Geochemical and electron paramagnetic characteristics of quartz from a multi-stage vein environment, Cowarra gold deposit, New South Wales

The characterisation of quartz using trace element geochemistry and electron paramagnetic resonance measurements has been tested for different generations of quartz veining in the multi-stage hydrothermal vein system at Cowarra. Quartz closely associated with gold mineralisation can be distinguished from earlier and later quartz generations in the mineralised environment, and both types can be distinguished from regional, barren quartz veins. These separate stages of quartz veins are also recognised from their fluid inclusion characteristics. Geochemical differences in the quartz partly reflect the presence of minor mineral inclusions, particularly sulfides and arsenopyrite.The study highlights the importance of understanding the paragenetic sequence of quartz vein development in a mineralised environment and the need for careful, thorough sampling before attempting geochemical and EPR characterisation of quartz as an exploration technique.     

Spatial and isotopic analysis of watershed soil loss and reservoir sediment accumulation rates in Lake Anna, Virginia, USA

Soil erosion and associated sedimentation are a threat to the sustainable use of surface water resources through the loss of volume storage capacity and conveyance of pollutants to receiving water bodies. The RUSLE2 empirical model and isotopic sediment core analyses were used to evaluate watershed erosion and reservoir sediment accumulation rates for Lake Anna, in Central Virginia. A sediment flux rate of 66,000 Mg/year was estimated from the upper basin and land use was determined to be the primary factor contributing to soil erosion. Barren lands and agricultural activities were estimated to contribute the most sediment (>20 Mg/ha/year), whereas forested and herbaceous landscapes were less likely to erode (<0.3 Mg/ha/year). Eleven separate ²¹⁰Pb-based estimates of sediment accumulation were used to construct reservoir-scale sedimentation rates. Sedimentation rates in the upper reaches of the reservoir were variable, ranging from 2.3 to 100 Mg/ha/year, with a median rate of 8.4 Mg/ha/year. Historical sedimentation showed an increase in annual accumulation from 1972 to present. Based on these data the reservoir has experienced a 2% loss of volume storage capacity since impoundment in 1972. Results from this study indicate that Lake Anna is not currently experiencing excessive sedimentation and erosion problems. However, the predominance of highly erosive soils (soil erodibility factor >0.30) within the watershed makes this system highly vulnerable to future anthropogenic stressors.     

A Truncated Pareto Model to Estimate the Under Recovery of Large Diamonds

The metallurgical recovery processes in diamond mining may, under certain circumstances, cause an under-recovery of large diamonds. In order to predict high quantiles or tail probabilities we use a Bayesian approach to fit a truncated Generalized Pareto Type distribution to the tail of the data consisting of the weights of individual diamonds. Based on the estimated tail probability, the expected number of diamonds larger than a specified weight can be estimated. The difference between the expected and observed frequencies of diamond weights above an upper threshold provides an estimate of the number of diamonds lost during the recovery process.     

Morphosedimentary analysis of the Limoeiro Stream (center-northern Minas Gerais State,Brazil): clues to the eastward tilting of southern Espinhaco range sites

The morphosedimentary evolution of a sector of the southern Espinhaco range (northern Minas Gerais State, Brazil) and its regional neotectonic setting are presented herein. The studied site is a stream at base level flowing along the western border of the range. Its identification was accomplished by using remote sensing techniques including the analysis of 3D slope models generated with shuttle radar topography mission images. The main geomorphological features of the identified site were surveyed in a 1:500 scale. In addition, seven stratigraphic logs are described. A regional geologic compilation and facies diagrams were used as a basis for the integration of the geomorphological and stratigraphic data, which produced some conclusions about the recent tectonic reactivations at the eastern border of Sao Francisco Craton. The results point to a local eastward tilting of the Espinhaco range. This fact is in accordance with previous findings in neighboring areas and results in the asymmetric evolution of the fluvial valley, as well as the regional relief.     

Late Quaternary Bison diminution on the Great Plains of North America: evaluating the role of human hunting versus climate change

Body size changes of Bison and mortality age structure data document the effects of climate-driven environmental change and human hunting pressure on large mammals in North America. Morphometric and mortality data are drawn from 58 archaeological and 9 paleontological localities dating between 37,000 and 250 calBP. Proxy information on body size is based on measurements recorded on 901 adult calcanei (os calcis) and 1026 humeri. In addition, published mortality profiles from 24 archaeological faunal assemblages spanning the last 14,000 years were used to approximate the age structure of bison populations. These results suggest that dramatic diminution in bison body size occurred in several short bursts, rather than a continuous gradual decline. These periods of rapid size reduction correlate with times of ecological reorganization, when aridity-driven changes in grasslands decreased forage quality and availability. Mortality age data indicate that the decrease in body size occurred in a context where there was no evidence for a progressively severe juvenile bias in bison populations. Overall, it appears that the changes in body size were a reaction to environmental conditions rather than the result of human predation pressure.     

