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     

Petrology of mafic lavas within the Onega plateau, central Karelia: evidence for 2.0 Ga plume-related continental crustal growth in the Baltic Shield

The Onega plateau constitutes part of a vast continental flood basalt province in the SE Baltic Shield. It consists of Jatulian-Ludikovian submarine volcanic, volcaniclastic and sedimentary sequences attaining in places 4.5?km in thickness. The parental magmas of the lavas contained ～10% MgO and were derived from melts generated in the garnet stability field at depths 80–100?km. The Sm-Nd mineral and Pb-Pb whole-rock isochron ages of 1975?±?24 and 1980?±?57 Ma for the upper part of the plateau and a SHRIMP U-Pb zircon age of 1976?±?9 Ma for its lower part imply the formation of the entire sequence within a short time span. These ages coincide with those of picrites in the Pechenga-Imandra belt (the Kola Peninsula) and komatiites and basalts in the Karasjok-Kittilä belt (Norway and Finnmark). Together with lithostratigraphic, chemical and isotope evidence, these ages suggest the derivation of the three provinces from a single large (～2000?km in diameter) mantle plume. These plume-generated magmas covered ～600,000?km² of the Baltic Shield and represent a major contribution of juvenile material to the existing continental crust at 2.0 Ga. The uppermost Onega plateau lavas have high (Nb/Th)_N?=?1.4–2.4, (Nb/La)_N= 1.1–1.3, positive ?Nd(T) of +3.2 and unradiogenic Pb-isotope composition (μ₁?= 8.57), comparable with those of modern oceanic plume-derived magmas (oceanic flood basalt and ocean island basalt). These parameters are regarded as source characteristics. The lower sequences have (Nb/Th)_N= 0.58–1.2, (Nb/La)_N= 0.52–0.88 and ?Nd(T) =?2.6. They have experienced mixing with 10–30% of continental crust and resemble contaminated lavas from other continental flood basalt provinces. The estimated Nb/U ratios of 53?±?4 in the uncontaminated rocks are similar to those found in the modern mantle (～47) suggesting that by 2.0 Ga a volume of continental crust similar to the present-day value already existed.     

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.     

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.     

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.     

Experiments on canopy/soil leaching effects of air pollutants in model ecosystems with forest trees

In 1982 an experiment was started at the University of Hohenheim to investigate the long term effects of O₃, SO₂ and simulated acid rain in realistic concentrations, single and in combination, on mineral cycling, biochemistry, physiology and anatomy of spruce-, fir- and beech seedlings in modelecosystems. During the 5 year duration of this experiment definite effects on mineral cycling were observed. Most noticeable are throughfall enrichment with sulfate through dry deposition of SO₂, connected with elevated leaching of calcium, magnesium, manganese, zink and ammonia from needles, in total leading to an enhanced acid input to the soil. The consequence of this was that after 15 months the water percolating the soils in the lysimeters of these treatments was acidified, with elevated flowrates of sulfate, manganese, calcium and magnesium. Effects on mineral cycling are discussed in connection with observations of other groups working in the modelecosystems.     

Middle to Late Pleistocene environments based on stable organic carbon and nitrogen isotopes of loess-palaeosol sequences from the Carpathian Basin

Stable organic carbon and nitrogen isotopes can be used to interpret past vegetation patterns and ecosystem qualities. Here we present these proxies for two loess-palaeosol sequences from the southern Carpathian Basin to reconstruct the palaeoenvironment during the past 350 ka and establish regional commonalities and differences. Before now, isotopic studies on loess sequences from this region were only conducted on deposits from the last glacial cycle. We conducted methodological tests involving the complete decalcification of the samples prior to stable isotope analyses. Two decalcification methods (fumigation method and wet chemical acidification), different treatment times, and the reproducibility of carbon isotope analyses were tested. Obtained results indicate that the choice of the decalcification method is important for organic carbon stable isotope analyses of loess-palaeosol sequences because ratios vary by more than 10‰ between the wet chemical and fumigation methods, due to incomplete carbonate removal by the latter. Therefore, we suggest avoiding the fumigation method for studies on loess-palaeosol sequences. In addition, our data show that samples with TOC content <0.2% bear increased potential for misinterpretation of their carbon isotope ratios. For our sites, C₃-vegetation is predominant and no palaeoenvironmental shifts leading to a change of the dominant photosynthesis pathway can be detected during the Middle to Late Pleistocene. Furthermore, the importance of further stable nitrogen isotope studies is highlighted, since this proxy seems to reflect past precipitation patterns and reveals favourable conditions in the southern Carpathian Basin, especially during interstadials.     

Oxygen isotope partitioning during oxidation of pyrite by H2O2 and its dependence on temperature

A detailed experimental study was conducted to investigate mechanisms of pyrite oxidation by determining product yields and oxygen isotopic fractionation during reactions between powdered pyrite (FeS₂) with aqueous hydrogen peroxide (H₂O₂). Sealed silica-tube experiments utilized aliquots of pyrite that were reacted with 0.2 M H₂O₂ for 7 to 14 days at 4 to 150 °C. No volatile sulfur species were detected in any experiment. The only gaseous product recovered was elemental oxygen inferred to result from decomposition of H₂O₂. Aqueous sulfate (S_aq) was the only sulfur product recovered from solution. Solid hydrated ferric iron sulfates (i.e., water-soluble sulfate fraction, S_ws) were recovered from all experiments. Ferric oxide (hematite) was detected only in high temperature experiments.Reactants were selected with large differences in initial δ¹⁸O values. The oxygen isotopic compositions of oxygen-bearing reactants and products were analyzed for each experiment. Subsequent isotopic mass-balances were used to identify sources of oxygen for reaction products and to implicate specific chemical reaction mechanisms. δ¹⁸O of water did not show detectable change during any experiment. δ¹⁸O of sulfate was similar for S_aq and S_ws and indicated that both H₂O and H₂O₂ were sources of oxygen in sulfate. Low-temperature experiments suggest that H₂O-derived oxygen was incorporated into sulfate via Fe³⁺ oxidation, whereas H₂O₂-derived oxygen was incorporated into sulfate via oxidation by hydroxyl radicals (HO). These two competing mechanisms for oxygen incorporation into sulfate express comparable influences at 25 °C. With increasing reaction temperatures from 4 to 100 °C, it appears that accelerated thermal decomposition and diminished residence time of H₂O₂ limit the oxygen transfer from H₂O₂ into sulfate and enhance the relative importance of H₂O-derived oxygen for incorporation into sulfate. Notably, at temperatures between 100 and 150 °C there is a reversal in the lower temperature trend resulting in dominance of H₂O₂-derived oxygen over H₂O-derived oxygen. At such high temperatures, complete thermal decomposition of H₂O₂ to water and molecular oxygen (O₂) occurs within minutes in mineral-blank experiments and suggests little possibility for direct oxidation of pyrite by H₂O₂ above 100 °C. We hypothesize that a Fe-O₂ mechanism is responsible for oxygenating pyrite to sulfate using O₂ from the preceding thermal decomposition of H₂O₂.