Impact of experimental parameters for manometric equipment on CO2 isotherms measured: Comment on “Inter-laboratory comparison II: CO2 isotherms measured on moisture-equilibrated Argonne premium coals at 55°C and up to 15 MPa” by Goodman et al. (2007)

Modelling the sorption properties of coals for carbon dioxide under supercritical conditions is necessary for accurate prediction of the sequestering ability of coals in seams. We present recent data for sorption curves of three dry Argonne Premium coals, for carbon dioxide, methane and nitrogen at two different temperatures at pressures up to 15 MPa. The sorption capacity of coals tends to decrease with increasing temperature. An investigation into literature values for sorption of nitrogen and methane by charcoal also show sorption capacities that decrease dramatically with increasing temperature. This is inconsistent with expectations from Langmuir models of coal sorption, which predict a sorption capacity that is independent of temperature. We have successfully fitted the isotherms using a modified Dubinin–Radushkevich equation that uses gas density rather than pressure. A simple pore-filling model that assumes there is a maximum pore width that can be filled in supercritical conditions and that this maximum pore width decreases with increasing temperature, can explain this temperature dependence of sorption capacity. It can also explain why different supercritical gases give apparently different surface sorption capacities on the same material. The calculated heat of sorption for these gases on these coals is similar to those found for these gases on activated carbon.     

Swelling-induced volumetric strains internal to a stressed coal associated with CO2 sorption

It is generally accepted that typical coalbed gases (methane and carbon dioxide) are sorbed (both adsorbed and absorbed) in the coal matrix causing it to swell and resulting in local stress and strain variations in a coalbed confined under overburden pressure. The swelling, interactions of gases within the coal matrix and the resultant changes in the permeability, sorption, gas flow mechanics in the reservoir, and stress state of the coal can impact a number of reservoir-related factors. These include effective production of coalbed methane, degasification of future mining areas by drilling horizontal and vertical degasification wells, injection of CO₂ as an enhanced coalbed methane recovery technique, and concurrent CO₂ sequestration. Such information can also provide an understanding of the mechanisms behind gas outbursts in underground coal mines.The spatio-temporal volumetric strains in a consolidated Pittsburgh seam coal sample were evaluated while both confining pressure and carbon dioxide (CO₂) pore pressure were increased to keep a constant positive effective stress on the sample. The changes internal to the sample were evaluated by maps of density and atomic number determined by dual-energy X-ray computed tomography (X-ray CT). Early-time images, as soon as CO₂ was introduced, were also used to calculate the macroporosity in the coal sample. Scanning electron microscopy (SEM) and photographic images of the polished section of the coal sample at X-ray CT image location were used to identify the microlithotypes and microstructures.The CO₂ sorption-associated swelling and volumetric strains in consolidated coal under constant effective stress are heterogeneous processes depending on the lithotypes present. In the time scale of the experiment, vitrite showed the highest degree of swelling due to dissolution of CO₂, while the clay (kaolinite) and inertite region was compressed in response. The volumetric strains associated with swelling and compression were between ± 15% depending on the location. Although the effective stress on the sample was constant, it varied within the sample as a result of the internal stresses created by gas sorption-related structural changes. SEM images and porosity calculations revealed that the kaolinite and inertite bearing layer was highly porous, which enabled the fastest CO₂ uptake and the highest degree of compression.     

Mitigation of asphaltics deposition during CO2 flood by enhancing CO2 solvency with chemical modifiers

