Despite current and projected future reliance on lithium as a resource, deficiencies remain in genesis models of closed-basin Li brines. Subsurface geochemical interactions between water and bulk solid phases from lacustrine sediments, are shown here to be the most important process for brine genesis and sustainability of the Clayton Valley, NV brine deposit. A new subsurface basin model was developed and used to select Li-bearing solids to test the release mechanisms for Li. Ash (20-350 ppm Li) and bulk sediments (1000-1700 ppm Li) samples across depths in the basin represent the majority of the subsurface Li-bearing materials. Temperature dependent (25-95 ^oC) batch reaction experiments using low-salinity groundwater from the basin indicate a positive relationship between the amount of Li released and temperature. Four-step sequential extractions on a subset of bulk sediments indicate most Li is released from water and weak acid-soluble portions with approximately 30% of the total Li contained in the sediments released overall. We conceptualize that lithium is released from these samples via three mechanisms: 1) release of adsorbed Li; 2) cation exchange of Li and Mg and; 3) possible minor release from silicate structure at elevated temperatures. Based on these results and the abundance of Li-bearing sediments in the subsurface we estimate the mean Li mass in the basin materials to be between 24.4 to 58.0 Mt. This Li provides a continuous supply from water-rock interactions. This is now the largest known accumulation of Li in a basin-fill continental setting on a global scale.

Demand for lithium for batteries is growing rapidly with the global push to decarbonize energy systems. The Salar de Atacama, Chile holds ∼42% of the planet's reserves in the form of brine hosted in massive evaporite aquifers. The mining of these brines and associated freshwater use has raised concerns over the environmental responsibility of lithium extraction, yet large uncertainties remain regarding fundamental aspects of governing hydrological processes in these environments. This incomplete understanding has led to the perpetuation of misconceptions about what constitutes sustainable or renewable water use and therefore what justifies responsible allocation. We present an integrated hydrological assessment using tritium and stable oxygen, and hydrogen isotopes paired with remotely sensed and terrestrial hydroclimate data to define unique sources of water distinguished by residence time, physical characteristics, and connectivity to modern climate. Our results describe the impacts of prolonged drought on surface and groundwaters and demonstrate that nearly all inflow to the basin is composed of water recharged >65 years ago. Still, modern precipitation is critical to sustaining important wetlands around the salar. Recent large rain events have increased surface water and vegetation extents and terrestrial water storage while mining‐related water withdrawals have continued. As we show, poor conceptualizations of these complex hydrological systems have perpetuated the misallocation of water and the misattribution of impacts. These fundamental issues apply to arid regions globally. Our new framework for hydrological assessment in these basins moves beyond calculating gross inputs‐outputs at a steady state to include all compartmentalized stores that constitute “modern” budgets.

The Salar de Atacama contains one of the world's most important lithium resources and hosts unique and fragile desert ecosystems. Water use issues of the hyper‐arid region have placed it at the center of global attention. This work combines geochemical and hydrogeologic data with remote sensing analysis to address differences in water zones in the marginal environments of the salar. Water samples from across the inflow to brine transition were collected over the period 2012–2016 and analyzed for ẟD, ³H, ⁸⁷Sr/⁸⁶Sr and major and minor elements. The ẟD values range from about −64‰ to +20‰, ³H as R_mod from 0.01 to 0.36 and the ⁸⁷Sr/⁸⁶Sr from 0.70750 to 0.70804 with highest ẟD and ³H occurring in the regions of open water. Geochemical modeling results indicate inflow and shallow transition zone waters are saturated with respect to calcite, whereas all others are saturated with respect to calcite, gypsum, and halite. Long‐term remote‐sensing of surface water body extents indicate that extreme precipitation events are the primary driver of surface area changes as exemplified by an increase in size of the lagoons by a factor of 2.7 after a storm. A new conceptual model of the freshwater to brine transition zone that incorporates variability in aquifer geology, hydrology and geochemistry to explain important marginal water bodies is presented. The subsurface brines in the transition zone and the halite nucleus are geochemically distinct compared to the groundwater discharge features (e.g., lagoons) over modern time scales which aids in conceptualizing the transition zone system.

