Extending the prediction of the thermodynamic properties of clay minerals to the trapping of trace elements

The thermodynamic properties of clay minerals, which control the stability of these minerals in solution, are still a matter of debate in spite of recent advances (Gailhanou et al., submitted). This is especially the case for the minerals that may structurally include trace elements and potential radionuclides such like Ni, Cd, Co, Cr, Mn, Pb, ... The usual methods developed in order to predict thermodynamic properties are parameterised using a given set of minerals. For clay minerals, the latter are mainly composed by Si, Al, Fe and Mg, apart from the alkalis elements (Chermak and Rimstidt, 1989), which means that predictions are limited to minerals whose layers are composed by Si, Al, Fe and Mg. At the vicinity of H&ILW disposal cells, the possible interactions between clay rock or engineered barrier and waste degradation products can result in the appearance of clay minerals that may structurally include radionuclides within an irreversible trapping process. This work aims at proposing a method for predicting the thermodynamic properties of such minerals. Theoretical principle and selection of calibration phases Vieillard (1994) has developed a methodology of estimation based on the difference of electronegativity by considering three scales of values of the parameter HO=(Mz+clay) in the three sites of phyllosilicates. We have considered the work of Vieillard (1994) that originally applies to the estimate of H0f and extended it to the estimate of Cp(T), S0 and V. Some popular estimate methods (Chermak and Rimstidt, 1989) are based on the hypothesis that the thermodynamic property of a mineral can be obtained by combining the properties of its components. An improvement of this principle had consisted in decomposing minerals into their polyhedral components (Chermak and Rimstidt, 1989). Now, we can write the fictive solution equilibrium with a basic polyhedral component MxOy as: and assumming the entropy of this fictive reaction is zero, we can define a SO= parameter as: . The value for the oxide analog of the polyhedral unit is obtained by implementing S0 of the oxide in the S0(MxOy) term. We have also defined, from the same reasoning, similar parameters for heat capacity and volume of the basic polyhedral components: ; . Results and discussion On Figure 1, we have displayed, for entropy, the correlation obtained between calculated values of SO= for the polyhedral unit and for the oxide analog. A straight line and a second-order function are obtained, for the interlayer and octahedral cations, respectively, with a good correlation coefficient. Fig. 1 - Development of predictive capacity for entropy estimates The implementation of the derived semi-empirical, first or second order relations allows to estimate the thermodynamic properties of a clay mineral, MX80 (Na0.409K0.024Ca0.009(Si3.738Al0.262)(Al1.598Mg0.214Fe3+0.173Fe2+0.035)O10(OH)2) in the present case, loaded by 6 radionuclides and to compare the values with the results obtained by Gailhanou et al. (submitted).The results can be expressed in terms of the concentrations for the elements Ni, Cd, Co, Cr, Mn and Pb and in terms of energetic potential with respect to the measurements performed by Gailhanou et al. (submitted)

Selection of coals of different maturities for CO2 Storage by modelling of CH4 and CO2 adsorption isotherms

International audienceCO2 injection in unmineable coal seams could be one interesting option for both storage and methane recovery processes. The objective of this study is to compare and model pure gas sorption isotherms (CO2 and CH4) for well-characterised coals of different maturities to determine the most suitable coal for CO2 storage. Carbon dioxide and methane adsorption on several coals have been investigated using a gravimetric adsorption method. The experiments were carried out using both CO2 and CH4 pure gases at 25 °C from 0.1 to 5 MPa (1 to 50 bar). The experimental results were fitted using Temkin's approach but also with the corrected Langmuir's and the corrected Tóth's equations. The two last approaches are more accurate from a thermodynamical point of view, and have the advantage of taking into account the fact that experimental data (isotherms) correspond to excess adsorption capacities. These approaches allow better quantification of the adsorbed gas. Determined CO2 adsorption capacities are from 0.5 to 2 mmol/g of dry coal. Modelling provides also the affinity parameters of the two gases for the different coals. We have shown these parameters determined with adsorption models could be used for classification and first selection of coals for CO2 storage. The affinity ratio ranges from a value close to 1 for immature coals to 41 for high rank coals like anthracites. This ratio allows selecting coals having high CO2 adsorption capacities. In our case, the modelling study of a significant number of coals from various ranks shows that anthracites seem to have the highest CO2 storage capacities. Our study provides high quality affinity parameters and values of CO2 and CH4 adsorption capacities on various coals for the future modelling of CO2 injection in coal seams

Natural gas of radiolytic origin: An overlooked component of shale gas.

