Browsing by Subject "Geochemistry"

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    Aspects of the geochemistry of Onverwacht Group lavas from the Barberton Greenstone Belt
    (1980) Smith, Hudson Stuart
    The 3540 million year old komatiitic and tholeiitic lavas in the Onverwacht Group (Barberton greenstone belt) crop out in the rugged terrain of the eastern Transvaal lowveld. The results of an investigation into the geochemistry of the lavas, mainly from the three lower Formations of the Onverwacht Group - the Lower Ultramafic Unit (LUU) - are reported. While the lavas generally show excellent textural preservation, their primary phases have usually been reconstituted to greenschist facies mineral assemblages. Although original phenocryst phases are often pseudomorphed, they can still be identified from occasionally preserved relict grains and from the secondary mineral assemblages. In this way all the major phases that occur in the various lava types could be identified. However, before the geochemical data could be used to examine the effects of partial melting and/or crystal fractionation processes in the development of the magma compositions, it was necessary to investigate which elements had been redistributed by later metamorphic and other alteration events that have occurred in the history of the lavas.
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    Assessment of long-term air pollution impacts on soil properties in the vicinity of Arnot power station on the South African highveld
    (1997) Van Tienhoven, Anne Mieke; Fey, Martin V; Willis, James
    Atmospheric pollution on the South African high veld is perceived as a concern because of the combination of heavy industry and climatic features that prevail in the region. The frequent occurrence of surface inversions (80 - 90 % of days in the winter months), permits the accumulation of pollutants near ground level. Although industrial stacks, and those of power stations in particular, are generally able to emit gaseous and particulate pollutants above the boundary layer, looping and fumigation of plumes may occur under convective conditions. Under such circumstances, the concentration of pollutants at ground level may be high, especially within 4 km of the stack. Since considerable damage to European and North American ecosystems has occurred as a result of atmospheric pollution, concerns were first raised in a report by Tyson, Kruger and Louw in 1988, that similar effects may be taking place on the eastern highveld region of South Africa. The current study was prompted in direct response to these concerns. The first major objective was to establish long-term monitoring sites whereby changes in the pedosphere in response to atmospheric inputs could be detected. The second objective was to characterise the soil collection and to determine whether any impacts are detectable at this early stage. Arnot power station was selected as the focal point of the study as it is a base-load power station, is the most distant from the industrial centres of Witbank, Middelburg and Gauteng and has been in operation for over twenty years. Fifteen sampling sites located in an arc ranging ENE to SE downwind of the power station were selected. Both topsoil and subsoil were sampled at each site. Details of geographical co-ordinates and site features were noted to enable reproducible resampling. Sampling took place in August 1996, but three sites were visited again in October and resampled to test the reproducibility of sampling. Although not statistically comparable, the soils of each site showed similar results for key analyses, which included EC, pH, organic carbon and acid neutralising capacity.
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    The chemical characterisation of authigenic carbonates from the Witbank no. 2 coal seam : environmental and diagenetic implications
    (1991) Van der Spuy, David
    Six different types of authigenic carbonate were identified associated with the no.2 coal seam in the Witbank basin. These are: l) cell-filling carbonate, 2) early formed spberulites, 3) massive carbonates, 4) cleat-filling carbonate, 5) fracture-filling carbonates and 6) carbonate cement of associated sands. The textural relationships, depth of burial and chemical evolution of these carbonates were studied with the aid of X-ray diffraction, total organic carbon analysis, vitrinite reflectance, reflected and transmitted light microscopy, scanning electron microscopy and electron microprobe analysis. Comparison with the studies of Matsumoto and Iijima (1981), Curtis and Coleman (1986) and other literature showed the Witbank carbonates to have followed a fairly complex path in terms of chemical evolution. The chemistry of the earliest cell-filling carbonates is indicative of an early brackish, alkaline environment with high sulphate levels, with occasional local oxidising conditions prevailing during precipitation. Spherulite chemistry is largely representative of the continuation of alkaline conditions with high sulphate supply. Those forming closer to palaeohighs are sideritic and possibly reflect the input of fresher run-off water, allowing more acidic conditions locally. Compositional zonation of some examples indicates initial acidic conditions and later alkaline conditions. Massive carbonates are considered to have formed, at least in some cases, from amalgamations of these earlier spherulites. They are high-Ca carbonates, siderite or dolomite. A number of the high-Ca massive carbonates were found to be aragonite. These are considered to have precipitated from water with high ionic strength, in the presence of humic acids. The chemistries of these massive carbonates are representative of the continuation of relatively, alkaline conditions, or, in some cases, represent a strong brackish or marine imprint over the earlier fresh water chemistries. Chemical trends and isotope data suggest continued formation with burial. Later formed carbonates filling cleats and fractures show more diverse compositions and are interpreted as the results of mixing of pore waters at depth, primary silicate dissolution and later percolation of groundwaters after uplift. The overall evolution of the authigenic carbonates in the Witbank no.2 seam leads to the interpretation that the early swamp was only locally "fresh", and provides strong evidence for a marine influence at both early and late stages of deposition and diagenesis.
