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.     

Chemical effects of sulfur dioxide co-injection with carbon dioxide on the reservoir and caprock mineralogy and permeability in depleted gas fields

The most suitable candidates for subsurface storage of CO₂ are depleted gas fields. Their ability to retain CO₂ can however be influenced by the effect which impurities in the CO₂ stream (e.g. H₂S and SO₂) have on the mineralogy of reservoir and seal. In order to investigate the effects of SO₂ we carried out laboratory experiments on reservoir and cap rock core samples from gas fields in the northeast of the Netherlands. The rock samples were contained in reactor vessels for 30 days in contact with CO₂ and 100 ppm SO₂ under in-situ conditions (300 bar, 100 °C). The vessels also contained brine with the same composition as in the actual reservoir. Furthermore equilibrium modeling was carried out using PHREEQC software in order to model the experiments on caprock samples.After the experiments the permeability of the reservoir samples had increased by a factor of 1.2–2.2 as a result of dissolution of primary reservoir minerals. Analysis of the associated brine samples before and after the experiments showed that concentrations of K, Si and Al had increased, indicative of silicate mineral dissolution.In the caprock samples, composed of carbonate and anhydrite minerals, permeability changed by a factor of 0.79–23. The increase in permeability is proportional to the amount of carbonate in the caprock. With higher carbonate content in comparison with anhydrite the permeability increase is higher due to the additional carbonate dissolution. This dependency of permeability variations was verified by the modeling study. Hence, caprock with a higher anhydrite content in comparison with carbonate minerals has a lower risk of leakage after co-injection of 100 ppmv SO₂ with CO₂.     

Dissolution of altered tuffaceous rocks under conditions relevant for CO2 storage

We conducted CO₂–water–rock interaction experiments to elucidate the dissolution characteristics and geochemical trapping potential of three different altered andesitic to rhyolitic tuffaceous rocks (Tsugawa, Ushikiri and Daijima tuffaceous rock) relative to fresh mid-ocean ridge basalt. The experiments were performed under 1 MPa CO₂ pressure to reproduce the water–rock–CO₂ interactions in CO₂ storage situations. Basalt showed high acid neutralization potential and rapid dissolution of silicate minerals. Two of the tuffaceous rocks (Ushikiri and Daijima) showed relatively high solubility trapping potential, mainly due to the dissolution of carbonate minerals in the andesitic Ushikiri tuffaceous rock and the ion-exchange reaction with zeolite minerals in the rhyolitic Daijima tuffaceous rock. The mineral trapping potential of the Ushikiri tuffaceous rock was found to be relatively high, due to the rapid dissolution of Mg- and Ca-bearing silicate minerals. Our experimental results suggest that regions of porous and andesitic tuffaceous rock hold global promise as CO₂ storage sites.     

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.     

Reactive transport simulation study of geochemical CO2 trapping on the Tokyo Bay model – With focus on the behavior of dawsonite

A long-term (up to 10 ka) geochemical change in saline aquifer CO₂ storage was studied using the TOUGHREACT simulator, on a 2-dimensional, 2-layered model representing the underground geologic and hydrogeologic conditions of the Tokyo Bay area that is one of the areas of the largest CO₂ emissions in the world. In the storage system characterized by low permeability of reservoir and cap rock, the dominant storage mechanism is found to be solubility trapping that includes the dissolution and dissociation of injected CO₂ in the aqueous phase followed by geochemical reactions to dissolve minerals in the rocks. The CO₂–water–rock interaction in the storage system (mainly in the reservoir) changes the properties of water in a mushroom-like CO₂ plume, which eventually leads to convective mixing driven by gravitational instability. The geochemically evolved aqueous phase precipitates carbonates in the plume front due to a local rise in pH with mixing of unaffected reservoir water. The carbonate precipitation occurs extensively within the plume after the end of its enlargement, fixing injected CO₂ in a long, geologic period.Dawsonite, a Na–Al carbonate, is initially formed throughout the plume from consumption of plagioclase in the reservoir rock, but is found to be a transient phase finally disappearing from most of the CO₂-affected part of the system. The mineral is unstable relative to more common types of carbonates in the geochemical evolution of the CO₂ storage system initially having formation water of relatively low salinity. The exception is the reservoir-cap rock boundary where CO₂ saturation remains very high throughout the simulation period.     

