Crystallization processes of the illite-smectite (I-S) mixed-layer mineral series during alteration of felsic vitric materials in volcaniclastic sediments through two drill holes (IT-2 and IT-8) near the Kakkonda active geothermal system, Japan, were examined by optical microscopy, scanning and transmission electron microscopy (SEM and TEM), electron microprobe analysis, X-ray diffraction (XRD), and oxygen isotope analysis. Temperatures measured through the drill holes increased nearly linearly with depth up to 317°C at the bottom (1700 m) of IT-8. Homogenization temperature measurements of fluid inclusions indicated that the alteration occurred at temperatures similar to the present temperatures. In selected volcaniclastic rocks, excluding andesitic rocks and black shales, clay minerals occurred as glass replacements and pore fillings as seen under SEM and optical microscopy, and exhibited predominantly euhedral hexagonal and elongated forms under TEM, implying that they precipitated in situ through hydrolytic reactions of glass and fluid. Based on XRD examination, I-S minerals showed a sigmoidal variation in illite layer percentage (%I) in the range of ∼150 to 220°C and R0 I-S minerals with intermediate %I between 20 and 40% rarely occurred (where R is the Reichweite parameter). The chemical composition also showed a specific variation with depth. Intermediate clays including smectite and I-S minerals are enriched in Al compared to those reported previously from hydrothermal alteration of almost equivalent parent rocks. The oxygen isotope data indicated that the reacting solution was percolating groundwater in the shallow levels and with fossil seawater in the deeper levels. Furthermore, calculating the fluid/rock (W/R) ratio from the isotope variations revealed that the alteration occurred at a nearly constant W/R ratio condition irrespective of %I. Consequently, the observed specific variations in structure and chemical composition of I-S minerals reflect the compositional variations of fluid participating in the crystallization at given temperatures under the conditions of a given original rock and constant W/R ratio. High pH and Na-rich solutions generated by progressive hydrolytic reactions between felsic glass and groundwater favored the precipitation of Al-rich smectite up to ∼150°C and was followed by precipitation of an aluminous R1 I-S mineral with few intermediate R0 I-S minerals at higher temperatures. The crystallization obeys Ostwald’s step rule behavior of smectite illitization processes under a high geothermal gradient.