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    Chemical characterisation of landfill leachate and its potential mobility through the Cape Flats sand
    (1996) Harraway, Trevor John; Fey, Martin V; Willis, James P
    Researchers have expressed concern about pollution of groundwater at Coastal Park, a large, general waste landfill situated on the False Bay coastline above the Cape Flats Aquifer. The landfill was constructed without a liner, but with an average 2m separation of calcareous sand providing a "buffer" zone between the waste pile and the water table. Water balance studies and application of a model, FLOW, have predicted that leachate will be generated seasonally. This study was initiated as a result of uncertainties about hydrological and geochemical aspects, such as the hydraulic conductivity of the soil in the buffer zone and the degree of leachate attenuation occurring in this zone. The Coastal Park soil was classified as an aeolian, calcareous, medium quartzitic sand with negligible organic carbon content. Extreme clay-depletion would render the soil almost incapable of leachate attenuation, although calcite and aragonite, found by X-ray diffractometry, would impart a significant pH buffering capacity to the soil. The solid phase of a locally-derived landfill leachate (sampled from Vissershok landfill, about 35 km NW of Cape Town) was found to contain amorphous sulfides of iron and heavy metals, and green rusts which are mixtures of Fe²⁺ - Fe³⁺ hydroxides, in addition to organic matter. The solid phase was isolated by centrifugation, freeze-dried, and analyzed by XRF and XRD. Distribution coefficients of heavy metals in the leachate (at pH 7.7) demonstrated the high affinity of heavy metals, such as Cu, Zn, Cr, Ni and Pb, for the solid phase. The leachate solid phase consists of amorphous solids, with high Ca and Cl concentrations in the liquid phase leading to halite and calcite formation upon evaporation of the liquid phase. According to locally specified requirements by Department of Water Affairs and Forestry, a landfill liner material must have a hydraulic conductivity (K) not higher than 1 x 10⁻⁷cm.s⁻¹. Air dried samples of Coastal Park soil were treated with various amendments to test their efficacy as landfill liners. An 8 % kaolinite plus 4 % gypsum treatment was the most effective, maintaining a minimum K of 10⁻⁴⁵ cm.s⁻¹, which, however, is still higher than the local requirement. Amendment with 8 % Na-bentonite initially achieved a minimum K of 10⁻⁷·⁸ cm.s⁻¹, but the high electrical conductivity (EC) of the leachate (26.8mS.cm⁻¹) caused shrinking and severe side-wall seepage, which rapidly enhanced hydraulic conductivity, reaching a maximum K of about 10⁻⁴·⁷ cm.s⁻¹. Both treatments of the sand do show promise as possible liners, although the use of higher percentage concentrations of clay should be investigated further. LEACHW (the water regime submodel of LEACHM) was used to predict leachate discharge from the Coastal Park landfill, assuming a hypothetical capping system of 1 or 2 m soil depth with 0, 50, 70, or 90 % vegetation cover (Acacia cyclops), and based on the assumption that drainage from this layer into the waste pile contributes directly to leachate generation. The model predicted that under average rainfall conditions the landfill, with a 2 m soil depth and 0 % vegetation cover, would not generate leachate. However, under the wettest conditions not even a 90% vegetation cover and 2 m soil cover would be sufficient to prevent the landfill from generating leachate, suggesting that, under such conditions, a more effective leachate management strategy, such as leachate collection sumps, should be implemented. This exercise demonstrated the use of LEACHM as an alternative means of predicting leachate discharge from landfill sites.
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    The determination of several metals in organic separates of selected South African shales
    (1970) Marchant, James William; Danchin, Bobby
    Some or all of the elements Li, Na, K, Rb, Cs, Mg, Ca, Sr, Cr, Mo, Mn, Fe, Co, Ni, Cu, Ag, Au, Zn, Pb and Tl are determined by Atomic Absorption Spectroscopy in soluble organic and total organic separates from thirty-six samples of South African carboniferous shales. The whole rock values for most of these elements in the samples are known and can be compared with the corresponding values of the organic fraction. A colloidal technique is developed to extract fairly pure kerogen from the shales. Rb, Cs, Ca, Cr, Co, Ni, Cu, Zn and Pb are concentrated in the organic fraction. The results for Rb, Cs and Ca are unexpected. The elements are apparently associated with a sub-fraction of the organic fraction. Several new organic geochemical parameters are developed to interpret the results. Interelement correlations in the various fractions of the shales, the relationship between metal content and organic content, the relationship between concentration of metals by organic matter and residence time, and the use of the metal content of the organic fraction as a paleosalinity test are discussed.
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    Diamonds and related minerals from the Dokolwayo Kimberlite, Kingdom of Swaziland
    (1991) Daniels, L R M
    Several physical characteristics, the carbon isotopic compositions, inclusion mineralogy, and distribution of the Dokolwayo diamonds were investigated. A representative suite of concentrate garnet megacrysts and macrocrysts were analyzed for their compositions. Concentrate macrocryst spinels and silicate inclusions recovered from these spinels were analyzed. The physical characteristics of the diamonds investigated were mass, size, morphology and colour. The relationship between mass and size in a population of diamonds recovered from a single hypabyssal intrusion and the general production as a whole, was found to be statistically the same. The most recognizable morphology is the dodecahedron. Octahedra decrease in significance with a decrease in size. Colourless stones predominate. Brown stones are more common than yellow stones, which is uncommon in primary southern Africa diamond populations. Diamonds characterized by "Tanganyika naats" have hitherto not been described from southern Africa. The relationship between the various physical characteristics investigated indicate that the general Dokolwayo diamond population consists of at least four sub-populations.
