Kinetics and Mechanisms of Acid-pH Weathering of Pyroxenes
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Monasterio-Guillot, L., Rodriguez Navarro, C., & Ruiz-Agudo, E. (2021). Kinetics and mechanisms of acid-pH weathering of pyroxenes. Geochemistry, Geophysics, Geosystems, 22, e2021GC009711. [https://doi. org/10.1029/2021GC009711]
PatrocinadorSpanish Government European Commission CGL2015-70642-R CGL2015-73103-EXP; European Commission (ERDF fund); European Commission European Commission Joint Research Centre 691712 PCI2019-111931-2; Junta de Andalucia RNM179; University of Granada (Unidad Cientifica de Excelencia) UCE-PP2016-05; Spanish Government BES-2016-078468
Weathering of primary silicate minerals under acidic conditions occurs in contexts as varied as acid mine drainage, volcanic environments, soils, stone monuments subjected to acid rain or Geological Carbon Storage (GCS). Considering the abundance of pyroxenes on the Earth crust, knowledge of their weathering kinetics and mechanisms may help to optimize carbonate yield in GCS. Here we report experimental results from the reaction of the clinopyroxenes augite and diopside in acidic solutions. Dissolution at far-from-equilibrium conditions results in the formation of etch pits where crack initiate and propagate by stress corrosion and pressure exerted by swelling of an amorphous, gel-like Si-rich phase, which precipitates despite the undersaturation of the bulk solution and whose formation is highly controlled by the heterogeneity of the mineral surface and the local transport mechanism. These precipitates are commonly localized within deep etch pits and cracks, characterized by a low fluid renewal where high Si-concentrations can be reached locally, so that supersaturation with respect to amorphous silica can occur. Cracks and silica precipitates are most abundant in the case of augite weathered in flow-through experiments. This is related to its faster reaction rate compared to diopside, most likely due to its higher iron content. Finally, in the case of diopside an amorphous magnesium silicate hydrate (M-S-H) precursor forms, which represents an indirect evidence of the high pH conditions prevailing at the diopside-solution interface during dissolution.