Unusual perforations in phlogopite crystals from caldara di manziana (Italy) caused by sulphuric acid generated by microbial oxidation of h2s emanations

Phlogopite flakes strewn on the soil of Caldara di Manziana (Italy) display multiple minute perforations. The site is a caldera linked to recent volcanism (90 ka to 0.8 Ma) with present emanations of CO2 (~150 t d) and H2S (~2.55 t d). Stereomicroscopy and SEM-EDX observation of the phlogopite crystals shows holes and depressions <200 ?m to 2 mm across. They are circular, pseudo-hexagonal, or irregular. Within the depressions, there are deposits of phlogopite alteration products consistent with a sulphuric acid attack, showing loss of Mg and K. Some are thin and homogeneous; others are thick, irregular, and chemically heterogeneous, including plates, flakes, tubes of Fe-beidellite or Fe-bearing halloysite, silica, Fe oxides, and gypsum. Areas of phlogopite surface are also altered. Sulphuric acid is produced from the H2S gas by the mediation of sulphuroxidizing bacteria. Pseudo-hexagonal perforations are interpreted to result from slow acid attack with dissolution controlled by phlogopite crystal symmetry. Some depressions developed surrounding films of pseudo-hexagonal shape, interpreted as jarosite crystallizing radially outwards from the depressions. This style of acid attack is possibly promoted by local high humidity and precipitation that generate long-lived water droplets and films on mineral surfaces where sulphuric acid is active for prolonged times.