Trace elements in the Merensky Reef and adjacent norites Bushveld Complex South Africa

Trace elements were analysed in rocks and minerals from three sections across the Merensky Reef in the Rustenburg Platinum Mine in the Bushveld Complex of South Africa. Whole rocks and separated minerals were analysed by inductively coupled plasma-mass-spectrometer (ICP-MS) and in situ analyses were carried out by ion microprobe and by laser-source ICP-MS. Merensky Reef pyroxenites contain extremely high concentrations of a wide range of trace elements. These include elements incompatible with normal silicate minerals as well as siderophile and chalcophile elements. For major elements and compatible trace elements, the measured concentrations in cumulus phases and the bulk rock compositions are similar. For highly incompatible elements, however, concentrations in bulk rocks are far higher than those measured in the cumulus phases. In situ analyses of plagioclase have far lower concentrations of Th, Zr and rare earth elements than ICP-MS analyses of bulk separates of plagioclase, a difference that is attributed to the presence of trace-element-rich accessory phases in the bulk mineral separates. We used these data to calculate the trace-element composition of the magmas parental to the Merensky Unit and adjacent norites. We argue that there is no reason to assume that the amount of trapped liquid in the Merensky orthopyroxenite was far greater than in the norites and we found that the pyroxenite formed from a liquid with higher concentrations of incompatible trace elements than the liquid that formed the norites. We propose that the Bushveld Complex was fed by magma from a deeper magma chamber that had been progressively assimilating its crustal wall rocks. The magma that gave rise to the Merensky Unit was the more contaminated and unusually rich in incompatible trace elements, and when it entered the main Bushveld chamber it precipitated the unusual phases that characterize the Merensky Reef. The hybrid magma segregated sulphides or platinum-group-element-rich phases during the course of the contamination in the lower chamber. These phases accumulated following irruption into the main Bushveld chamber to form the Merensky ore deposits.     

Evolution of organic matter degradation in Cretaceous black shales inferred from authigenic barite: A reaction-transport model

A reaction-transport model was used to infer the long-term evolution of anaerobic organic matter degradation in Cretaceous black shales from the distribution of authigenic barite in sediments drilled at Demerara Rise (ODP Leg 207, Site 1258). In these sediments, sulfate-reduction and methanogenesis are the major pathways of organic matter decomposition and the depth-distribution of authigenic barite serves as an indicator for the temporal evolution of the sulfate-methane transition zone (SMTZ), the strength of the biogenic methane flux and, ultimately, the organic matter reactivity in the black shales over geological timescales. Organic matter degradation is described according to the reactive continuum model approach and parameters values are determined by inverse modeling, based on present-day porewater and authigenic barite profiles. Fully transient simulations were performed over a period of 100 Myrs and indicate that important features of the biogeochemical dynamics are associated to changes in the boundary forcing. Hiatuses in sediment accumulation rate result in quasi-steady-state conditions and lead to distinct accumulations of authigenic barites in the SMTZ. The inversely determined parameters reveal that the reactivity of the organic matter was already low (apparent first order rate constant ) at the time of its deposition in the Cretaceous. The geochemical characteristics of sediments drilled at Demerara Rise, as well as the presence of specific biomarkers, suggest that this low reactivity is most likely due to the euxinic palaeo-conditions which favored the sulfurization of the organic matter. Simulation results predict average initial organic carbon contents between 8.1 and 9.5 wt%, implying a high preservation efficiency of the organic matter (between 79% and 89%). Calculated mass accumulation rates (between 0.43 and 0.5 ) compare well with estimations for the western basin of the Cretaceous southern North Atlantic. Simulation results thus indicate that the enhanced preservation of organic matter under euxinic conditions may have been the main cause for the formation of organic-rich Cretaceous black shales at Demerara Rise.     

