Cooperite and braggite from the Bushveld Complex: implications for the miscibility gap and identification

Analyses of the Pt-Pd-Ni sulphides cooperite, braggite, and vysotskite reported from worldwide occurrences seem to imply a continuum of compositions between vysotskite and cooperite, with no obvious miscibility gap. This is contrary to the experimentally confirmed miscibility gap between cooperite and braggite, and the established compositional gap between co-existing cooperite and braggite from the Merensky Reef. Although the only unambiguous way of distinguishing between cooperite and braggite is to obtain structural information through X-ray diffraction or equivalent techniques, most identification of Pt-Pd-Ni sulphides is based on microanalytical techniques due to the small grain size of most platinum-group minerals. Ni contents also have to be considered because a classification based on the Pt/Pd ratio alone can be very misleading. Naming of Pt-Pd-Ni sulphide compositions with high Pt contents based on qualitative or semi-quantitative analyses should be avoided. Natural Pt-Pd-Ni sulphides which project into the compositional gap (established by experimental work) cannot be named without supporting structural information. Compositions of grains, which plot inside the gap, are considered to be metastable and to result from the loss of Pd through interaction with hydrothermal fluids.     

Genetic sequence stratigraphy of cool water slope carbonates (Pleistocene Eucla Shelf, southern Australia)

The south Australian Eucla Shelf belongs to the world's largest cool-water carbonate sedimentary system. During the Pleistocene, it exported large amounts of sediment to the shelf edge and upper slope resulting in an expanded sedimentary wedge. Wedge-internal clinoforming seismic reflectors suggest a stacking of the deposits into genetic sequences. High-resolution stable oxygen and carbon isotope, point counting, grain size, and carbonate mineralogical XRD analyses were carried out to characterize these genetic sequences along a dip-parallel transect of three ODP Leg 182 drill holes located between the shelf edge and upper slope. Oxygen and carbon isotope fluctuations show that the genetic sequences formed as a response to sea level fluctuations. Within the genetic sequences, facies differentiation and sediment volume partitioning occur along the transect. Lowstand deposits are fine grained and contain more sponge spicules and micrite. Highstand deposits are coarse grained with tunicate spicules, brown bioclasts, as well as bryozoan and corallinacean debris. Boundaries separating highstand and lowstand deposits are triggered by sea level fall, and are expressed as abrupt grain size changes or as turning points in grain-size trends. Analyzed components vary in abundance along the transect. Genetic sequences show dip-parallel variations in thickness combined with changing relative proportions of lowstand versus highstand deposits.     

Volcanisme de l'ı̂le aux Pingouins,archipel Crozet,témoin de l'hétérogénéité du manteau fertile au sud de l'océan IndienPenguins Island,Crozet archipelago,volcanic evidence for a heterogeneous mantle in the southern Indian Ocean

Despite its small area (5.6 km²), the Penguins Island brings magmatic information concerning mantle geochemical heterogeneities in southwestern Indian Ocean. The volcanism that built the island was firstly associated with marine deposits, and secondly with aerial, giving then abundant volcanic breccias and lava flows. The rocks are weakly differentiated and result of magmatic fractionation from picritic to tephritic types. KAr ages are near 1.1 Ma. The magmatic source may be related to a HIMU reservoir or to EMI ± EMII ones, depending on the geochemical evidences that are taken into account. However, comparisons with the Marion Island, on the same oceanic plateau and far to the west, as well as with Kerguelen Islands, far to the east, suggest a very heterogeneous mantle source. To cite this article: A. Giret et al., C. R. Geoscience 334 (2002) 481–488.     

