Mineralization of atmospheric CO2 via fluid reaction with mafic/ultramafic rocks

Atmospheric CO2 has increased nearly 50% since the Industrial Revolution, due primarily to increased fossil fuel combustion, cement production, and deforestation. Although subterranean reservoirs are presently considered the most viable sink for anthropogenically liberated CO2, concerns exist over the stability of these systems and their impacts on regional tectonics, aquifers, and subterranean microbial ecosystems. Direct mineralization of CO2 at the Earth's surface provides an alternative capable of generating useful carbon-negative mineral byproducts that may be used to supplement or replace conventional carbon-positive building materials, like cement. However, mineralization of anthropogenic CO2 requires large sources of alkalinity to convert CO2 to CO32-, and divalent cations (e.g., Mg2+, Ca2+, Fe2+, etc.) to bond with the aqueous CO32-. Ultramafic and mafic rocks, such as peridotites, serpentinites, and basalts, are globally abundant, naturally occurring sources of the divalent cations, and alkalinity required for CO2 mineralization. Here, we present the results of accelerated reactions between ultramafic/mafic rocks, water, and CO2/N2 gases, aimed at quantifying the carbonation potential of mafic/ultramafic rocks. Rock-fluid-gas batch reactions were carried out in vented 4 L borosilicate glass flasks filled with 3 L DI water and 200 g acetone-washed, 49-180μm-diameter grains of four ultramafic/mafic rock types: peridotite, dunite, websterite and basalt. Each of the four rock-water mixtures was reacted under pure CO2 and pure N2 and at 25 and 200 °C, for a total of 16 reactions. Mixtures were continuously heated and stirred for 14 days. Samples (330 mL) were obtained at 0, 1, 6, 24, 48, 96, 168, and 336 hrs and filtered at 0.4 μm. The pH of filtered samples was measured with a single-junction Ag/AgCl glass electrode, salinity was determined with a conductivity probe, total alkalinity (TA) was determined by closed-cell potentiometric Gran titration, and DIC was determined by coulometry (all calibrated with certified reference materials). [CO32-], [HCO3-], and [OH-] were calculated from TA and DIC. For all reactions, pH (range: 5.5 - 9.7), TA, DIC, [CO32-], and [HCO3-] increased dramatically within the first several hours of the experiment, and then either steadily increased, plateaued, or declined, in some cases increasing again after the decline. After the initial spike, DIC increased with time under 25 °C, but decreased under 200 °C. Salinity and [OH-] increased steadily throughout most reactions. Lack of correlation of abrupt, short-lived declines in pH, TA, DIC, [CO32-], and [HCO3-] with [OH-] between 24 and 48 hrs at 200 °C suggests sudden precipitation of carbonate minerals, rather than production of silicic acid. Temperature generally increased reaction rates to a greater extent under CO2 than under N2, and substantially more OH- ions were liberated from rocks at 200 °C than at 25 °C. Reaction kinetics will be further constrained from mineralogy, elemental composition, and carbonate content of reaction products, enabling more precise quantification of the carbonation potential of the ultramafic/mafic rock types.