Lithium Storage and Release From Lacustrine Sediments: Implications for Lithium Enrichment and Sustainability in Continental Brines

Abstract Despite current and projected future reliance on lithium (Li) 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 (1,000–1,700 ppm Li) samples across depths in the basin represent the majority of the subsurface Li‐bearing materials. Temperature dependent (25°C–95°C) 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 Li is released from these samples via three mechanisms: (a) release of adsorbed Li; (b) cation exchange of Li and Mg and; (c) possible minor release from the 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 and 58.0 Mt which 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

Hydrogeological controls on spatial patterns of groundwater discharge in peatlands

Peatland environments provide important ecosystem services including water and carbon storage, nutrient processing and retention, and wildlife habitat. However, these systems and the services they provide have been degraded through historical anthropogenic agricultural conversion and dewatering practices. Effective wetland restoration requires incorporating site hydrology and understanding groundwater discharge spatial patterns. Groundwater discharge maintains wetland ecosystems by providing relatively stable hydrologic conditions, nutrient inputs, and thermal buffering important for ecological structure and function; however, a comprehensive site-specific evaluation is rarely feasible for such resource-constrained projects. An improved process-based understanding of groundwater discharge in peatlands may help guide ecological restoration design without the need for invasive methodologies and detailed site-specific investigation. Here we examine a kettle-hole peatland in southeast Massachusetts historically modified for commercial cranberry farming. During the time of our investigation, a large process-based ecological restoration project was in the assessment and design phases. To gain insight into the drivers of site hydrology, we evaluated the spatial patterning of groundwater discharge and the subsurface structure of the peatland complex using heat-tracing methods and ground-penetrating radar. Our results illustrate that two groundwater discharge processes contribute to the peatland hydrologic system: diffuse lower-flux marginal matrix seepage and discrete higher-flux preferential-flow-path seepage. Both types of groundwater discharge develop through interactions with subsurface peatland basin structure, often where the basin slope is at a high angle to the regional groundwater gradient. These field observations indicate strong correlation between subsurface structures and surficial groundwater discharge. Understanding these general patterns may allow resource managers to more efficiently predict and locate groundwater seepage, confirm these using remote sensing technologies, and incorporate this information into restoration design for these critical ecosystems

Hydrogeologic and Geochemical Distinctions in Freshwater‐Brine Systems of an Andean Salar

Abstract 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 Rmod 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