Cross-section through the frontal Japan Trench subduction zone: Geochemical evidence for fluid flow and fluid–rock interaction from DSDP and ODP pore waters and sediments

Abstract Fluids and sediments from Deep Sea Drilling Project/Ocean Drilling Program Legs (56, 57, 87 and 186) along a transect extending from the subducting plate, across the midslope and upper slope of the Japan Trench forearc were analyzed for B and B isotopes in order to assess their composition and fluid–sediment interaction. At the reference Site 436 on the subducting plate, changes in B contents and B isotopes are controlled by the lithology and diagenesis only. The midslope Sites 440 and 584 showed stronger variations in the B geochemistry, which can be related to diagenesis and tectonic dewatering along faults. The strongest changes in the B geochemistry were observed on the upper slope Sites 1150 and 1151, where profound down‐hole freshening (chlorinities as low as ～310 mmol) coincides with a B enrichment (up to 9.3 × seawater concentration). The B isotope pore fluid profile of Site 1150 displayed a bimodal variation with depth, first increasing to values more positive than seawater, then shifting to lower signatures typical for deep‐seated fluids, whereas Site 1151 showed a constant B decrease with depth. Sites 1150 and 1151 sediments showed B increases with depth to values as high as ～164 p.p.m. and isotopic compositions ranging from ～+4 to ?9‰. A linear decrease in B_solid/B_fluid ratio, suggests that B geochemistry of the upper slope sites is controlled by fluid–rock interaction and deep‐seated fluid flow, whereas constant B_solid/B_fluid ratios were observed at the reference site on the incoming plate. This fluid overprint is probably caused by normal faults in the sediment cover which might be interconnected to deep thrusts in the underlying Cretaceous accreted wedge. This suggests that the erosive Japan Trench margin is characterized by back‐flux of deep‐seated, B‐enriched fluids into the ocean, which is facilitated by extensional normal faulting as a result of tectonic erosion and subsidence.     

Bank-derived carbonate sediment transport and dissolution in the Hawaiian Archipelago

This investigation used two approaches to examine the flux of bank-derived carbonate particles and determine the potential influence of benthic carbonate particle dissolution on the carbon chemistry of the waters around the Hawaiian Archipelago. First, the particle flux near several representative carbonate banks in the Hawaiian Archipelago was measured and compared with the flux at a distal site (ALOHA) approximately 100 km north of Oahu, Hawaii. The results of four sediment trap deployments on three carbonate banks in the Hawaiian Archipelago demonstrate that the flux of bank-derived carbonate particles are consistently one to two orders of magnitude higher than the fluxes at the distal station. Furthermore, the mineralogy of the carbonate flux near the banks, which includes very soluble bank-derived aragonite and magnesian calcite particles, is distinctly different from that of the distal fluxes. Second, the chemistry of the waters at each bank station along the archipelago was characterized and compared with the chemistry of the distal waters to determine if differences in the particle flux were reflected in the carbon chemistry. Higher alkalinity and carbonate ion concentrations were observed around all of the banks studied. The saturation state of these waters suggests that the dissolution of some magnesian calcite and aragonite phases could explain the higher alkalinity values. Calculations suggest that the dissolution of benthically-derived aragonite and magnesian calcite may be an important component of the North Pacific alkalinity budget and a potential sink for anthropogenic CO₂.     

Analysis of undisturbed layers of a waste deposit landfill – Insights into the transformation and transport of organic contaminants

Comprehensive GC/MS analysis was applied to both the mobile liquid phase (seepage water) and the immobile solid matter of discrete layers derived from a waste deposit landfill. The vertical distribution of organic compounds supports information on the transport, transfer and transformation processes with depth and, consequently, with time.Numerous low molecular weight organic contaminants of natural and xenobiotic origin were identified and partially quantified. Several were selected to act as molecular indicators for different processes. Interpretation of their occurrence and concentration profiles (considering possible waste sources) and their molecular properties allowed us to (i) differentiate immobile and mobile fractions, (ii) reveal restrictions in the vertical transport by transfer processes between particulate and water phase, (iii) identify dynamic accumulations of individual contaminants and (iv) estimate approximate residence times. In addition, intensive degradation processes were pointed out for the natural fraction of the organic matter by way of determination of specific transformation products. Besides the transformation of natural components, transformation of numerous xenobiotics was recognised. In particular, with respect to an important group of contaminants, the phthalate-based plasticisers, a detailed view of (i) the influence of transfer and transport phenomena on transformation processes as well as (ii) the consecutive appearance of different degradation steps in both seepage water and solid waste was pointed out. The information provides a valuable base for the prediction of the long term behaviour of organic contaminants in waste deposit landfills.     

