Kinetics and mechanism of forsterite dissolution at 25 degrees C and pH from 1 to 12

摘要

The forward dissolution rate of San Carlos forsterite Fo(91) was measured at 25 degrees C in a mixed-flow reactor as a function of pH (1 to 12), ionic strength (0.001 to 0.1 M), Sigma CO2 (0 to 0.05 M), aqueous magnesium (10(-6) to 0.05 M) and silica (10(-6) to 0.001 M) concentrations. In CO2-free solutions, the rates decrease with increasing pH at 1 less than or equal to pH less than or equal to 8 with a slope close to 0.5. At 9 less than or equal to pH less than or equal to 12, the rates continue to decrease but with a smaller slope of similar to 0.1. Addition of silica to solution at pH above 8.8 leads to reduction of up to 5 times in the dissolution rate, Magnesium ions have no effect on forsterite dissolution rate at pH from 3 to 6 and 10(-5) < [Mg2+](tot) < 0.04 M. Aqueous carbonate ions strongly inhibit dissolution in alkaline solutions when aCO(3)(2-) > 10(-4) M. In acidic and slightly alkaline solutions, forsterite dissolution is controlled by the decomposition of a silica-rich/magnesium-deficient protonated precursor complex. This complex is formed by exchange of two hydrogen ions for a Mg atom on the forsterite surface followed by polymerization of partially protonated SiO4 tetrahedra and rate-controlling H+ penetration into the leached layer and its adsorption on silica dimers. This accounts for the observed 0.5 order dependence of dissolution rate on H+ activity. In alkaline solutions, dissolution is controlled by the decomposition of Mg hydrated sites in a Mg-rich layer formed by silica preferential release. Within this conceptual model, forsterite forward rate of dissolution can be accurately described for a wide variety of solution compositions assuming two parallel reactions occurring at silica-rich and hydrated Mg surface sites: R+ (mol/cm(2)/s) = 2.38 x 10(-11) {>Si2O-H+ } + 1.62 x 10(-10) { >MgOH2+} where {>i} stands for surface species concentration (mol/m(2)). This equation describes the weak dependence of dissolution rates on pH in alkaline solutions and the inhibiting effect of carbonate ions and dissolved silica when the hydration of surface Mg atoms with formation of >MgOH2+ is the rate-controlling step for dissolution. It follows that the decrease of forsterite dissolution rate with increasing carbonate concentration at pH greater than or equal to 9 in natural aquatic systems results in a decrease of atmospheric CO2 consumption, i.e., unlike for feldspars, there is a negative feedback between pCO(2) and forsterite weathering rate. This should be taken into account when modeling the effect of mafic mineral weathering on CO2 global balance. Copyright (C) 2000 Elsevier Science Ltd. [References: 42]