The Development of Stylolites in Carbonate Formation: Implication for CO2 Sequestration

The impact of CO2 sequestration on the host formation is an issue occurring over geologic time. Laboratory tests can provide important results to investigate this matter but have limitations due to a relatively short timeline. Based on literature review and core sample observation, naturally occurred geological phenomena, stylolites are studied in this paper for understanding CO2 sequestration in deep carbonate formations. Stylolites are distinctive and pervasive structures in carbonates that are related to water-assisted pressure solution. Pressure solution involving stylolitization is thought to be the main mechanism of compaction and cementation for many carbonates. In parallel, CO2 sequestration in carbonate formation involves extensive chemical reactions among water, CO2 and rock matrix, favoring chemical compaction as a consequence. An analogue between stylolites and CO2 sequestration induced formation heterogeneity exists in the sense of chemical compaction, as both pressure solution in stylolites and CO2 enriched solution in CO2 sequestration in carbonate formations may all introduce abnormal porous regions. The shear and/or tension fractures associated with stylolites zones may develop vertically or sub-vertically; all these give us alert for long-term safety of CO2 sequestration. Thus a study of stylolites will help to understand the CO2 sequestration in deep carbonate formation in the long run.     

Reactions between olivine and CO_2-rich seawater at 300℃:Implications for H_2 generation and CO_2 sequestration on the early Earth

To understand the influence of fluid CO_2 on ultramafic rock-hosted seafloor hydrothermal systems on the early Earth,we monitored the reaction between San Carlos olivine and a CO_2-rich NaCl fluid at 300 C and 500 bars.During the experiments,the total carbonic acid concentration(∑XO_2) in the fluid decreased from approximately 65 to 9 mmol/kg.Carbonate minerals,magnesite,and subordinate amount of dolomite were formed via the water-rock interaction.The H_2 concentration in the fluid reached approximately 39 mmol/kg within 2736 h,which is relatively lower than the concentration generated by the reaction between olivine and a CO2-free NaCl solution at the same temperature.As seen in previous hydrothermal experiments using komatiite,ferrous iron incorporation into Mg-bearing carbonate minerals likely limited iron oxidation in the fluids and the resulting H_2 generation during the olivine alteration.Considering carbonate mineralogy over the temperature range of natural hydrothermal fields,H_2 generation is likely suppressed at temperatures below approximately 300℃ due to the formation of the Mg-bearing carbonates.Nevertheless,H_2 concentration in fluid at 300℃ could be still high due to the temperature dependency of magnetite stability in ultramafic systems.Moreover,the Mg-bearing carbonates may play a key role in the ocean-atmosphere system on the early Earth.Recent studies suggest that the subduction of carbonated ultramafic rocks may transport surface CO_2 species into the deep mantle.This process may have reduced the huge initial amount of CO_2 on the surface of the early Earth.Our approximate calculations demonstrate that the subduction of the Mg-bearing carbonates formed in komatiite likely played a crucial role as one of the CO_2 carriers from the surface to the deep mantle,even in hot subduction zones.     

Regional Geochemistry and Fluid Flow in the Palaeogene Aquifers of the Gaoyou Subbasin in the Southern Part of North Jiangsu Basin, China

Chemical analysis of groundwater in petroliferous basins can be an effective way to determine the regional hydrogeological regime and to evaluate the preservation conditions of hydrocarbons. This paper presents the hydrochemical distribution of both individual aquifers and different structural units within the Palaeogene strata of the Gaoyou subbasin in the North Jiangsu Basin, east China. The results show that the salinity of the Palaeogene aquifers in the Gaoyou subbasin displays a systematic increase from the central deep depression to the periphery areas, and shows a reverse trend as the burial depth increases. Salinity maps of individual aquifers suggest that formation water in the deep layers at the centre of the study area probably retains original features of fresh lake water. Geofluids near the central deep depression of the Gaoyou subbasin migrate vertically through the Zhenwu and Hanliu faults, while those of the northern slope belt mainly flow laterally through aquifers. Both low and high salinity formation water can be found in the hydrocarbon producing areas. The low salinity zones commonly affected by infiltrated meteoric water are unfavourable conditions for the preservation of trapped hydrocarbons.     

