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Minerals 2019, 9, 766 11 of 21 Minerals 2019, 9, x FOR PEER REVIEW 12 of 22 Figure 7. Li and Mg concentrations of brines from Gorleben and Morsleben. For comparison, the Li Figure 7. Li and Mg concentrations of brines from Gorleben and Morsleben. For comparison, the content of the groundwater-monitoring network from Morsleben and the Li content of the rocks Li content of the groundwater-monitoring network from Morsleben and the Li content of the rocks from Gorleben are displayed. In addition, the development of the Li content in evaporating seawater (blue line) and the first precipitates from seawater are shown. from Gorleben are displayed. In addition, the development of the Li content in evaporating seawater (blue line) and the first precipitates from seawater are shown. The Mg concentration in modern seawater according to Reference [40] is 0.1278 wt. %. The development of the Mg concentration during evaporation of seawater is described in Figure 7. The Mg conIcnetnhetrGaotriloebneninsitem, boridnesranndsesoamweaetxermpalcarciolyrsdeilencgtedtorocRksef(pehryelnlocsielic[a4te0-b]eiasrin0g.1s2tr7at8a wt. %. The from the z3TM and z4TS) as well as brines from the Morsleben site have been investigated development of the Mg concentration during evaporation of seawater is described in Figure 7. geochemically. Depending on stratigraphic unit and lithology, the mineralogical composition and In the Gorleben site, brines and some exemplarily selected rocks (phyllosilicate-bearing strata from hence, the Li concentrations of the rocks, vary between <1 μg/g (typical rock salt) and 330 μg/g the z3TM and(pzh4ylTloSsi)liacastew-bealrlinagssbtrraitan,ezs3GfrTo, dmeepthderiMllinogrGsole10b0e5n). Tshiteephyalvloesilbiceaten-cointvaienisntgigstartaetadargeeochemically. composed of halite, anhydrite, quartz, muscovite and chlorite. We assume that these phyllosilicates Depending on stratigraphic unit and lithology, the mineralogical composition and hence, the Li are Li carriers, but alternative Li sources, like fluid inclusions with metamorphic brines, could be concentrations of the rocks, vary between <1 μg/g (typical rock salt) and 330 μg/g (phyllosilicate-bearing possible. In addition, organic compounds may play a role in elevating Li concentrations. Examples strata, z3GT,indteheispcodnrteixltliwnegreGobos1er0v0ed5)in. soTuhrce rpohckyslolof osillificealdteb-rcinoens itnaithneinGgulfsotfraMteaxicaoreandcoAmlbeprotased of halite, [23]. anhydrite, quartz, muscovite and chlorite. We assume that these phyllosilicates are Li carriers, but Most of the Gorleben brines are enriched with respect to Li, and brines with high Mg contents alternative Li sources, like fluid inclusions with metamorphic brines, could be possible. In addition, show higher Li concentrations (Figure 7). The highest Li concentration (up to 401 μg/g) has been detected in a brine with a high Mg content of about 7.5 wt. % (Figure 7). The Li values are organic compounds may play a role in elevating Li concentrations. Examples in this context were significantly higher than in seawater of the highest evaporation stage (26 μgLi/g). Therefore, it is observed in source rocks of oil field brines in the Gulf of Mexico and Alberta [23]. assumed that the investigated solutions are generated from the interaction with phyllosilicates Most of the Gorleben brines are enriched with respect to Li, and brines with high Mg contents containing Li. A relationship between Li occurrences in brines and Li-bearing phyllosilicates in clay- and salt-rich strata, detected in several salt deposits in Germany, had already been suggested by show higher Li concentrations (Figure 7). The highest Li concentration (up to 401 μg/g) has been References [3,10]. The Li-enriched solutions in both salt deposits are interpreted as internal detected in a brine with a high Mg content of about 7.5 wt. % (Figure 7). The Li values are significantly metamorphic brines originating from potash seams, as fluids migrated through fissures and porous higher than inaresaesainwphaytlelorsiolifcathe-ebeharignghsetrsattaedvuaripngordaiatgieonnesistangdeth(e2s6altμstgruLcit/ugre).evTolhuetiroen.fLoirre,prietseisntsassumed that an additional geochemical signature. the investigated solutions are generated from the interaction with phyllosilicates containing Li. A The majority of the solution occurrences observed in the Gorleben exploration mine are relationship between Li occurrences in brines and Li-bearing phyllosilicates in clay- and salt-rich strata, halite-saturated, and some very highly concentrated K-Mg brines. However, some samples are detectedinsesvoleurtiaonlsoaflltowdecopnocesnitrsatiinonGsweirthmreasnpeyc,thtoaMdgalnrdeLaidayndbaereunnsautugrgatedstweidthbreyspRecetftoerheanlitce.es[3,10]. The These are fresh water-derived (e.g., groundwater) and infiltrate the exploration mine through the Li-enriched solutions in both salt deposits are interpreted as internal metamorphic brines originating shafts (external solutions; Figure 7). Other halite under saturated brines are interpreted to be from potash seams, as fluids migrated through fissures and porous areas in phyllosilicate-bearing strata technical solutions, caused by underground road construction and mine ventilation. during diagenesis and the salt structure evolution. Li represents an additional geochemical signature. The majority of the solution occurrences observed in the Gorleben exploration mine are halite-saturated, and some very highly concentrated K-Mg brines. However, some samples are solutions of low concentrations with respect to Mg and Li and are unsaturated with respect to halite. These are fresh water-derived (e.g., groundwater) and infiltrate the exploration mine through the shafts (external solutions; Figure 7). Other halite under saturated brines are interpreted to be technical solutions, caused by underground road construction and mine ventilation. In the Morsleben salt mine, two solution accesses are currently active. The brines of mining claim 1a plot on or a little bit above the evaporation line of the Li/Mg ratio (Figure 7), representing probably highly evaporated relictic Permian seawater, or metamorphic brines of internal origin demonstrated by the Rb/Br ratios [35]. The brines of mining claim H plot below the evaporation trend line (Li/Mg), indicating fresh water which interacted with salt minerals (also proven by Rb/Br ratios in Reference [35]).PDF Image | Lithium Occurrences in Brines from Two German Salt Deposits
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