CO₂ injected in the reservoir of McElroy Field, TX, for a CO₂ flood was in the supercritical state. Supercritical CO₂ fluid is capable of extracting light and intermediate hydrocarbons from rocks but is unable to extract heavy hydrocarbons and asphaltics. Therefore, plugging of asphaltics in reservoir rocks and a consequent reduction in injectivity and recovery may result when CO₂ only is used in enhanced oil recovery. By adding common solvents as chemical modifiers, the flooding fluid shows marked improvement in solvency for heavy components of crudes due to its increased density and polarity. Numerous supercritical CO₂ fluid extractions of dolomite rock from the Grayburg Formation containing known amount of spiked McElroy crude oil have been carried out to evaluate extraction efficiencies of CO₂ and CO₂ with chemical modifiers at various temperatures and pressures. All experiments show that extraction efficiency increases with increasing CO₂ pressure but decreases with increasing temperature. Addition of chemical modifiers to CO₂ also shows improved extraction efficiency and reduced asphaltic deposits. Under the pressure and temperature similar to McElroy reservoir conditions; chemically modified CO₂ yielded almost 3 times as much oil extracts as those in extractions with CO₂ only. It also reduced the asphaltics content in extracted rocks to nearly one half; indicating its potential for mitigating asphaltics plugging of formation rocks     

Oxygen isotope exchange between H2O and CO2 at elevated CO2 pressures: Implications for monitoring of geological CO2 storage

Traditionally, the application of stable isotopes in Carbon Capture and Storage (CCS) projects has focused on δ¹³C values of CO₂ to trace the migration of injected CO₂ in the subsurface. More recently the use of δ¹⁸O values of both CO₂ and reservoir fluids has been proposed as a method for quantifying in situ CO₂ reservoir saturations due to O isotope exchange between CO₂ and H₂O and subsequent changes in δ¹⁸O_H2O values in the presence of high concentrations of CO₂. To verify that O isotope exchange between CO₂ and H₂O reaches equilibrium within days, and that δ¹⁸O_H2O values indeed change predictably due to the presence of CO₂, a laboratory study was conducted during which the isotope composition of H₂O, CO₂, and dissolved inorganic C (DIC) was determined at representative reservoir conditions (50 °C and up to 19 MPa) and varying CO₂ pressures. Conditions typical for the Pembina Cardium CO₂ Monitoring Pilot in Alberta (Canada) were chosen for the experiments. Results obtained showed that δ¹⁸O values of CO₂ were on average 36.4 ± 2.2‰ (1σ, n = 15) higher than those of water at all pressures up to and including reservoir pressure (19 MPa), in excellent agreement with the theoretically predicted isotope enrichment factor of 35.5‰ for the experimental temperatures of 50 °C. By using ¹⁸O enriched water for the experiments it was demonstrated that changes in the δ¹⁸O values of water were predictably related to the fraction of O in the system sourced from CO₂ in excellent agreement with theoretical predictions. Since the fraction of O sourced from CO₂ is related to the total volumetric saturation of CO₂ and water as a fraction of the total volume of the system, it is concluded that changes in δ¹⁸O values of reservoir fluids can be used to calculate reservoir saturations of CO₂ in CCS settings given that the δ¹⁸O values of CO₂ and water are sufficiently distinct.     

卫星遥感探测大气CO2浓度研究最新进展

大气CO₂是一种重要的长寿命温室气体,卫星遥感探测大气CO₂浓度,可以连续地获得其全球时空分布变化情况,进而提高对大气CO₂源汇分布及区域和全球碳循环的认识,进一步增强对全球气候变化的研究和预测。卫星遥感探测大气CO₂浓度已经开始成为一个新的研究领域,文章综合论述了利用卫星平台遥感探测大气CO₂浓度分布的最新研究状况。首先简单地叙述了现阶段对大气CO₂浓度时空分布和变化情况的直接仪器观测结果,在此基础上比较全面地综述了卫星遥感测量大气CO₂浓度的主要方法及获得的结果,包括利用近红外反射太阳光谱或地气热红外发射辐射光谱及两者的组合进行得模拟和卫星实测反演研究,最后简单地进行了总结和展望。     

Determination of carbon fractionation factor between aqueous carbonate and CO2(g) in two-direction isotope equilibration