Diagenetic reactions in reservoir strata and geochemical properties of pore fluid and its origin in Songliao Basin

The reservoirs of the SOngliao Basin are composed of typical unstable sandstones,with high percentages of volcanic fragments and feldspar,In the course of sedimentation and burying,a series of physical and chemical reactions took place between minerals and pore water and water-rock reactions and ion exchange caused changes in ion assemblage of pore water,Hydration-hydrolysis,dissolution and the albitization of feldspar made many ions free from their framework and inter into the pore water,and induced the precipitation of a large amount of authigenic minerals such as smectite and chlorite,During the diagenesis of sandstone.diagenetic reactions involved several stages with increasing depth,and so did the precipitation of authigenic minerals and the transformaiton of minerals.The migration of ions is related with the precipitation,transformation and dissolution of authigenic minerals.Thus,to deepen our study on sandstone diagenesis is an important link for the analysis of ion migration in the evolution of pore water ,the origin and evolution of pore water could be tracked in terms of the geochemistry of fluid inclusions in authigenic minerals.And the isotopic composition of the authigenic mineral calcite can provide its genetic information.     

Short term validated geochemical model of CO2 sequestration

In this work we present a new approach to modeling the effects of CO2 sequestration that was tested in the Weyburn test site. The Weyburn oil-pull is recovered from Midale Beds （at 1300-1500 m depth）. This formation consists of Mississippian shallow marine evaporific carbonates that can be divided into two units： （1） the dolomific ＂Marly＂ and ii） the underlying calcitic ＂Vuggy＇, sealed by an anhydrite cap-rock. Presently, about 3 billions mc of supercrifical CO2 have been injected into the ＂Phase Al＂ injection area. The aim of our model is to reconstruct （1） the chemical composition of the reservoir; （2） the geochemical evolution of the reservoir with time as CO2 is injected and （3） the boundary conditions. The geochemical modeling was performed by using the code PRHEEQC （V2.11） software package. The ＂primitive brine＂ composition was calculated on the basis of the chemical equilibriums among the various phases, assuming reservoir equilibrium conditions for the mineral assemblage with respect to a Na-Cl （Cl/Na= 1.2） water, at T of 62℃ and P of 150 bars via thermodynamic corrections to the code database. A comparison between the chemical composition of the ＂primitive brine＂ and that analytically determined on water samples collected before the CO2 injection shows an agreement within 10%. Furthermore, we computed the kinetic evolution of the reservoir by considering the local equilibrium and the kinetically controlled reactions while taking it into account the CO2 injected during four years of monitoring. The calculated chemical composition after CO2 injection is consistent with the analytical data of samples collected in 2004, with the exception of calcium and magnesium contents.     

Authigenic Gypsum in Gas-Hydrate Associated Sediments from the East Coast of India (Bay of Bengal)

Authigenic gypsum crystals, along with pyrite and carbonate mineralization, predominantly calcites were noticed in distinct intervals in a 32 m long piston core, collected in the gas hydrate- bearing sediments in the northern portion of the Krishna-Godavari basin, eastern continental margin of India at a water depth of 1691 m. X-ray diffraction and energy dispersive spectrum studies confirm presence of pyrite, gypsum, calcite, and other mineral aggregates. The occurrence of gypsum in such deep sea environment is intriguing, because gypsum is a classical evaporite mineral and is under saturated with respect to sea water. Sedimentological, geochemical evidences point to diagenetic formation of the gypsum due to oxidation of sulphide minerals (i.e. pyrite). Euhedral, transparent gypsum crystals, with pyrite inclusions are cemented with authigenic carbonates, possibly indicating that they were formed authigenically in situ in the gas hydrate-influenced environment due to late burial diagenesis involving sulphate reduction and anaerobic oxidation of methane (AOM). Therefore, the authigenic gypsums found in sediments of the Krishna-Godavari and Mahanadi offshore regions could be seen as one of the parameters to imply the presence of high methane flux possibly from gas hydrate at depth.     

