Electron transfer at the mineral/water interface: Selenium reduction by ferrous iron sorbed on clay

The mobility and availability of the toxic metalloid selenium in the environment are largely controlled by sorption and redox reactions, which may proceed at temporal scales similar to that of subsurface water movement under saturated or unsaturated conditions. Since such waters are often anaerobic and rich in Fe²⁺, we investigated the long-term (?1 month) kinetics of selenite sorption to montmorillonite in the presence of Fe²⁺ under anoxic conditions. A synthetic montmorillonite was used to eliminate the influence of structural Fe. In the absence of aqueous Fe²⁺, selenite was sorbed as outer-sphere sorption complex, covering only part of the positive edge sites, as verified by a structure-based MUSIC model and Se K-edge XAS (X-ray absorption spectroscopy). When selenite was added to montmorillonite previously equilibrated with Fe²⁺ solution however, slow reduction of Se and formation of a solid phase was observed with Se K-edge XANES (X-ray absorption near-edge spectroscopy) and EXAFS (extended X-ray absorption fine-structure) spectroscopy. Iterative transformation factor analysis of XANES and EXAFS spectra suggested that only one Se reaction product formed, which was identified as nano-particulate Se(0). Even after one month, only 75% of the initially sorbed Se(IV) was reduced to this solid species. Mössbauer spectrometry revealed that before and after addition and reduction of Se, 5% of total sorbed Fe occurred as Fe(III) species on edge sites of montmorillonite (≈2 mmol kg⁻¹). The only change observed after addition of Se was the formation of a new Fe(II) species (15%) attributed to the formation of an outer-sphere Fe(II)-Se sorption complex. The combined Mössbauer and XAS results hence clearly suggest that the Se and Fe redox reactions are not directly coupled. Based on the results of a companion paper, we hypothesize that the electrons produced in the absence of Se by oxidation of sorbed Fe(II) are stored, for example by formation of surface H₂ species, and are then available for the later Se(IV) reduction. The slow reaction rate indicates a diffusion controlled process. Homogeneous precipitation of an iron selenite was thermodynamically predicted and experimentally observed only in the absence of clay. Interestingly, half of Fe was oxidized in this precipitate (Mössbauer). Since DFT calculations predicted the oxidation of Fe at the water-FeSe solid interface only and not in the bulk phase, we derived an average particle size of this precipitate which does not exceed 2 nm. A comparison with the Mössbauer and XAS spectra of the clay samples demonstrates that such homogenous precipitation can be excluded as a mechanism for the observed slow Se reduction, emphasizing the role of abiotic, heterogeneous precipitation and reduction for the removal of Se from subsurface waters.     

Impacts of convection schemes on simulating tropical-temperate troughs over southern Africa

This study examines southern African summer rainfall and tropical temperate troughs (TTTs) simulated with three versions of an atmospheric general circulation model differing only in the convection scheme. All three versions provide realistic simulations of key aspects of the summer (November–February) rainfall, such as the spatial distribution of total rainfall and the percentage of rainfall associated with TTTs. However, one version has a large bias in the onset of the rainy season. Results from self-organizing map (SOM) analysis on simulated daily precipitation data reveals that this is because the occurrence of TTTs is underestimated in November. This model bias is not related to westerly wind shear that provides favorable conditions for the development of TTTs. Rather, it is related to excessive upper level convergence and associated subsidence over southern Africa. Furthermore, the model versions are shown to be successful in capturing the observed drier (wetter) conditions over the southern African region during El Niño (La Niña) years. The SOM analysis reveals that nodes associated with TTTs in the southern (northern) part of the domain are observed less (more) often during El Niño years, while nodes associated with TTTs occur more frequently during La Niña years. Also, nodes associated with dry conditions over southern Africa are more (less) frequently observed during El Niño (La Niña) years. The models tend to perform better for La Niña events, because they are more successful in representing the observed frequency of different synoptic patterns.     

