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.     

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.     

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.     

Metamorphic CO2 production from calc-silicate rocks via garnet-forming reactions in the CFAS–H2O–CO2 system

The type and kinetics of metamorphic CO₂-producing processes in metacarbonate rocks is of importance to understand the nature and magnitude of orogenic CO₂ cycle. This paper focuses on CO₂ production by garnet-forming reactions occurring in calc-silicate rocks. Phase equilibria in the CaO–FeO–Al₂O₃–SiO₂–CO₂–H₂O (CFAS–CO₂–H₂O) system are investigated using P–T phase diagrams at fixed fluid composition, isobaric T–X(CO₂) phase diagram sections and phase diagram projections in which fluid composition is unconstrained. The relevance of the CFAS–CO₂–H₂O garnet-bearing equilibria during metamorphic evolution of calc-silicate rocks is discussed in the light of the observed microstructures and measured mineral compositions in two representative samples of calc-silicate rocks from eastern Nepal Himalaya. The results of this study demonstrate that calc-silicate rocks may act as a significant CO₂ source during prograde heating and/or early decompression. However, if the system remains closed, fluid–rock interactions may induce hydration of the calc-silicate assemblages and the in situ precipitation of graphite. The interplay between these two contrasting processes (production of CO₂-rich fluids vs. carbon sequestration through graphite precipitation) must be considered when dealing with a global estimate of the role exerted by decarbonation processes on the orogenic CO₂ cycle.     

Thermochemistry of sulfide liquids IV: density measurements and the thermodynamics of O–S–Fe–Ni–Cu liquids at low to moderate pressures

We present the results of a series of density experiments in the system O–S–Fe–Ni–Cu. These experiments were designed to extend our understanding of the physical properties of sulfide liquids, and to extend one-bar thermochemical models for sulfide liquids to apply to low to moderate pressures. Density measurements indicate both positive and negative deviations from linear mixing of partial molar volumes across this five-dimensional composition space. In terms of the homogeneous speciation model of Kress (in Contrib Mineral Petrol 154:191–204, 2007), the best fit to experimental data can be achieved by starting with a model where the volume of formation reaction for associated species initially is set to zero. Further refinement of this first-order fit yields a volume mixing model which reproduces experimental data to within nearly the estimated experimental uncertainty. Experimental ultrasonic and X-ray absorption data from the literature, along with the bulk modulus–volume relation of Anderson and Nafe (J Geophys Res 16:3951–3963, 1965), allow the estimation of the pressure dependence of partial molar volumes for sulfide liquid species. The resulting combined thermochemical model should be valid to about 2,000 K and 3 GPa. Application of this thermochemical model in a simple adiabatic magma ascent scenario confirms earlier work suggesting that the pressure dependence of sulfur solubility in sulfide-saturated magma will decrease with increasing pressure along geologically reasonable paths in P–T–– space.     

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.     

Shear modulus, heat capacity, viscosity and structural relaxation time of Na2O–Al2O3–SiO2 and Na2O–Fe2O3–Al2O3–SiO2 melts

The configurational heat capacity, shear modulus and shear viscosity of a series of Na₂O–Fe₂O₃–Al₂O₃–SiO₂ melts have been determined as a function of composition. A change in composition dependence of each of the physical properties is observed as Na₂O/(Na₂O + Al₂O₃) is decreased, and the peralkaline melts become peraluminous and a new charge-balanced Al-structure appears in the melts. Of special interest are the frequency dependent (1 mHz–1 Hz) measurements of the shear modulus. These forced oscillation measurements determine the lifetimes of Si–O bonds and Na–O bonds in the melt. The lifetime of the Al–O bonds could not, however, be resolved from the mechanical spectrum. Therefore, it appears that the lifetime of Al–O bonds in these melts is similar to that of Si–O bonds with the Al–O relaxation peak being subsumed by the Si–O relaxation peak. The appearance of a new Al-structure in the peraluminous melts also cannot be resolved from the mechanical spectra, although a change in elastic shear modulus is determined as a function of composition. The structural shear-relaxation time of some of these melts is not that which is predicted by the Maxwell equation, but up to 1.5 orders of magnitude faster. Although the configurational heat capacity, density and shear modulus of the melts show a change in trend as a function of composition at the boundary between peralkaline and peraluminous, the deviation in relaxation time from the Maxwell equation occurs in the peralkaline regime. The measured relaxation times for both the very peralkaline melts and the peraluminous melts are identical with the calculated Maxwell relaxation time. As the Maxwell equation was created to describe the timescale of flow of a mono-structure material, a deviation from the prediction would indicate that the structure of the melt is too complex to be described by this simple flow equation. One possibility is that Al-rich channels form and then disappear with decreasing Si/Al, and that the flow is dominated by the lifetime of Si–O bonds in the Al-poor peralkaline melts, and by the lifetime of Al–O bonds in the relatively Si-poor peralkaline and peraluminous melts with a complex flow mechanism occurring in the mid-compositions. This anomalous deviation from the calculated relaxation time appears to be independent of the change in structure expected to occur at the peralkaline/peraluminous boundary due to the lack of charge-balancing cations for the Al-tetrahedra.     