Methane and sulfide fluxes in permanent anoxia: In situ studies at the Dvurechenskii mud volcano (Sorokin Trough, Black Sea)

The Dvurechenskii mud volcano (DMV) is located in permanently anoxic waters at 2060 m depth (Sorokin Trough, Black Sea). The DMV was studied during the RV Meteor expedition M72/2 as an example of an active mud volcano system, to investigate the significance of submarine mud volcanism for the methane and sulfide budget of the anoxic Black Sea hydrosphere. Our studies included benthic fluxes of methane and sulfide, as well as the factors controlling transport, consumption and production of both compounds within the sediment. The pie-shaped mud volcano showed temperature anomalies as well as solute and gas fluxes indicating high fluid flow at its summit north of the geographical center. The anaerobic oxidation of methane (AOM) coupled to sulfate reduction (SR) was repressed in this zone due to the upward flow of sulfate-depleted fluids through recently deposited subsurface muds, apparently limiting microbial methanotrophic activity. Consequently, the emission of dissolved methane into the water column was high, with an estimated rate of 0.46 mol m⁻² d⁻¹. On the wide plateau and edge of the mud volcano surrounding the summit, fluid flow and total methane flux were lower, allowing higher SR and AOM rates correlated with an increase in sulfate penetration into the sediment. Here, between 50% and 70% of the methane flux (0.07-0.1 mol m⁻² d⁻¹) was consumed within the upper 10 cm of the sediment. The overall amount of dissolved methane released from the entire mud volcano structure into the water column was significant with a discharge of 1.3 × 10⁷ mol yr⁻¹. The DMV maintains also high areal rates of methane-fueled sulfide production and emission of on average 0.05 mol m⁻² d⁻¹. This is a difference to mud volcanoes in oxic waters, which emit similar amounts of methane, but not sulfide. However, based on a comparison of this and other mud volcanoes of the Black Sea, we conclude that sulfide and methane emission into the hydrosphere from deep-water mud volcanoes does not significantly contribute to the sulfide and methane inventory of the Black Sea.     

Nanoparticles in natural systems II: The natural oxide fraction at interaction with natural organic matter and phosphate

Information on the particle size and reactive surface area of natural samples and its interaction with natural organic matter (NOM) is essential for the understanding bioavailability, toxicity, and transport of elements in the natural environment. In part I of this series (Hiemstra et al., 2010), a method is presented that allows the determination of the effective reactive surface area (A, m²/g soil) of the oxide particles of natural samples which uses a native probe ion (phosphate) and a model oxide (goethite) as proxy. In soils, the natural oxide particles are generally embedded in a matrix of natural organic matter (NOM) and this will affect the ion binding properties of the oxide fraction. A remarkably high variation in the natural phosphate loading of the oxide surfaces (Γ, μmol/m²) is observed in our soils and the present paper shows that it is due to surface complexation of NOM, acting as a competitor via site competition and electrostatic interaction. The competitive interaction of NOM can be described with the charge distribution (CD) model by defining a ≡NOM surface species. The interfacial charge distribution of this ≡NOM surface species can be rationalized based on calculations done with an evolved surface complexation model, known as the ligand and charge distribution (LCD) model. An adequate choice is the presence of a charge of −1 v.u. at the 1-plane and −0.5 v.u. at the 2-plane of the electrical double layer used (Extended Stern layer model).The effective interfacial NOM adsorption can be quantified by comparing the experimental phosphate concentration, measured under standardized field conditions (e.g. 0.01 M CaCl₂), with a prediction that uses the experimentally derived surface area (A) and the reversibly bound phosphate loading (Γ, μmol/m²) of the sample (part I) as input in the CD model. Ignoring the competitive action of adsorbed NOM leads to a severe under-prediction of the phosphate concentration by a factor ∼10 to 1000. The calculated effective loading of NOM is low at a high phosphate loading (Γ) and vice versa, showing the mutual competition of both constituents. Both constituents in combination usually dominate the surface loading of natural oxide fraction of samples and form the backbone in modeling the fate of other (minor) ions in the natural environment.Empirically, the effective NOM adsorption is found to correlate well to the organic carbon content (OC) of the samples. The effective NOM adsorption can also be linked to DOC. For this, a Non-Ideal Competitive adsorption (NICA) model is used. DOC is found to be a major explaining factor for the interfacial loading of NOM as well as phosphate. The empirical NOM-OC relation or the parameterized NICA model can be used as an alternative for estimating the effective NOM adsorption to be implemented in the CD model for calculation of the surface complexation of field samples. The biogeochemical impact of the NOM-PO₄ interaction is discussed.     