Accumulation and transport behaviour of 241americium, 60cobalt and 134cesium by eggs of the spotted dogfish Scyliorhinus canicula

An experimental study examined the 96-h net influx from seawater of the anthropogenic radionuclides (241)Am, (60)Co and (134)Cs through the egg-case of the spotted dogfish Scyliorhinus canicula. Net influx directly through the wall of the egg-case was greatest for (134)Cs, then (241)Am and lastly (60)Co. Within the egg-case wall itself the measured concentration factors (CFs) and their gradients in the external, median and internal layers showed that for both (241)Am and (60)Co they were >10(3) in the external layer and declined by an order of magnitude in the interior layer. In contrast (134)Cs had a CF of only about three in the external layer which declined by a factor of 2 towards the two more internal layers of the egg-case. The egg-case apertures, that open within the prehatching stage of embryological development, significantly (P<0.05) increased the net influx of (241)Am and (60)Co to the interior of the egg-case, although their water concentrations were still lower than those in the labelled seawater bath. In contrast, the aperture did not increase the net influx of (134)Cs whose water concentrations equilibrated with those in seawater. Together these results indicate that the egg-case wall is very permeable to (134)Cs, representing little barrier to its movement, and hence consistent with the lack of importance of the aperture in determining its internal water concentrations in the egg-case. In contrast, (241)Am and (60)Co show much higher rates of accumulation by the egg-case, consistent with the measured reduced permeability of its wall, and therefore giving greater prominence to its aperture in the net transfer of these two radionuclides to the egg case's interior. The presence of the embryo within its egg-case did not significantly (P>0.05) affect the rates of influx of radioisotopes, with the exception of an interactive effect for (60)Co with the egg-case aperture (P<0.05). The CF of only (241)Am in the embryo itself relative to the external seawater concentration was significantly (P<0.05) enhanced by the presence of the aperture.     

Sublimation of the Martian CO2 Seasonal South Polar Cap

The polar condensation/sublimation of CO₂, that involve about one fourth of the atmosphere mass, is the major Martian climatic cycle. Early observations in visible and thermal infrared have shown that the sublimation of the Seasonal South Polar Cap (SSPC) is not symmetric around the geographic South Pole.Here we use observations by OMEGA/Mars Express in the near-infrared to detect unambiguously the presence of CO₂ at the surface, and to estimate albedo. Second, we estimate the sublimation of CO₂ released in the atmosphere and show that there is a two-step process. From Ls=180° to 220°, the sublimation is nearly symmetric with a slight advantage for the cryptic region. After Ls=220° the anti-cryptic region sublimation is stronger. Those two phases are not balanced such that there is 22% ± 9 more mass the anti-cryptic region, arguing for more snow precipitation. We compare those results with the MOLA height measurements. Finally we discuss implications for the Martian atmosphere about general circulation and gas tracers, e.g. Ar.     

The Arctic Ocean—a Canadian perspective from IPY

Canada??s IPY program funded seven marine projects spanning the North American Arctic. Work embraced oceanography, air-sea interactions, storm response, paleo-climate and trace-element chemistry. Notable findings are emerging. Conditions in the Beaufort were unusual in 2007, with very high air pressure bringing strong winds, rapid ice drift, thin winter ice, enhanced shelf-break upwelling and a maximum in freshwater retention in the Beaufort Gyre. A mapping of trace chemicals suggests that Arctic mid-depth circulation may also have reversed. Study of Canadian Arctic through-flow revealed a net annual seawater export of 44,000 cubic kilometres from the Arctic to Baffin Bay. Observations of sea ice, sustained through the IPY, affirmed that ice cover is the key attribute of Arctic seas, with wind as a potent agent in its variation. Surveys have shown that the anthropogenic decline in seawater alkalinity is aggravated in the Arctic by low temperature and low salinity resulting from ice melt. Careful experiments have revealed that Arctic phytoplankton growth is constrained by scarcity of dissolved iron where light levels are low. A manganese fingerprint in sediments has tracked changing sea level during the Ice Age. Sediment-core analysis has revealed the Arctic Oscillation as a dominant cause of long-period climate variations during the Holocene. One project has demonstrated how multi-tasked vessels can maintain a watch on Canada??s Arctic within a reliable affordable logistic framework, while a wave forecast model developed by another for the Beaufort is suitable for operational use.     