The experiments were conducted in the open CO₂ system to find out the equilibrium fractionation between the carbonate ion and CO₂(g). The existence of isotopic equilibrium was checked using the two-direction approach by passing the CO₂−N₂ gases with different δ¹³C compositions (− 1.5‰ and − 23‰) through the carbonate solution with δ¹³C = − 4.2‰. The Δ_{CO3T²⁻−CO2(g)} equilibrium fractionation is given as 6.03 ± 0.17‰ at 25 °C. Discussion is provided about the significance of carbonate complexing in determination of Δ_{CO3T²⁻−CO2(g)} and Δ_{HCO3T⁻−CO2(g)} fractionations. Finally, an isotope numerical model of flow and kinetics of hydration and dehydroxylation is built to predict the isotopic behaviour of the system with time.     

Fugacities and free energies of CO2 at high pressures and temperatures

Fugacity and free-energy values have been calculated from p-v-t data for CO₂ in the temperature range from 50 to 1000°C, at pressures from 25 to 1400 bars.     

High-density early CO2 fluids in the ultrahigh-temperature granulites of Ihouhaouene (In Ouzzal, Algeria)

Fluid inclusion studies in rocks from the Lower Proterozoic granulites from western Hoggar (Algeria) provide new evidence for the hypothesis that a CO₂-rich, H₂O-poor fluid was present during the high-grade metamorphism. CO₂ inclusions represent the main fluid trapped in the Ihouhaouene ultrahigh-temperature (over 1000 °C) and high-pressure (10 to 14 kbar) granulites. The microthermometric and Raman microspectrometric measurements indicate that the carbonic fluid is mainly composed of CO₂ with minor amounts of CH₄ and N₂ detected in some inclusions (< 4 mol% CH₄). Carbonic fluid densities range from 1.18 to 0.57 g/cm³. The highest densities are recorded in superdense carbonic inclusions presenting evidence of the earliest trapping and they correspond to the fluid densities expected for the P–T conditions of the peak of metamorphism in the area previously determined from mineral geothermobarometers. Lower densities of carbonic fluids mainly result from the reequilibration of earlier trapped fluid inclusions during retrograde metamorphism and final uplift of the metamorphic terrane, but a new influx of carbonic fluids during the retrograde event remains possible. Carbonic fluids can be produced in situ from decarbonation reactions in interlayered impure marbles during the prograde event or derived from CO₂ flushing from underlying basic intrusions. The aqueous fluids present large variations of composition (0.5 to 30 wt.% NaCl equivalent) and densities (1.16 to 0.57 g/cm³). They clearly correspond to post-metamorphic fluids because they mainly occur along microfractures, they do not show any evidence of immiscibility with the carbonic fluids and mixed aquo-carbonic inclusions have not been observed. The percolation of aqueous fluids is related to the Pan-African tectonometamorphic event.     

CO2 and sulfuric acid controls of weathering and river water composition

Reactions of CO₂ with carbonate and silicate minerals in continental sediments and upper part of the crystalline crust produce HCO₃⁻ in river and ground waters. H₂SO₄ formed by the oxidation of pyrite and reacting with carbonates may produce CO₂ or HCO₃⁻. The ratio, ψ, of atmospheric or soil CO₂ consumed in weathering to HCO₃⁻ produced depends on the mix of CO₂ and H₂SO₄, and the proportions of the carbonates and silicates in the source rock. An average sediment has a CO₂ uptake potential of ψ = 0.61. The potential increases by inclusion of the crystalline crust in the weathering source rock. A mineral dissolution model for an average river gives ψ = 0.68 to 0.72 that is within the range of ψ = 0.63 to 0.75, reported by other investigators using other methods. These results translate into the CO₂ weathering flux of 20 to 24 × 10¹²mol/yr.     

