Experimental identification of CO2–oil–brine–rock interactions: Implications for CO2 sequestration after termination of a CO2-EOR project

Carbon dioxide enhanced oil recovery (CO₂-EOR) has been widely applied to the process of carbon capture, utilization, and storage (CCUS). Here, we investigate CO₂–oil–water–rock interactions under reservoir conditions (100 °C and 24 MPa) in order to understand the fluid–rock interactions following termination of a CO₂-EOR project. Our experimental results show that CO₂-rich fluid remained the active fluid controlling the dissolution–precipitation processes in an oil-undersaturated sandstone reservoir; e.g., the dissolution of feldspar and calcite, and the precipitation of kaolinite as well as solid phases comprising O, Si, Al, Na, C, and Ti. Mineral dissolution rates were reduced in the case that mineral surfaces were coated by oil. Mineral wettability and composition, and oil saturation were the main controls on the exposed surface area of grains, and mineral wettability in particular led to selective dissolution. In addition, the permeability of the reservoir decreased substantially due to the precipitation of kaolinite and solid-phase particles, and due to the clogging of less soluble mineral particles released by the dissolution of K-feldspar and carbonate cement, whereas porosity increased. The results provide insight into potential formation damage resulting from CO₂-EOR projects.     

Interpreting CO2–SIc relationship to estimate CO2 baseline in limestone aquifers

Saturation index with respect to calcite (SIc) and equilibrium CO₂ partial pressure are important parameters to study groundwater in limestone aquifers. Aside from their use in time series, CO₂ and SIc are used to estimate the baseline of CO₂ in the vadose zone. The objective of this paper is to present conceptual examples on the use of the CO₂–SIc relationship to have new information from usual parameters. Case study was considered as an example of use from Cussac site, a limestone aquifer in southwest of France. The result showed that CO₂ baseline in unsaturated zone is found close to 25,000 ± 1,000 ppm.     

Thermodynamic modeling of binary CH4–CO2 fluid inclusions

An equation of state (EOS) explicit in Helmholtz free energy has been improved to calculate the PVTx and vapor–liquid phase equilibrium properties of CH₄–CO₂ fluid mixture. This EOS, where four mixing parameters are used, is based on highly accurate EOSs recommended by NIST for pure components (CH₄ and CO₂) and contains a simple generalized departure function presented by Lemmon and Jacobsen (1999). Comparison with experimental data available indicates that the EOS can calculate both vapor–liquid phase equilibrium and volumetric properties of this binary fluid system with accuracy close to that of experimental data up to high temperature and pressure within full range of composition. The EOS of CH₄–CO₂ fluid, together with the updated Gibbs free energy model of solid CO₂ (dry ice), is applied to calculate the CH₄ content (x_CH4) and molar volume (V_m) of the CH₄–CO₂ fluid inclusion based on the assumption that the volume of an inclusion keeps constant during heating and cooling. $V_{\text{m}}-x_{{\text{CH}}_4}$ diagrams are presented, which describe phase transitions involving vapor, liquid and CO₂ solid phases of CH₄–CO₂ fluid inclusions. Isochores of CH₄–CO₂ inclusions at given $x_{{\text{CH}}_4}$ and V_m can be easily calculated from the improved EOS.     

Hydrogen incorporation into forsterite in Mg2SiO4–K2Mg(CO3)2–H2O and Mg2SiO4–H2O–C at 7.5–14.0 GPa

Experiments on water solubility in forsterite in the systems Mg₂SiO₄–K₂Mg(CO₃)₂–H₂O and Mg₂SiO₄–H₂O–C were conducted at 7.5–14.0 GPa and 1200–1600 °C. The resulting crystals contain 448 to 1480 ppm water, which is 40–70% less than in the forsterite–water system under the same conditions. This can be attributed to lower water activity in the carbonate-bearing melt. The water content of forsterite was found to vary systematically with temperature and pressure. For instance, at 14 GPa in the system forsterite–carbonate–H₂O the H₂O content of forsterite drops from 1140 ppm at 1200 °C to 450 ppm at 1600 °C, and at 8 GPa it remains constant or increases from 550 to 870 ppm at 1300–1600 °C. Preliminary data for D-H-bearing forsterite are reported. Considerable differences were found between IR spectra of D-H- and H-bearing forsterite. The results suggest that CO₂ can significantly affect the width of the olivine-wadsleyite transition, i.e., the 410-km seismic discontinuity, which is a function of the water content of olivine and wadsleyite.     

