Uranyl adsorption onto montmorillonite: Evaluation of binding sites and carbonate complexation

The fate and transport of uranium in contaminated soils and sediments may be affected by adsorption onto the surface of minerals such as montmorillonite. Extended X-ray absorption fine structure (EXAFS) spectroscopy has been used to investigate the adsorption of uranyl (UO₂²⁺) onto Wyoming montmorillonite. At low pH (∼4) and low ionic strength (10⁻³ M), uranyl has an EXAFS spectrum indistinguishable from the aqueous uranyl cation, indicating binding via cation exchange. At near-neutral pH (∼7) and high ionic strength (1 M), the equatorial oxygen shell of uranyl is split, indicating inner-sphere binding to edge sites. Linear-combination fitting of the spectra of samples reacted under conditions where both types of binding are possible reveals that cation exchange at low ionic strengths on SWy-2 may be more important than predicted by past surface complexation models of U(VI) adsorption on related montmorillonites. Analysis of the binding site on the edges of montmorillonite suggests that U(VI) sorbs preferentially to [Fe(O,OH)₆] octahedral sites over [Al(O,OH)₆] sites. When bound to edge sites, U(VI) occurs as uranyl-carbonato ternary surface complexes in systems equilibrated with atmospheric CO₂. Polymeric surface complexes were not observed under any of the conditions studied. Current surface complexation models of uranyl sorption on clay minerals may need to be reevaluated to account for the possible increased importance of cation exchange reactions at low ionic strengths, the presence of reactive octahedral iron surface sites, and the formation of uranyl-carbonato ternary surface complexes. Considering the adsorption mechanisms observed in this study, future studies of U(VI) transport in the environment should consider how uranium retardation will be affected by changes in key solution parameters, such as pH, ionic strength, exchangeable cation composition, and the presence or absence of CO₂.     

Bioaccumulation of gold by sulfate-reducing bacteria cultured in the presence of gold(I)-thiosulfate complex

A sulfate-reducing bacterial (SRB) enrichment, from the Driefontein Consolidated Gold Mine, Witwatersrand Basin, Republic of South Africa, was able to destabilize gold(I)-thiosulfate complex and precipitate elemental gold. The precipitation of gold was observed in the presence of active (live) SRB due to the formation and release of hydrogen sulfide as an end-product of metabolism, and occurred by three possible mechanisms involving iron sulfide, localized reducing conditions, and metabolism. The presence of biogenic iron sulfide caused significant removal of gold from solutions by adsorption and reduction processes on the iron sulfide surfaces. The presence of gold nanoparticles within and immediately surrounding the bacterial cell envelope highlights the presence of localized reducing conditions produced by the bacterial electron transport chain via energy generating reactions within the cell. Specifically, the decrease in redox conditions caused by the release of hydrogen sulfide from the bacterial cells destabilized the solutions. The presence of gold as nanoparticles (<10 nm) inside a sub-population of SRB suggests that the reduction of gold was a part of metabolic process. In late stationary phase or death phase, gold nanoparticles that were initially precipitated inside the bacterial cells, were released from the cells and deposited in the bulk solution as addition of gold nanoparticles that already precipitated in the solution. Ultimately, the formation of micrometer-scale sub-octahedral and octahedral gold and spherical aggregates containing octahedral gold was observed.     

Hydrocarbons generated by hydropyrolysis of suspended marine particulate organic matter: Relationship to the oceanography of the Black Sea and the Rhodes Gyre

The suspended particulate organic matter, SPOM, in the autumnal Black Sea has been characterised using catalytic hydropyrolysis (HyPy) of the total (bound plus free) lipid material. The technique, which generates maximum yields of volatile products from sediments, kerogens and phytoplankton, was followed using gas chromatography and gas chromatography/mass spectrometry. The generated alkanes were dominated by n-C₁₈, hypothesised to arise predominantly from unsaturated C₁₈ fatty acids. Steranes were generated from reductive conversion of free and bound sterols. The generation of branched alkanes and especially of hopanes provided formal evidence for the participation of bacteria in the mineralisation of the SPOM. Whereas similar distributions of n-alkanes were generated from SPOM sampled from different depths of the comparatively well-stirred Rhodes Gyre (eastern Mediterranean), mineralisation of the SPOM at each depth of the central Black Sea produced characteristic changes in the composition and concentration of the HyPy products. Depth profiles of the n-alkanes generated from SPOM in the region of the Rim Current were affected by the local hydrography. Polynuclear aromatic hydrocarbons (PAHs) of anthropogenic origin were present in the surface waters of the central Black Sea. Some methyl benzenes, thiophenes and pyrroles were also generated.     

