Far from equilibrium enstatite dissolution rates in alkaline solutions at earth surface conditions

• Published in: Geochimica et cosmochimica acta Vol. 75; no. 23; pp. 7486 - 7493
• Main Authors: Halder, Sougata, Walther, John V.
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 01.12.2011
• Subjects: Atmospheres; Atmospherics; Carbon dioxide; carbonation; Dissolution; Enstatite; Magnesium; Mathematical models; nitrogen; silicon; temperature
• ISSN: 0016-7037; 1872-9533
• DOI: 10.1016/j.gca.2011.09.013

Far from equilibrium enstatite dissolution rates both open to atmospheric CO 2 and CO 2 purged were measured as a function of solution pH from 8 to 13 in batch reactors at room temperature. Congruent dissolution was observed after an initial period of incongruent dissolution with preferential Si release from the enstatite. Steady-state dissolution rates in open to atmospheric CO 2 conditions decrease with increase in solution pH from 8 to 12 similar to the behavior reported by other investigators. Judging from the pH 13 dissolution rate, rates increase with pH above pH 12. This is thought to occur because of the increase in overall negative surface charges on enstatite as Mg surface sites become negative above pH 12.4, the pH of zero surface charge of MgO. Steady-state dissolution rates of enstatite increase above pH 10 when CO 2 was purged by performing the experiments in a N 2 atmosphere. This suggests inhibition of dissolution rates above pH 10 when experiments were open to the atmosphere. The dissolved carbonate in these solutions becomes dominantly CO 3 2− above pH 10.33. It is argued that CO 3 2− forms a >Mg 2–CO 3 complex at positively charged Mg surface sites on enstatite, resulting in stabilization of the surface Si–O bonds. Therefore, removal of solution carbonate results in an increase in dissolution rates of enstatite above pH 10. The log rate of CO 2-purged enstatite dissolution in moles per cm 2 per s as a function of increasing pH above pH 10 is equal to 0.35. This is consistent with the model of silicate mineral dissolution in the absence of surface carbonation in alkaline solutions proposed earlier in the literature.