Stable Isotope Geochemistry of the Beishan Stratabound Sphalerite-Pyrite Deposit, Guangxi

Based on lead isotope data, it has been shown that lead in the Beishan stratabound sphalerite-pyrite deposit came mainly from the oldland and its underlying basement rocks and, subordinately, the Devonian itself or the seawater at that time. As to its primary source, upper crust lead was predominant. while lower crust lead or upper mantle lead was subordinate. Sulfur was formed mainly through bacterial reduction of marine carbonates. The carbon and oxygen isotopic analyses for carbonate rocks and minerals have demonstrated that carbonate rocks in the Beishan area are normal marine sediments. The isotopic characteristics of the carbonate rocks are intermediate between those of the northern Guangdong and central Hunan, but closer to those of the central Hunan basin. The formation of the Beishan deposit underwent: a depositional-diagenetic mineralization stage and a successive post-diagenetic enrichmentremoulding one.     

达索普冰川海拔7100m处粒雪中空气的封闭

The air-bubble formation has been studied experimentally in the Dasuopu ice core from the northern slope of Mount Xixabangma. It was found that air-channel volume decreases gradually, but the firn remains permeable down to the depth above the transition of firn to ice, i. e., about the depth of the air-channels closing off to be isolated bubbles. Apparently, there exists an age difference between air trapped in bubbles and surrounding ice. Only when the air channels close off completely, the age of the air increases in the same rate as the surrounding ice. Air-bubbles formed in different depths at different sites depending on accumulation rate and mean annual temperature, but approximately at a mean density of 0.79～0.83 Mg·m -3 . The air-channels in the Dasuopu firn core closed rapidly in the depth between 40 and 47 m, and 50% of air-bubbles were formed in the depth of 45 m. It is calculated that the age difference between air and its surrounding ice is 59 a, and the bulk age distribution width of air trapped in ice bubbles is 11 a.     

Pyrite-hydrocarbon Interaction under Hydrothermal Conditions: an Alternative Origin of H2S and Organic Sulfur Compounds in Sedimentary Environments

Sulfate rocks and organic sulfur from sedimentary organic matter are conventionally assumed as the original sulfur sources for hydrogen sulfide(H_2S) in oil and gas reservoirs. However,a few recent experiments preliminarily indicate that the association of pyrite and hydrocarbons may also have implications for H_2S generation,in which water effects and natural controls on the evolution of pyrite sulfur into OSCs and H_2S have not been evaluated. In this study,laboratory experiments were conducted from 200 to 450° C to investigate chemical interactions between pyrite and hydrocarbons under hydrothermal conditions. Based on the experimental results,preliminary mechanism and geochemical implications were tentatively discussed. Results of the experiments showed that decomposition of pyrite produced H_2S and thiophenes at as low as 330°C in the presence of water and n-pentane. High concentrations of H_2S were generated above 450°C under closed pyrolysis conditions no matter whether there is water in the designed experiments. However,much more organic sulfur compounds(OSCs) were formed in the hydrous pyrolysis than in anhydrous pyrolysis. Generally,most of sulfur liberated from pyrite at elevated temperatures was converted to H_2S. Water was beneficial to breakdown of pyrite and to decomposition of alkanes into olefins but not essential to formation of large amounts of H_2S,given the main hydrogen source derived from hydrocarbons. In addition,cracking of pyrite in the presence of 1-octene under hydrous conditions was found to proceed at 200°C,producing thiols and alkyl sulfides. Unsaturated hydrocarbons would be more reactive intermediates involved in the breakdown of pyrite than alkanes. The geochemistry of OSCs is actually controlled by various geochemical factors such as thermal maturity and the carbon chain length of the alkanes. This study indicates that the scale of H_2S gas generated in deep buried carbonate reservoirs via interactions between pyrite and natural gas should be much smaller than that of thermochemical sulfate reduction(TSR) due to the scarcity of pyrite in carbonate reservoirs and the limited amount of long-chained hydrocarbons in natural gas. Nevertheless,in some cases,OSCs and/or low contents of H_2S found in deep buried reservoirs may be associated with the deposited pyrite-bearing rock and organic matters(hydrocarbons),which still needs further investigation.     

