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Abstract: Thermodynamic simulations of reactions among SO2-bearing CO2-dominated gas, water and mineral phases predict that FeIII in sediments should be converted almost entirely to dissolved FeII 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 300bar with hematite, 1.0m NaCl, 0.5m 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 ∼17h, and nucleation of siderite at ∼600h. 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 ∼1400h, as indicated by coexistence of hematite with metastable pyrite and elemental sulfur. However, the results confirm that FeIII 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. [Copyright &y& Elsevier]

Abstract: We present a novel method for geologic sequestration of anthropogenic CO2 in ferrous carbonate, using ferric iron present in widespread redbeds and other sediments. Iron can be reduced by SO2 that is commonly a component of flue gas produced by combustion of fossil fuel, or by adding SO2 or H2S derived from other industrial processes to the injected waste gas stream. Equilibrium and kinetically controlled geochemical simulations at 120 bar and 50 and 100 °C with SO2 or H2S show that iron can be transformed almost entirely to siderite thereby trapping CO2, and simultaneously, that sulfur can be converted predominantly to dissolved sulfate. If there is an insufficient amount of sulfur-bearing gas relative to CO2 as for typical flue gas, then some of the iron is not reduced, and some of the CO2 is not sequestered. If there is an excess of sulfur-bearing gas, then complete iron reduction is ensured, and some of the iron precipitates as pyrite or other solid iron sulfide, depending on their relative precipitation kinetics. Gas mixtures with insufficient sulfur relative to CO2 can be used in sediments containing Ca, Mg, or other divalent metals capable of precipitating carbonate minerals. For quartz arenite with an initial porosity of 21% and containing 0.25 wt.% Fe2O3, approximately 0.7 g of CO2 is sequestered per kg of rock, and the porosity decrease is less than 0.03%. Sequestration of CO2 using ferric iron has the advantage of disposing of SO2 that may already be present in the combustion gas. [Copyright &y& Elsevier]

In a series of water-rock reaction simulations, we assess the processes of serpentinization of harzburgite and related calcium metasomatism resulting in rodingite-type alteration, and seafloor carbonate chimney precipitation. At temperatures from 25 to 300°C (P = 10 to 100 bar), using either fresh water or seawater, serpentinization simulations produce an assemblage commonly observed in natural systems, dominated by serpentine, magnetite, and brucite. The reacted waters in the simulations show similar trends in composition with decreasing water-rock ratios, becoming hyper-alkaline and strongly reducing, with increased dissolved calcium. At 25°C and w/r less than ∼32, conditions are sufficiently reducing to yield H2 gas, nickel-iron alloy and native copper. Hyperalkalinity results from OH− production by olivine and pyroxene dissolution in the absence of counterbalancing OH− consumption by alteration mineral precipitation except at very high pH; at moderate pH there are no stable calcium minerals and only a small amount of chlorite forms, limited by aluminum, thus allowing Mg2+ and Ca2+ to accumulate in the aqueous phase in exchange for H+. The reducing conditions result from oxidation of ferrous iron in olivine and pyroxene to ferric iron in magnetite. Trace metals are computed to be nearly insoluble below 300°C, except for mercury, for which high pH stabilizes aqueous and gaseous Hg°. In serpentinization by seawater at 300°C, Ag, Au, Pd, and Pt may approach ore-forming concentrations in sulfide complexes. Simulated mixing of the fluid derived from serpentinization with cold seawater produces a mineral assemblage dominated by calcite, similar to recently discovered submarine, ultramafic rock-hosted, carbonate mineral deposits precipitating at hydrothermal vents. Simulated reaction of gabbroic or basaltic rocks with the hyperalkaline calcium- and aluminum-rich fluid produced during serpentinization at 300°C yields rodingite-type mineral assemblages, including grossular, clinozoisite, vesuvianite, prehnite, chlorite, and diopside. [Copyright &y& Elsevier]

Abstract: Deep-saline aquifers are potential repositories for excess CO2, currently being emitted to the atmosphere from anthropogenic activities, but the reactivity of supercritical CO2 with host aquifer fluids and formation minerals needs to be understood. Experiments reacting supercritical CO2 with natural and synthetic brines in the presence and absence of limestone and plagioclase-rich arkosic sandstone showed that the reaction of CO2-saturated brine with limestone results in compositional, mineralogical, and porosity changes in the aquifer fluid and rock that are dependent on initial brine composition, especially dissolved calcium and sulfate. Experiments reacting CO2-saturated, low-sulfate brine with limestone dissolved 10% of the original calcite and increased rock porosity by 2.6%. Experiments reacting high-sulfate brine with limestone, both in the presence and absence of supercritical CO2, were characterized by the precipitation of anhydrite, dolomitization of the limestone, and a final decrease in porosity of 4.5%. However, based on favorable initial porosity changes of about 15% due to the dissolution of calcite, the combination of CO2 co-injection with other mitigation strategies might help alleviate some of the well-bore scale and formation-plugging problems near the injection zone of a brine disposal well in Paradox Valley, Colorado, as well as provide a repository for CO2. Experiments showed that the solubility of CO2 is enhanced in brine in the presence of limestone by 9% at 25 °C and 6% at 120 °C and 200 bar relative to the brine itself. The solubility of CO2 is enhanced also in brine in the presence of arkosic sandstone by 5% at 120 °C and 300 bar. The storage of CO2 in limestone aquifers is limited to only ionic and hydraulic trapping. However, brine reacted with supercritical CO2 and arkose yielded fixation and sequestration of CO2 in carbonate mineral phases. Brine desiccation was observed in all experiments containing a discrete CO2 phase, promoting porosity-reducing precipitation reactions in aquifers near saturation with mineral phases. [Copyright &y& Elsevier]