Reaction mechanisms of smectite illitization associated with hydrothermal alteration from Ponza Island, Italy

A hydrothermally altered rhyolitic hyaloclastite from Ponza island, Italy, has four alteration zones with unique clay assemblages: (1) a non-pervasive argillic zone characterized by smectite; (2) a propylitic zone with inters tratified illite-smectite (I-S) containing 10-85% illite (I); (3) a silicic zone composed of I-S with greater than or equal to 90% I and pure illite; and (4) a sericitic zone with I-S ranging from 66% I to pure illite. Atomic force microscopy reveals abrupt changes in particle morphology with illiti zation, including initial changes from anhedral plates to laths and then to euhedral plates and hexagonal plates. I-S particles progressively thicken with illitization and mean particle area (basal plane) remains constant fro m pure smectite to I-S with 80% I. However, particle area increases from 90 to 100% illite. Computer modeling of I-S structural forms indicates octahe dral cation ordering progressively changes from cis-vacant smectite to inte rstratified cis- and trans-vacant I-S, and then to trans-vacant illite. In addition, polytypes progressively change from 1M(d) to 1M, and then to 2M(1 ) illite. Electron-microprobe and X-ray fluoresence analyses show that I-S chemistry progressively changes during illitization, evolving toward a phen gitic composition with similar to0.89 fixed interlayer K+ per O-10(OH)(2). Octahedral Mg2+ shows little change with illitization, varying from 0.3 to 0.5 cations per O-10(OH)(2). The layer charge of smectite is similar to0.38 equivalents per O-10(OH)(2). On the basis of abrupt changes in morphology and progressive changes in pol ytype and chemistry, smectite illitization on Ponza involved a dissolution and recrystallization mechanism with multiple stages of nucleation and crys tal growth. In this multi-step model, temperature of alteration provided th e major control for the layer composition, polytype, and morphology of I-S crystallites. Other factors that may play a secondary role include: K+ avai lability, water-rock ratio, and permeability. Alternatively, the mechanism of I-S and illite formation at Ponza and other hydrothermal environments ma y occur by direct precipitation of I-S crystallites from rhyolite glass and may not involve progressive reactions of smectite precursors.