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General geology of Li brines (basins, tectonics, and stratigraphy) Figure 1 shows the global distribution of the locations of Li brines or salt lakes detailed in Table 1. We include the best known brines from North America, South America (Argen- tina, Bolivia, and Chile), and Asia (China) that are enriched in Li, irrespective of whether the brines are in production or not. Other well-known brines that contain Li include those with relatively lower Li concentration in lakes such as Great Salt Lake, Searles Lake, and the Dead Sea (Table 1), as well as oil field brines such as that from the Smackover Formation (Gulf Coast, United States) or the Devonian strata of the northeast- ern United States. The majority of important Li‐rich brines are located in the Altiplano‐Puna region of the Central Andes of South America. Houston et al. (2011) classified the salars in the Altiplano‐Puna region of the Central Andes in terms of two end members, “immature clastic” or “mature halite,” primarily using (1) the relative amount of clastic versus evaporite sediment; (2) cli- matic and tectonic influences, as related to altitude and lat- itude; and (3) basin hydrology, which controls the influx of fresh water. The immature classification refers to basins that generally occur at higher (wetter) elevations, contain alternat- ing clastic and evaporite sedimentary sequences dominated by gypsum, have recycled salts, and a general low abundance of halite. Mature refers to salars in arid to hyperarid climates, which occur in the lower elevations of the region, reach halite saturation, and have intercalated clay and silt and/or volcanic deposits. An important point made by Houston et al. (2011) is the relative significance of aquifer permeability which is con- trolled by the geological and geochemical composition of the aquifers. For example, immature salars may contain large vol- umes of easily extractable Li‐rich brines simply because they are comprised of a mixture of clastic and evaporite aquifer materials that have higher porosity and permeability. Our conceptual model for Li brines is shown in Figure 2. The model seeks to account for the sources, sinks, and processes that mobilize, sequester, and concentrate Li. This model is developed primarily from the information we have gathered over the past few years on the brines at Clayton Valley, Nevada, United States, and Salar de Atacama, Chile, which are further described in the following sections. The concepts of Houston et al. (2011) are specific to the range of salars observed in the Altiplano‐Puna region of the Cen- tral Andes and are not necessarily transferable, in a global sense, to other Li‐rich brines. Our conceptual model cap- tures the framework of Houston et al. (2011), albeit with less specificity. We also recognize the earlier summaries by Asher‐Bolander (1982, 1991), which describe a model for the formation of Li‐rich clays and provide a brief description of factors contributing to the formation of Li‐rich brines, in particular emphasizing the importance of hydrothermal activity in concentrating Li. Effects of geochemistry, climate, and hydrogeology on evolution of the Li brine resource Geochemical characteristics: The minimum, maximum and average Li concentrations for the brines and lakes in this study are listed in Table 1. These values are compiled from various sources detailed in Appendix 1. Because some of the basins do not have minimum and maximum Li concentration data reported in the literature we use the average Li concen- trations to compare basins. The lowest average Li concentra- tion is 10 mg/L in Searles Lake, California, and the highest average Li concentration is 1,400 mg/L for the brine in Salar de Atacama, Chile. Average seawater contains 0.2 mg/L Li. The potentially important sources of Li to brines include high‐silica volcanic rocks, preexisting evaporites and brines, hydrotherm clays, and hydrothermal fluids. The relative role of Li leaching from source rocks by low- and high-tempera- ture fluids versus Li sourced in magmatic fluids themselves is not known and studies addressing this topic are scant. A study by Price et al. (2000) suggests that Li in the Clayton Valley, Nevada, brine is leached by groundwater from vol- canic tuffs and that process alone can account for all the Li in the brines. However, experimental weathering studies by Jochens and Munk (2011) have shown that less than 10 g/L Li are released from these volcanic rocks when exposed to water at ambient conditions. Godfrey et al. (2013) reported similar findings from low-temperature leaching of Li from volcanic rocks near Salar del Hombre Muerto, Argentina. Risacher and Fritz (2009) concluded that Li and B in Andean salars are derived from the weathering of ignimbrites. Yu et al. (2013) demonstrated that playas in the Qaidam basin receive Li transported by streams that is ultimately sourced from upstream hydrothermal inputs. They also hypothesized that source(s) of Li are from alteration of volcanic rocks by hydrothermal fluids and/or from direct connection to differ- entiated magmatic sources. Hofstra et al. (2013) reported that fluid inclusions in quartz phenocrysts from high‐silica volcanic rocks in the Great Basin region of the United States contain elevated Li concentrations relative to their host vitric matri- ces, suggesting that volcanic glass is a significant and readily available source of Li released to the environment via weath- ering processes and that fluid inclusions in erupted volcanic rocks may ultimately be an important Li source. The predictive sequence of evaporite formation in closed‐ basin salt lakes was established by Hardie and Eugster (1970) and Eugster and Hardie (1978). Their model indicates that there are three major fluid pathways or “chemical divides” that result during evaporation, which are dictated by the ini- tial ionic composition of the fluid. Here we summarize the essence of their models in order to set a context for Li‐enriched brines, but the reader is referred to Eugster (1980), Eugster and Hardie (1978), and Hardie and Eugster (1970) for more details. Path 1 occurs when there is an excess of bicarbon- ate compared to the alkaline earth elements (referred to as “soft water”), which produces the typical precipitation path from calcite to trona with no gypsum because the parent water is low in Ca and Mg. Examples from Eugster (1980) include Alkali Valley, Oregon, and Lake Magadi, Kenya. The Wilkins Peak member of the Eocene Green River Forma- tion in southwestern Wyoming contains 25 major trona beds and is an example of a large volume geologic trona deposit. Path 2 occurs when there is an excess of alkaline earth ele- ments compared to bicarbonate (referred to as “hard water”) and in this case gypsum is precipitated after calcite and the path divides into a sulfate‐rich system such as Saline Valley, California, or sulfate‐poor system such as Bristol Dry Lake, LITHIUM BRINES: A GLOBAL PERSPECTIVE 341PDF Image | Lithium Brines A Global Perspective
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