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Minerals 2020, 10, 284 6 of 34 All three dry lakes have been mined since the early 1900s for different evaporite minerals: halite at BDL and CDL, and halite and gypsum at DDL. BDL and CDL currently have extraction operations for CaCl2, which is used as an additive to oil well completion fluids and drilling muds, highway maintenance and de-icing, as a desiccant, and for other manufacturing processes [11]. Brines from the shallow subsurface are pumped to the surface and evaporated in long ditches, where halite is precipitated to remove sodium. The subsurface brines have very little measurable carbonate alkalinity (HCO3/CO3) or sulfate (SO4) and relatively low concentrations of magnesium (Mg) and potassium (K) (data in [12,13]). There are many different sources of Li and Ca to playa brines. For Li sources, sources of Li include dissolution of lithium-rich rocks, loess, or volcanic ash (tephra), long groundwater flow paths, recycled lithium in the playa, and geothermal fluids [1], although most highly concentrated lithium brines are thought to have originated from geothermal fluids [14–17]. Calcium is abundant in the Earth’s crust and may be sourced from many different rock types including dissolution of carbonates and feldspars in siliciclastic rocks, or dissolution of carbonate inclusions in highly metamorphosed rocks [18]. However, there are few sources of Ca-rich solutions to playas that do not also contain HCO3. Abundant HCO3 in solution would limit the amount of Ca left in solution after carbonate precipitation (HCO3 would remove Ca from solution due to calcite precipitation [9]). Hardie [19] suggested that the Ca at Bristol and Cadiz came from geothermal solutions in a process similar to the Na–Ca–Cl brines in geothermal fluids occurring at depth in the Salton Sea geothermal field. However, although Na–Ca–Cl brines are not common, they do form in relatively diverse environments, including Antarctic saline lakes [20], Canadian and Fennoscandian shield aquifers [21], and mid-ocean ridges [22]. Many of the continental-sourced brines have limited or no geothermal source for calcium and have been explained by water–rock interaction and cation exchange [20,21], or secular variation in the composition of ocean water [22]. In the Barstow-Bristol Trough, there is little evidence of long-term geothermal sources for Ca (or Li) ions, over the millions of years the basins have existed. However, two basalt extrusions, one at Lava Hills northwest of BDL and one south of Lead Mountain (Figure 1), may provide sources of heating approximately 3 million years ago. There is also a ~79,000-year-old cinder cone, Amboy Crater in the BDL basin [23]. No geothermal or relatively recent (last 1–2 million years) of basalt have been found in CDL or DDL, but tertiary volcanic rocks crop out in the northern parts of the Cadiz basin and to the east of DDL (Figure 2A). There has been renewed interest in the lithium resources of the BDL and CDL basins and knowledge of the source and hydrologic conditions that concentrate Li is important for assessing the resource potential and for determining the sustainability of the resource. Although groundwater has been thought to contribute solutes for evaporation in the playa center [4], recent work in other basins has suggested that the basin-center brine and alluvial fan groundwater are different hydrologic systems, and do not interact on short time scales (years) [24]. The purpose of this paper is to assess the evidence of how Li is concentrated and sourced within the Bristol Trough, particularly in the BDL and CDL basins. In addition, if the source of Li is geothermal fluid, the origin of Ca in the solution would likely be the same, and therefore an evaluation of Ca and other trace elements that are associated with geothermal fluid needs to be included in this assessment. We hypothesize that Li and Ca are sourced locally within the sediments and ashes within the basins, and that if geothermal sources do exist in the basin, they likely were most active when the basin first formed. We also hypothesize that alluvial fan groundwater contributes solutes to the playa brines. 2. Geologic and Hydrologic Background of the Barstow-Bristol Trough Bristol Dry Lake is situated in the Mojave Desert region of southeastern San Bernardino County, California (Figure 1). Detailed descriptions of the geologic and hydrologic framework of the Bristol Dry Lake basin can be found in [25–28], but detailed descriptions of the Cadiz and Danby basins are lacking. This section summarizes the descriptions in [26–28], adds some new information on the hydrology from the current study, and describes what little knowledge exists for the other two basins.PDF Image | Bristol Dry Lake Brine Compared to Brines from Cadiz
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