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    Economic geology of the refractory clays in the Union of South Africa with particular reference to the Transvaal deposits
    (1949) Warde, John M; Warde, John M; Jacobs, H
    The purpose of this thesis is to describe the occurrence, nature, properties, and utilization of the refractory clays in South Africa with particular reference to the Transvaal deposits, focusing on those characteristics which may be of direct value in the future development of this important mineral resource. Principal attention has been devoted to producing areas and-generally confined to those materials used in the production of fire-clay refractories; however, in many cases these identical clays are employed in the manufacture of "golden brown" building brick, sewer pipe, earthenware, etc. A fundamental study of the constitution of the commercial refractory clays was carried out on selected samples obtained from operating workings. The differential thermal method of analysis was featured in these studies, supple mented by X-ray examination and other recognized determinative procedures. The basic data so obtained were correlated, where possible, with the ceramic properties of the clays in order to lead to a better understanding of the relationship between the refractory clays and the ware made from them.
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    The effect of industrial practices on stream sediments, and the impact of these sediments on the geochemistry of a wetland
    (1997) Lake, James Andrew; Willis, James; Fey, Martin V
    The objective of this study was to characterise the impact that a major industrial operation, situated at Somerset West and involved in the manufacturing of a diverse range of chemicals, has had on the sediments of the drainage system that drains the site on which these activities occur. Furthermore, the impact of these sediments on the geochemistry of a wetland, Wagenveldt vlei, situated downstream of the complex, has been investigated. Sediment cores and water samples were collected at a number of locations down the length of the drain . The water samples were analysed to determine which constituents were present in solution. The cores were separated into a top and bottom layer which were analysed separately to determine their geochemical composition. In some instances a lack of time resulted in some of the analyses being performed on only a select number of samples. An experiment was performed on the sediments collected from the bottom layer to determine what would happen if the sediments became oxic and the sulphides and organic matter in the sediments were oxidised.
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    Factors influencing the mobility of uranium, thorium and rare earth elements at the Steenkampskraal monazite, North Western Cape
    (1997) Glendinning, John Edward; Willis, James
    It is well known that the release of long-lived radionuclides to the water path is probably the most relevant radiological risk originating from an underground repository. Transuranic elements (ie. all elements with an atomic number greater than 92 (U)) do not have any non-radioactive isotopes and are very rare in natural materials. The long term geochemical behaviour of these elements must thus be derived from chemical analogues such as the rare earth elements (REE), Th and U. Steenkampskraal monazite mine, situated 350 km north of Cape Town, has been found to be an excellent locality for the study of these elements, due to the high concentration of these elements in the ore as well as the ideal geology, which consists of low permeability rocks with groundwater flow governed by fractures. The ore body consists of a monazite [(REE, Th, U)P04], apatite [Ca₃P0₄)₂], chalcopyrite [CuFeS] and magnetite [FeP₄] veindeposit. Water was sampled from six boreholes in the vicinity of the mine and five wi.ndpumps on the surrounding farm Nabeep and Brandewynskraal. Surface water samples were taken from the slimes dam, an ephemeral stream on the western side of the mine, as well as from the surface of a road shortly after rain, below the tailings. Four water samples were taken from within the underground mine workings (Mainshaft, Main shaft extension, Sump on level 3 and Inclined shaft). Colloids were sampled from three of the boreholes and a precipitate was taken from the surface of the main shaft water. Soils were sampled along two transects away from the mine on the eastern and western side of the ore body. Due to the topography of the area, surface contamination could only occur on these two sides. Stable isotopes of oxygen (8 180) and hydrogen ((8 180) indicated the presence of two distinct groups of waters within the vicinity of the mine. One group is composed of unevaporated waters and includes all borehole sand the water sampled in the inclined shaft. The water moving through the inclined shaft is in contact with the ground water. A second group of highly evaporated waters was present in the slin1es dam samples as well as the underground water samples not directly in contact with groundwater. Groundwater contamination by REE-bearing phosphate minerals has resulted in measurable concentrations of U, Th and REE in all mine waters and boreholes in the near vicinity of the mine. The chondritenormalized REE patterns of the water samples are sin1ilar to those displayed by monazite, with a distinctive Eu depletion and an obvious enrichment in LREE with respect to HREE. Monazite-normalized REE patterns for the selected borehole waters show a marked fractionation between LREE and HREE, with the HREE strongly enriched in the aqueous phase. Heavy REE have been shown to have a greater tendency for complexatioi1 and a greater affinity for mineral surfaces. In the present study, the three boreholes in which colloids were found had high concentrations of U, Th and REE. It is likely that colloidal transport of these elements is the dominant mechanism of transport.