High Pressure-Differential Thermal Analysis and Ultrasonic Wave Amplitude Analysis of Ice-Water Equilibrium at 1.5-5.0GPa

Water is the most active component in all geological systems.It has an important effect on the physical properties of minerals and melts.It also plays a key role in the evolution of the Earth.Accurate thermodynamics data on water are currently confined to pressures below 1.0GPa and temperatures below 900℃.Presented in this paper are new data available on the P-T properties of water at pressures up to 5.0GPa,develoged from differential thermal analysis and ultrasonic wave amplitude analysis.It has been found that there may exist another ternary point at 3.0GPa and that ultrasonic wave amplitude change of ice-water transition shows two inflection points above 2.0GPa, consistent with the two peaks of differential thermal curves above 2.0GPa .It may be a new phenomenon which needs further study.     

无机生油假说及其在中国的应用前景

无机生油假说认为,原油和天然气和近地表的生物物质没有根本联系,它们是生成于地幔内的非生物来源的碳氢化合物。因而油气不是一个不可再生资源,而是一个可再生资源。无机生油假说得到地质学、物理学和化学等三个基本学科的支持。在地质观察上,发现全球许多大油田的油气储藏与原始生物物质之间数量上有巨大落差,难于解释它们是由生物生成的。此外,有许多地区在结晶基底或变质基底内,或直接位于其上的沉积岩中发现石油。从生物生油假说来说,也是无法理解的。在化学上,早在二战期间,德国已由人工合成石油(费托合成),并生产了占德国战争中用油的9%的石油。无可争辩地说明,无机可以生成石油。根据化学(物理学)热力学理论分析确认,甲烷是唯一一种在标准温压条件(温度为298.15 K;压力为101325 Pa)下稳定的碳氢化合物,从甲烷形成正常烷属烃只有在压力>3×106kPa、温度>700°C时(相当于地下深度约100 km)才有可能。在地壳内的温压条件下由生物变质形成石油的假说,与化学热力学的基本原则相抵触。从氧化的有机分子,如碳水化合物(C6H12O6)形成较高的碳氢化合物在任何条件下都是不可能的。根据我国长期对深部构造的研究,笔者认为在中国东部及西太平洋蘑菇云岩石圈地幔发育的地区是寻找巨型无机油气田的有利地区,建议在发育蘑菇云岩石圈地幔地区开展无机油气田的勘探,并在无机油气田远景地区布置超深参数钻,以评价含油气远景。另外建议加强物探工作,尤其是研究地震勘探处理基底内三维含油气构造的技术。     