CO2地质处置研究进展

减少CO2向大气排放的一个主要的方法是将其隔离在地下深部，即CO2地质处置。CO2地质处置的方法主要包括：含水层处置，海洋处置，利用CO2开采油气以及煤层甲烷气体等。含水层处置有三种机制：（1）水力学方法；（2）溶解的方法；（3）矿物处置。CO2地质处置是可行的技术方法，在实际中已有了应用。在难以获得复杂的深部含水层环境的情况下，地球化学数值模拟方法在评价地质处置CO2可行性上具有重要的作用。     

An improved cubic model for the mutual solubilities of CO2–CH4–H2S–brine systems to high temperature,pressure and salinity

The phase behavior of CO₂–CH₄–H₂S–brine systems is of importance for geological storage of greenhouse gases, sour gas disposal and enhanced oil recovery (EOR). In such projects, reservoir simulations play a major role in assisting decision makings, while modeling the phase behavior of the relevant CO₂–CH₄–H₂S–brine system is a key part of the simulation. There is a need for an equation of state (EOS) for such system which is accurate, with wide application range (pressure, temperature and aqueous salinity), computationally efficient and easy for implementation in a reservoir simulator.In this study, an improved cubic EOS model of the system CO₂–CH₄–H₂S–brine is developed based on the modifications of the binary interaction parameters in Peng–Robinson EOS, which is widely implemented in reservoir simulators. Thus the new model is suited for numerical implementation in reservoir simulators.The available experimental data of pure gas brine equilibrium and gas mixture solubility in water/brine are carefully reviewed and compared with the new model. From the comparison, the new model can accurately reproduce (1) the CO₂–brine mutual solubility data at temperature from 0 °C to 250 °C, pressure from 1 bar to 1000 bar and NaCl molality (mole number in 1 kg water, molal is used for short) from 0 to 6 molal, (2) CH₄–brine mutual solubility data at temperature from 0 °C to 250 °C, pressure from 1 bar to 2000 bar and NaCl molality from 0 to 6 molal, (3) H₂S–brine mutual solubility data at temperature from 0 °C to 250 °C, pressure from 1 bar to 200 bar and NaCl molality from 0 to 6 molal, and (4) has good accuracy for gas mixture solubility in brine.     

CO2 Input Dynamics and Air–Sea Exchange in a Large New England Estuary

Repeated surveys of the Kennebec estuary, a macrotidal river estuary in Maine, USA, between 2004 and 2008 found spatial and temporal variability both in sources of carbon dioxide (CO₂) to the estuary and the air–sea flux of estuary CO₂. On an annual basis, the surveyed area of the Kennebec estuary had an area-weighted average partial pressure of CO₂ (pCO₂) of 559 μatm. The area-weighted average CO₂ flux to the atmosphere was 3.54 mol C m^?2 year^?1. Overall, the Kennebec estuary was an annual source of 7.2?×?10⁷ mol CO₂ to the atmosphere. Distinct seasonality in estuarine pCO₂ was observed, with shifts in the seasonal pattern evident between lower and higher salinities. Fluxes of CO₂ from the estuary were elevated following two summertime storms, and inputs of riverine CO₂ outweighed internal estuarine CO₂ inputs in nearly all months. River and estuarine inputs of CO₂ represented 68 and 32 % of the total CO₂ contributions to the estuary, respectively. This study examines the variability of CO₂ in a large New England estuary, and highlights the comparatively high contribution of CO₂ from riverine sources.     

