Oxidation and metal-insertion in molybdenite surfaces: evaluation of charge-transfer mechanisms and dynamics

Molybdenum disulfide (MoS₂), a layered transition-metal dichalcogenide, has been of special importance to the research community of geochemistry, materials and environmental chemistry, and geotechnical engineering. Understanding the oxidation behavior and charge-transfer mechanisms in MoS₂ is important to gain better insight into the degradation of this mineral in the environment. In addition, understanding the insertion of metals into molybdenite and evaluation of charge-transfer mechanism and dynamics is important to utilize these minerals in technological applications. Furthermore, a detailed investigation of thermal oxidation behavior and metal-insertion will provide a basis to further explore and model the mechanism of adsorption of metal ions onto geomedia.     

A Parameterization of Dry Thermals and Shallow Cumuli for Mesoscale Numerical Weather Prediction

For numerical weather prediction models and models resolving deep convection, shallow convective ascents are subgrid processes that are not parameterized by classical local turbulent schemes. The mass flux formulation of convective mixing is now largely accepted as an efficient approach for parameterizing the contribution of larger plumes in convective dry and cloudy boundary layers. We propose a new formulation of the EDMF scheme (for Eddy Diffusivity\Mass Flux) based on a single updraft that improves the representation of dry thermals and shallow convective clouds and conserves a correct representation of stratocumulus in mesoscale models. The definition of entrainment and detrainment in the dry part of the updraft is original, and is specified as proportional to the ratio of buoyancy to vertical velocity. In the cloudy part of the updraft, the classical buoyancy sorting approach is chosen. The main closure of the scheme is based on the mass flux near the surface, which is proportional to the sub-cloud layer convective velocity scale w _*. The link with the prognostic grid-scale cloud content and cloud cover and the projection on the non- conservative variables is processed by the cloud scheme. The validation of this new formulation using large-eddy simulations focused on showing the robustness of the scheme to represent three different boundary layer regimes. For dry convective cases, this parameterization enables a correct representation of the countergradient zone where the mass flux part represents the top entrainment (IHOP case). It can also handle the diurnal cycle of boundary-layer cumulus clouds (EUROCS\ARM) and conserve a realistic evolution of stratocumulus (EUROCS\FIRE).     

Climate variability and trends in downscaled high-resolution simulations and projections over Metropolitan France

In order to fulfill the society demand for climate information at the spatial scale allowing impact studies, long-term high-resolution climate simulations are produced, over an area covering metropolitan France. One of the major goals of this article is to investigate whether such simulations appropriately simulate the spatial and temporal variability of the current climate, using two simulation chains. These start from the global IPSL-CM4 climate model, using two regional models (LMDz and MM5) at moderate resolution (15–20 km), followed with a statistical downscaling method in order to reach a target resolution of 8 km. The statistical downscaling technique includes a non-parametric method that corrects the distribution by using high-resolution analyses over France. First the uncorrected simulations are evaluated against a set of high-resolution analyses, with a focus on temperature and precipitation. Uncorrected downscaled temperatures suffer from a cold bias that is present in the global model as well. Precipitations biases have a season- and model-dependent behavior. Dynamical models overestimate rainfall but with different patterns and amplitude, but both have underestimations in the South-Eastern area (Cevennes mountains) in winter. A variance decomposition shows that uncorrected simulations fairly well capture observed variances from inter-annual to high-frequency intra-seasonal time scales. After correction, distributions match with analyses by construction, but it is shown that spatial coherence, persistence properties of warm, cold and dry episodes also match to a certain extent. Another aim of the article is to describe the changes for future climate obtained using these simulations under Scenario A1B. Results are presented on the changes between current and mid-term future (2021–2050) averages and variability over France. Interestingly, even though the same global climate model is used at the boundaries, regional climate change responses from the two models significantly differ.     

Late Miocene to Quaternary slip history across the Qiulitag anticline in the southern Tianshan piedmont

In this study, we reconstruct the Miocene to Quaternary shortening history across the Qiulitag anticline, a complex fault‐bend fold located in southern Tianshan. We studied the Yaha and Kuche sections, where we combined surface structural measurements and seismic imaging to model the stratigraphic horizons. The history of folding was reconstructed based on magnetostratigraphic analyses and eight cosmogenic burial ages in Kuche. Pleistocene deformation rates were also quantified in Yaha based on a deformed fluvial terrace that we dated to ~67 ka using a cosmogenic depth profile. Our results suggest that the fold grew at a mean slip rate of 0.9–1.3 mm/a in both sections but accelerated to ~2.5 mm/a during the Pleistocene in Kuche. These results support a migration of the deformation towards the basin during the Pleistocene and suggest that most of the present deformation in the Tianshan is accommodated across the external structures of the range.     

Earth system curator: metadata infrastructure for climate modeling

The Earth System Curator is a National Science Foundation sponsored project developing a metadata formalism for describing the digital resources used in climate simulations. The primary motivating observation of the project is that a simulation/model’s source code plus the configuration parameters required for a model run are a compact representation of the dataset generated when the model is executed. The end goal of the project is a convergence of models and data where both resources are accessed uniformly from a single registry. In this paper we review the current metadata landscape of the climate modeling community, present our work on developing a metadata formalism for describing climate models, and reflect on technical challenges we have faced that require new research in the area of Earth Science Informatics.     