江西兴国县潜在偏硅酸矿泉水水化学特征及水质健康功能评价

江西兴国县地下水中富含偏硅酸,水资源丰富,但对矿泉水资源禀赋等研究相对薄弱,开展该县偏硅酸矿泉水水化学特征和健康功能研究,可为当地发展矿泉水产业、实施乡村振兴战略提供基础支撑。本文应用数理统计、水化学分析、离子比值等多种分析方法研究了兴国县潜在偏硅酸矿泉水的分布、水化学特征以及成因与物质来源,并基于感官指数和健康指数对其健康功能进行了评价。结果表明：潜在偏硅酸矿泉水主要分布在岩浆岩裂隙含水岩组、碎屑岩孔隙裂隙含水岩组和变质岩裂隙含水岩组中,这三类含水岩组的调查水样中,发现潜在偏硅酸矿泉水的比例分别为48.5%、45.7%、29.6%,且主要分布在海拔400m以下区域。潜在偏硅酸矿泉水的偏硅酸含量多集中在32~40mg/L之间,主要来自硅酸盐矿物的水解;在变质岩、岩浆岩裂隙含水岩组区,偏硅酸的富集以溶滤作用为主;在碎屑岩孔隙裂隙含水岩组区,偏硅酸的富集受溶滤作用和阳离子交替吸附作用共同影响。该县岩浆岩裂隙含水组区潜在偏硅酸矿泉水口感最佳,深层碎屑岩孔隙含水组区潜在偏硅酸矿泉水健康指数相对较高。本文认为,兴国县矿泉水勘查开发靶区宜以岩浆岩裂隙含水岩组区和深层碎屑岩孔隙裂隙含水岩组区为主。研究成果可为揭示兴国县偏硅酸矿泉水资源价值和功能提供参考。     

CO2-water-basalt interaction. Numerical simulation of low temperature CO2 sequestration into basalts

The interaction between CO₂-rich waters and basaltic glass was studied using reaction path modeling in order to get insight into the water-rock reaction process including secondary mineral composition, water chemistry and mass transfer as a function of CO₂ concentration and reaction progress (ξ). The calculations were carried out at 25-90 °C and pCO₂ to 30 bars and the results were compared to recent experimental observations and natural systems. A thermodynamic dataset was compiled from 25 to 300 °C in order to simulate mineral saturations relevant to basalt alteration in CO₂-rich environment including revised key aqueous species for mineral dissolution reactions and apparent Gibbs energies for clay and carbonate solid solutions observed to form in nature. The dissolution of basaltic glass in CO₂-rich waters was found to be incongruent with the overall water composition and secondary mineral formation depending on reaction progress and pH. Under mildly acid conditions in CO₂ enriched waters (pH <6.5), SiO₂ and simple Al-Si minerals, Ca-Mg-Fe smectites and Ca-Mg-Fe carbonates predominated. Iron, Al and Si were immobile whereas the Mg and Ca mobility depended on the mass of carbonate formed and water pH. Upon quantitative CO₂ mineralization, the pH increased to >8 resulting in Ca-Mg-Fe smectite, zeolites and calcite formation, reducing the mobility of most dissolved elements. The dominant factor determining the reaction path of basalt alteration and the associated element mobility was the pH of the water. In turn, the pH value was determined by the concentration of CO₂ and extent of reaction. The composition of the carbonates depended on the mobility of Ca, Mg and Fe. At pH <6.5, Fe was in the ferrous oxidation state resulting in the formation of Fe-rich carbonates with the incorporation of Ca and Mg. At pH >8, the mobility of Fe and Mg was limited due to the formation of clays whereas Ca was incorporated into calcite, zeolites and clays. Competing reactions between clays (Ca-Fe smectites) and carbonates at low pH, and zeolites and clays (Mg-Fe smectites) and carbonates at high pH, controlled the availability of Ca, Mg and Fe, playing a key role for low temperature CO₂ mineralization and sequestration into basalts. Several problems of the present model point to the need of improvement in future work. The determinant factors linking time to low temperature reaction path modeling may not only be controlled by the primary dissolving phase, which presents challenges concerning non-stoichiometric dissolution, the leached layer model and reactive surface area, but may include secondary mineral precipitation kinetics as rate limiting step for specific reactions such as retrieved from the present reaction path study.     

