The Role of pH, Temperature, and NH 4 + during Mica Weathering

Phyllosilicates are abundant materials both on Earth and Mars, and the weathering of these minerals is an essential part of a wide variety of geochemical cycles. Alteration mainly takes place at the solution–mineral interface and needs to be fully understood in order to correctly model global water–rock interactions. To directly link the physicochemical solution properties to the dominant surface processes controlling phyllosilicate alteration, we used a custom-built hydrothermal atomic force microscope to study in situ the surface reactivity of biotite, phlogopite, and muscovite in contact with aqueous solutions for a broad range of temperatures and pH values. On the basis of our microscopic observations correlated with previously obtained macroscopic dissolution rates, we have constructed a tentative weathering diagram for mica minerals connecting the dominant surface mechanisms and bulk dissolution behavior to the physicochemical solution properties (pH, T, and speciation). The resulting diagram can be divided into two main areas: low-grade weathering occurring at low temperatures and mildly acidic to neutral pH and high-grade weathering taking place at high temperatures and low pH, separated by a transition zone. Each of these areas is characterized by a series of chemical and physical surface processes, which can be related directly or indirectly to incongruent and congruent bulk dissolution. The transition temperatures and pH values depend on the type of mica, with biotite being the most reactive one and muscovite the least reactive one. It is noteworthy that for close to neutral pH conditions the presence of NH4+ shifts the transitions from low- to high-grade weathering to a significantly lower temperature