Glacierized coastal catchments of the Gulf of Alaska (GoA) are undergoing rapid hydrologic fluctuations in response to climate change. These catchments deliver dissolved and suspended inorganic and organic matter to nearshore marine environments, however, these glacierized coastal catchments are relatively understudied and little is known about total solute and particulate fluxes to the ocean. We present hydrologic, physical, and geochemical data collected during April–October 2019–2021 from 10 streams along gradients of glacial fed to non‐glacial (i.e., precipitation) fed, in one Southcentral and one Southeast Alaska region. Hydrologic data reveal that glaciers drive the seasonal runoff patterns. The ẟ¹⁸O signature and specific conductance show distinctive seasonal variations in stream water sources between the study regions apparently due to the large amounts of rain in Southeast Alaska. Total dissolved solids concentrations and yields were elevated in the Southcentral region, due to lithologic influence on dissolved loads, however, the hydroclimate is the primary driver of the timing of dissolved and suspended yields. We show the yields of dissolved organic carbon is higher and that the δ¹³C_POC is enriched in the Southeast streams illustrating contrasts in organic carbon export across the GoA. Finally, we illustrate how future yields of solutes and sediments to the GoA may change as watersheds evolve from glacial influenced to precipitation dominated. This integrated analysis provides insights into how watershed characteristics beyond glacier coverage control properties of freshwater inputs to the GoA and the importance of expanding study regions to multiple hydroclimate regimes.

Despite the prevalence of density‐dependent flow systems in the brine‐rich aquifers of arid climates and coastal aquifers, the impact of realistic geologic conditions on interface geometry and density‐dependent time‐sensitive dynamics remains poorly constrained. Salar de Atacama provides an analog for exploring interface dynamics in arid regions. A site‐specific two‐dimensional hydrostratigraphic interpretation is used to examine the dynamics of the brine‐to‐freshwater interface. With the same simulation framework and core data, a separate parametric series of hydraulic conductivity distributions with varying horizontal continuity provides a mechanistic explanation for observed dynamics. Comparing modeled interfaces and their sensitivity to perturbations in recharge in each realization yields insight into interface dynamics coupled with horizontal continuity in subsurface heterogeneity. Recharge fluctuation is introduced to each distribution following the interface reaching a dynamic steady state. Metrics for results evaluation include interface slope geometry, interface width, migration length, and response rate. Analyses suggest that the average slope of the modeled interface shallows by 0.01 and 0.05 m ⋅ m⁻¹for an increase in continuity of highly permeable pathways by a factor of two and three, respectively. Increasing continuity also increases the overall response times and the variability in response. Results indicate that accurate representations of transient dynamics in modeling density‐dependent brine‐to‐freshwater interface dynamics requires the consideration of heterogeneity, as saline intrusion in the highest continuity group extends over twice as far on average and the modeled interface takes over 43% more time on average to reach a new dynamic steady state when compared to their homogeneous counterparts.

High‐latitude glacierized coastal catchments of the Gulf of Alaska (GoA) are undergoing rapid hydrologic changes in response to climate change and glacial recession. These catchments deliver important nutrients in the form of both inorganic and organic matter to the nearshore marine environment, yet are relatively understudied with respect to characterization of the sediment and solute generation processes and total yields. Using multiple linear regression informed by Bayesian Information Criterion analysis we empirically demonstrate how watershed characteristics affect suspended sediment and solute generation as represented by concentration‐discharge relationships. We find that watershed mean slope and relief control solute generation and that solute yields are influenced most by glacier coverage. We contribute a new flux and concentration‐discharge based conceptualization for understanding solute cycles across a hydroclimatic gradient of GoA watersheds that can be used to better understand future watershed responses to rapid hydrologic change.