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Minerals 2020, 10, 284 26 of 34 In order to further assess the geothermal influence in the Bristol Trough brines, geothermometry calculations were conducted to constrain the maximum temperature to which the brines were subjected (Table 1). The equilibrium-based Na–K geothermometer does not provide reliable temperatures below 150 ◦C. Therefore, although temperatures calculated using the Na–K geothermometer agree with the Mg-Li geothermometer, the Na–K geothermometer is used as a check of the Mg–Li geothermometer, because most calculated temperatures are below 150 ◦C. Although it has been suggested that the empirical relation between Li and Mg should be linear due to unexplained reasons [54], the decreased solubility of dolomite and ankerite with increasing temperature and the relative incompatibility of Li released by progressive silicate mineral dissolution at higher temperatures has been suggested to decrease the Mg/Li ratio with increasing temperature [50]. Kharaka and Mariner [53] also suggested that due to the almost identical crystalline ion radii of Mg and Li, they can substitute for each other in amphiboles, pyroxenes, micas and clays. Although not explicitly suggested, this would mean that at higher temperatures, Mg is incorporated into these minerals and Li is released. In Bristol Trough chemical analyses, the Mg to Li concentration is not constant in all analyses and is different between the few alluvial fan samples and basin brine samples in BDL (Figure 9B). Alluvial fan waters in BDL give low reservoir temperatures of generally less than 100 ◦C (data in [12,13]), whereas brine samples yield reservoir temperatures of approximately 160–117 ◦C. This means that there is either a different source of water between the alluvial fan and basin center, or there are chemical reactions that are either releasing Li or sequestering Mg from the water. Given that other elements correlate relatively closely between the alluvial fan and brine samples, it appears that chemical reactions are more likely to explain the variations in Mg/Li ratios than different fluid sources. If this is correct, the higher reservoir temperatures in the basin center, may overestimate the maximum temperature to which the brines have been subjected. There is some overlap in calculated temperatures between BDL and CDL brines, but none of the brines have been subjected to apparent temperatures greater than approximately 160 ◦C using the Mg–Li geothermometer, with slightly higher temperatures using equilibrium geothermometers at BDL (data and calculations in [12,13]). There appears to be a decrease in temperature from BDL to DDL of approximately 50–100 ◦C, although CDL temperatures only appear to be slightly lower than BDL. Deep Salton Sea geothermal temperatures are approximately 300–400 ◦C [42,43] and so if geothermal water is entering the basin, it is (1) coming from water that is not as hot as Salton Sea water, (2) coming from a shallower depth that has cooled substantially, or (3) mixing with cool alluvial groundwater. None of the brines in the Bristol Trough have current temperatures greater than approximately 25 ◦C, which suggests that if heating occurred, it was in the distant past. Strontium isotopes were analyzed by [26] for celestite nodules on the north and south margin of BDL. The average 87Sr/86Sr ratio of 5 samples was 0.7122424 ± 0.0000941. This value is higher than strontium isotope measurements from Salton Sea geothermal fluids of 0.711225 ± 0.000179 [42,43,65] but is consistent with the strontium isotopic composition of global igneous rocks (granites and rhyolites) [66] that are widespread throughout the basin (Figure 2A). This indicates that strontium is likely sourced from the watershed rather than geothermal fluids, even though there is a strong correlation between Li and Sr (Figure 9A). Araoka [14] found that Li was likely sourced from geothermal fluids in Clayton Valley, Nevada, to the northeast of the Bristol Trough, but found that Sr was likely derived from the local watershed. Dolginko [67] used fluid inclusions in unaltered halite crystals from the cores analyzed by [25,27] to show that the brine composition has not changed with depth within the top 500 m of sediment. This indicates that if the Li and Ca came from a geothermal source, it was present in the basin more than 3 million years ago [26,28,68], and the brine composition has not changed over time. This is also likely the case for CDL and DDL.PDF Image | Bristol Dry Lake Brine Compared to Brines from Cadiz
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