Differentiation and crystallization conditions of basalts from the Kerguelen large igneous province: an experimental study

Phase relations of basalts from the Kerguelen large igneous province have been investigated experimentally to understand the effect of temperature, fO₂, and fugacity of volatiles (e.g., H₂O and CO₂) on the differentiation path of LIP basalts. The starting rock samples were a tholeiitic basalt from the Northern Kerguelen Plateau (ODP Leg 183 Site 1140) and mildly alkalic basalt evolved from the Kerguelen Archipelago (Mt. Crozier on the Courbet Peninsula), representing different differentiation stages of basalts related to the Kerguelen mantle plume. The influence of temperature, water and oxygen fugacity on phase stability and composition was investigated at 500 MPa and all experiments were fluid-saturated. Crystallization experiments were performed at temperatures between 900 and 1,160°C under oxidizing (log fO₂ ~ ΔQFM + 4) and reducing conditions (log fO₂ ~ QFM) in an internally heated gas-pressure vessel equipped with a rapid quench device and a Pt-Membrane for monitoring the fH₂. In all experiments, a significant influence of the fO₂ on the composition and stability of the Mg/Fe-bearing mineral phases could be observed. Under reducing conditions, the residual melts follow a tholeiitic differentiation trend. In contrast, melts have high Mg# [Mg²⁺/(Mg²⁺ + Fe²⁺)] and follow a calk-alkalic differentiation trend at oxidizing conditions. The comparison of the natural phenocryst assemblages with the experimental products allows us to constrain the differentiation and pre-eruptive conditions of these magmas. The pre-eruptive temperature of the alkalic basalt was about 950–1,050°C. The water content of the melt was below 2.5 wt% H₂O and strongly oxidizing conditions (log fO₂ ~ ΔQFM + 2) were prevailing in the magma chamber prior to eruption. The temperature of the tholeiitic melt was above 1,060°C, with a water content below 2 wt% H₂O and a log fO₂ ~ ΔQFM + 1. Early fractionation of clinopyroxene is a crucial step resulting in the generation of silica-poor and alkali-rich residual melts (e.g., alkali basalt). The enrichment of alkalis in residual melts is enhanced at high fO₂ and low aH₂O.     

Detailed seismic stratigraphy of Lago Puyehue: implications for the mode and timing of glacier retreat in the Chilean Lake District

Lago Puyehue is a glacigenic lake in the Chilean Lake District (40°S) with a complex deglaciation history. A detailed seismic–stratigraphic study of its sedimentary infill indicates a much earlier retreat of the glacier from the Lago Puyehue basin than the neighbouring glacier from the Lago Rupanco basin. Because of their close proximity, Rupanco meltwater streams played an important part in the depositional processes of Lago Puyehue. A timing discrepancy between the in‐lake ages of a sediment core and the outer‐lake ages of moraine deposits (re)opens the discussion on the timing of deglaciation in the Southern Hemisphere. Copyright © 2011 John Wiley & Sons, Ltd.     

Late Holocene high precipitation events recorded in lake sediments and catchment geomorphology,Lake Vuoksjávrátje,NW Sweden

In this paper, we show the potential of combining multi‐proxy analysis of lake sediments with catchment geomorphology to better understand palaeoenvironmental changes. Previous studies have suggested that alpine lakes in N Sweden may be highly sensitive to variations in catchment erosion and precipitation, and that this sensitivity may influence ecologically based reconstructions of past temperature changes. We analysed lake sediments covering the last 5100 years from the alpine Lake Vuoksjávrátje in NW Sweden in order to identify different erosional regimes in the lake catchment, sediment sources and lake sedimentary processes, which ultimately affect the palaeoecological record. The measured proxies include elemental geochemistry from XRF core scanning, grain size, sediment accumulation rates, fraction of terrestrial organic carbon and geomorphological mapping, supported by previously published chironomid and total organic carbon data. From the integrated results we identified time intervals when increased intensity of precipitation altered sedimentation and lake catchment erosional processes. The most prominent event occurred c. 2900 cal. a BP and is interpreted to be the result of excessive precipitation, possibly related to the climatic shift towards cooler and wetter conditions referred to as the 2.8 ka event.