Reactivity of micas and cap-rock in wet supercritical CO2 with SO2 and O2 at CO2 storage conditions

Seal or cap-rock integrity is a safety issue during geological carbon dioxide capture and storage (CCS). Industrial impurities such as SO₂, O₂, and NOx, may be present in CO₂ streams from coal combustion sources. SO₂ and O₂ have been shown recently to influence rock reactivity when dissolved in formation water. Buoyant water-saturated supercritical CO₂ fluid may also come into contact with the base of cap-rock after CO₂ injection. Supercritical fluid-rock reactions have the potential to result in corrosion of reactive minerals in rock, with impurity gases additionally present there is the potential for enhanced reactivity but also favourable mineral precipitation.The first observation of mineral dissolution and precipitation on phyllosilicates and CO₂ storage cap-rock (siliciclastic reservoir) core during water-saturated supercritical CO₂ reactions with industrial impurities SO₂ and O₂ at simulated reservoir conditions is presented. Phyllosilicates (biotite, phlogopite and muscovite) were reacted in contact with a water-saturated supercritical CO₂ containing SO₂, or SO₂ and O₂, and were also immersed in the gas-saturated bulk water. Secondary precipitated sulfate minerals were formed on mineral surfaces concentrated at sheet edges. SO₂ dissolution and oxidation resulted in solution pH decreasing to 0.74 through sulfuric acid formation. Phyllosilicate dissolution released elements to solution with ∼50% Fe mobilized. Geochemical modelling was in good agreement with experimental water chemistry. New minerals nontronite (smectite), hematite, jarosite and goethite were saturated in models. A cap-rock core siltstone sample from the Surat Basin, Australia, was also reacted in water-saturated supercritical CO₂ containing SO₂ or in pure supercritical CO₂. In the presence of SO₂, siderite and ankerite were corroded, and Fe-chlorite altered by the leaching of mainly Fe and Al. Corrosion of micas in the cap-rock was however not observed as the pH was buffered by carbonate dissolution. Ca-sulfate, and Fe-bearing precipitates were observed post SO₂-CO₂ reaction, mainly centered on surface cracks and an illite rich illite-smectite precipitate quantified. Water saturated impure supercritical CO₂ was observed to have reactivity to rock-forming biotite, muscovite and phlogopite mineral separates. In the cap-rock core however carbonates and chlorite were the main reacting minerals showing the importance of assessing actual whole core.     

Evolution of nC16H34-water–mineral systems in thermal capsules and geological implications for deeply-buried hydrocarbon reservoirs

Organic-inorganic interactions between hydrocarbons and most minerals in deeply buried reservoirs remain unclear. In this study, gold capsules and fused silica capillary capsules (FSCCs) with different combinations of nC₁₆H₃₄, water (distilled water, CaCl₂ water) and minerals (quartz, feldspar, calcite, kaolinite, smectite, and illite) were heated at 340 °C for 3–10 d, to investigate the evolution and reaction pathways of the organic–inorganic interactions in different hot systems.After heating, minerals exhibited little alteration in the anhydrous systems. Mineral alterations, however, occurred obviously in the hydrous systems. Different inorganic components affected nC₁₆H₃₄ degradation differently. Overall, water promoted the free-radical thermal-cracking reaction and step oxidation reaction but suppressed the free-radical cross-linking reaction. The impact of CaCl₂ water on the nC₁₆H₃₄ degradation was weaker than the distilled water as high Ca²⁺ concentration suppressed the formation of free radicals. The presence of different waters also affects the impact of different minerals on nC₁₆H₃₄ degradation, via its impact on mineral alterations. In the anhydrous nC₁₆H₃₄-mineral systems, calcite and clays catalyzed generation of low-molecular-weight (LMW) alkanes, particularly the clays. Quartz, feldspar, and calcite catalyzed generation of high-molecular-weight (HMW) alkanes and PAHs, whereas clays catalyzed the generation of LMW alkanes and mono-bicyclic aromatic hydrocarbons (M-BAHs). In the hydrous nC₁₆H₃₄-distilled water–mineral systems, all minerals but quartz promoted nC₁₆H₃₄ degradation to generate more LMW alkanes, less HMW alkanes and PAHs. In the nC₁₆H₃₄-CaCl₂ water–mineral systems, the promotion impact of minerals was weaker than that in the systems with distilled water.This study demonstrated the generation of different hydrocarbons with different fluorescence colors in the different nC₁₆H₃₄-water–mineral systems after heating for the same time, implying that fluorescence colors need to be interpreted carefully in investigation of hydrocarbon charging histories and oil origins in deeply buried reservoirs. Besides, the organic–inorganic interactions in different nC₁₆H₃₄-water–mineral systems proceeded in different pathways at different rates, which likely led to preservation of liquid hydrocarbons at different depth (temperature). Thus, quantitative investigations of the reaction kinetics in different hydrocarbon-water-rock systems are required to improve the prediction of hydrocarbon evolution in deeply buried hydrocarbon reservoirs.     