Metamorphic degassing of carbonates in the contact aureole of the Aguablanca Cu–Ni–PGE deposit,Spain

Analysis of magmatic and sedimentary rocks of several large igneous provinces has demonstrated that the release of gas during plutonic-metamorphic processes may be linked to global climate change and mass extinctions. Aguablanca, one of the largest Cu–Ni–PGE deposits in Europe, formed during the Variscan orogeny when a mafic magma intruded limestones and shales, creating a contact aureole composed of marble, skarn and hornfels. Our petrological and geochemical investigation of the aureole provides evidence that a combination of the two processes led to the formation of the ore deposit: The assimilation of terrigenous sediments supplied S to the magma while the assimilation of carbonates changed the oxygen fugacity and decreased the solubility of sulfur in the magma. The metamorphic assemblages in the contact aureole are directly related to heterogeneity of the protolith and particularly to the original proportions of calcite and clay. We modeled carbon dioxide degassing during contact metamorphism and showed that pure limestone is relatively unproductive because of its high reaction temperature. The presence of clay, however, leads to the formation of calc-silicates and significantly enhances CO₂ degassing. Our estimations suggest that degassing of the Aguablanca contact aureole released about 74.8 Mt of CO₂, a relatively low volume that we attribute to the composition of the host rock, mainly a pure limestone. A far larger volume of carbon dioxide was emitted by the contact metamorphism of dolostones in the contact aureole of Panzhihua (part of Emeishan large igneous province, SW China). We propose that the level of emission of carbon dioxide depends strongly on the nature of the protolith and has to be considered when predicting environmental impact during the emplacement of large igneous provinces.     

Conflicting Sm-Nd whole rock and U-Pb zircon ages for Archean lavas from Newton Township, Abitibi Belt, Ontario

Archean komatiitic and tholeiitic lavas from Newton Township, Ontario, have a sufficient range of Sm-Nd ratios to define a well-constrained line on the normal ¹⁴³Nd/¹⁴⁴Nd vs. ¹⁴⁷Sm/¹⁴⁴Nd isochron plot. The data give an isochron age of 2826 ± 64Ma, and an initial ε_Ndof+2.65 ± 0.26. However, U-Pb analysis of zircons from a dacitic volcaniclastic that underlies the komatiite-tholeiite suite give an age of 2697 ± 1.1Ma. There is strong evident that the zircon age is the eruption age, suggesting that the older Sm-Nd age is incorrect and probably results from mixing between isotopically distinct mantle sources. At the time of eruption, the sources had ε_Nd values from about +4.2 to +1.6, indicating that the Archean mantle in this area was markedly heterogeneous and not uniformly depleted.     

Direct determination of the quartz-coesite transition by in situ X-ray measurements

The quartz-coesite transition has been determined over the temperature range 600–1100° C by in Situ X-ray measurements with NaCl as internal pressure standard. An internally heated high-pressure X-ray apparatus (Belt-type) was used which is based on the principle developed by Freud and Sclar (1969). The obtained quartz-coesite equilibrium line may be represented by the equation P=31±1+0.0075 T where P is in kb and T in ° C.     

Ore deposits associated with mafic magmas in the Kaapvaal craton

Mafic and ultramafic magmatism played an important role in the 3.5 Ga long history of the Kaapvaal craton. The oldest (3.5 Ga) greenstone belts contain mafic and ultramafic volcanics that erupted in an oceanic environment, probably in oceanic plateaus. Then followed a series of continental flood basalts, from the ∼3.4 Ga old Commondale and Nondweni sequences, to the 180 Ma Karoo basalts. The history was dominated, however, by the emplacement, 2.1 Ga ago, of the Bushveld complex, an enormous layered ultramafic-mafic-felsic intrusion. Three types of ore deposits might be found in such a sequence: Ni-Cu-Fe sulfides in komatiites of the greenstone belts; “Noril'sk-type” Ni-Cu-PGE deposits in the Karoo and other flood basalts; and deposits of Cr, platinum-group elements (PGE) and V in the Bushveld and other layered intrusions. Only the latter are present. It is tempting to attribute the absence of komatiite-hosted deposits to the specific character of the ultramafic rocks in Kaapvaal greenstone belts, which are older that the 2.7 Ga komatiites that host deposits in Australia, Canada and Zimbabwe, and are of the less-common “Al-depleted” type. However, a review of mantle melting processes found no obvious connection between the character of the mantle melts and their capacity to form ore deposits. The lack of this type of deposit may be due to differences in the volcanic environment, or it may be fortuitous (the Barberton and other belts are small and could fit into deposit-free parts of the much larger Australian or Canadian belts). Still more puzzling is the absence of Noril'sk-type deposits. The Karoo and older flood basalt sequences appear to contain all the important elements of the volcanic sequences that host the Siberian deposits. It is now recognised that these deposits formed through the segregation of sulfide from magma flowing rapidly through conduits en route from deeper magma chambers to the surface. An exploration approach aimed at understanding the fluid dynamics of such systems seems warranted. Although the Bushveld intrusion has been studied for decades and its deposits are taken as type examples of magmatic mineralisation, the origin of its PGE deposits remains unclear. Opinion is divided on the relative importance of sulfide segregation from magma filling a large chamber at the time of emplacement, and the scavanging of PGE from fluids circulating through cumulates at a late magmatic stage. Answers to these questions may come from studies designed to gain a better understanding of the mechanisms through which the magma chamber filled and solidified. Received: 15 September 1996 / Accepted: 7 January 1997     