Predicting selenite adsorption by soils using soil chemical parameters in the constant capacitance model

The constant capacitance model, a chemical surface complexation model, was applied to selenite, Se(IV), adsorption on 36 soils selected for variation in soil chemical properties. The constant capacitance model was able to fit Se(IV) adsorption by optimizing one monodentate Se(IV) surface complexation constant and the surface protonation constant. A general regression model was developed for predicting these surface complexation constants for Se(IV) from easily measured soil chemical characteristics. These chemical properties were inorganic carbon content, organic carbon content, iron oxide content, aluminum oxide content, and surface area. The prediction equations were used to obtain values for the surface complexation constants for four additional soils, thereby providing a completely independent evaluation of the ability of the constant capacitance model to describe Se(IV) adsorption. The model’s ability to predict Se(IV) adsorption was quantitative on one soil and semi-quantitative on three soils. Incorporation of these prediction equations into chemical speciation-transport models will allow simulation of soil solution Se(IV) concentrations under diverse non-calcareous agricultural and environmental conditions without the requirement of soil specific adsorption data and subsequent parameter optimization.     

Cryptotephras in the Lateglacial ICDP Dead Sea sediment record and their implications for chronology

Due to a lack of visible tephras in the Dead Sea record, this unique palaeoenvironmental archive is largely unconnected to the well-established Mediterranean tephrostratigraphy. Here we present first results of the ongoing search for cryptotephras in the International Continental Drilling Program (ICDP) sediment core from the deep Dead Sea basin. This study focusses on the Lateglacial (~15–11.4 cal. ka BP), when Lake Lisan – the precursor of the Dead Sea – shrank from its glacial highstand to the Holocene low levels. We developed a glass shard separation protocol and counting procedure that is adapted to the extreme salinity and sediment recycling of the Dead Sea. Cryptotephra is abundant in the Dead Sea record (up to ~100 shards cm^-3), but often glasses are physically and/or chemically altered. Six glass samples from five tephra horizons reveal a heterogeneous geochemical composition, with mainly rhyolitic and some trachytic glasses potentially sourced from Italian, Aegean and Anatolian volcanoes. Most shards likely originate from the eastern Anatolian volcanic province and can be correlated using major element analyses with tephra deposits from swarm eruptions of the Süphan Volcano ~13 ka BP and with ashes from Nemrut Volcano, presumably the Lake Van V-16 volcanic layer at ~13.8 ka BP. In addition to glasses that match the TM-10-1 from Lago Grande di Monticchio (15 820±790 cal. a BP) tentatively correlated with the St. Angelo Tuff of Ischia, we further identified a cryptotephra with glass analyses which are chemically identical with those of the PhT1 tephra in the Philippon peat record (13.9–10.5 ka BP), and also a compositional match for the glass analyses of the Santorini Cape Riva Tephra (Y-2 marine tephra, 22 024±642 cal. a BP). These first results demonstrate the great potential of cryptotephrochronology in the Dead Sea record for improving its chronology and connecting the Levantine region to the Mediterranean tephra framework.     

Homogenization of the transport behavior of nonlinearly adsorbing pollutants in physically and chemically heterogeneous aquifers

This paper addresses the question of how spatial variability in the hydraulic and chemical properties of groundwater systems affects the transport and sorption behavior of pollutants at the field scale. In this paper, we limit our investigations on pollutants that adsorb according to an equilibrium controlled nonlinear Freundlich sorption isotherm. The new contribution of this paper is take into account not only spatially variable Freundlich distribution coefficients _KS$K_S$ but spatially variable Freundlich nonlinearity parameters p as well. Using a homogenization theory approach, we shortly review the impact of spatially variable hydraulic properties on the transport and extend the theory to spatially variable chemical properties. We show that spatially variable Freundlich exponents cause a very different field scale transport and sorption behavior than spatial variations in the distribution coefficients only since in the first case field scale Freundlich parameters and field scale dispersion coefficients become concentration dependent. In particular, field scale retardation is much larger than small-scale retardation.