Numerical simulation of CO2 disposal by mineral trapping in deep aquifers

Carbon dioxide disposal into deep aquifers is a potential means whereby atmospheric emissions of greenhouse gases may be reduced. However, our knowledge of the geohydrology, geochemistry, geophysics, and geomechanics of CO₂ disposal must be refined if this technology is to be implemented safely, efficiently, and predictably. As a prelude to a fully coupled treatment of physical and chemical effects of CO₂ injection, the authors have analyzed the impact of CO₂ immobilization through carbonate mineral precipitation. Batch reaction modeling of the geochemical evolution of 3 different aquifer mineral compositions in the presence of CO₂ at high pressure were performed. The modeling considered the following important factors affecting CO₂ sequestration: (1) the kinetics of chemical interactions between the host rock minerals and the aqueous phase, (2) CO₂ solubility dependence on pressure, temperature and salinity of the system, and (3) redox processes that could be important in deep subsurface environments. The geochemical evolution under CO₂ injection conditions was evaluated. In addition, changes in porosity were monitored during the simulations. Results indicate that CO₂ sequestration by matrix minerals varies considerably with rock type. Under favorable conditions the amount of CO₂ that may be sequestered by precipitation of secondary carbonates is comparable with and can be larger than the effect of CO₂ dissolution in pore waters. The precipitation of ankerite and siderite is sensitive to the rate of reduction of Fe(III) mineral precursors such as goethite or glauconite. The accumulation of carbonates in the rock matrix leads to a considerable decrease in porosity. This in turn adversely affects permeability and fluid flow in the aquifer. The numerical experiments described here provide useful insight into sequestration mechanisms, and their controlling geochemical conditions and parameters.     

On the interaction of pure and impure supercritical CO2 with rock forming minerals in saline aquifers: An experimental geochemical approach

The aim of this experimental study was to evaluate and compare the geochemical impact of pure and impure CO₂ on rock forming minerals of possible CO₂ storage reservoirs. This geochemical approach takes into account the incomplete purification of industrial captured CO₂ and the related effects during injection, and provides relevant data for long-term storage simulations of this specific greenhouse gas. Batch experiments were conducted to investigate the interactions of supercritical CO₂, brine and rock-forming mineral concentrates (albite, microcline, kaolinite, biotite, muscovite, calcite, dolomite and anhydrite) using a newly developed experimental setup. After up to 42 day (1000 h) experiments using pure and impure supercritical CO₂ the dissolution and solution characteristics were examined by XRD, XRF, SEM and EDS for the solid, and ICP–MS and IC for the fluid reactants, respectively. Experiments with mixtures of supercritical CO₂ (99.5 vol.%) and SO₂ or NO₂ impurities (0.5 vol.%) suggest the formation of H₂SO₄ and HNO₃, reflected in pH values between 1 and 4 for experiments with silicates and anhydrite and between 5 and 6 for experiments with carbonates. These acids should be responsible for the general larger amount of cations dissolved from the mineral phases compared to experiments using pure CO₂. For pure CO₂ a pH of around 4 was obtained using silicates and anhydrite, and 7–8 for carbonates. Dissolution of carbonates was observed after both pure and impure CO₂ experiments. Anhydrite was corroded by approximately 50 wt.% and gypsum precipitated during experiments with supercritical CO₂ + NO₂. Silicates do not exhibit visible alterations during all experiments but released an increasing amount of cations in the reaction fluid during experiments with impure CO₂. Nonetheless, precipitated secondary carbonates could not be identified.     

Factors affecting the dissolution kinetics of volcanic ash soils: dependencies on pH,CO2, and oxalate

