The Role of Gas-Silicate Chemisorption Reactions in Modifying Planetary Crusts and Surfaces

Evidence for gas-solid reactions is found throughout the solar system: for example, sulfidation reactions in some meteorites and secondary phases coating lunar pyroclastic glasses. On Earth, the products of gas-solid reactions are documented in volcanic systems, metalliferous mineral deposits, impact craters, and on dust or meteorites after passage through the atmosphere - such reactions are also likely on the surfaces of Mars and Venus. To understand the chemical dynamics of such gas-solid reactions, we are undertaking systematic experiments and thermochemical modelling. Experiments were conducted in a vertical gas-mixing furnace at 600 - 800 °C and 1 bar, using SO2and a range of Ca-bearing materials: labradorite, feldspar glass and anorthosite (rock). In each case, anhydrite formed rapidly. In shorter experiments with labradorite, isolated anhydrite is observed surrounded by 'moats' of Ca-depleted silicate. In longer experiments, anhydrite is found as clusters of crystals that, in some cases, extend from the substrate forming precarious 'towers' (Figure). Anhydrite fills cracks in porous samples. We propose that the nucleation and rapid growth of anhydrite on the surface of these Ca-rich phases occurs by chemisorption of SO2(g) molecules with slightly negatively charged oxygen onto available near-surface calcium with slight positive charge. Anhydrite growth is sustained by SO2(g) chemisorption and Ca migration through the reacting silicate lattice, accelerated by increased bond lengths at high temperature. Significantly, the chemisorption reaction indicates that SO2 disproportionates to form both oxidized sulfur (as anhydrite) and a reduced sulfur species (e.g., an S* radical ion). On Earth, in the presence of H2O, the predominant reduced sulfur species is H2S, through an overall reaction: 3CaAl2Si2O8 + 4 SO2(g)+ H2O(g) → 3CaSO4 + 3Al2SiO5 + 3SiO2 + H2S(g)The reduced sulfur may react with gas phase Fe, Ni, Zn and Cu cluster compounds to form metal sulfides. This is observed on the km-scale through co-existing anhydrite and sulphide in porphyry copper deposits on Earth. Chemisorption reactions with S-gases may also be responsible for sulfide coatings on lunar glass beads; sulfate minerals with volcanic rocks on Mars (e.g., Home Plate); and putative sulfate minerals on Venus and the early Earth.