TEM study of Mg distribution in micrite crystals from the Mishrif reservoir Formation (Middle East, Cenomanian to Early Turonian)

Microporous limestones composed of micrite crystals constitute sizeable hydrocarbon reservoirs throughout the world and especially in the Middle East. However, the crystallization history of micrites is poorly understood. Scanning electronic microscopy (SEM) with X-ray energy dispersive spectroscopy (EDS) studies give morphological and bulk composition information about micrites, but no information exists on the distribution of minor elements inside micrite grains. This study proposes Mg maps obtained with X-ray EDS combined with scanning transmission electron microscopy (STEM) of micrite crystals from the Mishrif reservoir Formation (Middle East, Cenomanian to Early Turonian). Three types of Mg distribution were observed through micrite crystals from five different samples: (1) homogenous Mg concentration, (2) small Mg-enriched areas close to the center of the crystal, and (3) geometric Mg impoverishments near crystal edges and parallel to present crystallographic faces. The homogenous Mg distribution is the most frequent and is found both in microporous and in tight micrites. The second type of distribution showing small Mg-enriched areas inside micrite crystals relatively close to their center comes from a microporous sample located below an emersive surface. These enriched areas may correspond to crystal seeds. The third type of distribution was observed in micrite crystals from another microporous sample situated just below an emersive surface. The Mg-poor zones probably represent overgrowths that precipitated in contact with less Mg-rich meteoric fluid

Fe(III) reduction during pyruvate fermentation by Desulfotomaculum reducens strain MI-1

Desulfotomaculum reducens MI-1 is a Gram-positive, sulfate-reducing bacterium also capable of reducing several metals, among which is Fe(III). Very limited knowledge is available on the potential mechanism(s) of metal reduction among Gram-positive bacteria, despite their preponderance in the microbial communities that inhabit some inhospitable environments (e.g., thermal or hyperthermal ecosystems, extreme pH or salinity environments, heavy metal or radionuclide contaminated sediments). Here, we show that in the presence of pyruvate, this micro-organism is capable of reducing both soluble Fe(III)-citrate and solid-phase hydrous ferric oxide, although growth is sustained by pyruvate fermentation rather than Fe(III) respiration. Despite the fact that Fe(III) reduction does not support direct energy conservation, D.reducens uses it as a complementary means of discarding excess reducing equivalent after H-2 accumulation in the culture headspace renders proton reduction unfavorable. Thus, Fe(III) reduction permits the oxidation of greater amounts of pyruvate than fermentation alone. Fe(III) reduction by D.reducens is mediated by a soluble electron carrier, most likely riboflavin. Additionally, an intracellular electron storage molecule acts as a capacitor and accumulates electrons during pyruvate oxidation for slow release to Fe(III). The reductase responsible for the transfer of electrons from the capacitor to the soluble carrier has not been identified, but data presented here argue against the involvement of c-type cytochromes

Combined scanning transmission X-ray and electron microscopy for the characterization of bacterial endospores

Endospores (also referred to as bacterial spores) are bacterial structures formed by several bacterial species of the phylum Firmicutes. Spores form as a response to environmental stress. These structures exhibit remarkable resistance to harsh environmental conditions such as exposure to heat, desiccation, and chemical oxidants. The spores include several layers of protein and peptidoglycan that surround a core harboring DNA as well as high concentrations of calcium and dipicolinic acid (DPA). A combination of scanning transmission X-ray microscopy, scanning transmission electron microscopy, and energy dispersive spectroscopy was used for the direct quantitative characterization of bacterial spores. The concentration and localization of DPA, Ca2+, and other elements were determined and compared for the core and cortex of spores from two distinct genera: Bacillus subtilis and Desulfotomaculum reducens. This micro-spectroscopic approach is uniquely suited for the direct study of individual bacterial spores, while classical molecular and biochemical methods access only bulk characteristics

U(VI) reduction by spores of Clostridium acetobutylicum

Vegetative cells of Clostridium acetobutylicum are known to reduce hexavalent uranium (U(VI)). We investigated the ability of spores of this organism to drive the same reaction. We found that spores were able to remove U(VI) from solution when H, was provided as an electron donor and to form a U(IV) precipitate. We tested several environmental conditions and found that spent vegetative cell growth medium was required for the process. Electron microscopy showed the product of reduction to accumulate outside the exosporium. Our results point towards a novel U(VI) reduction mechanism, driven by spores, that is distinct from the thoroughly studied reactions in metal-reducing Proteobacteria. (C) 2010 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved

