Li and Ca Enrichment in the Bristol Dry Lake Brine Compared to Brines from Cadiz and Danby Dry Lakes, Barstow-Bristol Trough, California, USA

Abstract

Relatively few discharging playas in western United States extensional basins have high concentrations of lithium (Li) and calcium (Ca) in the basin-center brines. However, the source of both these ions is not well understood, and it is not clear why basins in close proximity within the same extensional trough have notably different concentrations of Li and Ca. In the Barstow-Bristol Trough, California, USA, three playas in separate topographically closed basins vary in Li and Ca concentrations from northwest to southeast: 71–110 mg/L Li and 17–65 g/L Ca at Bristol Dry Lake, 20–80 mg/L Li and 7.5–40 g/L Ca at Cadiz Dry Lake, and <5 mg/L Li and <0.5 g/L Ca at Danby Dry Lake. Using new and historic data from recently drilled wells (2017–2018), it has been determined that there is minimal variation of temperature, Li, and major ion concentrations with depth (down to 500 m), suggesting that the brines are well mixed and likely to circulate slowly due to density driven flow. Although it has been postulated that geothermal fluids supply the Li and Ca to Bristol and Cadiz closed basins, there is little to no surface evidence for geothermal fluids, except for a young (80,000-year-old) volcanic crater in Bristol Dry Lake. However, major-ion chemistry of fluid inclusions in bedded halite deposits show no change in brine chemistry over the last 3 million years in Bristol Dry Lake indicating that the source of lithium is not related to these recent basaltic eruptions. Mg–Li geothermometry of basin-center brines indicates that Bristol and Cadiz brines have possibly been heated to near 160 °C at some time and Danby brine water has been heated to less than 100 °C, although Cadiz and Danby lakes have no known surface geothermal features. The difference in Li concentrations between the different basins is likely caused by variable sources of both ions and the hydrology of the playas, including differences in how open or closed the basins are, recharge rates, evaporative concentration, permeability of basin-center sediments, and the possible amount of geothermal heating. The differences in Ca concentrations are more difficult to determine. However, historic groundwater data in the basins indicate that less saline groundwater on the north side of the basins has molar Ca:HCO3 and Ca:SO4 ratios greater than one, which indicates a non-saline groundwater source for at least some of the Ca. The similar Li and Ca concentrations in Bristol and Cadiz lakes may be because they are separated only by a low topographic divide and may have been connected at times in the past three million years. All three basins are at least Miocene in age, as all three basins have been interpreted to contain Bouse Formation sediments at various depths or in outcrop. The age of the basins indicates that there is ample time for concentration of Li and Ca in the basins even at low evaporation rates or low geothermal inputs. The source of Li for brines in Bristol and Cadiz basins is postulated to be from ancient geothermal fluids that no longer exist in the basin. The source of Li to the sediment may be either geothermal fluids or dissolution and concentration of Li from tephra layers and detrital micas or clays that are present in the sediments, or a combination of both. The source of Ca must at least partially come from groundwater in the alluvial fans, as some wells have Ca:HCO3 ratios that are greater than one. The source of Ca could be from the dissolution of Ca-bearing igneous rocks in the surrounding catchments with limited HCO3 contribution, or dilute geothermal water migrating up through faults in the basin margin. The relatively low concentration of Li and Ca in Danby playa is likely caused by a lack of sources in the basin and because the basin was (or is) partially hydrologically open to the south, reducing the effectiveness of evaporative concentration of solutes. Bristol Dry Lake is likely the only hydrologically closed basin of the three because although Cadiz has a similar brine chemistry and salinity, there is almost no halite deposition in the basin. It is only Bristol Dry Lake that contains 40% halite in its basin center.