calcite) and silicates (berthierine and tourmaline). Alkali-bearing brines persistently exploit the BIF mainly through karstification-related secondary porosity, are evidently carrying iron and are proposed to participate in or control the iron enrichment by facilitating removal of silica. The source of metals, sulfur and carbon is attributed to the underlying Campbellrand dolomites and especially to the upper Gamogaan Formation. The unconformable contact between BIF and the overlying shales is suggested as a suitable fluid conduit for the development of the observed BIF and shale-derived high-grade hematite iron ore.
- Full Text:
- Date Issued: 2017
- Authors: Papadopoulos, Vlassis
- Date: 2017
- Subjects: Banded iron formation , Transvaal Supergroup (South Africa) , Groups (Stratigraphy) South Africa , Lithostratigraphy , Petrology South Africa , Geochemistry South Africa
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/65189 , vital:28702
- Description: The Manganore iron-formation (MIF) of the Transvaal Supergroup is host to the most important high-grade iron ore bodies in South Africa. Prevailing models for ore genesis invoke supergene processes performing during a long period of erosion, oxidation and weathering under tropical lateritic conditions while the role of potential hydrothermal processes is not addressed. Lack of detailed petrographical and geochemical data necessitated reexamination of the MIF through new and existing drill core exploration material. Thorough petrographical investigation revealed a multi-event complex alteration history involving hydrothermal activity. Iron and silica mobility during alteration is demonstrated by a series of replacement, overprinting, crosscutting textures, extensive silicification and hematitization. Metasomatized textures such as pseudomorphs of primary magnetite, carbonate minerals and chert pods/lenses point to an alteration occurring in layer- controlled fronts and link stratigraphically the MIF to Kuruman and Griquatown iron- formations. Whole-rock geochemical data verify textural observations suggesting strong enrichment of iron or silica in meter-scale horizons, expressed by different generations of quartz and hematite. High-grade iron ore is highly enriched in TiO2 and Al2O3 compared to the protolith while both BIF and iron ore display highly increased concentrations of trace elements (transition metals and HFSE). Oxygen isotopes from different quartz textures reveal little to none isotopic exchangement during alteration whereas O isotopes from hematite are in concert to values from literature and suggest two different generations of hematite. A total of 20 minerals apart from quartz and hematite were documented. An earlier alkali/HFSE alteration event that is believed to have affected the overlying Gamagara shales is recorded in the BIF by the presence of muscovite, apatite, rutile, zircon and xenotime. A later and possibly ongoing event of succeeding hydrothermal pulses involves mainly sulphates (gypsum, baryte, celestine), pyrite, carbonates (siderite, calcite) and silicates (berthierine and tourmaline). Alkali-bearing brines persistently exploit the BIF mainly through karstification-related secondary porosity, are evidently carrying iron and are proposed to participate in or control the iron enrichment by facilitating removal of silica. The source of metals, sulfur and carbon is attributed to the underlying Campbellrand dolomites and especially to the upper Gamogaan Formation. The unconformable contact between BIF and the overlying shales is suggested as a suitable fluid conduit for the development of the observed BIF and shale-derived high-grade hematite iron ore.
- Full Text:
- Date Issued: 2017
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