SignificanceNatural gas is a key fossil fuel as the world transitions away from coal toward less polluting energy sources in an attempt to minimize the impact of global climate change. Historically, the origin of natural gas produced from conventional reservoirs has been determined based on gas compositional data and stable isotope fingerprints of methane, ethane, and higher n-alkanes, revealing three dominant sources of natural gas: microbial, thermogenic, and abiotic. In our detailed synthesis of published natural gas data from a variety of unconventional hydrocarbon reservoirs worldwide, we demonstrate that there is a previously overlooked source of natural gas that is generated by radiolysis of organic matter in shales

Thermodynamic evidence of giant salt deposit formation by serpentinization: an alternative mechanism to solar evaporation

International audienceThe evaporation of seawater in arid climates is currently the main accepted driving mechanism for the formation of ancient and recent salt deposits in shallow basins. However, the deposition of huge amounts of marine salts, including the formation of tens of metres of highly soluble types (tachyhydrite and bischofite) during the Aptian in the South Atlantic and during the Messinian Salinity Crisis, are inconsistent with the wet and warm palaeoclimate conditions reconstructed for these periods. Recently, a debate has been developed that opposes the classic model of evaporite deposition and argues for the generation of salt by serpentinization. The products of the latter process can be called "dehydratites". The associated geochemical processes involve the consumption of massive amounts of pure water, leading to the production of concentrated brines. Here, we investigate thermodynamic calculations that account for high salinities and the production of soluble salts and MgCl2-rich brines through sub-seafloor serpentinization processes. Our results indicate that salt and brine formation occurs during serpentinization and that the brine composition and salt assemblages are dependent on the temperature and CO2 partial pressure. Our findings help explain the presence and sustainability of highly soluble salts that appear inconsistent with reconstructed climatic conditions and demonstrate that the presence of highly soluble salts probably has implications for global tectonics and palaeoclimate reconstructions

Mineralogical and isotopic record of biotic and abiotic diagenesis of the Callovian-Oxfordian clayey formation of Bure (France)

International audienceThe Callovian-Oxfordian (COx) clayey unit is being studied in the Eastern part of the Paris Basin at depths between 400 and 500 m depth to assess of its suitability for nuclear waste disposal. The present study combines new mineralogical and isotopic data to describe the sedimentary history of the COx unit. Petrologic study provided evidence of the following diagenetic mineral sequence: (1) framboidal pyrite and micritic calcite, (2) iron-rich euhedral carbonates (ankerite, sideroplesite) and glauconite (3) limpid calcite and dolomite and celestite infilling residual porosity in bioclasts and cracks, (4) chalcedony, (5) quartz/calcite. Pyrite in bioturbations shows a wide range of δ34S (−38‰ to +34.5‰), providing evidence of bacterial sulphate reduction processes in changing sedimentation conditions. The most negative values (−38‰ to −22‰), measured in the lower part of the COx unit indicate precipitation of pyrite in a marine environment with a continuous sulphate supply. The most positive pyrite δ34S values (−14‰ up to +34.5‰) in the upper part of the COx unit indicate pyrite precipitation in a closed system. Celestite δ34S values reflect the last evolutionary stage of the system when bacterial activity ended; however its deposition cannot be possible without sulphate supply due to carbonate bioclast dissolution. The 87Sr/86Sr ratio of celestite (0.706872-0.707040) is consistent with deposition from Jurassic marine-derived waters. Carbon and oxygen isotopic compositions of bulk calcite and dolomite are consistent with marine carbonates. Siderite, only present in the maximum clay zone, has chemical composition and δ18O consistent with a marine environment. Its δ13C is however lower than those of marine carbonates, suggesting a contribution of 13C-depleted carbon from degradation of organic matter. δ18O values of diagenetic chalcedony range between +27‰ and +31‰, suggesting precipitation from marine-derived pore waters. Late calcite crosscutting a vein filled with chalcedony and celestite, and late euhedral quartz in a limestone from the top of the formation have lower δ18O values (not, vert, similar+19‰), suggesting that they precipitated from meteoric fluids, isotopically close to present-day pore waters of the formation. Finally, the study illustrates the transition from very active, biotic diagenesis to abiotic diagenesis. This transition appears to be driven by compaction of the sediment, which inhibited movement of bacterial cells by reduction of porosity and pore sizes, rather than a lack of inorganic carbon or sulphates