The hydromagnesite playas of Atlin, British Columbia, Canada: A biogeochemical model for CO2 sequestration

Anthropogenic greenhouse gas emissions may be offset by sequestering carbon dioxide (CO₂) through the carbonation of magnesium silicate minerals to form magnesium carbonate minerals. The hydromagnesite [Mg₅(CO₃)₄(OH)₂·4H₂O] playas of Atlin, British Columbia, Canada provide a natural model to examine mineral carbonation on a watershed scale. At near surface conditions, CO₂ is biogeochemically sequestered by microorganisms that are involved in weathering of bedrock and precipitation of carbonate minerals. The purpose of this study was to characterize the weathering regime in a groundwater recharge zone and the depositional environments in the playas in the context of a biogeochemical model for CO₂ sequestration with emphasis on microbial processes that accelerate mineral carbonation.Regions with ultramafic bedrock, such as Atlin, represent the best potential sources of feedstocks for mineral carbonation. Elemental compositions of a soil profile show significant depletion of MgO and enrichment of SiO₂ in comparison to underlying ultramafic parent material. Polished serpentinite cubes were placed in the organic horizon of a coniferous forest soil in a groundwater recharge zone for three years. Upon retrieval, the cube surfaces, as seen using scanning electron microscopy, had been colonized by bacteria that were associated with surface pitting. Degradation of organic matter in the soil produced chelating agents and acids that contributed to the chemical weathering of the serpentinite and would be expected to have a similar effect on the magnesium-rich bedrock at Atlin. Stable carbon isotopes of groundwater from a well, situated near a wetland in the southeastern playa, indicate that  12% of the dissolved inorganic carbon has a modern origin from soil CO₂.The mineralogy and isotope geochemistry of the hydromagnesite playas suggest that there are three distinct depositional environments: (1) the wetland, characterized by biologically-aided precipitation of carbonate minerals from waters concentrated by evaporation, (2) isolated wetland sections that lead to the formation of consolidated aragonite sediments, and (3) the emerged grassland environment where evaporation produces mounds of hydromagnesite. Examination of sediments within the southeastern playa–wetland suggests that cyanobacteria, sulphate reducing bacteria, and diatoms aid in producing favourable geochemical conditions for precipitation of carbonate minerals.The Atlin site, as a biogeochemical model, has implications for creating carbon sinks that utilize passive microbial, geochemical and physical processes that aid in mineral carbonation of magnesium silicates. These processes could be exploited for the purposes of CO₂ sequestration by creating conditions similar to those of the Atlin site in environments, artificial or natural, where the precipitation of magnesium carbonates would be suitable. Given the vast quantities of Mg-rich bedrock that exist throughout the world, this study has significant implications for reducing atmospheric CO₂ concentrations and combating global climate change.     

Seasonality of bedrock weathering chemistry and CO2 consumption in a small watershed, the White River, Vermont

The draw down of CO₂ from the atmosphere during mineral weathering plays a major role in the global budget of this greenhouse gas. Silicate minerals remove twice the CO₂ of carbonate minerals per mole of calcium in runoff during weathering. Bedrock weathering chemistry was investigated in the White River watershed of northeastern USA to investigate whether there are seasonal differences in carbonate and silicate weathering chemistry. Geographic Information Systems analyses of bedrock geology were combined with major element concentrations in river waters to gain an understanding of the consistency of mineral weathering during three seasons. The percent of carbonate mineralogy comprising the bedrock in tributaries of the White River varied from less than 5% to 45% by area. A mass balance calculation using major element concentrations in waters was applied to estimate the seasonal relationships between bedrock geology and bicarbonate flux. In all tributaries and the main stem of the White River the highest calculated percent of bicarbonate from carbonate mineral weathering was measured in the late fall. The results suggest that carbonate and silicate bedrock weathering processes are seasonally controlled. Thus single season sampling could not accurately represent an entire year's geochemical budget. In the White River, water samples obtained solely during the summer would consistently underestimate the total yearly source of bicarbonate from carbonate bedrock weathering. The same sample set would also provide data that would lead to an underestimation of the yearly atmospheric CO₂ draw down by bedrock weathering in the watershed. For example at four of the seven locations studied there was an almost two-fold difference between summer and spring calculated atmospheric CO₂ consumption rates.     