The molar volume of FeO–MgO–Fe2O3–Cr2O3–Al2O3–TiO2 spinels

We define and calibrate a new model of molar volume as a function of pressure, temperature, ordering state, and composition for spinels in the supersystem (Mg, Fe²⁺)(Al, Cr, Fe³⁺)₂O₄ ? (Mg, Fe²⁺)₂TiO₄. We use 832 X-ray and neutron diffraction measurements performed on spinels at ambient and in situ high-P, T conditions to calibrate end-member equations of state and an excess volume model for this system. The effect on molar volume of cation ordering over the octahedral and tetrahedral sites is captured with linear dependence on Mg²⁺, Al³⁺, and Fe³⁺ site occupancy terms. We allow standard-state volumes and coefficients of thermal expansion of the end members to vary within their uncertainties during extraction of the mixing properties, in order to achieve the best fit. Published equations of state of the various spinel end members are analyzed to obtain optimal values of the bulk modulus and its pressure derivative, for each explicit end member. For any spinel composition in the supersystem, the model molar volume is obtained by adding excess volume and cation order-dependent terms to a linear combination of the five end-member volumes, estimated at pressure and temperature using the high-T Vinet equation of state. The preferred model has a total of 9 excess volume and order-dependent parameters and fits nearly all experiments to within 0.02 J/bar/mol, or better than 0.5 % in volume. The model is compared to the current MELTS spinel model with a demonstration of the impact of the model difference on the estimated spinel-garnet lherzolite transition pressure.     

Metastable phenomena on calcite {101̄4} surfaces growing from Sr2+–Ca2+–CO32− aqueous solutions

In situ atomic force microscopy (AFM) experiments, scanning electron microscopy (SEM) imaging and composition analysis, and X-ray diffraction have provided information about the growth, dissolution and transformation processes promoted by Sr²⁺–Ca²⁺–CO₃²⁻ aqueous solutions in contact with calcite {101̄4} surfaces. Experiments have shown a wide variety of surface phenomena, such as the influence of the Sr-bearing newly-formed surface on the subsequent growth (template effect), the growth and subsequent dissolution of surfaces and the nucleation of secondary three-dimensional nuclei on calcite surfaces. These phenomena reveal the metastability of the crystallisation system and are a consequence of the interplay between thermodynamics (the relative stability of the two calcite and aragonite structure solid solutions that can be formed), supersaturation of the aqueous solution with respect to the two possible solid solutions, and the crystallographic control of the surfaces on cation incorporation.     

Geochemical modelling of CO2–water–rock interactions in a potential storage formation of the North German sedimentary basin

The lower Triassic/Bunter sandstone and lower Jurassic/Rhät formations of the Northern Germany sedimentary basin constitute feasible reservoirs for the storage of CO₂ from combustion of fossil fuels or industrial production processes. This study presents analyses of geochemical interactions between CO₂, formation fluid and rock of these potential reservoirs using geochemical modelling in order to assess the short and long term impact of CO₂ sequestration. Batch equilibrium modelling was performed first for assessing the consistency of fluid and mineralogy field data and for identifying potential secondary minerals under the influence of injected CO₂. Inclusion of reaction kinetics in the batch models allowed an observation of reaction paths and to estimate the time frame of geochemical reactions. Finally, one-dimensional equilibrium reactive transport modelling was used in order to investigate the direction of reactions under conditions of fluid flow and mass transport and to quantify feedbacks of reactions on transport processes.Results of the simulations performed show that dawsonite may act as the main CO₂ storage mineral in both formations, while the carbonates calcite and dolomite dissolve over time. Also, changes in porosity and permeability are significant in the equilibrium reactive transport simulations. The time scale of kinetically controlled reactions observed in the kinetic batch modeling, however, suggests that CO₂ mineral trapping in both formations requires very long time frames, and hence other mechanisms such as structural or solubility trapping seem to be more relevant within the injection or early post-injection phase for the studied formations.     

