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Abstract 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. 

ABSTRACT RationaleStable oxygen isotope measurements in silicate clays, such as smectite and kaolinite, provide crucial information for understanding Earth's climate history and environmental changes. Despite a growing interest in the oxygen isotope analysis of silicate clays and clay‐rich sediments, there lacks a consensus on the preparation and standardization of clay mineral samples. To improve the accuracy and interlaboratory comparisons of clay isotope measurements, especially those involving laser fluorination techniques, newly established kaolinite and smectite oxygen isotope standards are much needed. MethodsWe employed conventional nickel bomb fluorination combined with dual‐inlet isotope ratio mass spectrometry to establish precise δ¹⁸O and Δ′¹⁷O values for leached clay reference materials KGa‐1b and SHCa‐1, a kaolinite and a hectorite/smectite, respectively. We further measured leached KGa‐1b and SHCa‐1 pressed into pellets with a lithium fluoride as a binding agent for the laser fluorination method, allowing us to test the reproducibility between methods and utilize a standard laser chamber drift correction scheme. ResultsThe laser fluorination technique yielded highly precise and reproducible δ¹⁸O and Δ′¹⁷O measurements for the KGa‐1b and SHCa‐1, aligning with bomb values of δ¹⁸O. This confirms the method's reliability and comparability to conventional isotope measurement techniques while also stressing the importance of proper sample preparation and laser chamber drift corrections. ConclusionsThis study demonstrates that laser fluorination is an effective method for accurately measuring the stable oxygen isotope composition of silicate clays or clay‐rich sediments when corrected with known silicate clay standards. These methods offer a valuable methodology for future research and applications that will significantly improve our understanding of past climate and environmental conditions. 

Southwestern North America is currently experiencing a multidecadal megadrought, with severe consequences for water resources. However, significant uncertainty remains about 21st century precipitation changes in this semi-arid region. Paleoclimatic records are essential for both contextualizing current change, and for helping constrain the sensitivity of regional hydroclimate to large-scale global climate. In this paper, we present a new 2.8 Ma to present compound-specific isotopic record from Clayton Valley, the site of a long-lived paleolake in the southern Great Basin. Hydrogen and carbon isotopes from terrestrial plant leaf waxes provide evidence of past shifts in rainfall seasonality as well as ecosystem structure, and help contextualize the formation of this lithium-rich lacustrine basin. Our results suggest that regional hydroclimates underwent a substantial reorganization at the Plio-Pleistocene boundary, especially between 2.6 and 2.0 Ma. In this interval, a reduced latitudinal temperature gradient in the North Pacific likely resulted in a northward shift in storm tracks, and a reduction in winter rainfall over the southern Great Basin. This occurred against a background of increased summer rainfall and a greater accumulation of lithium in the lake basin. Our interpretation is corroborated by a compilation of Plio-Pleistocene north Pacific sea surface temperature records, as well as an isotope-enabled model simulation. Overall, these results suggest that past shifts in rainfall seasonality helped set the stage for the development and dessication of lithium-rich lacustrine deposits. 

The stable isotopic composition of soil-formed carbonate, and bulk geochemistry of preserved soil matrix, can provide regionally constrained records of hydroclimatic change throughout deep-time. The SK cores, spanning over 10 km of sediment drilled from the Songliao Basin in Northeast China, represent near continuous terrestrial deposition across the late Jurassic to early Paleogene. In this study we analyze SK-1n paleosol core samples spanning late Maastrichtian to early Danian to interpret the regional hydroclimate response to global climate change, concurrent with Deccan Traps volcanism and the Chicxulub impact. Building on numerous paleosol carbonate datasets from the Sifangtai and Mingshui formations, we present ~40 new carbonate clumped isotope measurements at ca. 10 – 20 kyr resolution between 66.3 to 65.5 Ma. We produce a new kernel-smoothed temperature record and estimate the δ18O of soil porewater (δ18Opw), and δ13C of soil CO2 (δ13Cs) from new and previously published datasets. Molecular weathering ratios, derived from bulk geochemistry, are used to reconstruct weathering (CIA-K), clay formation (Al/Si), soil drainage (Ba/Sr), and calculate mean annual precipitation (MAP) via established transfer functions. Preliminary results suggest elevated K-Pg boundary temperatures, averaging ~30 °C, that decline by ~10 °C over the following 500 kyr. Post-impact cooling may contribute to a negative δ18Ocarb excursion (-2.5‰) at ~65.8 Ma. Further, stable subhumid MAP (~1100 mm/yr) across the dataset suggests negligible amount effect influence. Mean δ18Opw (-6.9‰) is largely stable, and does not reflect regional monsoon seasonality. Instead, stable δ18Opw indicates a consistent moisture source, a potential persistent seasonal bias in carbonate formation. Binning all compiled δ18Opw by soil profile depth reveals statistically significant enrichment in the upper 60 cm of soil profiles, and accounts for variability in the δ18Opw (σ = 1.16‰). Soil respiration, modeled from δ13Cs, increases from ca. 700 to 2000 gC/m2/year across the K-Pg boundary, indicating increased productivity despite declining pCO2 and available phosphorus. Future work will expand the temporal range of isotopic measurements (~72 to 65 Ma) and contextualize our latest Cretaceous results within a spatial framework across Asia.