Tracing olivine carbonation and serpentinization in CO2-rich fluids via magnesium exchange and isotopic fractionation

Chemical exchange between seawater and the oceanic crust is thought to play a significant role in the regulation of the global magnesium (Mg) cycle, yet relatively little is known about the rates and mechanisms of Mg exchange in these crustal environments. In this study we experimentally characterize the extent, and nature, of Mg isotope fractionation during the carbonation and serpentinization of olivine (one of the principal minerals found in ultramafic rocks) under hydrothermal conditions. Olivine alteration was found to be incongruent, with the reactant fluid composition varying according to the extent of olivine dissolution and the precipitation of secondary minerals. In mildly acid water (pH ∼ 6.5), olivine dissolved to form Mg-Fe carbonate solid solutions and minor chrysotile. Upon carbonation and a decrease of CO2 in the water, the pH increased to >8, with chrysotile and brucite becoming the dominant alteration minerals. The Mg-rich carbonates preferentially incorporated lighter Mg isotopes, resulting in a ∼0.5‰ increase of the δ26Mg composition of the fluid relative to olivine during the initial carbonation and serpentinization reactions. This was followed by a decrease in δ26Mg under higher pH conditions associated with the formation of brucite. Our experimental and modeling results therefore demonstrate that the δ26Mg composition of fluids involved in olivine alteration reflect the type and quantity of secondary Mg minerals formed, which in turn depend on the pH and CO2 concentration of the water. Comparison of these results with natural groundwaters and geothermal waters from basaltic terrains indicate that the δ26Mg composition of natural waters are likely to also be controlled by mafic rock dissolution and the preferential incorporation of isotopically light Mg into carbonates and isotopically heavy Mg into Mg-Si minerals. Together, these findings improve our understanding of Mg isotope systematics during water-rock interaction, and suggest that δ26Mg may be a useful tool for tracing reactions that are critical to geological CO2 sequestration