玄武岩CO2 地质封存研究进展

玄武岩CO2 地质封存相比于常规的封存技术（如驱油驱气注入封存和深部咸水层封存）,具有能促进快速碳矿化、封存效果长期且安全及封存容量巨大等明显优点。目前玄武岩CO2 封存理论方面的研究已经取得了大量进展：① 对常见主要成岩矿物的封存能力进行了排序;② 进一步了解玄武岩的矿物成分、玄武岩层内孔隙分布特征及其形成机理;③ 完善了对玄武岩CO2 封存机理、反应速率及影响因素等方面的认识;④ 查明了玄武岩在地球上的分布并评估了各种典型玄武岩的封存潜力;⑤ 发现适合于CO2 封存的场地主要包括大陆溢流型玄武岩、洋底高原玄武岩和洋中脊玄武岩等三种类型,并对目标储层选择提出了初步评价标准。本文在综述玄武岩固碳机理、玄武岩CO2 地质封存潜力及封存场地与目标储层选择的基础上,介绍了世界上已有的三个玄武岩CO2 地质封存工程示范项目：冰岛Carbfix、美国Wallula和日本Nagaoka,探讨了玄武岩CO2 地质封存存在的若干问题：① 反应速率受多种因素影响,对最终封存效果起着决定性作用;② 堵塞或压裂和保护层会影响注入封存的稳定性或可持续性;③ 封存潜力评价方法和结果不同;④ 封存场地选址和储层选择缺乏统一标准与规范;⑤ Carbfix方法的使用受限。     

玄武岩CO2地质封存研究进展

玄武岩CO2地质封存相比于常规的封存技术(如驱油驱气注入封存和深部咸水层封存),具有能促进快速碳矿化、封存效果长久且安全及封存容量巨大等明显优点.目前玄武岩CO2封存理论方面的研究已经取得了大量进展:①对常见主要成岩矿物的封存能力进行了排序;②进一步了解玄武岩的矿物成分、玄武岩层内孔隙分布特征及其形成机理;③完善了对玄...     

地下水中CO2成因分析

通过对前人成果的总结认为,不同地区由于水文地质条件不同,其地下水中CO2 成因也大不相同。地下水的CO2 的成因主要有来源于大气溶解;土壤及水中有机物分解和生物呼吸;深部热源造成碳酸盐岩或矿物变质;直接由岩浆分泌;除碳酸外其它酸对碳酸盐矿物的溶解; 热水中暂时硬度去除等类型。至于具体到某一地区其地下水中CO2 主要成因为何种,以及各种成因CO2 在地下水中所占比例是多少,应结合具体情况并综合各种相关因素来分析确定。      

Comparison of CO2 Dynamics and Air–Sea Gas Exchange in Differing Tropical Reef Environments

An array of MAPCO₂ buoys, CRIMP-2, Ala Wai, and Kilo Nalu, deployed in the coastal waters of Hawaii, have produced multi-year high temporal resolution CO₂ records in three different coral reef environments off the island of Oahu, Hawaii. This study, which includes data from June 2008 to December 2011, is part of an integrated effort to understand the factors that influence the dynamics of CO₂–carbonic acid system parameters in waters surrounding Pacific high-island coral reef ecosystems and subject to differing natural and anthropogenic stresses. The MAPCO₂ buoys are located on the Kaneohe Bay backreef, and fringing reef sites on the south shore of Oahu, Hawaii. The buoys measure CO₂ and O₂ in seawater and in the atmosphere at 3-h intervals, as well as other physical and biogeochemical parameters (conductivity, temperature, depth, chlorophyll-a, and turbidity). The buoy records, combined with data from synoptic spatial sampling, have allowed us to examine the interplay between biological cycles of productivity/respiration and calcification/dissolution and biogeochemical and physical forcings on hourly to inter-annual time scales. Air–sea CO₂ gas exchange was also calculated to determine whether the locations were sources or sinks of CO₂ over seasonal, annual, and interannual time periods. Net annualized fluxes for CRIMP-2, Ala Wai, and Kilo Nalu over the entire study period were 1.15, 0.045, and ?0.0056 mol C m^?2 year^?1, respectively, where positive values indicate a source or a CO₂ flux from the water to the atmosphere, and negative values indicate a sink or flux of CO₂ from the atmosphere into the water. These values are of similar magnitude to previous estimates in Kaneohe Bay as well as those reported from other tropical reef environments. Total alkalinity (A_T) was measured in conjunction with pCO₂, and the carbonic acid system was calculated to compare with other reef systems and open ocean values around Hawaii. These findings emphasize the need for high-resolution data of multiple parameters when attempting to characterize the carbonic acid system in locations of highly variable physical, chemical, and biological parameters (e.g., coastal systems and reefs).