Dissolution kinetics of selected natural minerals relevant to potential CO2-injection sites − Part 1: A review

This publication provides a literature review on experimental studies of dissolution kinetics of mainly carbonates and feldspar group minerals, i.e. most common minerals at potential CO₂-injection and/or storage sites. Geochemical interaction processes between injected CO₂ and coexisting phases, namely reservoir and cap rock minerals and formation fluids close to the CO₂-injection site can be simulated by flow-through or mixed flow reactors, while processes far from the injection site and long-term processes after termination actual CO₂-injection can be mimicked by batch reactors. At sufficient small stirring rates or fluid flow rates as well as low solute concentrations flow-through reactors are also able to simulate processes far from the injection site. The experimental parameter temperature not only intensifies the dissolution process, the dominant dissolution mechanisms are also influenced by temperature. The dissolution mechanisms change from incongruent and surface controlled mechanisms at lower temperatures to congruent and transport controlled mechanisms at higher temperatures. The CO₂ partial pressure has only a second order influence on dissolution behavior compared to the influence of pH-value and ionic strength of the CO₂-bearing brine. Minerals exposed to CO₂-bearing brines at elevated temperatures and pressures are subject of alteration, leading to severe changes of reactive surfaces and potential precipitation of secondary minerals.Computational simulations of mineral reactions at potential CO₂ storage sites have therefore to include not only the time-resolved changes of dissolution behavior and hence kinetics of mineral dissolution, but also the influence of secondary minerals on the interaction of the minerals with CO₂-enriched brines.     

Brucite [Mg(OH2)] carbonation in wet supercritical CO2: An in situ high pressure X-ray diffraction study

Understanding mechanisms and kinetics of mineral carbonation reactions relevant to sequestering carbon dioxide as a supercritical fluid (scCO₂) in geologic formations is crucial to accurately predicting long-term storage risks. Most attention so far has been focused on reactions occurring between silicate minerals and rocks in the aqueous dominated CO₂-bearing fluid. However, water-bearing scCO₂ also comprises a reactive fluid, and in this situation mineral carbonation mechanisms are poorly understood. Using in situ high-pressure X-ray diffraction, the carbonation of brucite [Mg(OH)₂] in wet scCO₂ was examined at pressure (82 bar) as a function of water concentration and temperature (50 and 75 °C). Exposing brucite to anhydrous scCO₂ at either temperature resulted in little or no detectable reaction over three days. However, addition of trace amounts of water resulted in partial carbonation of brucite into nesquehonite [MgCO₃·3H₂O] within a few hours at 50 °C. By increasing water content to well above the saturation level of the scCO₂, complete conversion of brucite into nesquehonite was observed. Tests conducted at 75 °C resulted in the conversion of brucite into magnesite [MgCO₃] instead, apparently through an intermediate nesquehonite step. Raman spectroscopy applied to brucite reacted with ¹⁸O-labeled water in scCO₂ show it was incorporated into carbonate at a relatively high concentration. This supports a carbonation mechanism with at least one step involving a direct reaction between the mineral and water molecules without mediation by a condensed aqueous layer.     

