Oxidation of arsenopyrite and deposition of gold on the oxidized surfaces: A scanning probe microscopy, tunneling spectroscopy and XPS study

We have used ex situ atomic force microscopy (AFM), scanning tunneling microscopy and spectroscopy (STM/STS) and X-ray photoelectron spectroscopy (XPS) to study the surfaces of natural arsenopyrite samples that were electrochemically polarized in 1 M HCl, or leached in acidic solutions containing ferric iron salts, and then reacted with aqueous gold (III) chloride at ambient temperatures. For arsenopyrite oxidized on a positive-going potential sweep, progressively increasing amounts of surface Fe(III)-O and As-O species, and of S/Fe and S/As ratios in a non-stoichiometric sulfidic layer were found. The products formed in the sweep to a potential of 0.6 V (Ag/AgCl) of the passivity region are shaped in about 100 nm protrusions of two sorts, which are arranged in micrometer-size separate areas, while they are largely mixed at higher, “transpassive” potentials. The quantities of surface alteration substances notably decrease after leaching in ferric chloride and ferric sulfate acidic solutions. Passivation of arsenopyrite was suggested to associate with the disordered, metal-deficient surface layer having moderate excess of sulfur rather than with the products of arsenopyrite oxidation. Exposure of arsenopyrite to 10⁻⁵-10⁻³ M (pH 2) solutions results in the deposition of 8-50 nm gold particles; only a small fraction of the gold is present as Au(I)-S species. The electrochemical oxidation at 0.6 V or ageing of arsenopyrite in air promotes the subsequent gold deposition; in contrast, the amount of Au deposited on arsenopyrite that was treated by leaching in ferric chloride and sulfate solutions was about 10 times smaller than with polished arsenopyrite samples. It has been concluded that reducing agents formed as intermediates of arsenopyrite decomposition facilitate the Au⁰ cementation although other factors related to the surface state of the arsenopyrite play a role as well. A decrease in the tunneling current magnitudes with decreasing the Au⁰ particle size has been revealed using STS. This effect along with the increase by 0.2-0.5 eV in the XPS Au 4f binding energies were tentatively ascribed to retarding the electron transitions by emerging electrostatic charge on gold nanoparticles (Coulomb blockade). Possible mechanisms for the effects, and their potential role in the deposition and hydrometallurgy of “invisible” gold are discussed.     

A multi-proxy lacustrine record of Holocene climate change on northeastern Baffin Island, Arctic Canada

Reconstructions of past environmental changes are critical for understanding the natural variability of Earth's climate system and for providing a context for present and future global change. Radiocarbon-dated lake sediments from Lake CF3, northeastern Baffin Island, Arctic Canada, are used to reconstruct past environmental conditions over the last 11,200 years. Numerous proxies, including chironomid-inferred July air temperatures, diatom-inferred lakewater pH, and sediment organic matter, reveal a pronounced Holocene thermal maximum as much as 5°C warmer than historic summer temperatures from 10,000 to 8500 cal yr B.P. Following rapid cooling 8500 cal yr B.P., Lake CF3 proxies indicate cooling through the late Holocene. At many sites in northeastern Canada, the Holocene thermal maximum occurred later than at Lake CF3; this late onset of Holocene warmth is generally attributed to the impacts of the decaying Laurentide Ice Sheet on early Holocene temperatures in northeastern Canada. However, the lacustrine proxies in Lake CF3 apparently responded to insolation-driven warmth, despite the proximity of Lake CF3 to the Laurentide Ice Sheet and its meltwater. The magnitude and timing of the Holocene thermal maximum at Lake CF3 indicate that temperatures and environmental conditions at this site are highly sensitive to changes in radiative forcing.     

Sound waves in the intracluster medium

We present an analysis of the behaviour of a perturbed radio cocoon. Comparisons with observations of sound waves detected in the Perseus and Virgo clusters suggest the separations of observed ripples correspond to the natural oscillation frequency of the cocoon. An energy injection rate consistent with active galactic nucleus power is required to offset the strong acoustic damping of cocoon oscillations, suggesting the sources are in equilibrium with the intracluster medium (ICM), and the oscillations are effectively undamped. Viscous dissipation of sound waves provides ICM heating that can quench cooling flows on time-scales greatly exceeding the oscillation time-scale. Thermal conductivity is likely to be heavily suppressed.     

POLAR investigation of the Sun—POLARIS

The POLAR Investigation of the Sun (POLARIS) mission uses a combination of a gravity assist and solar sail propulsion to place a spacecraft in a 0.48 AU circular orbit around the Sun with an inclination of 75° with respect to solar equator. This challenging orbit is made possible by the challenging development of solar sail propulsion. This first extended view of the high-latitude regions of the Sun will enable crucial observations not possible from the ecliptic viewpoint or from Solar Orbiter. While Solar Orbiter would give the first glimpse of the high latitude magnetic field and flows to probe the solar dynamo, it does not have sufficient viewing of the polar regions to achieve POLARIS’s primary objective: determining the relation between the magnetism and dynamics of the Sun’s polar regions and the solar cycle.

Twentieth-century trends in the thermal growing season in the Greater Baltic Area

Phenological data have shown an increase of ca. 10 days in European growing season length in the latter part of the twentieth century. In general, these changes have been associated with global warming. Here we present a study of thermal growing season (GS) trends in the Greater Baltic Area, northern Europe. Yearly dates for the start, end and length of the GS were computed for 49 stations in the studied area, using daily mean temperature measurements. Trends and tendencies of the GS parameters were analysed within the twentieth century. We also examined GS trends in long records (starting before 1850) from the region. The results show a general increase of the length of the GS of ca one week since 1951 in the area, where the most considerable change has occurred in spring (starting ∼6 days earlier). The largest increases were found at stations adjacent to the Baltic Sea and North Sea, where some Danish stations showed significant increasing trends in the length of the GS of more than 20 days. The only tendency for a shorter GS was found in Archangelsk, north western Russia. The three longest records displayed large inter-annual and decadal variability, with tendencies for increased frequencies of longer growing seasons since the 1950s.     

