The temporal evolution of magnesium isotope fractionation during hydromagnesite dissolution, precipitation, and at equilibrium

This study provides experimental evidence of the resetting of the magnesium (Mg) isotope signatures of hydromagnesite in the presence of an aqueous fluid during its congruent dissolution, precipitation, and at equilibrium at ambient temperatures over month-long timescales. All experiments were performed in batch reactors in aqueous sodium carbonate buffer solutions having a pH from 7.8 to 9.2. The fluid phase in all experiments attained bulk chemical equilibrium within analytical uncertainty with hydromagnesite within several days, but the experiments were allowed to continue for up to 575 days. During congruent hydromagnesite dissolution, the fluid first became enriched in isotopically light Mg compared to the dissolving hydromagnesite, but this Mg isotope composition became heavier after the fluid attained chemical equilibrium with the mineral. The delta(26) Mg composition of the fluid was up to similar to 0.35% heavier than the initial dissolving hydromagnesite at the end of the dissolution experiments. Hydromagnesite precipitation was provoked during one experiment by increasing the reaction temperature from 4 to 50 degrees C. The delta(26) Mg composition of the fluid increased as hydromagnesite precipitated and continued to increase after the fluid attained bulk equilibrium with this phase. These observations are consistent with the hypothesis that mineral-fluid equilibrium is dynamic (i.e. dissolution and precipitation occur at equal, non-zero rates at equilibrium). Moreover the results presented in this study confirm (1) that the transfer of material from the solid to the fluid phase may not be conservative during stoichiometric dissolution, and (2) that the isotopic compositions of carbonate minerals can evolve even when the mineral is in bulk chemical equilibrium with its coexisting fluid. This latter observation suggests that the preservation of isotopic signatures of carbonate minerals in the geological record may require a combination of the isolation of fluid-mineral system from external chemical input and/or the existence of a yet to be defined dissolution/precipitation inhibition mechanism. (C) 2018 Elsevier Ltd. All rights reserved.