Another insight into illitization by K-Ar dating of micro- to nano-metric illite-type particles exchanged with alkylammonium cations

摘要

Micrometric and nanometric illite-rich size fractions of claystones, bentonites and shales were exchanged with alkylammonium cations that have the specificity of stoichiometrically replacing K in trioctahedral mica interlayers. The purpose of the study was a separate evaluation of the K-Ar ages of potentially dioctahedral residual particles not affected by alkylammonium leaching and of potentially trioctahedral illites that were exchanged by the organic molecules. The K-Ar ages of micrometric size fractions from an Estonian Blue Clay sample collected next to another studied previously show that, even if identical in their mineralogical characteristics, the fractions contain variable amounts of trioctahedral particles that are of different origins. The alkylammonium treatment modifies slightly, within analytical uncertainty, the K-Ar ages of the <0.1 and 0.1-0.4 μm size fractions from, respectively, 464±13 and 530±14 Ma before organic exchange to 480 ±11 and 546±12 Ma after. The K-Ar ages of alkylammonium exchanged nanometric size fractions from the rim and centre of a thick Upper Cretaceous bentonite bed in Montana suggest that trioctahedral illite-rich particles mineralogically and chemically homogeneous and about 30 Ma old precipitated next to older dioctahedral particles of ～60-65 Ma. The untreated mixtures consist of two generations of authigenic illite having apparently different di/trioctahedral layerings. The same type of authigenic di/trioctahedral illite layering could be demonstrated for nanometric illite particles of a bentonite bed from the East Slovak Basin, one size fraction appearing to even consist of a pure trioctahedral illite as the alkylammonium exchange emptied completely the illite interlayers. The nearby shale level consisted of detrital illite particles that were found to be of different ages, di/ trioctahedral layerings and therefore varied origin. K-Ar ages of alkylammonium exchanged micrometric to nanometric illite and illite-smectite mixed layers, either increasing or decreasing, appear to outline variable di/trioctahedral layering assemblages or independent particle mixtures resulting from a more complex smectite illitization process than the conventionally assumed homogeneous reaction. It could record changing chemical compositions of the interacting pore fluid during crystallization, even when illitization progressed slowly. Similar ages before and after alkylammonium exchange suggest a constant chemical composition and therefore an homogeneous dioctahedral crystal structure. Alternatively, a changing chemical composition of the fluids during illitization is potentially recorded by variable K-Ar ages of the alkylammonium-leached illite resulting from differentiated ion exchanges.