Laboratory experiments were conducted with volcanic ash soils from Mammoth Mountain, California to examine the dependence of soil dissolution rates on pH and CO₂ (in batch experiments) and on oxalate (in flow-through experiments). In all experiments, an initial period of rapid dissolution was observed followed by steady-state dissolution. A decrease in the specific surface area of the soil samples, ranging from 50% to 80%, was observed; this decrease occurred during the period of rapid, initial dissolution. Steady-state dissolution rates, normalized to specific surface areas determined at the conclusion of the batch experiments, ranged from 0.03 μmol Si m⁻² h⁻¹ at pH 2.78 in the batch experiments to 0.009 μmol Si m⁻² h⁻¹ at pH 4 in the flow-through experiments. Over the pH range of 2.78–4.0, the dissolution rates exhibited a fractional order dependence on pH of 0.47 for rates determined from H⁺ consumption data and 0.27 for rates determined from Si release data. Experiments at ambient and 1 atm CO₂ demonstrated that dissolution rates were independent of CO₂ within experimental error at both pH 2.78 and 4.0. Dissolution at pH 4.0 was enhanced by addition of 1 mM oxalate. These observations provide insight into how the rates of soil weathering may be changing in areas on the flanks of Mammoth Mountain where concentrations of soil CO₂ have been elevated over the last decade. This release of magmatic CO₂ has depressed the soil pH and killed all vegetation (thus possibly changing the organic acid composition). These indirect effects of CO₂ may be enhancing the weathering of these volcanic ash soils but a strong direct effect of CO₂ can be excluded.     

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.     

Time and temperature dependency of carbon dioxide triggered metal(loid) mobilization in soil

Assessing the influence of CO₂ on soil and aquifer geochemistry is a task of increasing interest when considering risk assessment for geologic carbon sequestration. Leakage and CO₂ ascent can lead to soil acidification and mobilization of potentially toxic metals and metalloids due to desorption or dissolution reactions. We studied the CO₂ influence on an Fe(III) (oxyhydr)oxide rich, gleyic Fluvisol sampled in close vicinity to a Czech mofette site and compared the short-term CO₂ influence in laboratory experiments with observations on long-term influence at the natural site. Six week batch experiments with/without CO₂ gas flow at 3 different temperatures and monitoring of liquid phase metal(loid) concentrations revealed two main short-term mobilization processes. Within 1 h to 1 d after CO₂ addition, mobilization of weakly adsorbed metal cations occurred due to surface protonation, most pronounced for Mn (2.5–3.3 fold concentration increase, mobilization rates up to 278 ± 18 μg Mn kg_soil⁻¹ d⁻¹) and strongest at low temperatures. However, total metal(loid) mobilization by abiotic desorption was low. After 1–3 d significant Fe mobilization due to microbially-triggered Fe(III) (oxyhydr)oxide dissolution began and continued throughout the experiment (up to 111 ± 24 fold increase or up to 1.9 ± 0.6 mg Fe kg_soil⁻¹ d⁻¹). Rates increased at higher temperature and with a higher content of organic matter. The Fe(III) mineral dissolution was coupled to co-release of incorporated metal(loid)s, shown for As (up to 16 ± 7 fold, 11 ± 8 μg As kg_soil⁻¹ d⁻¹). At high organic matter content, re-immobilization due to resorption reactions could be observed for Cu. The already low pH (4.5–5.0) did not change significantly during Fe(III) reduction due to buffering from sorption and dissolution reactions, but a drop in redox potential (from > +500 mV to minimum +340 ± 20 mV) occurred due to oxygen depletion. We conclude that microbial processes following CO₂ induction into a soil can contribute significantly to metal(loid) mobilization, especially at optimal microbial growth conditions (moderate temperature, high organic carbon content) and should be considered for carbon sequestration monitoring and risk assessment.     

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.     

Dissolution of jarosite [KFe3(SO4)2(OH)6] at pH 2 and 8: Insights from batch experiments and computational modelling

Jarosite [KFe₃(SO₄)₂(OH)₆] is a mineral that is common in acidic, sulphate-rich environments, such as acid sulphate soils derived from pyrite-bearing sediments, weathering zones of sulphide ore deposits and acid mine or acid rock drainage (ARD/AMD) sites. The structure of jarosite is based on linear tetrahedral-octahedral-tetrahedral (T-O-T) sheets, made up from slightly distorted FeO₆ octahedra and SO₄ tetrahedra. Batch dissolution experiments carried out on synthetic jarosite at pH 2, to mimic environments affected by ARD/AMD, and at pH 8, to simulate ARD/AMD environments recently remediated with slaked lime (Ca(OH)₂), suggest first order dissolution kinetics. Both dissolution reactions are incongruent, as revealed by non-ideal dissolution of the parent solids and, in the case of the pH 8 dissolution, because a secondary goethite precipitate forms on the surface of the dissolving jarosite grains. The pH 2 dissolution yields only aqueous K, Fe, and SO₄. Aqueous, residual solid, and computational modelling of the jarosite structure and surfaces using the GULP and MARVIN codes, respectively, show for the first time that there is selective dissolution of the A- and T-sites, which contain K and SO₄, respectively, relative to Fe, which is located deep within the T-O-T jarosite structure. These results have implications for the chemistry of ARD/AMD waters, and for understanding reaction pathways of ARD/AMD mineral dissolution.     