Boundedness of Turbulent Temperature Probability Distributions,and their Relation to the Vertical Profile in the Convective Boundary Layer

Higher-order moments, minima and maxima of turbulent temperature and water vapour mixing ratio probability density functions measured with an eddy-covariance system near the ground were related to each other and to vertical boundary-layer profiles of the same scalars obtained through airborne soundings. The dependence of kurtosis on squared skewness showed a kurtosis intercept below the Gaussian expectation, suggesting a compression of the probability density function by the presence of natural boundaries. This hypothesis was corroborated by comparing actual minima and maxima of turbulent fluctuations to estimates obtained from the first four sample moments by fitting a four-parameter beta distribution. The most sharply defined boundaries were found for the minima of temperature datasets during the day, indicating that negative temperature fluctuations at the sensor are limited by the availability of lower temperatures in the boundary layer. By comparison to vertical profiles, it could be verified that the turbulent minimum of temperature near the ground is close to the minimum of potential temperature in the boundary layer. The turbulent minimum of water vapour mixing ratio was found to be equal to the mixing ratio at a height above the minimum of the temperature profile. This height roughly agrees with the top of the non-local unstable domain according to bulk Richardson number profiles. We conclude that turbulence statistics measured near the surface cannot be solely explained by local effects, but contain information about the whole boundary layer including the entrainment zone.     

Urban malaria in Africa: an environmental and socio-economic modelling approach for Yaoundé, Cameroon

Most of the existing predictive malaria risks spatial models use very broad spatial scales, and they are usually built-up for continental or national outlines. These models usually do not account for the complexity of socio-economic variables intervening into the malaria transmission process as well malaria prevention strategies. These spatial and thematic shortcomings are particularly interesting when looking at urban environments. This paper explains why a focus on urban malaria overcomes these shortcomings. A set of environmental variables derived from remotely sensed and ground climate station sources was used to build-up an ecological model. An original data collection process based on GPS measurements and retrospective interviews was introduced for the creation of various geoepidemiological and geosocial variables. Multinomial logistic models were used to predict and evaluate the contribution of various thematically separated groups of variables to malaria risk. Finally, it was possible to statistically and spatially evaluate the contribution of ecologic, socio-ecologic, socio-economic and behavioural characteristics of these groups of variables to malaria risks.     

Threatened archaeological,historic, and cultural resources of the Georgia Coast: Identification,prioritization and management using GIS technology

Archaeological sites in beach and estuarine environments are continually threatened by diverse natural marine processes. Shoreline erosion, bluff retreat, and sea level rise all present potential for site destruction. Using historic maps, aerial imagery, and field survey methods in a GIS, 21 potentially significant archaeological sites on Georgia barrier islands were selected for determination of site‐specific rates of shoreline change using a powerful, new, moving‐boundary GIS analysis tool. A prioritized list of sites, based on the order of site loss from erosion, was generated to assist coastal managers in identifying and documenting sites most at risk. From the original selection of 21 sites, 11 sites were eroding, 8 shorelines were stable, and 2 shorelines were accreting. The methodology outlined here produces critical information on archaeological site loss rates and provides a straightforward means of prioritizing sites for detailed documentation. © 2010 Wiley Periodicals, Inc.     

Deuterium enrichments in chondritic macromolecular material—Implications for the origin and evolution of organics, water and asteroids

Here we report the elemental and isotopic compositions of the insoluble organic material (IOM) isolated from several previously unanalyzed meteorites, as well as the reanalyses of H isotopic compositions of some previously measured samples (Alexander et al., 2007). The IOM in ordinary chondrites (OCs) has very large D enrichments that increase with increasing metamorphism and decreasing H/C, the most extreme δD value measured being almost 12,000‰. We propose that such large isotopic fractionations could be produced in the OC parent bodies through the loss of isotopically very light H₂ generated when Fe was oxidized by water at low temperatures (<200 °C). We suggest that similar isotopic fractionations were not generated in the IOM of CV and CO chondrites with similar metamorphic grades and IOM H/C ratios because proportionately less water was consumed during metamorphism, and the remaining water buffered the H isotopic composition of the IOM even a H was being lost from it.Hydrogen would also have been generated during the alteration of CI, CM and CR carbonaceous chondrites. The IOM in these meteorites exhibit a considerable range in isotopic compositions, but all are enriched in D, as well as ¹⁵N, relative to terrestrial values. We explore whether these enrichments could also have been produced by the loss of H₂, but conclude that the most isotopically anomalous IOM compositions in meteorites from these groups are probably closest to their primordial values. The less isotopically anomalous IOM has probably been modified by parent body processes. The response of IOM to these processes was complex and varied, presumably reflecting differences in conditions within and between parent bodies.The D enrichments associated with H₂ generation, along with exchange between D-rich IOM and water in the parent bodies, means that it is unlikely that any chondrites retain the primordial H isotopic composition of the water ice that they accreted. The H isotopic compositions of the most water-rich chondrites, the CMs and CIs, are probably the least modified and their compositions (δD ? −25‰) suggest that their water did not form at large radial distances from the Sun where ice is predicted to be very D-rich. Yet models to explain the O isotopic composition of inner Solar System bodies require that large amounts of ice were transported from the outer to the inner Solar System.