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.     

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).     

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.     

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...     

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.     

三峡水库CO2、CH4通量监测分析研究

自成库以来,三峡水库CO₂、CH₄等温室气体通量较蓄水前发生明显改变。如何科学认识和客观评估三峡水库修建及运行对其CO₂、CH₄等温室气体通量的影响备受关注。本文简要回顾了自2009年以来在三峡水库开展CO₂、CH₄等温室气体通量监测与分析工作,综述认为,现阶段三峡水库温室气体排放以水-气界面扩散释放为主要途径。陆源输入的有机碳是主导三峡水库CO₂、CH₄产生的主要碳源,但在局部区段或时段自源性有机碳的贡献亦十分显著。同蓄水前相比,三峡水库碳排放量呈现为净增加,淹没效应约占水库C净增量的20%,库区内点面源污染负荷并未对CO₂排放的净增量产生显著贡献,阻隔效应和生态系统重建效应对三峡水库碳排放的净增量产生显著贡献。近10年来,监测方法比对、监测点位优化等工作在一定程度上完善了三峡水库温室气体通量监测体系。新方法、新技术的引入也为三峡水库温室气体通量监测分析提供了有利支撑和保障,但复杂水文环境...     

三峡水库澎溪河CO2、CH4气泡释放通量初探

气泡释放是天然水体中水-气交换的重要途径之一.采用改进的倒置漏斗型气泡通量监测装置于2012年3-8月期间对三峡支流澎溪河高阳平湖库湾水域进行气泡释放通量的监测研究.研究期间,研究水域CH4气泡释放通量变化范围为0.01 ～ 23288.64 μmol/(m2·d);CO2气泡释放通量变化范围为0～799.89 μmol/(m2·d).不同常规采样点CH4、CO2气泡释放通量均呈现出高度的时空异质性特征.但CH4气泡释放通量显著高于CO2气泡释放通量,且二者释放过程具有同步性.同国外已有水库监测结果相比,澎溪河回水区高阳平湖库湾水域CH4、CO2气泡释放通量位于中等水平.CH4气泡释放通量约为同期CH4扩散通量的0～ 1893.90％,超量释放下CH4气泡释放通量可达同水域CH4扩散通量的6270.5％±390.0％.CO2气泡释放通量仅占同期扩散通量绝对值的0～ 21.74‰,超量释放下,CO2气泡释放通量亦仅为同期扩散通量绝对值的40.33‰ ±0.93‰.CH4气泡释放通量在支流库湾水域对总通量的贡献不可忽视.     

Shock-induced CO2 loss from CaCO3; implications for early planetary atmospheres

We report new results of shock recovery experiments on single crystal calcite. Recovered samples are subjected to thermogravimetric analysis. This yields the maximum amount of post-shock CO₂, the decarbonization interval, ΔT, and the energy of association (or vaporization), ΔEV, for the removal of remaining CO₂ in shock-loaded calcite. Comparison of post-shock CO₂ with that initially present determines shock-induced CO₂ loss as a function of shock pressure. Incipient to complete CO₂ loss occurs over a pressure range of 10to 70GPa. The latter pressure should be considered a lower bound. Comparable to results on hydrous minerals, ΔT and ΔEV decrease systematically with increasing shock pressure. This indicates that shock loading leads to both the removal of structural volatiles and weakening of bonds between the volatile species and remainder of the crystal lattice.Optical and scanning electron microscopy (SEM) reveal structural changes, which are related to the shock-loading. Comparable to previous findings on shocked antigorite is the occurrence of dark, diffuse areas, which can be resolved as highly vesicular areas as observed with a scanning electron microscope. These areas are interpreted as representing quenched partial melts, into which shock-released CO₂ has been injected.The experimental results are used to place bonds on models of impact production of CO₂ during accretion of the terrestrial planets.     

