CO2-induced small water solubility in olivine and implications for properties of the shallow mantle

- Experimental hydration of olivine at high pressure and high temperature.
- Reduced water solubility under peridotite-saturated H2O-CO2-buffered conditions.
- Secondary modification of initial OH groups in many natural mantle olivines.
- Small water storage capacity in the shallow mantle than previous estimation.
- A novel mechanism of water depletion in mantle minerals by metasomatism.

H2O and CO2 are important components of fluids in the mantle at ∼30-150 km depth, and may affect strongly water dissolution in nominally anhydrous olivine; however, available experimental hydrogenation of olivine has been nearly exclusively carried out in coexistence with H2O (CO2-free). In this study, the effect of CO2 on water solubility in olivine has been investigated by H-annealing natural olivine under peridotite- and fluid-saturated conditions. Experiments were conducted at 1.5-5 GPa and 1100-1300 °C, with oxygen fugacity controlled by Ni-NiO and with either H2O or H2O-CO2 as buffering fluid. The olivine shows no change in composition during the experiments. The infrared spectra of the hydrated olivine are characterized by prominent OH bands from ∼3650 to 3000 cm−1 in all the runs, at both high frequency (>3450 cm−1) and low frequency (<3450 cm−1), and the H2O solubility is ∼120-370 ppm for the olivine in coexisting with H2O, and ∼65-180 ppm for the olivine in coexisting with H2O-CO2. When CO2 is present in the buffering fluid, the H2O solubility of olivine is reduced by a factor of ∼2, due to effect on the partitioning of water between minerals and coexisting fluid, and the measured H2O solubility shows independence on fluid composition (the molar ratio of CO2 to CO2 + H2O at ∼0.2-0.5) given pressure, temperature and oxygen fugacity. Olivine equilibrated in the shallow mantle is probably dominated by OH groups in the wavenumber ∼3650-3000 cm−1, and the intensity of OH bands at low frequency may be higher than or comparable to those at higher frequencies. The storage capacity of water in the shallow mantle in previous estimates may have been overestimated by a factor of at least ∼4 if the observed effect of CO2 on water solubility is correct. Our results have profound influence on understanding partial melting, electrical conductivity anomalies and metasomatism in the shallow mantle.