Toward the sustainable use of groundwater springs: A case study from Namibia

-The water supply in drylands mainly relies on groundwater, making it a crucial resource. Springs in southern Africa are often underutilized, and are neither protected nor monitored. Thus, the aim of this study was to evaluate their quality in a sample area in northwestern Namibia and to propose solutions for the sustainable use of springs. In total, 35 springs and hot springs were evaluated in the study area located in the drier part of Namibia (Pmean = 150–400 mm/year), an area highly impacted by ongoing climate change with longer and more frequent drought seasons. The springs there are mostly uncaptured and the discharge is in the form of surface runoff, which is mainly lost to the atmosphere by evaporation. Most of the studied springs were perennial, despite a severe drought period. Local communities rely on the springs mainly for livestock and human consumption, as well as for irrigation. However, 71% of the springs do not have any protective measures. The temperature, pH, conductivity and alkalinity were tested in situ. In total, 20 samples were collected and analyzed for major ions (boron, fluoride, silica and strontium) and total dissolved solids (TDS). The physical and inorganic results mostly indicated good and excellent quality water for human consumption, while the hot springs tended to have poor water quality in terms of Namibian standards, indicating that the water was not fit for human consumption

Family Firms and Firm Performance: Evidence from Japan

Corrigendum: Nature Structural and Molecular Biology 16 (12), 1331 (2009) doi:10.1038/nsmb1209-1331bInternational audienceThioredoxins (Trxs) are oxidoreductase enzymes, present in all organisms, that catalyze the reduction of disulfide bonds in proteins. By applying a calibrated force to a substrate disulfide, the chemical mechanisms of Trx catalysis can be examined in detail at the single-molecule level. Here we use single-molecule force-clamp spectroscopy to explore the chemical evolution of Trx catalysis by probing the chemistry of eight different Trx enzymes. All Trxs show a characteristic Michaelis-Menten mechanism that is detected when the disulfide bond is stretched at low forces, but at high forces, two different chemical behaviors distinguish bacterial-origin from eukaryotic-origin Trxs. Eukaryotic-origin Trxs reduce disulfide bonds through a single-electron transfer reaction (SET), whereas bacterial-origin Trxs show both nucleophilic substitution (SN2) and SET reactions. A computational analysis of Trx structures identifies the evolution of the binding groove as an important factor controlling the chemistry of Trx catalysis

The evolutionary history of the catenin gene family during metazoan evolution

<p>Abstract</p> <p>Background</p> <p>Catenin is a gene family composed of three subfamilies; p120, beta and alpha. Beta and p120 are homologous subfamilies based on sequence and structural comparisons, and are members of the armadillo repeat protein superfamily. Alpha does not appear to be homologous to either beta or p120 based on the lack of sequence and structural similarity, and the alpha subfamily belongs to the vinculin superfamily. Catenins link the transmembrane protein cadherin to the cytoskeleton and thus function in cell-cell adhesion. To date, only the beta subfamily has been evolutionarily analyzed and experimentally studied for its functions in signaling pathways, development and human diseases such as cancer. We present a detailed evolutionary study of the whole catenin family to provide a better understanding of how this family has evolved in metazoans, and by extension, the evolution of cell-cell adhesion.</p> <p>Results</p> <p>All three catenin subfamilies have been detected in metazoans used in the present study by searching public databases and applying species-specific BLAST searches. Two monophyletic clades are formed between beta and p120 subfamilies using Bayesian phylogenetic inference. Phylogenetic analyses also reveal an array of duplication events throughout metazoan history. Furthermore, numerous annotation issues for the catenin family have been detected by our computational analyses.</p> <p>Conclusions</p> <p>Delta2/ARVCF catenin in the p120 subfamily, beta catenin in the beta subfamily, and alpha2 catenin in the alpha subfamily are present in all metazoans analyzed. This implies that the last common ancestor of metazoans had these three catenin subfamilies. However, not all members within each subfamily were detected in all metazoan species. Each subfamily has undergone duplications at different levels (species-specific, subphylum-specific or phylum-specific) and to different extents (in the case of the number of homologs). Extensive annotation problems have been resolved in each of the three catenin subfamilies. This resolution provides a more coherent description of catenin evolution.</p

