No Arabic abstract
The formation of solid calcium carbonate (CaCO3) from aqueous solutions or slurries containing calcium and carbon dioxide (CO2) is a complex process of considerable importance in the ecological, geochemical and biological areas. Moreover, the demand for powdered CaCO3 has increased considerably recently in various fields of industry. The aim of this study was therefore to synthesize fine particles of calcite with controlled morphology by hydrothermal carbonation of calcium hydroxide at high CO2 pressure (initial PCO2=55 bar) and at moderate and high temperature (30 and 90 degrees C). The morphology of precipitated particles was identified by transmission electron microscopy (TEM/EDS) and scanning electron microscopy (SEM/EDS). In addition, an X-ray diffraction analysis was performed to investigate the carbonation efficiency and purity of the solid product. Carbonation of dispersed calcium hydroxide in the presence of supercritical (PT=90 bar, T=90 degrees C) or gaseous (PT=55 bar, T=30 degrees C) CO2 led to the precipitation of sub-micrometric isolated particles (<1$mu$m) and micrometric agglomerates (<5$mu$m) of calcite. For this study, the carbonation efficiency (Ca(OH)2-CaCO3 conversion) was not significantly affected by PT conditions after 24 h of reaction. In contrast, the initial rate of calcium carbonate precipitation increased from 4.3 mol/h in the 90bar-90 degrees C system to 15.9 mol/h in the 55bar-30 degrees C system. The use of high CO2 pressure may therefore be desirable for increasing the production rate of CaCO3, carbonation efficiency and purity, to approximately 48 kg/m3h, 95% and 96.3%, respectively in this study. The dissipated heat for this exothermic reaction was estimated by calorimetry to be -32 kJ/mol in the 90bar-90 degrees C system and -42 kJ/mol in the 55bar-30 degrees C system.
We present a study of gas-phase H2O and CO2 toward a sample of 14 massive protostars with the Short Wavelength Spectrometer (SWS) on board the Infrared Space Observatory (ISO). Modeling of the H2O spectra using a homogeneous model with a constant excitation temperature T_ex shows that the H2O abundances increase with temperature, up to a few times 10^-5 with respect to H2 for the hottest sources (T_ex ~500 K). This is still a factor of 10 lower than the H2O ice abundances observed toward cold sources in which evaporation is not significant (Keane et al. 2001). Gas-phase CO2 is not abundant in our sources. The abundances are nearly constant for T_ex>~100 K at a value of a few times 10^-7, much lower than the solid-state abundances of ~1--3 times 10^-6 (Gerakines et al. 1999). For both H2O and CO2 the gas/solid ratio increases with temperature, but the increase is much stronger for H2O than for CO2, suggesting a different type of chemistry. In addition to the homogeneous models, a power law model has been developed for one of our sources, based on the physical structure of this region as determined from submillimeter data by van der Tak et al. (1999). The resulting H2O model spectrum gives a good fit to the data.
Soil has been recognized as an indirect driver of global warming by regulating atmospheric greenhouse gases. However, in view of the higher heat capacity and CO2 concentration in soil than those in atmosphere, the direct contributions of soil to greenhouse effect may be non-ignorable. Through field manipulation of CO2 concentration both in soil and atmosphere, we demonstrated that the soil-retained heat and its slow transmission process within soil may cause slower heat leaking from the earth. Furthermore, soil air temperature was non-linearly affected by soil CO2 concentration with the highest value under 7500 ppm CO2. This study indicates that the soil and soil CO2, together with atmospheric CO2, play indispensable roles in fueling the greenhouse effect. We proposed that anthropogenic changes in soils should be focused in understanding drivers of the globe warming.
We propose a classification of exoplanet atmospheres based on their H, C, O, N element abundances below about 600 K. Chemical equilibrium models were run for all combinations of H, C, N, O abundances, and three types of solutions were found, which are robust against variations of temperature, pressure and nitrogen abundance. Type A atmospheres contain H2O, CH4, NH3 and either H2 or N2, but only traces of CO2 and O2. Type B atmospheres contain O2, H2O, CO2 and N2, but only traces of CH4, NH3 and H2. Type C atmospheres contain H2O, CO2, CH4 and N2, but only traces of NH3, H2 and O2. Other molecules are only present in ppb or ppm concentrations in chemical equilibrium, depending on temperature. Type C atmospheres are not found in the solar system, where atmospheres are generally cold enough for water to condense, but exoplanets may well host such atmospheres. Our models show that graphite (soot) clouds can occur in type C atmospheres in addition to water clouds, which can occur in all types of atmospheres. Full equilibrium condensation models show that the outgassing from warm rock can naturally provide type C atmospheres. We conclude that type C atmospheres, if they exist, would lead to false positive detections of biosignatures in exoplanets when considering the coexistence of CH4 and CO2, and suggest other, more robust non-equilibrium markers.
The dissolution of porous media in a geologic formation induced by the injection of massive amounts of CO2 can undermine the mechanical stability of the formation structure before carbon mineralization takes place. The geomechanical impact of geologic carbon storage is therefore closely related to the structural sustainability of the chosen reservoir as well as the probability of buoyancy driven CO2 leakage through caprocks. Here we show, with a combination of ex situ nanotomography and in situ microtomography, that the presence of dissolved CO2 in water produces a homogeneous dissolution pattern in natural chalk microstructure. This pattern stems from a greater apparent solubility of chalk and therefore a greater reactive subvolume in a sample. When a porous medium dissolves homogeneously in an imposed flow field, three geomechanical effects were observed: material compaction, fracturing and grain relocation. These phenomena demonstrated distinct feedbacks to the migration of the dissolution front and severely complicated the infiltration instability problem. We conclude that the presence of dissolved CO2 makes the dissolution front less susceptible to spatial and temporal perturbations in the strongly coupled geochemical and geomechanical processes.
CO2 has attracted considerable attention in the recent years due to its role in the greenhouse effect and environmental management. While its reaction with water has been studied extensively, the same cannot be said for reactivity in supercritical CO2 phase, where the conjugate acid/base equilibria proceed through different mechanisms and activation barriers. In spite of the apparent simplicity of the CO2 + H2O reaction, the collective effect of different environments has drastic influence on the free energy profile. Enhanced sampling techniques and well-tailored collective variables provide a detailed picture of the enthalpic and entropic drivers underscoring the differences in the formation mechanism of carbonic acid in the gas, aqueous and supercritical CO2 phases.