Pd/SiO2 catalysts: synthesis of Pd nanoparticles with the controlled size in mesoporous silicas

Synthesis of Pd nanoparticles with controlled size (d(Pd) = 1-3.6 nm) was carried out within the pores of the mesoporous HMS and SBA-15 silicas. Pd was ion-exchanged on non-calcined silicas, prepared by solvent extraction of the templates. A high concentration of silanol groups on the mesopore surface allowed attaining Pd loading up to 4.4. wt.%. The Pd/HMS and Pd/SBA-15 were characterised by chemical analysis, XRD, N2 adsorption-desorption and transmission electron microscopy (TEM) methods. The materials possess a high SSA and narrow pore size distribution. Introduction of Pd nanoparticles in HMS resulted in a progressive loss of the regularity in the mesoporous structure. On the contrary, all Pd/SBA-15 composites retained the original well-ordered 2D hexagonal structure of SBA-15. The thick walls of the SBA-15 framework are accounted for the higher stability observed. The TEM investigations confirmed that the Pd nanocrystals were located within the SBA-15 mesoporous framework channels. The particle size did not exceed the mesopore diameter (2-6 nm) at Pd loading of 0.1-4.4wt.%. Pd clusters were found to be resistant against sintering during air-calcination (550 degreesC, 4h). The catalyst 2.1%Pd/SBA-15 used in methane combustion at 520 degreesC demonstrated stable activity during 6h on stream

Highly dispersed gold on activated carbon fibers for low temperature CO oxidation

Gold nanoparticles of 2–5 nm supported on woven fabrics of activated carbon fibers (ACF) were effective during CO oxidation at room temperature. To obtain a high metal dispersion, Au was deposited on ACF from aqueous solution of ethylenediamine complex [Au(en)2]Cl3 via ion exchange with protons of surface functional groups. The temperature-programmed decomposition method showed the presence of two main types of functional groups on the ACF surface: the first type was associated with carboxylic groups easily decomposing to CO2 and the second one corresponded to more stable phenolic groups decomposing to CO. The concentration and the nature of surface functional groups was controlled using HNO3 pretreatment followed by either calcination in He (300–1273 K) or by iron oxide deposition. The phenolic groups are able to attach Au3+ ions, leading to the formation of small Au nanoparticles (9 nm) Au agglomerates after reduction by H2. These catalysts demonstrated lower activity as compared to the ones containing mostly small Au nanoparticles. Complete removal of surface functional groups rendered an inert support that would not interact with the Au precursor. The oxidation state of gold in the Au/ACF catalysts was controlled by X-ray photoelectron spectroscopy before and after the reduction in H2. The high-temperature reduction in H2 (673–773 K) was necessary to activate the catalyst, indicating that metallic gold nanoparticles are active during catalytic CO oxidation

Geochemical control on uranium(IV) mobility in a mining-impacted wetland

Wetlands often act as sinks for uranium and other trace elements. Our previous work at a mining-impacted wetland in France showed that a labile noncrystalline U(IV) species consisting of U(IV) bound to Al-P-Fe-Si aggregates was predominant in the soil at locations exhibiting a U-containing clay-rich layer within the top 30 cm. Additionally, in the porewater, the association of U(IV) with Fe(II) and organic matter colloids significantly increased U(IV) mobility in the wetland. In the present study, within the same wetland, we further demonstrate that the speciation of U at a location not impacted by the clay-rich layer is a different noncrystalline U(IV) species, consisting of U(IV) bound to organic matter in soil. We also show that the clay-poor location includes an abundant sulfate supply and active microbial sulfate reduction that induce substantial pyrite (FeS2) precipitation. As a result, Fe(II) concentrations in the porewater are much lower than those at clay-impacted zones. U porewater concentrations (0.02-0.26 mu M) are also considerably lower than those at the clay-impacted locations (0.21-3.4 mu M) resulting in minimal U mobility. In both cases, soil-associated U represents more than 99% of U in the wetland. We conclude that the low U mobility reported at clay-poor locations is due to the limited association of Fe(II) with organic matter colloids in porewater and/or higher stability of the noncrystalline U(IV) species in soil at those locations