Enthalpy of diaplectic labradorite glass

Enthalpies of solution in molten 2PbO·B₂O₃ at ～988 K have been measured for diaplectic labradorite glass from the Manicouagan impact crater and a fused glass formed from the same material. The enthalpies of solution of the diaplectic and fusion-formed glasses are 4,347 and 2,023 cal mol^?1, respectively. The more endothermic enthalpy of solution of the diaplectic glass indicates a greater relative energetic stability of about 2.3 kcal mol^?1. The data are consistent with Diemann and Arndt's (1984) structural model that suggests the diaplectic glass is more ordered than fusion-formed glass and with the presence of crystallites. Comparison of data to enthalpies of solution of crystalline labradorite (Carpenter et al. 1985) indicates a maximum percentage of crystalline relics of ～15–18%, also consistent with Diemann and Arndt's (1984) estimate of <17%. Thus the diaplectic glass is intermediate in thermochemical properties between normal glass and crystal (much closer to glass) and does not represent any state more unstable than normal fusion-formed glass.     

Cyclicities in Triassic platform carbonates: synchronizing radio-isotopic and orbital clocks

ABSTRACT Sedimentary cycles recorded in young sediments are often attributed to fluctuations of the Earth's climate on a 10⁴−10⁶-year scale which in turn is governed by periodic variations in solar insolation linked to orbital (Milankovitch) parameters. A spectacular example of cyclic stratal patterns in ancient deposits is the Middle Triassic Latemar carbonate platform (W Dolomites, N Italy). Based on spectral analyses from previous studies, a superimposition of precession (∼20 ka) and eccentricity (∼100 ka) controlled sea-level fluctuations has been suggested to account for the stacking hierarchy at Latemar, with ∼20 ka being assigned to each highest-order depositional cycle. Zircon U–Pb isotopic ages from volcanic-ash layers within the cyclic succession, corroborated by biostratigraphic constraints, suggest that the average time interval for every individual cycle is significantly smaller than the shortest Milankovitch period and therefore challenge previously published interpretations relating distinct spectral peaks to the above mentioned hierarchy. However, our new spectral data indicate that cyclicities resembling Milankovitch characteristics might exist, but on an entirely different scale. Our findings show that frequency spectra should only be interpreted in combination with robust age control. They also encourage the search for complementary mechanisms controlling carbonate deposition.     

Diagenetic mineralization in Pennsylvanian coals from Indiana, USA: C/C and O/O implications for cleat origin and coalbed methane generation

Cleats and fractures in southwestern Indiana coal seams are often filled with authigenic kaolinite and/or calcite. Carbon- and oxygen-stable isotope ratios of kaolinite, calcite, and coalbed CO₂ were evaluated in combination with measured values and published estimates of δ¹⁸O of coalbed paleowaters that had been present at the time of mineralization. δ¹⁸O_mineral and δ¹⁸O_water values jointly constrain the paleotemperature of mineralization. The isotopic evidence and the thermal and tectonic history of this part of the Illinois Basin led to the conclusion that maximum burial and heat-sterilization of coal seams approximately 272 Ma ago was followed by advective heat redistribution and concurrent precipitation of kaolinite in cleats at a burial depth of < 1600 m at  78 ± 5 °C. Post-Paleozoic uplift, the development of a second generation of cleats, and subsequent precipitation of calcite occurred at shallower burial depth between  500 to  1300 m at a lower temperature of 43 ± 6 °C. The available paleowater in coalbeds was likely ocean water and/or tropical meteoric water with a δ¹⁸O_water  − 1.25‰ versus VSMOW. Inoculation of coalbeds with methanogenic CO₂-reducing microbes occurred at an even later time, because modern microbially influenced ¹³C-enriched coalbed CO₂ (i.e., the isotopically fractionated residue of microbial CO₂ reduction) is out of isotopic equilibrium with ¹³C-depleted calcite in cleats.