Thermodynamic properties of copper carbonates — malachite Cu2(OH)2CO3 and azurite Cu3(OH)2(CO3)2

The thermodynamic properties of the copper carbonates malachite and azurite have been studied by adiabatic calorimetry, by heat-flux Calvet Calorimetry, by differential thermal analysis (DTA) and by thermogravimetrie (TGA) analysis. The heat capacities, C _p ⁰ of natural malachite and azurite have been measured between 3.8 and 300 K by low-temperature adiabatic calorimetry. The heat capacity of azurite exhibits anomalous behavior at low temperatures. At 298.15 K the molar heat capacities C _p ⁰ and the third law entropies S _298.15 ⁰ are 228.5±1.4 and 254.4±3.8 J mol^?1 K^?1 for azurite and 154.3±0.93 and 166.3±2.5 J mol^?1 K^?1 for malachite. Enthalpies of solution at 973 K in lead borate 2PbO·B₂O₃ have been measured for heat treated malachite and azurite. The enthalpies of decomposition are 105.1±5.8 for azurite and 66.1±5.0 kJ mol^? for malachite. The enthalpies of formation from oxides of azurite and malachite determined by oxide melt solution calorimetry, are ?84.7±7.4 and ?52.5±5.9 kJ mol^?1, respectively. On the basis of the thermodynamic data obtained, phase relations of azurite and malachite in the system Cu²⁺-H₂O-CO₂ at 25 and 75 °C have been studied.     

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.     

Determining the composition of C–H–O liquids following high-pressure and high-temperature diamond-trap experiments

Here, we present the first analytical technique (the quartz tube system technique—QTS) to directly analyze H₂O and CO₂ contents in liquids following high-pressure, high-temperature experiments in capsules containing mantle minerals and a diamond layer serving as a fluid/melt trap. In this technique, the capsule is frozen prior to opening; the diamond trap is cut out of the capsule and placed inside a N₂-filled quartz tube. The diamond trap is heated up to 900 °C to release the gases to an Infrared Gas Analyzer, which determines the CO₂ and H₂O contents. Three sets of experiments containing SiO₂ and CaCO₃ powders were performed at 6 GPa and 1,000 °C in order to calibrate and validate the technique. These experiments demonstrated that when samples are prepared in a N₂ environment, CO₂ and H₂O can be directly measured with an accuracy and precision of 2–3 and 3–4 %, respectively. The QTS technique (for H₂O and CO₂ determination) together with the cryogenic technique (total dissolved solids content) can be applied to diamond-trap capsules following HP–HT experiments in order to provide direct and complete liquid compositions coexisting with mantle material. The principal advantage of the QTS technique of direct analysis of volatile content in liquids over the indirect approach of mass balance calculations is the possibility of studying carbonated and hydrous liquid compositions in equilibrium with mantle material regardless of chemistry and pressure–temperature experimental conditions.     