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    A geochemical and stable isotope study of some rocks from the Bandelierkop formation, southern marginal zone of the Limpopo Belt, South Africa( vol.1 Text)
    (1989) Vennemann, Torsten Walter; Smith, Hudson Stuart
    The Bandelierkop Formation of the Southern Marginal Zone (SMZ) of the Limpopo Belt consists of metamorphosed ultramafic, mafic and sedimentary rocks. Metamorphic conditions indicated by the petrography of these different rock groups are consistent with upper amphibolite to granulite facies. The ultramafic and mafic rocks are geochemically akin to peridotitic-pyroxenitic intrusive rocks and high-Mg basalts respectively. Metamorphism of these two rock groups in the SMZ was an essentially closed system process, except for the highly volatile phases such as H₂O and CO₂. The metasediments appear to represent a sequence of high (Mg+Fe)-greywackes and/or deep-water shales with minor amounts of iron formation material. The unusually mafic character of the metasediments can be ascribed to a high ultramafic + mafic source component to the original sediment. Some modification of the major and trace element compositions of the pelitic rocks has been caused by the removal of partial melts and the metamorphism of the pelitic rocks is not therefore considered to have occurred under closed system conditions. Variable extraction of partial melts is implied by the chemical variations shown by the pelitic rocks and is also suggested by the presence of large pegmatitic felsic bodies which are commonly found close to the pelitic rocks. Detailed petrographic study of the Bandelierkop Formation rocks suggests an increase in metamorphic grade, and/or a decrease in water activity, from south to north within the Southern Marginal Zone. Peak metamorphic conditions of 730°C + 65°C at pressures of 6.1 ± 1.5 kbars may be deduced from a careful application of several cation thermometers and barometers on selected mineral analyses. A rigorous application of garnet-biotite thermometry to the pelitic rocks indicates that the transition from orthoamphibole gneisses in the south to orthopyroxene-bearing rocks in the north of the SMZ terrane, is a function of changing biotite composition and/or decreasing water activities rather than an increase in metamorphic temperatures. In contrast to the major and trace element data, the stable isotope data for the ultramafic and mafic rocks in the SMZ indicate open system behaviour for some of these rocks, but closed system behaviour for the pelites. Extraction of SO to 70% partial melts from the pelitic rocks, should not, however, have affected the δ¹⁸O value of the restite. Petrological and stable isotope data in the SMZ rocks are consistent with retrogression in all these rocks and open system behaviour for oxygen in some ultramafic and mafic rocks, being caused by the crystallization and accompanying fluid release of melts produced during prograde metamorphism of the pelitic rocks. Small scale (-5 to 30m's) heterogeneity is implied by both oxygen and carbon stable isotope compositions of closely spaced rock samples, even for those collected from within large "shear zones", suggesting small fluid/rock ratios for most of the samples in the high-grade terrane or heterogeneous stable isotopic compositions of the fluids. Furthermore, a similarity in mineral-mineral stable isotope fractionation factors is observed for all the pelitic rocks, including the orthoamphibole gneisses found immediately south of the orthopyroxene isograd. These features preclude the presence of pervasive fluid infiltration after peak metamorphism. Two implications are, that granulite facies metamorphism in the SMZ terrane was not caused by an influx of mantle derived CO₂-rich fluid and, that the orthoamphibole gneisses are not retrogressed equivalents of the granulites found to the north of the orthopyroxene isograd. It is suggested that this isograd represents a change in the water activities of the rocks during metamorphism. Apparent disequilibria in mineral - mineral stable isotope fractionations observed amongst different minerals within any one pelitic rock, may be explained by a combination of the crystallization of residual melt within these rocks and oxygen diffusion amongst minerals which have not reached their oxygen-closure. The concordant quartz-plagioclase, quartz-biotite and plagioclase-biotite oxygen isotope equilibration temperatures are taken to represent minimum crystallization temperatures for the melts (-560°C), while successively higher quartz-orthopyroxene, quartz-amphibole and quartz-garnet oxygen isotope equilibration temperatures are a function of increasing closure temperatures for the orthopyroxene, amphibole and garnet respectively. The minimum estimate to peak metamorphic temperatures is given by the quartz-garnet oxygen isotope temperature averaging 736 + 52°C. If oxygen diffusion experiments performed in hydrothermal systems are appropriate for the SMZ rocks, then cooling rates for the SMZ terrane could have been as low as 12 to 25°C/My over a temperature range of 480 to 600°C. Stable isotope modeling of hypothetical fluids that may have been in equilibrium with the high-grade rocks, suggests that a mixture of CO₂ and H₂O, with CO₂/H₂O mole ratios > 0.1 can precipitate both quartz and carbonate of stable isotope composition similar to those determined for quartz and carbonate from the mineralized Archaean lode gold deposits of the Murchison and Pietersburg greenstone belts. A model involving granulite facies metamorphism, partial melt extraction and subsequent release of fluids, Au, K and S upon crystallization of such melts, appears to be viable for gold mineralization occuring in the adjacent lower grade greenstone belts and in the high-grade terrane of the Southern Marginal Zone.
