Evolution of Li-rich Brines

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. Full article

The Li-rich brine contained within the halite body of the Salar de Atacama is uncommon for two reasons: First, it has an exceptionally high Li concentration, even compared to other closed basins in the Li triangle of South America; and second, it is widespread within the halite nucleus and not restricted to a localized area. This study focusses on the southern half of the salar where Li production occurs and draws comparisons with its northern neighboring basin through which the Loa river flows. Concentration and isotope data for water inflowing to this part of the salar were obtained from surface inflow as well as wells located within the alluvial fans on its eastern margin. Lithium varies between 0.2 and 20 mg/L before reaching the salar where small amounts of the brine and or salts that precipitated from it can increase its concentration up to 400 mg/L or higher. The δ⁷Li of the inflow water varies between +4.9‰ and +11.2‰ and increases to +12.6‰ within the salar margin, consistent with salar brine based on reported measurements. Boron isotopes indicate that it is unlikely that solutes are derived from sedimentary evaporites or mineral cements, unlike the situation in the adjacent Loa basin. Water that flows through an aquifer laterally confined by a basement block and a line of volcanoes has a notably higher δ⁷Li than other inflow water, around +9‰, and increasing to +10.5‰. δ⁷Li values are overall higher than were measured in the adjacent Loa basin, indicating that here the water–rock reactions for Li are more evolved due to longer residence times. Lithium concentrations increased with sodium and chloride, but sedimentary evaporites are shown to be unimportant from δ¹¹B. This is accounted for two ways: evaporated saline inflow leaks from higher elevation basins and inflows are partly derived from or modified by active volcanic systems. Active and dormant volcanoes plus the massive Altiplano–Puna magmatic body are important as heat sources, which enhance water–rock reactions. The large topographic difference between the mean elevation of Altiplano on which these volcanoes sit and the salar surface allows hydrothermal fluids, which would otherwise stay deep below the surface under the modern arc, to uplift at the salar. Full article

Widespread alteration in the Early–Middle Triassic volcanic ash of the Xiejiacao section, south China, has resulted in significant occurrences of lithium-rich K-bentonite deposits with economic potential. Detailed mineralogical and geochemical investigations of Li-rich K-bentonite deposits from the Xiejiacao section of Guangan city, South China, are presented here. The X-ray diffraction (XRD) data and major element chemistry indicates that the Li-rich K-bentonite deposits contain quartz, clay minerals, feldspar, calcite and dolomite, and the clay minerals are dominated by illite and ordered (R3) illite/smectite (I/S). The concentrations of major and trace elements in Li-rich K-bentonite deposits altered from volcanic ashes are most likely derived from felsic magmas, associated with intense volcanic arc activity. The composition of the clay components suggests that the Li-rich K-bentonite deposits are probably altered from the smectite during diagenesis, whereas smectite is mainly formed by submarine alterations of volcanic materials and subsequently the I/S derived from the volcanogenic smectite illitization. Moreover, accurate determination of the structure in I/S reveals that the temperatures reached by the sedimentary series are around 180 °C with a burial depth of ~6000 m. The widely distributed lithium-rich clay deposits strongly indicate widespread eruptions of volcanic ashes in the Early–Middle Triassic, which released huge amounts of volcanic ash. Lithium fixed in the illite and I/S is considered to have leached from the volcanogenic products by a mixed fluid source (i.e., meteoric, porewater and hydrothermal fluids). These Li-rich clay minerals in the marine basin contain economically extractable levels of metal and are a promising new target for lithium exploration. Full article

