Element mobility during alteration of silicic ash to kaolinite—a study of tonstein

A laterally persistent kaolinitic mudstone parting (tonstein) occurring in a Wyoming coal bed of Eocene age was sampled to estimate the compositional contrast with a probable silicic ash precursor, and to determine the compositional influence of leached ash on immediately adjacent coal. With the exception of Al, and possibly Ti, the tonstein is highly to moderately leached of major elements, relative to a range of compositions estimated for silicic ash of the region. In agreement with the behaviour of geochemically similar major elements, alkali trace elements (Rb, Cs) are highly leached, transition-series metals moderately leached, and Ga is residual. Additional immobile trace elements are Zr and Hf but some other trace elements that are considered relatively immobile during low-temperature alteration (Th, Ta, Nb, REE, Y) were apparently leached by the low-Eh, low-pH, organic-rich pore fluids of the coal-forming swamp. The migrational range of many of the leached elements is highly limited by the intimate association of tonstein with enclosing organic matter. Mixtures of coal + minor tonstein that occur within 20 mm of contacts are consistently enriched in some elements relative to either tonstein or nearby coal (U, Cu), or relative to calculated mixtures of tonstein and coal in their measured proportions (Th, Y, REE, Pb, Ba, V, Ti). Direct observations by fission-track radiography and electron microprobe indicate a preference of U and Fe for the organic component of mixtures. Metal fixation is probably by adsorption on insoluble organic matter (humic acids), or by precipitation as minor sulphides in these low-sulphur coals.