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    Geochemical aspects of the megacryst suite from the monastery kimberlite pipe
    (1977) Jakob, Wolf-Rainer Otto
    [Missing Pages - Abstract unavailable]
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    Geochemistry and mineralogy of selected Atlantic Ocean basalts
    (1980) Le Roex, Anton Powter; Erlank, A J; Reid, A M
    Bulk rock compositional variations in lavas from four localities in the Atlantic Ocean are evaluated quantitatively in terms of fractional crystallisation and partial melting models. Samples studied are from the Mid-Atlantic Ridge at 36°49 'N (FAMOUS), from the Islas Orcadas fracture zone on the Southwest Indian Ocean Ridge, from the Conrad fracture zone on the America-Antarctica Ridge and from Bouvet Island, situated at the southernmost tip of the Mid- Atlantic Ridge and in the vicinity of both the fracture zones mentioned above. Bulk rock major and trace element variations in selected basalts from the FAMOUS area, in conjunction with a detailed study of the chemistry of phenocryst minerals and associated melt inclusions are used to place constraints on the genetic relationships between the various lava types. The distribution of NiO in olivine and Cr-spinel phenocrysts distinguishes the picritic basalts, plagioclase phyric basalts and plagioclase-pyroxene basalts from the olivine basalts. The NiO content of these phenocrysts in the former three basalt types is low, or a given Mg Mg+Fe²⁺ atomic ratio of the mineral, relative to the phenocrysts in the olivine basalts. Consideration of the Zr/Nb ratio of the lavas similarly distinguishes the olivine basalts from the plagioclase phyric and plagioclase- pyroxene basalts but, in addition, distinguishes the picritic basalts from the former three basalt types.
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    Geochemistry and petrogenesis of kimberlite intrusions from the eastern lobe the Du Toitspan kimberlite pipe, South Africa
    (University of Cape Town, 2020) Ramokgaba, Lesego; Le Roex, Anton P; Robey, Jock V A
    The Du Toitspan kimberlite pipe located on the outskirts of Kimberley South Africa, is one four Cretaceous aged major kimberlite pipes from the well-known Kimberley cluster, the type locality for archetypal group I kimberlites. Twenty-seven samples representative of various kimberlite intrusions from the eastern lobe of the Du Toitspan kimberlite pipe have been analysed for their whole-rock geochemistry and mineral chemistry (olivine and phlogopite) with the aim of developing semi-quantitative models that constrain their petrogenesis and characterise their respective source region(s). Investigated intrusions include; D13-phlogopite kimberlite, D14-monticellite kimberlite, D17-serpentinized phlogopite kimberlite, and several narrow (<1m) calcite kimberlite dykes ranging in texture from aphanitic to macrocrystic. The aphanitic calcite dykes were further sub-divided into; a phlogopite-rich calcite kimberlite, a perovskite-rich calcite kimberlite, opaque-rich calcite kimberlites and serpentine calcit e kimberlites.
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    Geochemistry of the Sabie River Basalt Formation in the central Lebombo, Karoo Igneous Province
    (1988) Sweeney, Russell James; Sweeney, Russell James; Erlank, Tony; Duncan, Andy; Erlank, Tony; Duncan, Andy
    The Sabie River Basalt Formation is a group of tholeiitic basaltic rocks erupted ca 190 Ma ago in the eastern zone of the Karoo Igneous Province of southern Africa. It is traceable over a distance of 700 km from Zululand, northwards along the Lebombo monocline into the Transvaal and south-east Zimbabwe. An abrupt compositional change in this formation occurs about halfway down its length in the vicinity of the Sabie and Komati Rivers: basalts to the north are known to be enriched in certain incompatible elements relative to basalts in the south, which are comparable in geochemistry to most basaltic rocks in the southern part of the Karoo Igneous Province. New data obtained in this work include 134 major and trace element whole-rock analyses, some 400 analyses of constituent minerals, 38 ⁸⁷Sr/⁸⁶Sr ratio determinations, 19 ¹⁴³Nd/¹⁴⁴Nd ratio determinations, 16 common Pb determinations and 12 oxygen isotope analyses. The "normal" (N) and "enriched" basaltic rocks are distinguished by differences in the concentrations of Ti, P, Zr, Nb, Y, La, Ce and Nd (high field strength elements). Broadly these differences are substantiated by K, Rb, Ba and Sr, but with much more overlap. The "enriched" group of basaltic rocks has been further subdivided into a low-Fe "enriched" (LFE) group and a high-Fe "enriched" group (HFE). The LFE-group basalts, which predominate at the base of the stratigraphic sections, are considered to be equivalent to basalts occurring in the N. Lebombo. In the central Lebombo N-group basalts predominate in the mid- and upper portions of the sections and HFE-group basalt occurs near the top of each section. Interbedding of all basalt groups occurs in the Sabie River section at the northern end of the study area, while the N- and HFE-group basalts are interbedded in the Crocodile and Komati River sections further to the south. The decrease in LFE-group basalt abundance southwards is accompanied by an increase in N-group basalt abundance. HFE-group basalts appear to be unique to the central Lebombo area of the Karoo Igneous Province and are volumetrically less significant than N- or LFE-group basalts. Petrogenetic models involving closed-system fractional crystallization; coupled assimilation (of granitic crust) fractional crystallization; replenished, tapped and fractionated magma chambers and partial melting are examined. Granitic crustal contamination appears to have been significant only in some samples of the N group where assimilation of granitic material has proceeded in a bulk fashion described by an AFC model. RTF models are dynamically more realistic than closed-system fractional crystallization models and explain increases in incompatible elements with decreasing MgO in the LFE and HFE groups. Variations in the N group, however, require varying degrees of partial melting of a N-type source to be explained fully. RTF models may explain the absence of any stratigraphic correlations of element abundances in the three groups. The HFE group may be related to an uncontaminated N-type parent composition by a combination of continued fractional crystallization from an N-group parent composition and varying degrees of partial melting of an N-type source. The only petrogenetic process by which the N and LFE groups may be related is different degrees of partial melting. However, this demands a source composition which has no resemblance on trace element and isotopic grounds, to observed mantle xenolith compositions. The preferred model is one in which the LFE group is derived from old sub-cratonic mantle similar to garnet-bearing "cold" peridotite xenoliths and the N group from a source similar in composition to estimates of primitive mantle. The existence of two types of mantle derived continental flood basalt magmas occurs in other Mesozoic basalt provinces in "southern" Gondwanaland (e.g. Kirwanveggan of Antarctica, Etendeka of Namibia and the Parana Basin of South America). It is suggested that there is a geographical association of LFE-type basalts with Archaean crust (or Archaean crust re-worked in low temperature - high pressure events) and N-type basalts with post-Archaean crust (or Archaean crust re-worked in high temperature - low pressure events). This model suggests the derivation of the LFE group, from old sub-cratonic lithospheric mantle relatively enriched in incompatible elements and the N group being derived from more recently accreted and less enriched lithospheric mantle underlying younger crustal terraines.