Structure, thermodynamics, and diffusion in CaAl2Si2O8 liquid from first-principles molecular dynamics

We have performed first-principles molecular dynamics simulations of CaAl₂Si₂O₈ (anorthite) liquid at pressures up to 120 GPa and temperatures of 3000, 4000 and 6000 K. At the lowest degrees of compression the liquid is seen to accommodate changes in density through decreasing the abundance of 3- and 4-membered rings, while increases in coordination of network forming cations take effect at somewhat higher degrees of compression. Results are fit to a fundamental thermodynamic relation with 4th order finite strain and 1st order thermal variable expansions. Upon compression by a factor of two, the Grüneisen parameter (γ) is found to increase continuously from 0.35 to 1.10. Weak temperature dependence in γ is thermodynamically consistent with a slight decrease in isochoric heat capacity (C_V), for which values of between 4.4 and 5.2 Nk_B are obtained, depending on the temperature. Pressure and temperature dependence of self-diffusivities is found to be well represented by an Arrhenius relation, except at 3000 K and pressures lower than 5 GPa, where self-diffusivities of Si, Al, and O increase with pressure. Analysis of the lifetimes of individual coordination species reveals that this phenomenon arises due to the disproportionately high stability of 4-fold coordinated Si, and to a lesser extent 4-fold coordinated Al. Our results represent a marked improvement in accuracy and reliability in describing the physics of CaAl₂Si₂O₈ liquid at deep mantle pressures, pointing the way to a general thermodynamic model of melts at extreme pressures and temperatures relevant to planetary-scale magma oceans and deep mantle partial melting.     

Decoupling of As and Fe release to Bangladesh groundwater under reducing conditions. Part I: Evidence from sediment profiles

This study reexamines the notion that extensive As mobilization in anoxic groundwater of Bangladesh is intimately linked to the dissolution of Fe oxyhydroxides on the basis of analyses performed on a suite of freshly collected samples of aquifer material. Detailed sediment profiles extending to 40 to 70 m depth below the surface were obtained at six sites where local groundwater As concentrations were known to span a wide range. The sediment properties that were measured include (1) the proportion of Fe(II) in the Fe fraction leached in hot 1.2 N HCl, (2) diffuse spectral reflectance, and (3) magnetic susceptibility.In parallel with local concentrations of dissolved As ranging from <5 to 600 μg/L, Fe(II)/Fe ratios in shallow (gray) Holocene sands tended to gradually increase with depth from values of 0.3 to 0.5 to up to 0.9. In deeper (orange) aquifers of presumed Pleistocene age that were separated from shallow sands by a clay layer and contained <5 μg/L dissolved As, leachable Fe(II)/Fe ratios averaged ∼0.2. There was no consistent relation between sediment Fe(II)/Fe and dissolved Fe concentrations in groundwater in nearby wells. The reflectance measurements indicate a systematic linear relation (R² of 0.66; n = 151) between the first derivative transform of the reflectance at 520 nm and Fe(II)/Fe. The magnetic susceptibility of the shallow aquifer sands ranged from 200 to 3600 (x 10⁻⁹ m³/kg SI) and was linearly related (R² of 0.75; n = 29) to the concentrations of minerals that could be magnetically separated (0.03 to 0.79% dry weight). No systematic depth trends in magnetic susceptibility were observed within the shallow sands, although the susceptibility of deeper low-As aquifers was low (up to ∼200 × 10⁻⁹ m³/kg SI).This set of observations, complemented by incubation results described in a companion paper by van Geen et al. (this volume), suggests that the release of As is linked to the transformation of predominantly Fe (III) oxyhydroxide coatings on sand particles to Fe(II) or mixed Fe(II/III) solid phases with a flatter reflectance spectrum such as siderite, vivianite, or magnetite, without necessarily resulting in the release of Fe to groundwater. The very low As/Fe ratio of magnetically separated minerals compared to the As/Fe of bulk acid leachate (2 vs. 40 10⁻⁶, respectively) suggests that such a transformation could be accompanied by a significant redistribution of As to a mobilizable phase on the surface of aquifer particles.