Physical and numerical simulations of the presence of a forsterite transitional zone at high temperature and pressure: insight for scCO2 geological storage

Geological sequestration is one of the most effective ways to reduce greenhouse gases, such as carbon dioxide (CO₂). The deep oceanic crust dominated by ultrabasic rock could store CO₂ permanently. However, the storage mechanism has not been thoroughly understood because of the limited amount of research and experiments conducted. This study explored the reactive mechanisms of water–rock–gas in an ultrabasic system under different conditions. Forsterite, the most dominant mineral found in ultrabasic reservoirs, was used to conduct laboratory physical simulation experiments. Two experimental systems were designed including an scCO₂–forsterite–water system and an N₂–forsterite–water system. All experiments were performed for 1000 h at an experimental temperature of 150°C and a pressure of 150 bar, respectively, to mimic the geological conditions. The liquid products from the experiments were analysed by inductively coupled plasma-optical emission spectrometry, whereas the solid samples were analysed by scanning electron microscopy with energy disperse spectroscopy. Results showed that: (1) in the early stage during scCO₂/N₂–forsterite–water interaction, forsterite was dissolved with a reactive transitional zone forming on the surface, which caused H⁺ to enter into the silicate framework and accelerated the reaction; (2) in the N₂ system, the dissolution of forsterite was inhibited by the Mg²⁺ concentration after reaching its saturation in the late stage; and (3) in the scCO₂ system, magnesite was precipitated as a secondary mineral during the late stage, which promoted the dissolution of forsterite. As a result, the degree of dissolution of forsterite in the scCO₂ system was far higher than in the N₂ system. The experimental results are consistent with the numerical simulation using TOUGHREACT, a geochemical simulation procedure, which showed that CO₂ promotes the dissolution of forsterite greatly at high temperature and pressure.     

Monitoring of fluid–rock interaction and CO2 storage through produced fluid sampling at the Weyburn CO2-injection enhanced oil recovery site,Saskatchewan, Canada

The Weyburn Oil Field is a carbonate reservoir in south central Saskatchewan, Canada and is the site of a large CO₂ injection project for purposes of enhanced oil recovery. The Weyburn Field, in the Mississippian Midale Formation, was discovered in 1954 and was under primary production until secondary recovery by water flood began in 1964. The reservoir comprises two units, the Vuggy and the Marly, and primary and secondary recovery are thought to only have significantly depleted the Vuggy zone, leaving the Marly with higher oil saturations. In 2000, PanCanadian Resources (now EnCana), the operator of the field, began tertiary recovery by injection of CO₂ and water, primarily into the Marly. The advent of this project was an opportunity to study the potential for geological storage of CO₂.Using 43 Baseline samples collected in August 2000, before CO₂ injection at Weyburn, and 44 monitoring samples collected in March 2001, changes in the fluid chemistry and isotope composition have been tracked. The initial fluid distribution showed water from discovery through water flood in the Midale Formation with Cl ranging from 25,000 to 60,000 mg/L, from the NW to the SE across the Phase 1A area. By the time of Baseline sampling the produced water had been diluted to Cl of 25,000–50,000 mg/L as a result of the addition of make up water from the low TDS Blairmore Formation, but the pattern of distribution was still present. The Cl distribution is mimicked by the distribution of other dissolved ions and variables, with Ca (1250–1500 mg/L) and NH_{3 (aq)} increasing from NW to SE, and alkalinity (700–300 mg/L), resistivity, and H₂S (300–100 mg/L) decreasing. Based on chemical and isotopic data, the H₂S is interpreted to result from bacterial SO₄ reduction. After 6 months of injection of CO₂, the general patterns are changed very little, except that the pH has decreased by 0.5 units and alkalinity has increased, with values over 1400 mg/L in the NW, decreasing to 500 mg/L in the SE. Calcium has increased to range from 1250 to 1750 mg/L, but the pattern of NW–SE distribution is altered. Chemical and isotopic data suggest this change in distribution is caused by the dissolution of calcite due to water–rock reactions driven by CO₂. The Baseline samples varied from −22 to −12‰ δ¹³C (V-PDB) for CO₂ gas. The injected CO₂ has an isotope ratio of −20‰. The Monitor-1 samples of produced CO₂ ranged from −18 to −13‰, requiring a heavy source of C, most easily attributed to dissolution of carbonate minerals. Field measured pH had increased and alkalinity had decreased by the second monitoring trip (July 2001) to near Baseline values, suggesting continued reaction with reservoir minerals.Addition of CO₂ to water–rock mixtures comprising carbonate minerals causes dissolution of carbonates and production of alkalinity. Geochemical modeling suggests dissolution is taking place, however more detail on water–oil–gas ratios needs to be gathered to obtain more accurate estimates of pH at the formation level. Geological storage of CO₂ relies on the potential that, over the longer term, silicate minerals will buffer the pH, causing any added CO₂ to be precipitated as calcite. Some initial modeling of water–rock reactions suggests that silica sources are available to the water resident in the Midale Formation, and that clay minerals may well be capable of acting as pH buffers, allowing injected CO₂ to be stored as carbonate minerals. Further work is underway to document the mineralogy of the Midale Formation and associated units so as to define more accurately the potential for geological storage.     

