Controls on rapid rare earth element enrichment in sediments deposited by a continental-scale river system

Clay-hosted rare earth element (REE) deposits, generally considered products of extended subtropical weathering of REE-rich igneous protoliths, are a critical source of REEs globally. The Koppamurra deposit of southeast South Australia, in contrast, is developed in Pleistocene lacustrine clays overlying a REE-poor marine limestone. Here we examine the REE + Y (REY) sources and enrichment mechanisms of this unusual setting. We find that the greatest REY enrichment (up to 5000 ppm) occurs in lacustrine clays at the base of a ∼1–2 m thick contact zone with the underlying limestone. This zone features an increased proportion of leachable REYs (>50 %), increased smectite abundance and a sharp increase in pH from ∼5.0 to ∼8.3. Co-variation of HREEs with a suite of clay-specific elements demonstrates that HREEs are hosted mainly by Fe-rich smectite, with separate sorbed vs structurally bound HREE pools that are of similar magnitude. LREEs are mainly hosted in secondary LREE carbonates, these are preferentially intergrown with smectite but are only rarely present in kaolinite domains. Cerium occurs mainly as cerianite. The narrow range and overlapping εNd of samples within and above the REY enriched zone suggests that enrichment is related to internal redistribution within the clay unit. The clays are isotopically incompatible with local igneous or metasedimentary rocks, but ⁸⁷Sr/⁸⁶Sr and εNd isotopic fingerprinting shows that they were deposited by the Murray River, Australia's largest river system. Murray sediments are enriched in REY due to the presence of material eroded from the Lachlan Orogen granites of southeast Australia. Deposition of these sediments occurred in a coastal lacustrine setting analogous to the modern-day Coorong, with tectonic uplift and shoreline progradation allowing the onset of subaerial weathering ∼1–2 Mya. We propose that vertical and lateral solute transport allowed for the concentration of REEs in local depressions in the karst-weathering surface which separates the limestone and overlying clay, facilitated by water table oscillation and pore water redox cycling driven by seasonally contrasted rainfall. Poor soil drainage, evaporative concentration of soil waters and alkaline pH adjacent to the limestone immobilized REEs in secondary carbonates and Fe-rich smectite. Our findings illustrate that REE mobilization and enrichment in clay deposits can occur more rapidly, over a larger area and in a broader range of host phases and geologic settings than is currently appreciated, with important implications not only for REE exploration but also for the use of REEs as tracers in the Earth Sciences.