Fluid inclusions in Scourian granulites from the Lewisian complex of NW Scotland: evidence for CO2-rich fluid in Late Archaean high-grade metamorphism

In this paper the first fluid-inclusion data are presented from Late Archaean Scourian granulites of the Lewisian complex of mainland northwest Scotland. Pure CO₂ or CO₂-dominated fluid inclusions are moderately abundant in pristine granulites. These inclusions show homogenization temperatures ranging from − 54 to + 10 °C with a very prominent histogram peak at − 16 to − 32 °C. Isochores corresponding to this main histogram peak agree with P-T estimates for granulite-facies recrystallization during the Badcallian (750–800 °C, 7–8 kbar) as well as with Inverian P-T conditions (550–600 °C, 5 kbar). The maximum densities encountered could correspond to fluids trapped during an early, higher P-T phase of the Badcallian metamorphism (900–1000 °C, 11–12 kbar). Homogenization temperatures substantially higher than the main histogram peak may represent Laxfordian reworking (≤ 500 °C, < 4 kbar). In the pristine granulites, aqueous fluid inclusions are of very subordinate importance and occur only along late secondary healed fractures. In rocks which have been retrograded to amphibolite facies from Inverian and/or Laxfordian shear zones, CO₂ inclusions are conspicuously absent; only secondary aqueous inclusions are present, presumably related to post-granulite hydration processes. These data illustrate the importance of CO₂-rich fluids for the petrogenesis of Late Archaean granulites, and demonstrate that early fluid inclusions may survive subsequent metamorphic processes as long as no new fluid is introduced into the system.     

The ionization constants of aqueous MgCl2 at elevated temperatures and pressures—a revision

The ionization constants of aqueous MgCl₂ have been revised, in the light of recent measurements of electrical conductance, from the calculations reported previously by Frantz and Popp (1979).     

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

CO₂ 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.     

Melting relationships in the systems CaOCO2 and MgOCO2 to 33 kilobars

The melting temperatures of calcite and magnesite in the presence of excess CO₂ have been measured using Ag₂C₂O₄ in sealed capsules m a piston-cylinder apparatus. At 27 kbar, 11.5 wt % CO₂ dissolves in molten CaCO₂, depressing the freezing temperature from 1610 to 1505°C; and 6.5 wt % CO₂ dissolves in molten MgCO₃, depressing the freezing temperature from 1590 to 1510°C. The eutectic between calcite and lime was located at 1385°C at 27 kbar. These and other new results, combined with previously published data, permit completion of PT diagrams for the systems CaO-CO₂ and MgO-CO₂ from 1 bar to 35 kbar. The dissociation curve for each carbonate terminates at an invariant point where melting begins, at 40 bars and 1230°C for CaO-CO₂ and 23 kbar and 1550°C for MgO-CO₂ The differences between the two systems are explained by the different solubilities of CO₂ in the invariant liquids consequent upon the large pressure difference between the locations of these two invariant points. The results show that the temperatures for the beginning of melting of carbonates in the asthenosphere are lowered by about 100°C in the presence of CO₂.     

深部CO2泄漏对浅层地下水水质影响研究进展

由于盖层中存在的未知断层、裂隙或被废弃井穿透等原因,深部储存的CO₂可能会发生渗漏,并向上迁移进入浅部含水层,改变地下水中酸度和溶解组分的浓度分布。国外开展CO₂泄漏对浅层地下水水质影响相关研究尚处于起步阶段,且室内实验、野外试验和数值模拟等研究结果表明,CO₂泄漏对浅层地下水中pH和微量重金属组分浓度影响显著,虽浓度大多未超饮用水标准,但由于含水介质之间矿物组成的差异较大,有必要针对具体场地的地下水水质和矿物组分特征进行调查,研究CO₂侵入对地下水水质的影响,在总结已经达成共识和存在的问题基础上提出下一步研究趋势。     