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    The geochemistry, kinematics and geodynamics of the Gannakouriep dyke swarm
    (1992) Ransome, Ian G D; Erlank, A J; Reid, Dave
    The Gannakouriep dyke swarm comprises a linear swarm of north to northeast striking mafic dykes emplaced during late Proterozoic rifting in the Gariep belt. The swarm has a strike length of over 300 km crossing terrane boundaries of the Gordonia sub-province, Richtersveld igneous sub-province and 8 ushmanland sub-province of the Namaqua Mobile Province. The main axis of dyke intrusion is centred within the 2.0 Ga Richtersveld igneous sub-province where the density of dyking increases westwards across strike towards the Gariep belt, prior to disappearing within the sediment/basement contact of the para-autochthonous Port Nolloth Assemblage. An internal Rb-Sr mineral isochron, together with pyroxene K-Ar plateau and whole rock model TCHUR ages, indicate that the dyke swarm was intruded around 720 Ma. The majority of the dykes comprise subophitic relict gabbros and dolerites of alkali affinities replaced by metamorphic minerals of both greenschist and amphibolite facies. The greenstones are encountered within the NE striking eastern sector of the dyke swarm which records the original tensile stress field, whilst amphibolites are encountered in the northerly striking western sector of the swarm which has been rotated 26° anticlockwise during Pan-African (500-550 Ma) deformation in the Gariep belt. The latter age of regional metamorphism and deformation is supported by available K-Ar age data on whole rock samples and amphibole mineral separates. Integrated field relationships, continuum mechanics modelling and geochemical studies suggest that the swarm was initiated as a series of low level crustal magma chambers which subsequently gave rise to a series of dyke complexes that comprise the Gannakouriep dyke swarm. The geochemical variability between individual dyke complexes across the entire swarm is negligible; only slight differences being recorded by their high-field-strength element concentrations. The latter suggests that all dykes are genetically linked to a single mantle diapir, with only slight source characteristic heterogeneities. All dykes are ferro-tholeiites with no primitive (picritic) member being present. Geochemical trends recorded by the swarm are easily reconcilable in terms of fractionation of the phenocryst assemblage olivine, plagioclase, clinopyroxene, (ilmenite and Ti-magnetite). However an earlier phase of fractionation of essentially olivine and plagioclase at the base of the crust is suggested since constraints on the degree of partial melting (3-6%) imposed by REE patterns would derive an alkali basalt parental melt. The geodynamic relationship between the Gannakouriep dyke swarm and rifting in the Gariep belt is accounted for by a lithospheric plate model containing non-coincidental crustal and mantle weaknesses represented by late Namaquan D4n extensional faults and a mantle weakness possibly resulting from crustal thickening within the Richtersveld igneous sub-province during Namaquan tectonics.
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    The geochronology and geochemistry of Karoo volcanics in the Lebombo and adjacent areas
    (1980) Bristow, John William; Erlank, A J; Duncan, A R
    Karoo volcanics of Jurassic to Cretaceous age crop out in the eastern areas of southern Africa. These volcanics are well preserved in the Lebombo monocline which straddles the borders of South Africa, Swaziland and Mozambique, and in the Nuanetsi and Tuli synclines and Sabi monocline of south-east Zimbabwe. Geochronological and geochemical data have been used to evaluate the geochemistry of the rock types found in the above areas, particularly with respect to the mafic volcanics of the Lebombo. In the eastwardly dipping Lebombo monocline, nephelinites overlain by picrite basalts occur in the northern part of the volcanic succession whereas over the remaining area olivine-poor basalts are dominant. Rhyolitic volcanics in the form of massive flows overlie the basaltic rocks and attain their maximum thickness in Swaziland and the southern Lebombo. The rhyolites are notably thinner to the north of Swaziland and are overlain by an upper sequence of olivine-poor lavas with interdigitated rhyolite flows. Basic dykes are ubiquitous in the Lebombo whereas acid dykes, though present, tend to be localised. In Nuanetsi, picrite basalts, olivine-poor basalts and rhyolite flows with interbedded basic lavas crop out ina major synclinal structure. Dyke rocks are common and late Karoo intrusive complexes cut the lavas. Volcanic rocks in the Tuli syncline consist predominantly of picrite basalts and olivine poor lavas, whereas nephelinites, picrite basalts and olivine-poor lavas crop out in the Sabi Monocline.