Hydrogeochemical modelling of fluid–rock interactions triggered by seawater injection into oil reservoirs: Case study Miller field (UK North Sea)

A hydrogeochemical model is presented and applied to quantitatively elucidate interdependent reactions among minerals and formation water–seawater mixtures at elevated levels of CO₂ partial pressure. These hydrogeochemical reactions (including scale formation) occur within reservoir aquifers and wells and are driven by seawater injection. The model relies on chemical equilibrium thermodynamics and reproduces the compositional development of the produced water (formation water–seawater mixtures) of the Miller field, UK North Sea. This composition of the produced water deviates from its calculated composition, which could result solely from mixing of both the end members (formation water and seawater). This indicates the effect of hydrogeochemical reactions leading to the formation and/or the dissolution of mineral phases.     

An Evaporation Model for Formation of Carbonates in the ALH84001 Martian Meteorite

Small, discoid globules and networks of magnesium-iron-calcium carbonates occur within impact-produced fracture zones in the ALH84001 Martian meteorite. Because these carbonates contain or are associated with the hydrocarbons, single-domain magnetite and iron-sulfide grains, and purported microfossils that collectively have been cited as evidence for ancient Martian life, it is critically important to understand their formation. Previous hypotheses for the origin of the carbonates involve either alteration of the rock by hydrothermal fluids at relatively low temperatures, or formation from a CO₂-rich vapor at high temperatures. This paper explores an alternative mechanism–direct precipitation from a ponded evaporating brine infiltrating into fractures in the floor of an impact crater. Such a model can be reconciled with the observed carbonate compositional zoning and extreme stable-isotopic fractionations. If the carbonates formed in this manner, this removes a possible obstacle to the proposed existence of microbial remains in ALH84001; however, the cited evidence for life can be better explained by inorganic processes expected from brines in an evaporating alkaline lake, with an overprint of shock metamorphism and subsequent contamination by organic matter after falling to Earth.     

Alteration of the Callovo-Oxfordian clay from Meuse-Haute Marne Underground Laboratory (France) by alkaline solution: II. Modelling of mineral reactions

One of the French options for the final disposal of high-level radioactive waste is a deep geological repository. The Callovo-Oxfordian formation in the Meuse and Haute-Marne (France) was proposed, by the French agency for the management of radioactive wastes (ANDRA), to be the site of a research laboratory in order to evaluate in situ the interaction between the host formation and the engineered barriers.In the previous experimental part, secondary minerals such as zeolites, tobermorite and katoite have been observed after the alteration of the Callovo-Oxfordian clay under alkaline conditions. Three different reactions of phyllosilicates alteration have been proposed as a function of both pH and chemical composition of the reacting solutions. The aim of this work was to simulate the reaction between the Callovo-Oxfordian clay and high-pH solutions in order to validate the proposed alteration reactions from experimental data.The thermodynamic modelling of stability relationships among minerals in the Callovo-Oxfordian clay was performed using the solution speciation solubility modelling code KINDIS at 120 °C for different chemical media (NaOH, KOH and Ca(OH)₂). Input data were the mineralogical composition of the <2 μm fraction of Callovo-Oxfordian clay at nearly the same burial depth of the underground laboratory construction as well as the neoformed minerals observed after the experimental alteration of this clay (zeolites and cement phases). In the NaOH and KOH runs, anacime, phillipsite and chabazite, respectively were the first stable minerals which appeared at the beginning of modelling. In the Ca(OH)₂ runs, oversaturated with respect to portlandite, katoite and then tobermorite were the first minerals occurring at the beginning of the alteration. Smectites and illites were undersaturated whatever the chemical composition. Both minerals and the interstratified illite-smectite were less stable in Ca(OH)₂ than in NaOH and KOH solutions. Concerning the secondary minerals, a discussion is developed in order to improve modelling and to predict the long term reactions between clays and alkaline solutions.