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.     

Carbonation of alkaline paper mill waste to reduce CO2 greenhouse gas emissions into the atmosphere

The global warming of Earth’s near-surface, air and oceans in recent decades is a direct consequence of anthropogenic emission of greenhouse gases into the atmosphere such as CO₂, CH₄, N₂O and CFCs. The CO₂ emissions contribute approximately 60% to this climate change. This study investigates experimentally the aqueous carbonation mechanisms of an alkaline paper mill waste containing about 55 wt% portlandite (Ca(OH)₂) as a possible mineralogical CO₂ sequestration process. The overall carbonation reaction includes the following steps: (1) Ca release from portlandite dissolution, (2) CO₂ dissolution in water and (3) CaCO₃ precipitation. This CO₂ sequestration mechanism was supported by geochemical modelling of final solutions using PHREEQC software, and observations by scanning electron microscope and X-ray diffraction of final reaction products. According to the experimental protocol, the system proposed would favour the total capture of approx. 218 kg of CO₂ into stable calcite/ton of paper waste, independently of initial CO₂ pressure. The final product from the carbonation process is a calcite (ca. 100 wt%)-water dispersion. Indeed, the total captured CO₂ mineralized as calcite could be stored in degraded soils or even used for diverse industrial applications. This result demonstrates the possibility of using the alkaline liquid–solid waste for CO₂ mitigation and reduction of greenhouse effect gases into the atmosphere.     

Far from equilibrium enstatite dissolution rates in alkaline solutions at earth surface conditions

Far from equilibrium enstatite dissolution rates both open to atmospheric CO₂ and CO₂ purged were measured as a function of solution pH from 8 to 13 in batch reactors at room temperature. Congruent dissolution was observed after an initial period of incongruent dissolution with preferential Si release from the enstatite. Steady-state dissolution rates in open to atmospheric CO₂ conditions decrease with increase in solution pH from 8 to 12 similar to the behavior reported by other investigators. Judging from the pH 13 dissolution rate, rates increase with pH above pH 12. This is thought to occur because of the increase in overall negative surface charges on enstatite as Mg surface sites become negative above pH 12.4, the pH of zero surface charge of MgO.Steady-state dissolution rates of enstatite increase above pH 10 when CO₂ was purged by performing the experiments in a N₂ atmosphere. This suggests inhibition of dissolution rates above pH 10 when experiments were open to the atmosphere. The dissolved carbonate in these solutions becomes dominantly CO₃²⁻ above pH 10.33. It is argued that CO₃²⁻ forms a >Mg₂-CO₃ complex at positively charged Mg surface sites on enstatite, resulting in stabilization of the surface Si-O bonds. Therefore, removal of solution carbonate results in an increase in dissolution rates of enstatite above pH 10. The log rate of CO₂-purged enstatite dissolution in moles per cm² per s as a function of increasing pH above pH 10 is equal to 0.35. This is consistent with the model of silicate mineral dissolution in the absence of surface carbonation in alkaline solutions proposed earlier in the literature.     