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    Gradient ion chromatographic determination of rare earth elements in coal and fly ash
    (1992) Ridley, Mark K; Watkins, Ron; Willis, James P
    Rare Earth Element (REE) determination in samples of coal and fly ash was undertaken by gradient high performance ion chromatography (HPIC). Ion chromatographic analysis requires that samples be in solution and that the matrix transition metals be removed. Coal samples, weighing 0.20g, were successfully dissolved in sealed pressure vessels in a microwave oven. Standard ashing procedures, followed by acid dissolution, were carried out to allow comparison with the microwave digestion technique. A lithium metaborate/tetraborate fusion and acid dissolution technique was used for the dissolution of fly ash. For the technique of REE determination the sample matrix was removed by off-line cation exchange. In an initial stage of the HPIC analysis the transition metals were removed by anion exchange using pyridine-2,6 dicarboxylic acid. The REE were then analysed using gradient elution of oxalic and diglycolic acid. Typically a 100μ1 volume of sample solution was employed for REE determination, but in the case of low ash (low REE) coal samples, prepared by microwave digestion, on-line concentration of 3-5 ml of sample, was necessary. The separated REE were reacted with 4-(2-pyridylazo)-resorcinol (PAR) and detected photometrically using a visible light detector at a wavelength of 520nm. Reproducibility for each REE was typically better than 5%CoV. Results from the analysis of coal and fly ash international standard reference materials were in acceptable agreement with values from alternative analytical procedures. Smooth, coherent trends obtained when the data were plotted on chondrite and "shale composite" normalised diagrams provided some support for the accuracy of the technique. The application of HPIC to the determination of REE in coals was demonstrated by the analysis of a new international reference coal sample, USGS CLB-1. Differences in REE concentrations between coal samples prepared by microwave digestion and ashing were observed. The HPIC analytical technique was also applied to the determination of REE in fly ash. The REE concentrations of fly ash from sequential electrostatic precipitators, from Lethabo and Kendal power stations, were determined to elucidate the behaviour of REE after the combustion of coal. REE concentrations increased through the sequential precipitators.
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    Hydrogeochemical exploration at Tsumeb
    (1980) Marchant, James William; Orren, Michael J; Erlank, A J
    The Precambrian Otavi dolomites in the district of Tsumeb in Namibia are host to base metal mineralization but large tracts of these rocks occupy a mature pediplain and are deeply buried by transported overburden of Kalahari age. This sandy material makes exploration for minerals very difficult. Hydrogeochemistry was considered as a possible answer to the problem of prospecting in this region but a major obstacle was the lack of an undisturbed site for orientation studies. The Tsumeb mine was therefore used as a "surrogate" orientation target and water samples collected there were analyzed for about forty elements or ions. The data were plotted on long-sections through the orebody and examined with the aid of simple statistical calculations. The Na/Cl⁻ ratio proved to be a powerful index for identifying groups of waters with a common origin. It appeared that the most important of these groups of waters were not natural groundwaters but were being recycled. Millions of litres of water are pumped from the mine daily and a significant proportion finds its way back into the workings through seepage. This conclusion was supported by chemical data and by calculations in which the rates of pumping and recharge were balanced. Over the years the process of recycling has caused a rise in the concentrations of sodium, chloride and sulphate in the water arriving at the sumps in the mine. The other major components of these waters - Ca, Mg and HCO₃⁻ - are not affected to the same extent by recycling because of controls imposed by the carbonic system. It was not generally possible to establish rational links between the distributions of the trace elements, the major groups of related waters and the proximity of ore. Although some trace elements tended to be more abundant in samples from the upper parts of the mine, where exposure to broken, weathered ore is greatest, the value of this association was diminished by the fact that these waters are recycled effluents that cannot be equated with the natural groundwaters that would be in contact with any undiscovered ore-bodies similar to the Tsumeb lode. This conclusion was reinforced by the fact that some of the trace elements were relatively abundant in waters that were comparatively saline but which had not been exposed to oxidized ore. It was concluded that it would not be possible to interpret the trace element data from the mine waters unambiguously. Nevertheless it was clear that sulphate, Cu, Pb, Zn, Hg, Cd, Se, Te and perhaps U were being mobilized from the ore and that these were therefore all good "candidate'' pathfinders. Less probable candidates were Mo, Ge, As, Na and chloride. A second orientation study was then undertaken, using normal groundwaters from boreholes and springs on surface. Sampling was concentrated around the Tsumeb and Kombat mines as targets and waters were also obtained from background areas where dolomites were exposed. The chemical data were plotted on maps by computer and were examined with the aid of simple statistical calculations such as the cumulative frequency distribution. Although anthropogenic effects were apparent at both mines they were not severe and it was possible to be more confident about the prospective roles of the various chemical species in hydrogeochemical exploration for ores in the Otavi dolomites. These prospective roles may be summarized as follows: undetectable or of virtually no interest: pH, temperature, phosphate, K, Ti, Fe, li, Rb, Cs, V, Cr, Mo, Ag, Au, Cd, Hg, Tl, Ge, As, Sb, Bi, Se and Te; useful as iridicators of regional hydrogeochemical features not directly related to mineralization: Si, F⁻, Sr and Al; weak regional pathfinders: Ni and Co; probably good regional pathfinders: sulphate, Cu, Pb and Zn. Bicarbonate, Cl⁻, Na, Ca and Mg are not pathfinders but it is useful to have these data when considering the nature and significance of the samples and the abundances in them of the trace elements. Despite the identification of a suite of pathfinders it was not feasible to establish orientation criteria such as contrast ratios. An attempt was made to apply the findings of this orientation survey in an area to the northeast of Tsumeb, where dolomites are buried under thick sand and calcrete. An area of five thousand square kilometres was selected and all usable sources of groundwater within it were sampled. The following data were collected: total dissolved solids, pH, Ca, Mg, Na, bicarbonated chloride, sulphate, Cu, Pb and Zn. Hydrological data suggested that the regional movement of groundwater was from the exposed dolomites into the pediplain. The hydrogeochemical data showed that during this migration the major element composition of the groundwater changed ("metamorphosed") radically. Because of this metamorphism, very severe difficulties stood in the way of applying in the sandy pediplain what had been learned in the areas of well-exposed dolomite. An attempt was therefore made to provide tighter control between the lithology of the geological profile and the hydrogeochemistry of the associated formational waters in the pediplain. This work consisted of (a) a sampling program to try to ''fingerprint" specific formational waters. This proved to be impossible. (b) drilling four diamond drill holes near selected anomalies and studying the cores in detail. These revealed that the Kalahari beds were very thick (46 to >103m). In all cases the base of the overburden was far below the present water table and in some cases the overburden was underlain by unmineralized rocks other than dolomite. These results indicated that the hydrogeochemical anomalies were probably spurious and it was concluded that hydrogeochemical exploration in this kind of Kalahari terrane was not practicable.
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    An investigation into the determination of some volatile elements in silicate rocks employing d.c. arc emission spectroscopy in artificial atmospheres
    (1981) Baumgartner, Friedrich Carl; Erlank, A J
    The determination of 14 trace elements, namely As, Ag, Bi, Cd, Cu, Ga, Ge, Hg, In, Pb, Sb, Sn, Tl and Zn, in silicate rocks using d.c. arc optical emission spectrography (O.E.S.) and X-ray fluorescence spectroscopy (X.R,F.) was investigated. X.R.F, was shown to be capable of determining Cu, Ga, Pb and Zn in normal silicate rocks and Sn, As and Ge in samples enriched in these latter three elements. Improvement of the sensitivity of the trace elements selected employing d.c. arc excitation in artificial atmospheres was examined in detail. A Margoshes and Scribner (M & S) design gas jet was constructed, and proved to have numerous advantages over those gas jets which incorporate a glass canopy. Excitation in argon, argon-oxygen and nitrogen resulted in many advantages. The most prominent were, remarkable enhancement of the element Zn, and selective distillation of the volatile elements when the d.c. arc was surrounded by argon. The drastic reduction 1.n electrode temperature associated with excitation in argon resulted in an unacceptable decrease in the volatilization rates of the more abundant volatile elements. Several successful methods of overcoming these reduced volatilization rates were found. Increased amperage coupled with a special electrode design was one while the use of a small carrier electrode was another. It was also found that the carrier design electrode was most suitable for use with argon and nitrogen atmospheres as its use promoted selective distillation of the volatile elements. The lack of improvement in volatilization characteristics through the use of additives was attributed to the dominating influence of argon on electrode temperature. The principal advantage of excitation in argonoxygen was the suppression of CN emission essential for ultimate sensitivity of the element Tl. While excitation in nitrogen improved the volatilization characteristics of the more abundant elements, severe CN emission and increased spectral background limited the use of nitrogen to those elements with spectral lines not affected by CN emission.
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    An investigation of the combined use of cation exchange enrichment and spectrochemical analysis for the determination of trace constituents in common silicate rocks and chondrites
    (1960) Edge, Robert Arthur; Ahrens, L H
    The combined use of cation exchange enrichment and spectrochemical analysis has been investigated for determining trace constituents (particularly caesium and the rare earths) in common igneous rocks and chondritos. Cation exchange chromatography with hydrochloric acid elution was employed to resolve the complex mixtures obtained from rocks and meteorites into a number of fractions in which the concentration of various trace constituents were above their spectrochemical detection limits; the trace constituents are not required in a highly concentrated form. These elements may then be determined spectrochemically. Before developing suitable column procedures for the enrichment of trace constituents, the sequence with which both major and trace constituents of common igneous rooks and chondrites moved through cation exchange columns on elution with various concentrations of HCl were established. Perchloric acid was also investigated as an eluant. The spectrograph was used to monitor the effluent fractions obtained from the cation exchange columns. Suitable column conditions were then developed for concentrating several trace elements for spectrochemical analysis.