Contrasting isotopic signatures between anthropogenic and geogenic Zn and evidence for post-depositional fractionation processes in smelter-impacted soils from Northern France

Zinc isotopes have been studied along two smelter-impacted soil profiles sampled near one of the largest Pb and Zn processing plants in Europe located in northern France, about 50 km south of Lille. Mean δ⁶⁶Zn values along these two soil profiles range from +0.22 ± 0.17‰ (2σ) to +0.34 ± 0.17‰ (2σ) at the lowest horizons and from +0.38 ± 0.45‰ (2σ) to +0.76 ± 0.14‰ (2σ) near the surface. The δ⁶⁶Zn values in the lowest horizons of the soils are interpreted as being representative of the local geochemical background (mean value +0.31 ± 0.38‰), whereas heavier δ⁶⁶Zn values near the surface of the two soils are related to anthropogenic Zn. This anthropogenic Zn occurs in the form of franklinite (ZnFe₂O₄)-bearing slag grains originating from processing wastes at the smelter site and exhibiting δ⁶⁶Zn values of +0.81 ± 0.20‰ (2σ). The presence of franklinite is indicated by EXAFS analysis of the topsoil samples from both soil profiles as well as by micro-XANES analysis of the surface horizon of a third smelter-impacted soil from a distant site. These results indicate that naturally occurring Zn and smelter-derived Zn exhibit significantly different δ⁶⁶Zn values, which suggests that zinc isotopes can be used to distinguish between geogenic and anthropogenic sources of Zn in smelter-impacted soils. In addition to a possible influence of additional past sources of light Zn (likely Zn-sulfides and Zn-sulfates directly emitted by the smelter), the light δ⁶⁶Zn values in the surface horizons compared to smelter-derived slag materials are interpreted as resulting mainly from fractionation processes associated with biotic and/or abiotic pedological processes (Zn-bearing mineral precipitation, Zn complexation by organic matter, and plant uptake of Zn). This conclusion emphasizes the need for additional Zn isotopic studies before being able to use Zn isotopes to trace sources and pathways of this element in surface environments.     

Some constraints on the origin of phonolites from the Gregory Rift,Kenya, and inferences concerning basaltic magmas in the Rift System

Plateau-type phonolites of the Gregory Rift represent magmas with densities of about 2.3 g/cm³. These magmas must have erupted soon after their formation. The average depth of the bases of the approximately 100 to 300 magma chambers from which they erupted was between about 10 and about 24 km. The average vertical extent of the magma chambers was between about 3 and about 8 km. The aggregate volume of phonolitic magma formed beneath the Rift in Miocene times probably lies in the range of 0.5 to 1×10⁵ km³. Both the crystal fractionation model and the anatectic model for formation of this volume of phonolitic magma require the presence of a large reservoir of basaltic magma, probably picritic in character, with a volume of at least 5×10⁵ km³ and perhaps as much as 20×10⁵ km³. This reservoir presumably is now part of the dense basic intrusive complex along the Rift axis. The Miocene and Pliocene episodes of basaltic volcanism in this region may be related to eruption of evolved liquids from this reservoir.     

Tectonic systems and the deposition of iron-formation

The iron-formation group of chemically precipitated cherty iron-rich sediments ranges in age from Early Precambrian to Recent and is composed of a variety of lithological facies. Iron-formations are classified as Lake Superior and Algoma types to emphasize the contrasting conditions in the spectrum of sedimentary-tectonic environments in which they formed. Thick stratigraphic units of Lake Superior type iron-formation, which form the most extensive iron ranges of the world, are part of sedimentary-tectonic systems that developed along the margins of cratons or continental platforms and were deposited over extended periods of time under relatively stable tectonic conditions. The Algoma type iron-formations were deposited with volcanic rocks and greywacke in various tectonic-volcanic systems, formed under more dynamic tectonic conditions, but are otherwise comparable to present day spreading ridges on the ocean floor. The thick sequences of Lake Superior type iron-formation deposited between 2.7 and 2.0 Ga form part of major sedimentary-tectonic systems that extended along the margins of continents. Direct biogenic factors and the composition of the atmosphere probably had only limited influence on the precipitation of these chemical sediments.     

