Shock-induced volatile loss from a carbonaceous chondrite: implications for planetary accretion

Solid-recovery impact-induced volatile loss experiments on the Murchison C2M meteorite indicate that for an impact of a given velocity, H₂O and total volatiles are driven from the sample in the same proportion as present initially. We infer that the volatiles other than H₂O driven from the meteorite also have the same bulk composition as those of the starting material. Thus, the early bulk composition of an impact-induced atmosphere of a planet growing by accretion from material like Murchison would be the same as the volatile composition of the incident planetesimals. Incipient devolatilization of Murchison occurs at an initial shock pressure of about 11 GPa and complete devolatilization occurs at a pressure of about 30 GPa. If an Earth-sized planet were formed from the infall of planetesimals of Murchison composition, incipient and complete devolatilization of accreting planetesimals would occur when the planet reached approximately 12% and 27%, respectively, of its final radius. Thus, impact-induced devolatilization of accreting planetesimals and of the hydrated surface would profoundly affect the distribution of volatiles within the accreting planet. For example, for a cold, homogeneous accretion of a planet, prior to metallic core formation and internal differentiation, the growing planet would have a very small core with the same volatile content as the incident material, a volatile-depleted “mantle”, and an extremely volatile-rich surface.     

Correlations between13C and ΣCO2 in surface waters and atmospheric CO2

¹³C and ΣCO₂ data from the North and South Atlantic, the Antarctic, and the North and South Pacific are given. The δ¹³C of the ΣCO₂ in the deep water (～3000m) decreases from 1.7‰ in the North Atlantic to ?0.10‰ in the North Pacific. This change is attributed to the addition of about 158 μmoles of CO₂ per kg of seawater. The in-situ oxidation of organic matter accounts for 83% of this increase in ΣCO₂, while the remainder is attributed to dissolution of calcium carbonate.The δ¹³C of the dissolved CO₂ in mid-latitude surface water samples is controlled by a quasi-steady-state equilibrium with atmospheric CO₂ at a mean temperature of 16°C. The δ¹³C and ΣCO₂ values of Antarctic surface water samples suggest that these waters are derived from a mixture of North Atlantic deep water and equilibrated surface water.     

CO2/CaCl2 solution interfacial tensions under CO2 geological storage conditions: Influence of cation valence on interfacial tension

The effectiveness of CO₂ storage in deep saline aquifers and hydrocarbon reservoirs is governed, among other factors, by the interfacial tension between the injected CO₂ and formation water (brine). Experimental data on CO₂/water and CO₂/NaCl solution have revealed that the interfacial tension depends on the pressure, temperature and water salinity. However, there is still a lack of data for other salts (such as MgCl₂ and CaCl₂) which are also present in aquifers and carbonate reservoirs.     

Quantifying CO2 fluxes from soil surfaces to the atmosphere

Measurements of CO₂ fluxes from ground surface of the atmosphere (soil respiration) are needed to quantify biotic and abiotic reaction rates in unsaturated zones and to gain insight into the importance of these processes on global warming. The use of three techniques (dynamic closed chambers, static chambers, and gradient calculations) to determine soil respiration was assessed by measuring fluxes of microbially produced CO₂ from an unsaturated mesocosm (2.4 m dia.×3.2 m thick) and two unsaturated minicosms (0.58 m dia.×1.2 m thick), one maintained at 18–23 °C (HT) and the other at 5 °C (LT). By injecting known and constant CO₂ fluxes into the bottom of the HT minicosm and measuring the resulting fluxes, it was shown that the dynamic closed chamber (DCCS) technique yielded accurate measurements of fluxes over the range observed from natural unsaturated media. Over this same range, results showed that the concentration gradient method yielded reasonable estimates of fluxes but its accuracy was limited by uncertainties in both the concentration gradient and the gaseous diffusion coefficient in the soil atmosphere. The static chamber method underestimated the actual flux at higher CO₂ fluxes and when adsorption times of >24 h were used.     

Stability of forsterite + CO2 and its bearing on the role of CO2 in the mantle

An experimental determination of the reaction MgCO₃ + MgSiO₃ = Mg₂SiO₄ + CO₂ between 20 and 40 kbars and in the range 1000–1500°C yields an average pressure effect on the equilibrium of 44 bars/°C. This result shows that the assemblage forsterite and carbon dioxide is not stable under most pressure and temperature conditions expected in the upper mantle. Hypotheses requiring the presence of free CO₂ in the low-velocity zone, CO₂ as a drive mechanism for kimberlite emplacement, or action of a free CO₂ phase in ultramafic rocks may need considerable revision.     