Lithium deposits in tuffaceous sediments of the McDermitt caldera constitute possibly the world’s largest Li clay resource, yet their characteristics and origin are not established. The 40 × 25 km McDermitt caldera collapsed during the eruption of ~1000 km³ of a 16.4 Ma, zoned peralkaline to metaluminous tuff; minor caldera magmatism ceased by 16.1 Ma. About 200 m of sediments mostly composed of glass from regional pyroclastic eruptions accumulated in the caldera until about 15.7 Ma. Closed hydrologic system diagenesis (CHSD) altered the tuffaceous sediments to a consistent vertical mineral zonation of clay, analcime, K-feldspar, and albite. Entire sedimentary sections in the southern and western parts of the caldera basin have ≥1500 ppm Li. Lithium-rich intervals are dominantly claystone. The most thoroughly studied deposit is a laterally continuous, ~3000 ppm Li zone in the lower sedimentary section that also has high K, Rb, Mo, As, and Sb (and partly Mg and F). Lithium occurs as an illitic clay (tainiolite?). The overlying, upper sedimentary section averages <2000 ppm Li which resides in smectite (hectorite). A transitional zone has variably mixed smectite–illite clay and averages ~2000 ppm Li. An ⁴⁰Ar/³⁹Ar age of ~14.9 Ma on authigenic K-feldspar in the illite zone is ~1.2 Ma younger than the 16.1 Ma end of magmatism in the caldera, which mitigates against a simple hydrothermal origin. Closed hydrologic system diagenesis was essential to Li mineralization, but Li budget calculations suggest a source of Li in addition to the tuffaceous sediments is required. This additional source could be Li originally in highly enriched magma that entered the diagenetic system through either (1) Li in magma exsolved into a hydrous volatile phase during eruption. The Li-rich volatile phase coated glass shards or was trapped in pumice and was quickly leached by surface or groundwater upon deposition in the caldera. (2) Residual magma immediately following ash-flow eruption and caldera collapse generated Li-rich hydrothermal fluids that mixed with meteoric water in the closed caldera basin, generating a hybrid diagenetic fluid. The hydrothermal fluid and hybrid diagenetic fluids would have existed only during initial basin sedimentation between about 16.4 and 16.1 Ma. Full article

Lithium occurrences were detected in Upper Permian (Zechstein) salt rocks and saline solutions of the Gorleben and Morsleben salt structures, northern Germany. The brine occurrences were mainly connected to anhydrite rock-bearing formations and to lithological boundaries. Most of these brines display a high Mg content and were accordingly interpreted as intrasalinar solutions, which developed during sedimentation, diagenesis, and the subsequent rock–fluid interaction. These Mg-rich brines frequently show high Li concentrations. One of the assumptions made, is that Li was leached from phyllosilicates, since no natural Li-bearing salt minerals are known to date. To improve the understanding of the origin of Li in the brines, leaching experiments were performed on the Li-bearing phyllosilicate Lepidolite. Lepidolite with a Li content of 2.42 wt. % served as an analogue material, which was exposed to 18 saline solutions of different composition for a period of three years. The most pronounced leaching effect (53.36 µg Li/g in the brine) was observed during the interaction with a 0.03 mol/kg H₂O MgCl₂ solution, the second most pronounced by modern seawater interaction. The experiments show that the amount of Li leached from the lepidolite is dependent on brine composition. Full article

Salt lakes on the Qinghai-Tibetan Plateau (QTP) are remarkable for Li-rich brines. Along with the surging demand of Li, the Li-rich brines in salt lakes on the QTP are of great importance for China’s Li supply. Previous studies reported the geological, geographical, geochemical signatures of numerous salt lakes on the QTP; however, conclusive work and the internal relationships among the hydrochemistry, distribution and geological setting of Li-rich salt lakes are still inadequate. In this study, major and trace (Li, B) ionic compositions of 74 Li-rich salt lakes on the QTP were reviewed. The Li-rich brines cover various hydrochemical types (carbonate, sodium sulfate, magnesium sulfate, and chloride types) and present horizontal zoning from the southwest to the northeast along with the stronger aridity. The Li concentrations and Mg/Li ratios in these salt lakes range from 23 to 2895 mg/L, 0.0 to 1549.4, respectively. The distribution of these salt lakes is close to the major suture zones. Geothermal water is proposed to be the dominant source of Li in the investigated salt lakes, while weathering of Li-bearing sediments and igneous rocks, and brine migration provide a minor part of Li. Four factors (sufficient Li sources, arid climate, endorheic basin and time) should be considered for the formation of Li-rich brines in salt lakes on the QTP. Full article