Mobile uranium(IV)-bearing colloids in a mining-impacted wetland

Tetravalent uranium is commonly assumed to form insoluble species, resulting in the immobilization of uranium under reducing conditions. Here we present the first report of mobile U(IV)-bearing colloids in the environment, bringing into question this common assumption. We investigate the mobility of uranium in a mining-impacted wetland in France harbouring uranium concentrations of up to 14,000 p. p. m. As an apparent release of uranium into the stream passing through the wetland was observable, we examine soil and porewater composition as a function of depth to assess the geochemical conditions leading to this release. The analyses show the presence of U(IV) in soil as a non-crystalline species bound to amorphous Al-P-Fe-Si aggregates, and in porewater, as a distinct species associated with Fe and organic matter colloids. These results demonstrate the lability of U(IV) in these soils and its association with mobile porewater colloids that are ultimately released into surface water

Non-uraninite products of microbial U(VI) reduction

A promising remediation approach to mitigate subsurface uranium contamination is the stimulation of indigenous bacteria to reduce mobile U(VI) to sparingly soluble U(IV). The product of microbial uranium reduction is often reported as the mineral uraninite. Here, we show that the end products of uranium reduction by several environmentally relevant bacteria (Gram-positive and Gram-negative) and their spores include a variety of U(IV) species other than uraninite. U(IV) products were prepared in chemically variable media and characterized using transmission electron microscopy (TEM) and X-ray absorption spectroscopy (XAS) to elucidate the factors favoring/inhibiting uraninite formation and to constrain molecular structure/composition of the non-uraninite reduction products. Molecular complexes of U(IV) were found to be bound to biomass, most likely through P-containing ligands. Minor U(IV)-orthophosphates such as ningyoite [CaU(PO4)(2)], U2O(PO4)(2), and U-2(PO4)(P3O10) were observed in addition to uraninite. Although factors controlling the predominance of these species are complex, the presence of various solutes was found to generally inhibit uraninite formation. These results suggest a new paradigm for U(IV) in the subsurface, i.e., that non-uraninite U(IV) products may be found more commonly than anticipated. These findings are relevant for bioremediation strategies and underscore the need for characterizing the stability of non-uraninite U(IV) species in natural settings

Uranium speciation and stability after reductive immobilization in sediments

It has generally been assumed that the bioreduction of hexavalent uranium in groundwater systems will result in the precipitation of immobile uraninite (UO2). In order to explore the form and stability of uranium immobilized under these conditions, we introduced lactate (15 mM for 3 months) into flow-through columns containing sediments derived from a former uranium-processing site at Old Rifle, CO. This resulted in metal-reducing conditions as evidenced by concurrent uranium uptake and iron release. Despite initial augmentation with Shewanella oneidensis, bacteria belonging to the phylum Firmicutes dominated the biostimulated columns. The immobilization of uranium (similar to 1 mmol U per kg sediment) enabled analysis by Xray absorption spectroscopy (XAS). Tetravalent uranium associated with these sediments did not have spectroscopic signatures representative of U-U shells or crystalline UO2. Analysis by microfocused XAS revealed concentrated micrometer regions of solid U(IV) that had spectroscopic signatures consistent with bulk analyses and a poor proximal correlation (mu m scale resolution) between U and Fe. A plausible explanation, supported by biogeochemical conditions and spectral interpretations, is uranium association with phosphoryl moieties found in biomass; hence implicating direct enzymatic uranium reduction. After the immobilization phase, two months of in situ exposure to oxic influent did not result in substantial uranium remobilization. Ex situ flow-through experiments demonstrated more rapid uranium mobilization than observed in column oxidation studies and indicated that sediment-associated U(IV) is more mobile than biogenic UO2. This work suggests that in situ uranium bioimmobilization studies and subsurface modeling parameters should be expanded to account for non-uraninite U(IV) species associated with biomass. (C) 2011 Elsevier Ltd. All rights reserved