Capillary pressure for the sand–CO2–water system under various pressure conditions. Application to CO2 sequestration

Accurate modeling of storage of carbon dioxide (CO₂) in heterogeneous aquifers requires experiments of the capillary pressure as function of temperature and pressure. We present a method with which static drainage and imbibition capillary pressures can be measured continuously as a function of saturation at various temperature (T) and pressure (P) conditions. The measurements are carried out at (T, P) conditions of practical interest. Static conditions can be assumed as small injection rates are applied. The capillary pressure curves are obtained for the unconsolidated sand–distilled water–CO₂ system. The experimental results show a decrease of drainage and imbibition capillary pressure for increasing CO₂ pressures and pronounced dissolution rate effects for gaseous CO₂. Significant capillary pressure fluctuations and negative values during imbibition are observed at near critical conditions. The measurement procedure is validated by a numerical model that simulates the experiments.     

High-pressure phases of Co2GeO4, Ni2GeO4, Mn2GeO4 and MnGeO3: implications for the germanate-silicate modeling scheme and the Earth's mantle

In a diamond-anvil press coupled with YAG laser heating, the spinels of Co₂GeO₄ and Ni₂GeO₄ have been found to disproportionate into their isochemical oxide mixtures at about 250 kbar and 1400–1800°C in the same manner as their silicate analogues. At about the same P-T conditions MnGeO₃ transforms to the orthorhombic perovskite structure (space group Pbnm); the lattice parameters at room temperature and 1 bar are a₀ = 5.084 ± 0.002, b₀ = 5.214 ± 0.002, and c₀ = 7.323 ± 0.003Å with Z = 4 for the perovskite phase. The zero-pressure volume change associated with the ilmenite-perovskite phase transition in MnGeO₃ is ?6.6%. Mn₂GeO₄ disproportionates into a mixture of the perovskite phase of MnGeO₃ plus the rocksalt phase of MnO at P = 250kbar and T = 1400–1800°C. The concept of utilizing germanates as high-pressure models for silicates is valid in general. The results of this study support the previous conclusion that the lower mantle comprises predominantly the orthorhombic perovskite phase of ferromagnesian silicate.     

Melting relationships in CaO-CO2 and MgO-CO2 to 36 kilobars with comments on CO2 in the mantle

The melting curves of CaCO₃ and MgCO₃ have been extended to pressures of 36 kb by experiments in piston-cylinder apparatus. At 30 kb, the melting temperatures of calcite and magnesite are 1610°C and 1585°C, respectively. New data for the magnesite dissociation reaction permit the location of an invariant point for the assemblage magnesite + periclase + liquid + vapor near 26 kb-1550°C. New data are also presented for the calcite-aragonite transition at 800°C, 950°C and 1100°C. At pressures above 36–50 kb, calcite and magnesite melt at temperatures lower than the solidus of dry mantle peridotite. Natural and experimental evidence suggests that carbon dioxide in the Earth's mantle could be present in a variety of forms: (a) a free vapor phase, (b) vapor dissolved in silicate magma, (c) crystalline carbonate, (d) carbonatite liquid, (e) carbon-bearing silicate analogs, or (f) carbonato-silicates (such as scapolite, spurrite, tilleyite, and related compounds).     

High-pressure disproportionation of Co2SiO4 spinel and implications for Mg2SiO4 spinel

Co₂SiO₄ spinel has been found to disproportionate into its isochemically mixed oxides with rocksalt and rutile structures at pressures between 170 and 190 kbar and temperatures between 1400 and 1800°C in a diamond-anvil press. The exact disproportionation pressure is not certain due to transient increases in pressure during the local and rapid heating by a continuous YAG laser. The slope of the phase boundary between the spinel phase and the mixed oxides is calculated to be?33 ± 20bar/deg. This negative slope is consistent with the observed anomalously large entropy of CoO (relative to its isostructural oxides) in entropy vs.(MV)^?1/2 systematics, whereM is the formula weight andV the molar volume. The sign of the slope for a phase boundary in the disproportionation of spinel depends on the values of entropy of the rocksalt oxides as well as the inverse character exhibited in the spinel phases. The normal entropy of MgO suggests that the phase boundary for the disproportionation of Mg₂SiO₄ spinel has positive slope.     

Geochemical features of the geothermal CO2-watercarbonate rock system and analysis on its CO2 sources

Taking Huanglong Ravine and Kangding, Sichuan, and Xiage, Zhongdian, Yunnan, as examples, the authors summarize the hydrogeochemical and carbon stable isotopic features of the geothermal CO₂-water-carbonate rock system and analyze the CO₂ sources of the system. It was found that the hydrogeochemical and carbon stable isotopic features of such a system are different from those of shallow CO₂-water-carbonate rock system, which is strongly influenced by biosphere. The former has higher CO₂ partial pressure, and is rich in heavy carbon stable isotope. In addition, such a geothermal system is also different from that developed in igneous rock. The water in the latter system lacks Ca²⁺, and thus, there are few tufa deposits on ground surface, but it is rich in light carbon stable isotope. Further analysis shows that CO₂ of the geothermal CO₂-water-carbonate rock system is a mixture of metamorphic CO₂ and magmatic CO₂.     

