Clay Chemistry of the Thacker Pass Deposit, Nevada: Implications for the Formation of High-Grade Volcano-Sedimentary Lithium Resources

Volcano-sedimentary lithium (Li) deposits are a potential source of battery-grade Li, although the important factors controlling Li enrichment in these systems remain unclear. At Thacker Pass in Nevada, high-grade mineralization overprinted intracaldera lacustrine claystone made of authigenic Li-rich smectite with bulk grades of ~3,000 ppm Li, converting it to illitic claystone with grades of ~6,000 ppm Li. Some attribute this enrichment to burial diagenesis, whereas others propose lacustrine Li enrichment through leaching and climate-driven evapoconcentration enhanced by postdepositional hydrothermal alteration. To better understand Li enrichment in volcano-sedimentary systems, claystones from throughout Thacker Pass were analyzed using powder X-ray diffraction (PXRD), electron microprobe (EPMA), laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), and stable isotope (clay δ18O, δ17O, and δ2H and carbonate δ13C and δ18O) methods. Compositional data suggest that illitization is required to achieve clay Li grades above ~0.9 wt % in Mg silicate clays because of a charge-coupled substitution that requires filling interlayer vacancies with K. Clay chemical trends and computational modeling exercises also suggest that F may be important in the formation of Li-rich clays by lowering kinetic barriers to clay precursor growth and illitization. The results are incompatible with diagenetic smectite/illite formation but are consistent with a model wherein authigenic smectite was subjected to hydrothermal alteration in the presence of a K-, Li-, and F-rich fluid that permeated the stratigraphy through a network of normal faults associated with caldera resurgence. These results also enhance our understanding of Li clay formation in other volcano-sedimentary systems.