Sound velocity and elastic properties of Fe–Ni and Fe–Ni–C liquids at high pressure

The sound velocity (V _P) of liquid Fe–10 wt% Ni and Fe–10 wt% Ni–4 wt% C up to 6.6 GPa was studied using the ultrasonic pulse-echo method combined with synchrotron X-ray techniques. The obtained V _P of liquid Fe–Ni is insensitive to temperature, whereas that of liquid Fe–Ni–C tends to decrease with increasing temperature. The V _P values of both liquid Fe–Ni and Fe–Ni–C increase with pressure. Alloying with 10 wt% of Ni slightly reduces the V _P of liquid Fe, whereas alloying with C is likely to increase the V _P. However, a difference in V _P between liquid Fe–Ni and Fe–Ni–C becomes to be smaller at higher temperature. By fitting the measured V _P data with the Murnaghan equation of state, the adiabatic bulk modulus (K _S0) and its pressure derivative (K _S ^′ ) were obtained to be K _S0 = 103 GPa and K _S ^′  = 5.7 for liquid Fe–Ni and K _S0 = 110 GPa and K _S ^′  = 7.6 for liquid Fe–Ni–C. The calculated density of liquid Fe–Ni–C using the obtained elastic parameters was consistent with the density values measured directly using the X-ray computed tomography technique. In the relation between the density (ρ) and sound velocity (V _P) at 5 GPa (the lunar core condition), it was found that the effect of alloying Fe with Ni was that ρ increased mildly and V _P decreased, whereas the effect of C dissolution was to decrease ρ but increase V _P. In contrast, alloying with S significantly reduces both ρ and V _P. Therefore, the effects of light elements (C and S) and Ni on the ρ and V _P of liquid Fe are quite different under the lunar core conditions, providing a clue to constrain the light element in the lunar core by comparing with lunar seismic data.     

K2CO3—CaCO3体系中复碳酸盐的热化学

在熔融的２ＰｂＯ．Ｂ２Ｏ３中（９７４Ｋ）,用滴溶量热法测定了２９８Ｋ下由组分Ｋ２ＣＯ３和ＣａＣＯ３形成的复碳酸盐Ｋ２Ｃａ（ＣＯ３）２（它有胶方解石和碳钾钙石两种多型）和Ｋ２Ｃａ２（ＣＯ３）３为－７．２±５．８ｋＪ／ｍｏｌ。同时推算出了复碳酸盐生砀熵变ΔＳｔ。假定具有序结构的胶方解石的ΔＳｔ＝０,则碳钾钙石的生成熵为４０．９±５．１Ｊ／ｍｏｌ．Ｋ,Ｋ２Ｃａ２（ＣＯ３）３为３９．４±７．３Ｊ／ｍｏｌ．     

The Influence of Sodium and Potassium Chlorides on Phase Ratios in the Eclogite–CaCO3–H2O + CO2 System at 4 GPa and 1200–1300°C

To characterize the influence of alkaline metal chlorides on the phase ratios under melting of upper mantle eclogites, the eclogite–CaCO₃–NaCl–KCl system with Н₂О + СО₂-fluid was studied in the experiments under 4 GPa and 1200–1300°C. A low difference in temperatures (<100°C) was registered between the eclogite solidus and liquidus (>1200 and <1300°C, respectively), which is characteristic for the near-eutectic compositions. The phase proportions were peculiar for the absence of any silicate melt over the entire temperature range considered. The carbonate melt coexisted with clinopyroxene and garnet within 1200–1250°C, whereas a carbonate melt exclusively occurred under above-liquidus conditions at 1300°C. The melt quenching resulted in the formation of a multiphase fine-grained mixture of Ca, Na, and K carbonates and chlorides containing microinclusions of clinopyroxene and garnet. The occurrence of a high-calcium carbonate melt in Cl-containing eclogite systems might play a significant role in the mantle metasomatism of subduction zones characterized by the water–alkaline–chloride type of fluids.

