Abstract--Progressive alteration by seawater of an andesite in the Aegean Island of Milos and an ignimbrite in the Aegean Island of Kimolos, Greece, formed bentonites with or without zeolites. Both profiles are dominated by migration of alkalis and uptake of Mg, Fe and H20, while A1 and Ti are immobile. The relative removal of alkalis controls the formation of either smectite or zeolites. The behavior of Ca and Si depends on the chemistry of the parent rock. In the rhyolitic profile, alteration is controlled by gain of Mg, Fe 2 § and Ca and loss of Na, K and Si, while in the andesitic profile by gain of Mg and Fe 2 § and loss of Na, K and Ca. In both profiles, significant uptake of SO4 = was not observed. Moreover Zr, Nb, V and Ni are immobile and have been enriched residually, while Sr, Rb and Y are lost in both profiles. Thorium is immobile in the rhyolitic profile but is leached in the andesitic profile. Also, the rare earth elements (REE) display fractionation in both profiles; the degree of fractionation increases with the degree of alteration to bentonite. Fractionation of the REE in both profiles and mobility of Th in the andesitic profile are related to the existence of monazite (rhyolitic profile) and apatite (andesite profile). The REE and Th appear to partition into phosphates rather than smectite.The mobility of Y coupled with the immobility of Nb increases the Nb : Y ratio with advancing alteration, rendering discrimination diagrams that use this ratio to determine the nature of the prototiths misleading. Mass balance calculations showed that in the smectite-rich zones the water:rock (WR) ratio might be as high as 13:1 in both profiles, while in the zeolite-bearing zones it is about 5.5:1. Such WR ratios explain the observed extensive mass transfer and suggest that the pore fluid chemistry might overprint the chemical characteristics of the parent rocks controlling smectite and bentonite chemistry.

The chemistry of smectites from some bentonite deposits derived from intermediate rocks has been examined by electron microprobe methods. A large variation in chemical composition within very short distances, principally controlled by a well-defined negative relationship between Si and A1, and between A1VI and Fe 3+ and A1VI and Mg has been observed. On the other hand, Mg does not vary systematically with either Si or Fe3+. In several bentonites beidellite coexists with montmorillonite and there is a compositional transition between the two smectite minerals, implying the existence of a possible solid-solution series. This transition occurs only when Cheto-type montmorillonites are present, being absent for Wyoming-type montmorillonites. No compositional transition between Wyoming-and Cheto-type montmorillonite was observed. It is believed that the compositional variations reflect initial chemical gradients originated during the devitrification of the volcanic glass, due to the migration of chemical components.

No abstract

Abstract--The low-temperature alteration of a rhyolitic rock from Kimolos Island, Aegean, Greece, yielded an alteration profile characterized by gradual transition from fresh glass to bentonite containing homogeneous Chambers-type montmorillonite and then to a mordenite-bearing bentonite. Both mordenite and smectite were formed from poorly crystalline precursors, which probably had compositions comparable to that of the crystalline end-product. However, their composition may have been modified to some degree after reaction with the fluid phase. Particle length and width measurements of smectite crystals yielded lognormal profiles, which suggest supply-controlled crystal growth in an open system or random ripening in a closed system. The former mechanism is in accordance with the observed sustained supply of Mg and Fe by the fluid phase throughout the alteration profile and is believed to be the dominant formation mechanism of smectites in bentonites in general. In the mordenite-bearing zone, random ripening is expected in domains with low permeability, in which the system was essentially closed, favoring the formation of mordenite. The level of supersaturation with respect to smectite was probably lower in the mordenite-bearing zone. Smectite probably affected pore-fluid chemistry either through ion exchange or via dissolution of initially formed K-bearing smectite. The latter process raised the K+/(Na + + Ca 2+) activity ratio of the pore-fluid favoring K-bearing mordenite.

No abstract