Production and pelagic dissolution of biogenic silica in the Southern Ocean

Vertical distributions of particulate silica, and of production and dissolution rates of biogenic silica, were determined on two N-S transects across the Pacific sector of the Antarctic Circumpolar Current during the austral spring of 1978. Particulate silica profiles showed elevated levels in surface water and near the bottom, with low (35–110 nmol Si · 1^?1) and vertically uniform values through the intervening water column. Both the particulate silica content of the upper 200 m and the production rate of biogenic silica in the photic zone increased from north to south, reaching their highest values near the edge of the receding pack ice. A significant, but variable, fraction (18–58%) of the biogenic silica produced in the surface layer was redissolving in the upper 90–98 m. Net production of biogenic silica in the surface layer (production minus dissolution) was proceeding at a mean rate of ca. 2 mmol Si · m^?2 · day^?1. This is ca. 4 times greater than the most recent estimate of the mean accumulation rate of siliceous sediments beneath the ACC. We estimate, based on mass balance, that the mean dissolution rate of biogenic silica in subsurface water column in the Southern Ocean is 1.2–2.9 mmol Si · m^?2 · day^?1.     

Polymerization of silicate and aluminate tetrahedra in glasses,melts, and aqueous solutions—I. Electronic structure of H6Si2O7, H6AlSiO71−, and H6Al2O72−

As part of a study of the effect of geologically common network modifiers on polymerization in silicate melts, glasses, and silica-rich aqueous solutions, we have studied the energies, electronic structures, and inferred chemical properties of ^IVT-O-^IVT linkages in the tetrahedral dimers H₆,Si₂O₇, H₆AlSiO₇^1?, and H₆Al₂O₇^2? using semi-empirical molecular orbital theory (CNDO/2). Our results indicate that the electron donating character of the bridging oxygen, O(br), linking two tetrahedra increases with increasing T-O(br) bond length but decreases with decreasing T-O(br)-T angles and increasing O-T-O(br) angles. This increase or decrease of the donor character of O(br) coincides with an increase or decrease of the affinity of O(br) for hard acceptors. The calculated electronic structure for the H₆Si₂O₇ molecule is compared with the observed X-ray emission, absorption, and photoelectron spectra of quartz and vitreous silica; the reasonable match between calculated and observed oxygen Kα emission spectra of vitreous silica supports our assertion that non-bonded O(br) electron density energetically at the top of the valence band controls the chemical reactivity of ^IVT-O-^IVT linkages in polymerized tetrahedral environments.     

The glacial and interstadial sediments at the Burn of Benholm,Kincardineshire: evidence for onshore pre‐Devensian ice movement in northeast Scotland

Pebbly clays and diamictons containing marine shell fragments and peat lenses exposed beneath subglacially deposited Late Devensian till at the Burn of Benholm provide new insights into the glacial history of Quaternary sequences in eastern Scotland. The peat yielded pollen of interstadial affinity (including Bruckenthalia spiculifolia) and non‐finite radiocarbon dates. Comparisons with other pre‐Late Devensian pollen records in northern Scotland suggest that the peat lenses are remnants of an Early Devensian interstadial deposit, of Oxygen Isotope Substage 5c or 5a age. Reworked faunal assemblages in the shelly sediments include Quaternary marine molluscs of low boreal aspect, as well as Mesozoic and Palaeozoic microfossils. Amino acid ratios from fragments of Arctica islandica suggest that the shells are of Oxygen Isotope Stage 9 age or older. The fabric and composition of the shelly sediments are consistent with their emplacement as deformation till during the onshore movement of glacially transported rafts of marine sediment. Folded and sheared contacts between the shelly deposits, peat lenses and the overlying Late Devensian till indicate that the fossiliferous sediments were glacitectonised during the main Late Devensian glaciation, when ice moved from Strathmore and overrode the site from the southwest. British Geological Survey. © NERC 2000.     

Smart optics in ast

Smart optics means much more than adaptive optics on telescopes: these new technologies are changing the way space instruments are built and operated and are bringing new technologies into everyday life in the form of cheaper, lighter and more robust optical systems. Steve Welch, Peter Doel, Alan Greenaway and Gordon Love summarize the work of the Smart Optics Faraday Partnership in the UK.