Title: Mineral Carbonation in Mantle Peridotite of the Samail Ophiolite, Oman
Description: Carbon dioxide capture and storage will be necessary to mitigate the effects of global climate change. Mineral carbonation - converting carbon dioxide gas to carbonate minerals - is a permanent and environmentally benign mechanism for storing carbon dioxide. The peridotite section of the Samail Ophiolite is host to exceptionally well-developed, naturally occurring mineral carbonation and serves as a natural analog for an engineered carbon dioxide storage project. This work characterizes the geochemistry and hydrogeology of peridotite aquifers in the Samail Ophiolite. Water samples were collected from hyperalkaline springs, surface waters, and boreholes in peridotite, and recent mineral precipitates were collected near hyperalkaline springs. Samples were analyzed for chemical composition. Geochemical data were used to delineate water-rock-CO₂ reactions in the subsurface and constrain a reaction path model for the system. This model indicates that mineral carbonation in the natural system is limited by the amount of dissolved carbon dioxide in water that infiltrates deep into the aquifer.

The amount of carbon dioxide stored in the system could potentially be enhanced by carbon dioxide injection into the aquifer. Reaction path modeling suggests that injection of water at saturation with carbon dioxide at 100 bars pCO₂ and 90⁰C could increase the carbonation rate by a factor of up to 16,000 and bring carbonation efficiency to almost 100%. Dissolved gas samples from boreholes were collected at in situ conditions and analyzed for chemical composition. Boreholes with pH > 10 contain millimolar levels of dissolved hydrogen and/or methane, indicating these boreholes are located near areas of active low temperature serpentinization. Serpentinization rates were calculated using groundwater flow estimates and dissolved gas concentrations, and range from 3x10⁻⁸ to 2x10⁻⁶ volume fraction peridotite serpentinized per year. Additionally, laboratory incubation experiments show dissolved hydrogen can be stored in sealed copper tubes for at least three months with neither diffusive loss nor production of hydrogen from oxidation of the copper.

These experiments demonstrate that copper tubes can be practical containers for collecting and storing dissolved hydrogen in freshwater. Groundwater ages in the peridotite section of the Samail Ophiolite are investigated through analysis of tritium, dissolved noble gases, and stable isotopes. Tritium-³Helium dating was used to estimate the age of modern groundwaters (< 60 years old), and helium accumulation was used as relative age indicator for pre-bomb groundwaters (> 60 years old). Waters with pH < 9.3 have ages from 0-40 years, while waters with pH > 9.3 are all more than 60 years in age. Helium accumulation indicates pH < 10 waters contain only atmospheric and tritiogenic helium, while pH > 10 waters have accumulated 30-65% of their helium from radiogenic production or mantle helium. pH > 10 waters are thus significantly older than pH < 10 waters. Noble gas temperatures are generally around 32⁰C, close to the current mean annual ground temperature. One hyperalkaline borehole has noble gas temperatures 7⁰C cooler than the modern ground temperature, indicating the water at that site may have recharged during a glacial period.

Stable isotope data (Δ¹⁸O and Δ²H) for waters with pH < 11 plot between the northern and southern local meteoric water lines, in the typical range for modern groundwater. Hyperalkaline boreholes and springs are enriched in Δ¹⁸O, which suggests they recharged when the southern vapor source dominated, perhaps during glacial periods. Lastly, the potential for in situ mineral carbonation in peridotite is investigated through reactive transport modeling of dissolved CO₂ injection into a peridotite aquifer. Injection was simulated at two depths, 1.25 km and 2.5 km, with reservoir conditions loosely based on the peridotite section of the Samail Ophiolite. The dependence of carbonation extent (mass of carbon dioxide sequestered as carbonate minerals per unit volume) on different factors - such as permeability, reactive surface area, and temperature - was explored. Carbonation extent is strongly controlled by reactive surface area (RSA), with geometric RSA models producing 10 to 770 times more carbonation than conservative RSA models with the same initial permeabilities and temperatures.

The ratio of carbon dioxide supply to RSA is also a key factor. The ideal relationship between CO₂ supply and RSA appears to be from 5x10⁻⁴ to 0.2 kg CO₂ /day per m²/m³ RSA. Temperature has also has an impact on carbonation rate: for the same initial permeability, carbonation is 7-35% faster at 90⁰C than at 60⁰C. Simulations of a 50-year carbon dioxide injection show that fracture porosity and permeability do not become overly clogged and carbonation continues at a more or less constant rate. We estimate that one dissolved CO₂ injection well in peridotite could store 1.4 Mtons CO₂ in 30 years with a storage cost of $6/ton. This suggests that an engineered carbon dioxide storage project in peridotite could be both feasible and economical. In situ mineral carbonation in peridotite should continue to be investigated as a safe and permanent mechanism for carbon dioxide storage.