     

淡水碳酸盐湖泊中CaCO3—CO32-—HCO3-—CO2化学平衡对CO2的缓冲作用——以贵州百花湖为例

水体吸收的CO2转变为HCO3-,构成了碳酸盐水化学系统对CO2气体的缓冲,通常用Revelle因子（R）表征。陆地淡水系统释放的CO2是全球碳循环的重要组成部分,一方面,湖泊水体释放的CO2是来源于流域碳酸盐风化产物的输入,另一方面,碳酸盐的缓冲作用也是调节内陆水体CO2释放的重要因素,这两个结论看似是矛盾的。为了揭示碳酸盐循环对水体CO2的影响与缓冲机制,本研究选取一个碳酸盐岩地区的季节性分层湖泊（百花湖）,分析Revelle因子变化,并与非碳酸盐湖泊进行比较。结果发现,碳酸盐岩湖泊Revell因子平均为20.1±8.1（8.0~50.0）,大于表层海水的10.0（8.0~15.0）,也远大于非碳酸盐地区湖泊的3.9±3.9,较高的Revelle因子意味着对CO2的缓冲能力更弱。Revelle因子最大值46.4出现在夏季分层期的中部斜温层,对应的无机碳浓度为2.1 mmol?L-1、pH为8.38、总无机碳与碱度比接近1.0、CO2/CO32-等于1.0。实际观测与理论分析结果完全吻合,表明碳酸盐化学平衡是控制湖泊Revelle因子变化的主要因素。低pH的非碳酸盐岩系统可以溶解碳酸盐矿物,使pH升高,碱度增加,导致Revelle因子升高,在碳酸盐溶解达到平衡时Revelle因子升至最大。其后,无论是光合作用导致的碳酸盐沉淀还是呼吸作用导致的碳酸盐溶解,Revelle因子都会降低,新陈代谢导致碳酸盐系统的CO2缓冲能力增强。      

Low-temperature thermodynamic model for the system Na2CO3−MgCO3−CaCO3−H2O

A comprehensive low-temperature thermodynamic model for the geochemically important Na₂CO₃−MgCO₃−CaCO₃−H₂O system is presented. The model is based on calorimetrically determined Δ_fH°₂₉₈ values, S°₂₉₈ values and C°_p(T) functions taken from the literature as well as on μ°₂₉₈ values of solids derived in this work from solubility measurements obtained in our laboratories or by others. When these thermodynamic quantities were combined with temperature-dependent Pitzer parameters taken from the literature, solubilities calculated for a wide range of conditions agree well with experimental data. The results for several subsystems were summarized by depicting the respective phase diagrams. For the MgO−CO₂−H₂O subsystem, it was found that the commonly believed stability relations must be revised, i.e., in the temperature range covered, nesquehonite never becomes more stable than hydromagnesite at p_CO2 ≤ 1 atm. Although the recommended set of thermodynamic data on sparingly soluble solids was derived from experimental results on mainly NaClO₄ systems, it can be incorporated in databanks containing additional Pitzer parameters for modeling more complex fresh- or seawater systems.     

Thermochemistry of sulfide liquids III: Ni-bearing liquids at 1 bar

Experiments were performed in the system O–S–Fe–Ni designed to extend our understanding of the chemistry of sulfide liquids. Results indicate that adding nickel to Fe-rich sulfide liquids in equilibrium with silicate liquids extends their stability field to much higher oxygen fugacities and lower sulfur fugacities. Increasing Ni/Fe at a given temperature and sulfur and oxygen fugacity is accompanied by a significant decrease in the oxygen content of the sulfide liquid. Results of these experiments are combined with data from the literature to calibrate an associated regular solution model for O–S–Fe–Ni liquids. This model represents a complete refit of the associated regular solution model of Kress (Contrib Mineral Petrol 139:316–325, 2000). The resulting model is combined with the olivine solution model of Hirschmann (Am Mineral 76:1232–1248, 1991) to explore the effect of variations in oxygen and sulfur fugacities on the distribution of Fe and Ni between olivine and sulfide liquid. Predicted olivine–sulfide distribution trends parallel those observed by Gaetani and Grove (Geochim Cosmochim Acta 61:1829–1846, 1997), Gaetani and Grove (Earth Planet Sci Lett 169:147–163, 1999), Brenan and Caciagli (Geochim Cosmochim Acta 64:307–320, 2000) and Brenan (Geochim Cosmochim Acta 67:2663–2681, 2003), but are systematically offset toward lower predicted Ni in the sulfide. Nevertheless our results are consistent with the assertion that low K _D ^os values in magmatic ore deposits such as the J-M Reef reflect high iron contents in the sulfides combined with relatively high oxygen fugacities.

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