The Molecular Evolution of the p120-Catenin Subfamily and Its Functional Associations

p120-catenin (p120) is the prototypical member of a subclass of armadillo-related proteins that includes δ-catenin/NPRAP, ARVCF, p0071, and the more distantly related plakophilins 1–3. In vertebrates, p120 is essential in regulating surface expression and stability of all classical cadherins, and directly interacts with Kaiso, a BTB/ZF family transcription factor.To clarify functional relationships between these proteins and how they relate to the classical cadherins, we have examined the proteomes of 14 diverse vertebrate and metazoan species. The data reveal a single ancient δ-catenin-like p120 family member present in the earliest metazoans and conserved throughout metazoan evolution. This single p120 family protein is present in all protostomes, and in certain early-branching chordate lineages. Phylogenetic analyses suggest that gene duplication and functional diversification into “p120-like” and “δ-catenin-like” proteins occurred in the urochordate-vertebrate ancestor. Additional gene duplications during early vertebrate evolution gave rise to the seven vertebrate p120 family members. Kaiso family members (i.e., Kaiso, ZBTB38 and ZBTB4) are found only in vertebrates, their origin following that of the p120-like gene lineage and coinciding with the evolution of vertebrate-specific mechanisms of epigenetic gene regulation by CpG island methylation.The p120 protein family evolved from a common δ-catenin-like ancestor present in all metazoans. Through several rounds of gene duplication and diversification, however, p120 evolved in vertebrates into an essential, ubiquitously expressed protein, whereas loss of the more selectively expressed δ-catenin, p0071 and ARVCF are tolerated in most species. Together with phylogenetic studies of the vertebrate cadherins, our data suggest that the p120-like and δ-catenin-like genes co-evolved separately with non-neural (E- and P-cadherin) and neural (N- and R-cadherin) cadherin lineages, respectively. The expansion of p120 relative to δ-catenin during vertebrate evolution may reflect the pivotal and largely disproportionate role of the non-neural cadherins with respect to evolution of the wide range of somatic morphology present in vertebrates today

Polyfunctional T-Cell Responses Are Disrupted by the Ovarian Cancer Ascites Environment and Only Partially Restored by Clinically Relevant Cytokines

Host T-cell responses are associated with favorable outcomes in epithelial ovarian cancer (EOC), but it remains unclear how best to promote these responses in patients. Toward this goal, we evaluated a panel of clinically relevant cytokines for the ability to enhance multiple T-cell effector functions (polyfunctionality) in the native tumor environment.Experiments were performed with resident CD8+ and CD4+ T cells in bulk ascites cell preparations from high-grade serous EOC patients. T cells were stimulated with α-CD3 in the presence of 100% autologous ascites fluid with or without exogenous IL-2, IL-12, IL-18 or IL-21, alone or in combination. T-cell proliferation (Ki-67) and function (IFN-γ, TNF-α, IL-2, CCL4, and CD107a expression) were assessed by multi-parameter flow cytometry. In parallel, 27 cytokines were measured in culture supernatants. While ascites fluid had variable effects on CD8+ and CD4+ T-cell proliferation, it inhibited T-cell function in most patient samples, with CD107a, IFN-γ, and CCL4 showing the greatest inhibition. This was accompanied by reduced levels of IL-1β, IL-1ra, IL-9, IL-17, G-CSF, GM-CSF, Mip-1α, PDGF-bb, and bFGF in culture supernatants. T-cell proliferation was enhanced by exogenous IL-2, but other T-cell functions were largely unaffected by single cytokines. The combination of IL-2 with cytokines engaging complementary signaling pathways, in particular IL-12 and IL-18, enhanced expression of IFN-γ, TNF-α, and CCL4 in all patient samples by promoting polyfunctional T-cell responses. Despite this, other functional parameters generally remained inhibited.The EOC ascites environment disrupts multiple T-cell functions, and exogenous cytokines engaging diverse signaling pathways only partially reverse these effects. Our results may explain the limited efficacy of cytokine therapies for EOC to date. Full restoration of T-cell function will require activation of signaling pathways beyond those engaged by IL-2, IL-12, IL-18, and IL-21