ALBERT

Description: Magnesium calcites were synthesized from aqueous solutions supersaturated with respect to calcite at 25, 40, 60, and 80 °C in gas tight batch reactors for up to 35 days. Any amorphous material still present in the precipitates was removed using a partial dissolution treatment. Resulting purified Mg-calcite had Mg contents ranging from 6 to 32 mol% MgCO3. An isotopic steady-state was attained between the fluid and the precipitated solids within two weeks at 25 °C. δ18O values derived from the experiments at steady-state, depend on both temperature and the Mg content of the calcite in accord with: 1000lnαMg-calcite–H2O=18,030/T−32.42+(6×108/T3–5.47×106/T2+16,780/T−17.21)×CMg where αMg-calcite–H2O represents the calcite–water oxygen isotope fractionation factor, T refers to the temperature in °K and CMg denotes the mole percent of MgCO3 in the calcite. These results indicate that the addition of 5 mol% MgCO3 into the calcite increases 1000lnαMg-calcite–H2O by 0.88 as compared to that of pure calcite at 25 °C. This difference could lead to a 4.2 °C decrease in estimated formation temperature estimates. These results demonstrate that the accurate interpretation of oxygen isotope fractionation in magnesium calcites requires explicit provision for the effect of magnesium on oxygen isotope fractionation factors. Highlights ► The effect of Mg on calcite–aqueous fluid oxygen isotope fractionation was investigated. ► Mg incorporation is increasing the calcite–aqueous fluid oxygen isotope fractionation. ► This effect is reduced at higher temperatures. ► Obtained results are important for paleo-temperature estimation. Gadget timed out while loading

Description: The accurate interpretation of Si isotope signatures in natural systems requires knowledge of the equilibrium isotope fractionation between Si-bearing solids and the dominant Si-bearing aqueous species. Aqueous silicon speciation is dominated by silicic acid (H 4 SiO 4o ) in most natural aqueous fluids at pH 〈 8.5, but forms H 3 SiO 4⁻ , H 2 SiO 4²⁻ , and polymeric Si species in more alkaline fluids. In this study isotope exchange experiments were performed at bulk chemical equilibrium between amorphous silica (SiO 2 ∙0.32 H 2 O) and inorganic aqueous fluids at pH ranging from 5.8 to 9.9 at 25° and 75 °C with experiments running as long as 375 days. The three-isotope method was used to quantify the equilibrium Si isotope fractionation, Δ eq³⁰ Si, between amorphous silica and aqueous Si; at pH ∼ 6 this equilibrium fractionation factor was found to be 0.45 ± 0.2‰ at 25 °C, and 0.07 ± 0.6‰ at 75 °C. At more basic pH (〉9), equilibrium Si isotope fractionation factors between solid and aqueous solution are higher, at 1.63 ± 0.23‰ at 25 °C, and 1.06 ± 0.13‰ at 75 °C. Taking account of the distribution of the aqueous Si species, equilibrium Si isotope fractionation factors between H 3 SiO 4⁻ and H 4 SiO 4o of −2.34 ± 0.13‰ and −2.21 ± 0.05‰ at 25 and 75 °C, respectively, were determined. The distinct equilibrium isotope fractionation factors of H 3 SiO 4⁻ and H 4 SiO 4o , and its variation with temperature can be used to establish paleo-pH and temperature proxies. The application of the three-isotope method also provides insight into the rates of isotopic exchange. For the solid grain size used (∼20 nm), these rates match closely the measured bulk dissolution rates for amorphous silica for most of the isotope exchange process, suggesting the dominant and rate controlling isotope exchange mechanism in the experiments is detachment and reattachment of material at the amorphous silica surface.