Simulating spatiotemporal variations of atmospheric CO2 using a nested hemispheric model

A three-dimensional Eulerian nested model for transport, diffusion, and surface fluxes of CO₂ has been developed. The model is used to study the spatial and temporal variations of atmospheric CO₂ concentrations as a step towards a better understanding of the regional source pattern over Europe. The influence from the national surface characteristics, as e.g. fossil CO₂ emissions or ecosystem fluxes, can be treated on a continental or national level in the model. In the future the model can be used as a mean to corroborate national and EU-wide controls or reductions of carbon emissions. One of the major questions in the estimation of e.g. national CO₂ budgets is the quantification of surface ecosystem fluxes. In order to test the sensitivity of atmospheric CO₂ concentrations to ecosystem fluxes, two different parameterizations [J. Geophys. Res. 92 (1987) 2999] and [Global Biogeochem. Cycles 10 (1996) 269] have been implemented in the model. The model both with and without nest is validated by comparison with measurements and the different model results will be discussed. The results show that including a nested domain with higher spatial resolution significantly improves the model performance in some areas. In spite of regional deviations in the two sets of ecosystems fluxes no major differences are seen over Europe as a whole when either of the two parameterizations are included in the model and the results compared.     

MEIC-global-CO2: A new global CO2 emission inventory with highly-resolved source category and sub-country information

CO₂ emission inventory provides fundamental data for climate research and emission mitigation. Currently, most global CO₂ emission inventories were developed with energy statistics from International Energy Agency(IEA) and were available at country level with limited source categories. Here, as the first step toward a high-resolution and dynamic updated global CO₂ emission database, we developed a data-driven approach to construct seamless and highly-resolved ene...     

Modeling vertical stratification of CO2 injected into a deep layered aquifer

The vertical stratification of carbon dioxide (CO₂) injected into a deep layered aquifer made up of high-permeability and low-permeability layers, such as Utsira aquifer at Sleipner site in Norway, is investigated with a Buckley–Leverett equation including gravity effects. In a first step, we study both by theory and simulation the application of this equation to the vertical migration of a light phase (CO₂), in a denser phase (water), in 1D vertical columns filled with different types of porous media: homogeneous, piecewise homogeneous, layered periodic and finally heterogeneous. For each case, we solve the associated Riemann problems and propose semi-analytical solutions describing the spatial and temporal evolution of the light phase saturation. These solutions agree well with simulation results. We show that the flux continuity condition at interfaces between high-permeability and low-permeability layers leads to CO₂ saturation discontinuities at these interfaces and, in particular, to a saturation increase beneath low-permeability layers. In a second step, we analyze the vertical migration of a CO₂ plume injected into a 2D layered aquifer. We show that the CO₂ vertical stratification under each low-permeability layer is induced, as in 1D columns, by the flux continuity condition at interfaces. As the injection takes place at the bottom of the aquifer the velocity and the flux function decrease with elevation and this phenomenon is proposed to explain the stratification under each mudstone layer as observed at Sleipner site.     

Variations of near-surface atmospheric CO2 and H2O concentrations during summer on Muztagata

Expeditions during the summers of 2002 and 2003 implemented continuous monitoring of near-surface (2 m height) atmospheric CO₂ and H₂O concentrations at the 4500 m elevation on Muztagata. The resultant data sets reveal a slight decrease of CO₂ concentrations (of about 5 μmol·mol^-1) and changes in the diurnal variations from the end of June to the middle August. The daily maximum CO₂ concentrations occur between 02:30-05:30 AM (local time) and the minimum levels occur between 12:00-15:30 PM. The atmospheric CO₂ concentrations in the summer of 2002 were around 5 μmol·mol^-1 lower than those during the same period of 2003, whereas the diurnal amplitude was higher. In contrast, we found that the daily mean atmospheric H₂O content in 2003 was much lower than that in 2002 and there exists a striking negative correlation between CO₂ and H₂O concentrations. We therefore suggest that the near-surface atmospheric CO₂ concentration is affected not only by photosynthesis and respiration, but also by the air H₂O content in the glaciated region around Muztagata.     

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.     

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.     

Quantifying the impact of mineralogical heterogeneity on reactive transport modeling of CO2+O2 in-situ leaching of uranium

CO₂+ O₂ in-situ leaching(ISL) of sandstonetype uranium ore represents the third generation of solution mining in China.In this study,reactive transport modeling of the interaction between hydrodynamic and geochemical reactions is performed to enable better prediction and regulation of the CO₂+ O₂ in-situ leaching process of uranium.Geochemical reactions between mining solutions and rock,and the kinetic uranium dissolution controlled by O₂(aq...