微囊藻CO2-浓缩机制基因型的动态变化及其对CO2的竞争效应

由于具有高效的CO₂-浓缩机制,蓝藻在低CO₂浓度条件下具有竞争优势。然而,随着大气中CO₂浓度急剧增加,蓝藻CO₂-浓缩机制如何响应的研究较少。因此,本文以常见水华蓝藻——微囊藻为研究对象,通过对滇池微囊藻水华动态及不同CO₂-浓缩机制基因型进行监测,探讨蓝藻CO₂-浓缩机制基因的微进化特征及其动态变化。同时,设置高(0.08%)、中(0.04%)、低(0.02%)CO₂浓度(V/V)进一步揭示微囊藻不同CO₂-浓缩机制基因微进化对CO₂的竞争效应。结果表明:滇池无机碳浓度在4个采样点存在空间差异性,均呈现先降低后升高的趋势,并以HCO₃^-为主要无机碳存在形式。调查期间,东大河、观音山、洛龙河和生态所4个采样点的微囊藻均以sbtA基因型占绝对优势,相对丰度远高于bicA基因型。在不同水华时期,bicA基因型和sbtA基因型呈现相反的变化趋势,即从...     

Shock temperature in calcite (CaCO3) at 95-160 GPa

The temperatures induced in crystalline calcite (CaCO₃) upon planar shock compression (95-160 GPa) are reported from two-stage light gas gun experiments. Temperatures of 3300-5400 K are obtained by fitting six-channel optical pyrometer radiances in the 450-900 nm range to the Planck gray-body radiation law. Thermodynamic calculations demonstrate that these temperatures are some 400-1350 K lower than expected for vibronic excitations of the lattice with a 3R/mole-atom specific heat (R is gas constant). The temperature deficit along the Hugoniot is larger than that expected from only melting. In addition to melting, it appears likely that shock-induced decomposition of calcite occurs behind the shock front. We modeled disproportionation of calcite into CaO (solid) plus CO₂ (gas). For temperature calculations, specific heat at constant volume for 1 mole of CO₂ is taken to be 6.7R as compared to 9R in the solid state; whereas a mole of calcite and a mole of CaO have their solid state values 15R and 6R, respectively. Calculations suggest that the calcite decomposes to CaO and CO₂ at ∼110±10 GPa along the Hugoniot. Recent reanalysis of earlier VISAR measurements of particle velocity profiles [1] indicates that calcite shocked to 18 GPa undergoes disproportionation at much lower pressures upon isentropic expansion.     

Interfacial tension measurements and wettability evaluation for geological CO2 storage

Interfacial interactions, namely interfacial tension, wettability, capillarity and interfacial mass transfer are known to govern fluid distribution and behavior in porous media. Therefore the interfacial interactions between CO₂, brine and oil and/or gas reservoirs have a significant influence on the effectiveness of any CO₂ storage operations. However, data and knowledge of interfacial properties in storage conditions are scarce. This issue becomes particularly true in the case of deep saline aquifers where limited, economically driven, data collection and archiving are available. In this paper, we present a complete set of brine–CO₂ interfacial tension data at pressure, temperature and salinity conditions, representative of a CO₂ storage operation. A semi-empirical correlation is proposed to calculate the interfacial tension from the experimental data. Wettability is studied at pore scale, using glass micromodels in order to track fluids distribution as a function of the thermodynamic properties and wettability conditions for water–CO₂ systems. With this approach, we show that, in strongly hydrophilic porous media, the CO₂ does not wet the solid surface whereas; if the porous media has less hydrophilic properties the CO₂ significantly wets the surface.     

Oxygen diffusion rates in quartz exchanged with CO2

Oxygen self diffusion rates were determined in quartz samples exchanged with¹⁸O-enriched CO₂ between 745 and 900°C and various pressures, and the diffusion profiles were measured using an ion microprobe. The activation energy (Q) and preexponential factor (D₀) at P(CO₂) = P(tot) = 100 bar, for diffusion parallel to the c-axis are 159 ( ± 13) kJ/g atom and 2.10 (+0.75/ −0.55) × 10⁻⁸ cm²/s. This rate is approximately 100 times slower than that obtained from hydrothermal experiments and 100 times faster than a previous 1-bar quartz-O₂ exchange experiment. The oxygen diffusion rate measured at 0.6 bar, 888°C, and at 900°C in vacuum is in agreement with the previous 1-bar exchange experiments with¹⁸O₂. The effect of higher CO₂ pressures is small. At 900°C, the diffusion rate exchanged with CO₂ is = 2.35 × 10⁻¹⁵ cm²/s at 100 bar, 2.24 × 10⁻¹⁵ cm²/s at 3.45 kbar and 8.13 × 10⁻¹⁵ cm²/s at 7.2 kbar.There is probably a diffusing species, other than oxygen, that enhances the oxygen diffusion rate in these quartz-CO₂ systems, relative to that occurring at very low pressures or in a vacuum. The effect of this diffusing species, however, is not as strong as that associated with H₂O. Preserved oxygen isotope fractionations between coexisting minerals in a slowly cooled, high-grade metamorphic terrane will vary depending upon whether a water-rich phase was present or not. Closure temperatures will be approximately 100°C higher in rocks where no water-rich phase was present during cooling. The measured fractionations between coexisting minerals in metamorphic rocks may potentially be used as a sensor of water presence during retrogression.     

