Rare earth element fractionation in authigenic illite–smectite from Late Permian clastic rocks, Bowen Basin, Australia: implications for physico-chemical environments of fluids during illitization

Abstract

REE analyses were performed on authigenic illitic clay minerals from Late Permian mudrocks, sandstones and bentonites from the Bowen Basin (Australia). The mixed-layer illite–smectite exhibit REE patterns with an obvious fractionation of the HREE from the LREE and MREE, which is an apparent function of degree of illitization reaction. The highly illitic ( R≥3) illite–smectite from the northern Bowen Basin show a depletion of LREE relative to the less illitic ( R=0 and 1) clays. In contrast, an enrichment of HREE for the illite-rich clays relative to less illitic clays is evident for the southern Bowen Basin samples. The North American Shale Composite-normalized (La/Lu) sn ratios show negative correlations with the illite content in illite–smectite and positive correlations with the δ 18O values of the clays for both the northern and southern Bowen Basin samples. These correlations indicate that the increasing depletion of LREE in hydrothermal fluids is a function of increasing water/rock ratios in the northern Bowen Basin. Good negative correlations between (La/Lu) sn ratios and illite content in illite–smectite from the southern Bowen Basin suggest the involvement of fluids with higher alkalinity and higher pH in low water/rock ratio conditions. Increasing HREE enrichment with δ 18O decrease indicates the effect of increasing temperature at low water/rock ratios in the southern Bowen Basin. Results of the present study confirm the conclusions of some earlier studies suggesting that REE in illitic clay minerals are mobile and fractionated during illitization and that this fact should be considered in studies of sedimentary processes and in identifying provenance. Moreover, our results show that REE systematic of illitic clay minerals can be applied as an useful technique to gain information about physico-chemical conditions during thermal and fluid flow events in certain sedimentary basins.