CO2分压条件下煤中矿物质溶解度数值模拟

查明煤中矿物质在不同温度和CO₂分压条件下溶解度变化规律,能为注入CO₂过程中煤储层渗透率分析提供重要依据。借助水文地球化学模拟软件PHREEQC对在不同温度和CO₂分压条件下煤中各矿物的溶解度进行了水化学模拟,得出不同温度和CO₂分压条件下矿物质溶解度的变化规律。结果表明：在无CO₂分压时,随着温度的升高各矿物的溶解度增加;当溶液中CO₂分压增加到一定程度时,随着温度的升高各矿物的溶解度降低（石英除外）;在温度相同时,随着CO₂分压的增加,所有矿物（石英除外）溶解度均增加,方解石的溶解度随着CO₂分压的升高呈现出迅速增加的趋势,其他矿物随着CO₂分压的升高,溶解度增加的速率较为缓慢。     

干热岩热储建造的二氧化碳爆破致裂器优化设计

储层建造是商业化开采干热岩高温地热能的关键技术,二氧化碳爆破致裂技术为此提供了新思路。本文简述了二氧化碳爆破致裂技术,以及爆破过程中二氧化碳充装量、活化器用量、定压片厚度之间的关系。重点完善了用于干热岩储层建造的二氧化碳致裂器相关工作,设计了致裂器内部具体参数,优化了外部结构和系统,最终研发了一种可用于干热岩热储层建造的二氧化碳致裂器,为干热岩储层建造提供有效的技术手段,填补了耐高温高压的井下二氧化碳致裂器领域的空白。     

二氧化碳地质研究的意义及全球高含二氧化碳天然气的分布特点

二氧化碳地质研究具有重要的资源意义和地学意义。其资源意义表现在高纯CO₂天然气可视为珍贵的矿产资源,在工农业中有广阔的用途。CO₂地质研究的其它地学意义在于它是全球碳循环过程中的重要中枢,也是人类认识自然的极好指标。全球高含CO₂天然气的分布具有明显的区域性特点,主要分布在北美洛基山东麓、中国东部、南中国海、南澳大利亚和新西兰,等环太平洋国家和地区,还有欧洲喀尔巴阡地区和高加索地区。这些地区正好是中—新生代火山—岩浆活动激烈、构造十分发育、地热流值异常高的含烃或高含碳酸盐物质的沉积盆地。     

不同类型湿地CO2:CH4比例及其影响因素: 整合分析

湿地是温室气体二氧化碳(CO₂)和甲烷(CH₄)的主要来源之一,在全球碳循环中发挥着重要作用。由于CH₄在百年尺度上的全球增温潜势是CO₂的45倍,因此深入研究湿地CO₂:CH₄的排放比例及其影响因素对准确理解和预测湿地碳循环过程及其对未来全球变化的响应具有重要意义。本文采用文献整合分析方法,对比了不同类型湿地中CO₂:CH₄排放比例的特征及其影响因素。结果表明,藓类泥炭沼泽、滨海湿地和稻田中CO₂:CH₄排放比例显著高于草本沼泽、河流湿地和湖泊湿地等其他类型湿地;相关性分析研究发现,湿地CO₂:CH₄排放比例与pH和水位显著负相关,与盐度显著正相关。可见,藓类泥炭沼泽低水位和低pH抑制CH₄排放是导致其CO₂:CH₄排放比例较高的重要原因,而滨海湿地高盐分抑制CH₄排放是其CO₂:CH₄排放比例高的重要原因。与自然湿地相比,稻田CO₂:CH₄排放比例高与其人为施肥和稻草还田抑制CH₄排放有关。此外,大气温度、土壤温度、降水量、土壤含水率等因子也对湿地CO₂:CH₄排放比例具有重要影响,尽管它们之间的线性相关关系不显著。目前,湿地CO₂:CH₄排放比例和影响因素仍存在很大的不确定性,未来亟待加强不同类型湿地CO₂:CH₄排放比例及其关键影响因素研究。