Description: The dissolution rates of olivine have been considered by a plethora of studies in part due to its potential to aid in carbon storage and the ease in obtaining pure samples for laboratory experiments. Due to the relative simplicity of its dissolution mechanism, most of these studies provide mutually consistent results such that a comparison of their rates can provide insight into the reactivity of silicate minerals as a whole. Olivine dissolution is controlled by the breaking of octahedral M2+-oxygen bonds at or near the surface, liberating adjoining SiO44− tetrahedra to the aqueous fluid. Aqueous species that adsorb to these bonds apparently accelerate their destruction. For example, the absorption of H+, H2O and, at some conditions, selected aqueous organic species will increase olivine dissolution rates. Nevertheless, other factors can slow olivine dissolution rates. Notably, olivine dissolution rates are slowed by lowering the surface area exposed to the reactive aqueous fluid, by for example the presence and/or growth on these surfaces of either microbes or secondary phases. The degree to which secondary phases decelerate rates depends on their ability to limit access of the reactive aqueous fluids to the olivine surface. It seems likely that these surface area limiting processes are very significant in natural systems, lowering olivine surface reactivity in many environments compared to rates measured on cleaned surfaces in the laboratory. A survey of the literature suggests that the major factors influencing forsteritic olivine dissolution rates are 1) pH, 2) water activity, 3) temperature, and 4) mineral-fluid interfacial surface area. Evidence suggests that the effects of aqueous inorganic and organic species are relatively limited, and may be attributed at least in part to their influence on aqueous solution pH. Moreover, the observed decrease in rates due to the presence of secondary mineral coatings and/or the presence of microbes can be attributed to their ability to decrease olivine surface area directly exposed to the reactive aqueous fluid. As the reactivity of forsterite surfaces are spatially heterogeneous, its surface area normalized rates will tend to decrease as it dissolves even in the absence of a mineral or bacterial coating. Each of these factors limits and or influences the application of forsterite dissolution to 1) enhanced weathering efforts, 2) mineral carbonation, and 3) the low temperature generation of hydrogen or hydrocarbons via the oxidation of its divalent iron.

Description: Fluid-rock interactions in hydrothermal systems at or near mid-oceanic ridges (MOR) play a major role in determining the composition of the oceanic crust and seawater. To quantify the processes that govern cation exchange in these environments we have experimentally studied the isotopic evolution of δ26/24Mg in the fluid phase during seawater-basalt interaction at 250 and 290 °C. Mass balance constraints indicate that isotopically heavy Mg was preferentially incorporated into non-exchangeable (octahedral) sites in secondary clay minerals such as saponite (Mg-rich smectite), leaving residual fluids enriched in light Mg isotopes. The magnitude of fractionation observed during smectite precipitation in our experiments () ranged from ‰ to ‰. This observation, which contrasts with the preferential uptake of light Mg isotopes into biogenic and inorganic marine carbonates, highlights the potential utility of Mg isotopes as tracers of the precipitation dynamics of authigenic Mg-silicate and Mg-carbonate phases. Furthermore, although Mg isotopic fractionation is often masked by the almost complete removal of Mg in high temperature marine hydrothermal systems, our experiments demonstrate that it does become significant at lower temperatures where Mg removal by clay formation is incomplete. Under such conditions, this fractionation will create isotopically light fluids due to smectite precipitation, thus potentially represents an important component of the marine Mg isotope inventory.

Description: Highlights • Reaction path models quantified gas-charged waters/basalt interactions • Gas-charged freshwater and seawater compared • Geochemical reactions modelled at temperatures from 25 to 260°C • Optimal conditions for subsurface mineralization of CO2 and H2S identified Mineralization of freshwater-dissolved gases, such as CO2 and H2S, in subsurface mafic rocks is a successful permanent gas storage strategy. To apply this approach globally, the composition of locally available water must be considered. In this study, reaction path models were run to estimate the rate and extent of gas mineralization reactions during gas-charged freshwater and seawater injection into basalts at temperatures of 260, 170, 100, and 25°C. The calculations were validated by comparison to field observations of gas-charged freshwater injections at the CarbFix2 site (Iceland). The results show that more than 80% of the injected CO2 dissolved in freshwater or seawater mineralizes as Ca and Fe carbonates at temperatures ≤170°C after reaction of 0.2 mol/kgw of basalt, whereas at 260°C much lower carbon mineralization rates are observed in response to the same amount of basalt dissolution. This difference is due to the competition between carbonate versus non-carbonate secondary minerals such as epidote, prehnite, and anhydrite for Ca. In contrast, from 80 to 100% of the injected H2S is predicted to be mineralized as pyrite in all fluid systems at all considered temperatures. Further calculations with fluids having higher CO2 contents (equilibrated with 9 bar pCO2) reveal that i) the pH of gas-charged seawater at temperatures ≤170°C is buffered at ≤6 due to the precipitation of Mg-rich aluminosilicates, which delays CO2 carbonation; and ii) the most efficient carbonation in seawater systems occurs at temperatures 〈150°C as anhydrite formation is likely significant at higher temperatures.