Petroleum and aqueous inclusions from deeply buried reservoirs: Experimental simulations and consequences for overpressure estimates

Synthetic hydrocarbon and aqueous inclusions have been created in the laboratory batch reactors in order to mimic inclusion formation or re-equilibration in deeply buried reservoirs. Inclusions were synthesized in quartz and calcite using pure water and Mexican dead oil, or n-tetradecane (C₁₄H₃₀), at a temperature and pressure of 150 °C and 1 kbar. One-phase hydrocarbon inclusions are frequently observed at standard laboratory conditions leading to homogenization temperatures between 0 and 60 °C. UV epifluorescence of Mexican oil inclusions is not uniform; blue and green-yellow colored inclusions coexist; however, no clear evidence of variations in fluid chemistry were observed. Homogenization temperatures were recorded and the maxima of T_h plotted on histograms are in good agreement with expected T_h in a range of 6 °C. Broad histograms were reconstructed showing non-symmetrical T_h distributions over a 20 °C temperature range centered on the expected T_h. This histogram broadening is due to the fragility of the fluid inclusions that were created by re-filling of pre-existing microcavities. Such T_h histograms are similar to T_h histograms recorded on natural samples from deeply buried carbonate reservoirs. T_h values lower than those expected were measured for hydrocarbon inclusions in quartz and calcite, and for aqueous inclusions in calcite. However, the results confirm the ability of fluid inclusions containing two immiscible fluids to lead to PT reconstructions, even in overpressured environments.     

Strain response and re-equilibration of CH4-rich synthetic aqueous fluid inclusions in calcite during pressure drops

Aqueous fluids in sedimentary basins often contain dissolved methane, particularly in petroleum environments. PVTX (Pressure-Volume-Temperature-Composition) reconstructions performed using fluid inclusion data are largely based on the assumption that inclusions do not change from the time of trapping until the present. Many authors, however, consider that fluid inclusions can re-equilibrate, particularly in fragile minerals like calcite. In order to understand this re-equilibration phenomenon in the metamorphic domain, previous experiments have been performed under high PT conditions, but few have been performed at low to medium PT conditions such as those associated with sedimentary burial diagenesis, and no previous studies have examined CH₄-bearing aqueous inclusions in calcite.An experimental study of the preservation/modification of CH₄-rich synthetic fluid inclusions in calcite during isothermal decompression was conducted. An autoclave was used for accurate PTX control allowing equilibrium between liquid and vapour in the CH₄-H₂O system. PTX conditions were maintained at four stages of decreasing pressure, with each stage held for 7 days to simulate an isothermal pressure drop. In order of decreasing pressure, the pressure-temperature conditions monitored were 276 ± 10 bar at 180 ± 7 °C, 176 ± 10 bar at 180 ± 7 °C, 76 ± 10 bar at 180 ± 7 °C and 10 ± 3 bar at 180 ± 15 °C. At the end of the experiment, the calcite was recovered and analyzed by microthermometry and Raman microspectroscopy for PTX reconstruction. A careful procedure was adopted to limit re-equilibration of inclusions during analytical procedures. Four types of inclusion shapes and four types of strain patterns were differentiated. Classification of the petrographic strain patterns was carried out. These strain patterns were associated with inclusion stretching and/or leakage regarding CH₄, T_h and P_h compared to experimental conditions. Factors controlling the preservation or acquisition of strain patterns included the initial shape and size of the inclusion, and the pressure differential (ΔP) between the confining pressure (P_cf) and the internal pressure (P_i) within the inclusion. Most fluid inclusions seemed to be trapped during the first 7 days of the experiment, although few (4%) of these preserved the initial PT conditions of 276 ± 10 bar, whereas 8% preserved the second and third run of PT conditions. Overall, the majority of inclusions (88%) did not reflect accurately the PTX trapping conditions. A petrographic guide to the inclusions is presented here that allows strain identification for PVT reconstructions. Re-equilibration patterns and evidence for preferential methane leakage from aqueous inclusions in calcite are important findings revealed by this study, and may be useful for the reconstruction of post-trapping events in investigations of natural samples, and in other experiments using synthetic inclusions in calcite.     

A vibrational study of phase transitions among the GeO2 polymorphs

Infrared and Raman spectra of the quartz, rutile and amorphous forms of GeO₂ have been recorded under pressure and/or temperature, in order to study the crystalline to crystalline — or amorphous — transformations of this compound in the solid state. X-ray diffraction data shown that crystalline quartz-GeO₂ subjected to high pressure amorphizes. Infrared data are consistent with a gradual amorphisation of this compound at static pressures between 6 to 12 GPa at 300 K. With increasing pressure, the Ge-O distance appears to remain constant and amorphization is associated with a progressive change in the coordination of germanium atoms from fourfold to sixfold. This apparent change in coordination is not quenchable at room pressure. On decompression, the Ge in the amorphous form returns to tetrahedral coordination. The anharmonic parameters for the Raman modes of the quartz and rutile forms of GeO₂, have also been estimated from pressure and temperature shifts. These data have been used to calculate heat capacities and entropies of the two polymorphs at different pressures, with the Kieffer vibrational model. The calculated heat capacities at room pressure are within 1% of the experimental values between 20 and 1500 K. The calculated entropies are used to estimate the phase boundary in the (P, T) plane. The slope of the curve at room pressure (17 bar/K) is in good agreement with experimental values.