Multi-scale modeling of CO2 dispersion leaked from seafloor off the Japanese coast

A numerical simulation was conducted to predict the change of pCO₂ in the ocean caused by CO₂ leaked from an underground aquifer, in which CO₂ is purposefully stored. The target space of the present model was the ocean above the seafloor. The behavior of CO₂ bubbles, their dissolution, and the advection-diffusion of dissolved CO₂ were numerically simulated. Here, two cases for the leakage rate were studied: an extreme case, 94,600 t/y, which assumed that a large fault accidentally connects the CO₂ reservoir and the seafloor; and a reasonable case, 3800 t/y, based on the seepage rate of an existing EOR site. In the extreme case, the calculated increase in ΔpCO₂ experienced by floating organisms was less than 300 ppm, while that for immobile organisms directly over the fault surface periodically exceeded 1000 ppm, if momentarily. In the reasonable case, the calculated ΔpCO₂ and pH were within the range of natural fluctuation.     

Atmospheric14C changes resulting from fossil fuel CO2 release and cosmic ray flux variability

A high-precision tree-ring record of the atmospheric¹⁴C levels between 1820 and 1954 is presented. Good agreement is obtained between measured and model calculated 19th and 20th century atmospheric Δ¹⁴C levels when both fossil fuel CO₂ release and predicted natural variations in¹⁴C production are taken into account. The best fit is obtained by using a ?-diffusion model with an oceanic eddy diffusion coefficient of 3 cm²/s, a CO₂ atmosphere-ocean gas exchange rate of 21 moles m^?2 yr^?1 and biospheric residence time of 60 years.For trees in the state of Washington the measured 1949–1951 atmospheric Δ¹⁴C level was20.0±1.2%. below the 1855–1864 level. Model calculations indicate that in 1950 industrial CO₂ emissions are responsible for at least 85% of the Δ¹⁴C decline, whereas natural variability accounts for the remaining 15%.     

The join grossularite-calcite through the system CaO—Al2O3—SiO2—CO2 at 30 kilobars: Crystallization range of silicates and carbonates on the liquidus

At 30 kbar, calcite melts congruently at 1615°C, and grossularite melts incongruently to liquid + gehlenite (tentative identification) at 1535°C. The assemblage calcite + grossularite melts at 1450°C to produce liquid + vapor, with piercing point at about 49 wt.% CaCO₃. Vapor phase is present in all hypersolidus phase fields except for those with less than about 7% CaCO₃ or 8% Ca₃Al₂Si₃O₁₂. These results, together with known liquidus data for CaO—SiO₂—CO₂ and inferred results for CaO—Al₂O₃—CO₂ and Al₂O₃—SiO₂—CO₂, permit construction of the position of the CO₂- saturated liquidus surface in the quaternary system, and estimation of the positions of liquidus field boundaries separating some of the primary crystallization fields on this surface. The field of calcite is separated from those for grossularite and quartz by a field boundary with about 50% dissolved CaCO₃. Crystallization paths of silicate liquids in the range Ca₂SiO₄—Ca₃Al₂Si₃O₁₂—SiO₂, with some dissolved CO₂, will terminate at a quaternary eutectic on this field boundary, with the precipitation of calcite together with grossularite and quartz, at a temperature below 1450°C. Addition of Al₂O₃ to CaO—SiO₂—CO₂ in amounts sufficient to stabilize garnet thus causes little change in the general liquidus pattern as far as carbonates and silicates are concerned. With addition of MgO, we anticipate that silicate liquids with dissolved CO₂ will also follow liquidus paths to fields for the precipitation of carbonates; we conclude that similar paths link kimberlite and some carnbonatite magmas.     

A method for shipboard measurement of CO2 partial pressure in seawater

A dynamic method suitable for shipboard measurement of the partial pressure of CO₂ exerted by a seawater sample has been developed. The system consists of a paddle-wheel-type gas-water equilibrator and an infrared gas analyzer. Since the system is open to the atmosphere at the in-take and the exhaust ends, it can be operated stably on shipboard conditions. A precision of ±2% has been obtained for shipboard measurement of pCO₂.