The dissolution kinetics of atacamite in the acid range and the stability of atacamite containing soils from Namaqualand,South Africa

The Cu hydroxy mineral, atacamite, is commonly associated with saline environments and is generally thought to dissolve rapidly in the presence of fresh water. A Cu contaminated soil from the arid Namaqualand region, South Africa, shows atacamite as the dominant Cu containing mineral. The stability of the Cu phase in this soil was determined through equilibrium and leaching studies using both deionised water (DI) and a concentrated (0.5 M) NaCl solution. Initially a high concentration of exchangeable Cu was released from the soils leached with NaCl. Continued leaching with NaCl resulted in a substantial decrease in Cu release as atacamite equilibria started to control dissolved Cu. This suggests that an initial spike of Cu laden water will leach from the soils at the onset of a large rainfall event. Further additions of water will result in a lower but sustained release of Cu from the soil. The Cu contaminated soils are exposed to acidic sulphate leachate thus the dissolution kinetics of synthetic atacamite in the acidic range (pH 5.5–4.0) was determined in both NaCl and DI solutions. The kinetic data showed that atacamite dissolution rates are significantly higher in DI than in NaCl but the rates converge at pH 4. In comparison to common acid soluble minerals, atacamite displays a moderate dissolution rate (10^−9.55–10^−7.14 mol m⁻² s⁻¹) within the acid range (pH 5.5–4.0). The atacamite dissolution reaction order with respect to pH is 1.3 and 1.6 in DI and NaCl solutions, respectively, suggesting that dissolution rates of atacamite are highly pH dependent in the acid range. The type of acid used to lower the pH had no effect on the reaction kinetics, with HNO₃ and H₂SO₄ resulting in comparable dissolution rates of atacamite at pH 4.5.     

Solubility of carbon dioxide in aqueous fluids and mineral suspensions at 294 K and subcritical pressures

An experimental investigation has been carried on the solubility of CO₂ in water and 1 M NaCl between 0.3 and 4 MPa, in order to test the validity of the results given by various modelling codes. In addition to experiments with pure fluids, the effect of a range of likely reservoir minerals on CO₂–water interactions, including K-feldspar, kaolinite, calcite, Ca-montmorillonite and Na-montmorillonite were also investigated. In addition to measurements of CO₂ solubility, the pH of the CO₂-saturated suspensions was also measured directly at pressures of up to 1 MPa. The results demonstrate that predictions of CO₂ solubility made with PHREEQC and Geochemist’s Workbench agree to within 20% with the experimental value, provided corrections are first made off-line for the fugacity coefficient of CO₂, while predictions from standalone models are slightly more accurate. In the presence of mineral suspensions, PHREEQC and Geochemist’s Workbench give good results for calcite and kaolinite but underestimate the pH of montmorillonite-bearing assemblages while slightly overestimating the pH of K-feldspar suspensions. These results are significant because they indicate that CO₂-charged fluids reacted with clays may be less acidic than indicated by the models, which will impact predictions of the potential for dissolution of reservoir and cap rock minerals, as well as the potential for leaching of toxic metals.     

Ferric iron in sediments as a novel CO2 mineral trap: CO2–SO2 reaction with hematite

Thermodynamic simulations of reactions among SO₂-bearing CO₂-dominated gas, water and mineral phases predict that Fe^III in sediments should be converted almost entirely to dissolved Fe^II and siderite (FeCO₃), and that SO₂ should simultaneously be oxidized to dissolved sulfate. The reactions are however, subject to kinetic constraints which may result in deviation from equilibrium and the precipitation of other metastable mineral phases. To test the prediction, a laboratory experiment was carried out in a well stirred hydrothermal reactor at 150 °C and 300 bar with hematite, 1.0 m NaCl, 0.5 m NaOH, SO₂ in quantity sufficient to reduce much of the iron, and excess CO₂. The experiment produced stable siderite and metastable pyrite and elemental S. Changes in total dissolved Fe are consistent with nucleation of pyrite at ∼17 h, and nucleation of siderite at ∼600 h. Dissolution features present on elemental S at the conclusion of the experiment suggest nucleation early in the experiment. The experiment did not reach equilibrium after ∼1400 h, as indicated by coexistence of hematite with metastable pyrite and elemental sulfur. However, the results confirm that Fe^III can be used to trap CO₂ in siderite if partly oxidized S, as SO₂, is present to reduce the Fe with CO₂ in the gas phase.