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Minerals 2019, 9, 7x6F6OR PEER REVIEW 2 of 212 Muerto, Argentinia [8,18] and the Salar de Uyuni, Bolivia [8,19,20]. The main source of Li is related Argentinia [8,18] and the Salar de Uyuni, Bolivia [8,19,20]. The main source of Li is related to to water–rock interactions with volcanic country rock (Bolivia) [21]. These brines result from water–rock interactions with volcanic country rock (Bolivia) [21]. These brines result from evaporation. evaporation. Li concentrations of some oil field brines (e.g., Smackover Formation, Gulf Coast (TX Li concentrations of some oil field brines (e.g., Smackover Formation, Gulf Coast (TX and FL, and FL, USA [22,23]) may reach >100 mg/L [23]. However, apart from these general observations, USA [22,23]) may reach >100 mg/L [23]. However, apart from these general observations, only little only little knowledge exists about the principle geochemical behaviour of Li in evaporites, especially knowledge exists about the principle geochemical behaviour of Li in evaporites, especially in relation in relation to the interaction between brines and minerals. to the interaction between brines and minerals. In contrast to highly concentrated Li brines in salt deposits, there is no evidence of naturally In contrast to highly concentrated Li brines in salt deposits, there is no evidence of naturally occurring Li salts or hints of significant Li contents in naturally formed salt minerals. The occurrence occurring Li salts or hints of significant Li contents in naturally formed salt minerals. The occurrence of of Li-carnallite, interpreted to have formed in salt lakes in South America, motivated the first Li-carnallite, interpreted to have formed in salt lakes in South America, motivated the first experimental experimental and crystallographic studies [24,25]. The authors of Reference [26] published a and crystallographic studies [24,25]. The authors of Reference [26] published a probable Li SO probable Li2SO4 formation in Salar de Uyuni. In order to examine the behaviour of Li in this sys2tem4, formation in Salar de Uyuni. In order to examine the behaviour of Li in this system, the authors of the authors of Reference [26] evaporated these brines for up to 54 days. They found that during the Reference [26] evaporated these brines for up to 54 days. They found that during the first 34 days, first 34 days, the Li and SO4 concentrations in the brine increased, but from the 35th day, the theLiandSO concentrationsinthebrineincreased,butfromthe35thday,theconcentrationinthe concentration4in the solution decreased, which was interpreted as a result of LiSO4 precipitation solutiondecreased,whichwasinterpretedasaresultofLiSO precipitation(indirectproof). (indirect proof). 4 Currently, it is unknown if the detection of very low quantities of Li in the lower ppm range Currently, it is unknown if the detection of very low quantities of Li in the lower ppm range originate from fluid inclusions, or whether Li is incorporated in the crystal lattice of naturally formed originate from fluid inclusions, or whether Li is incorporated in the crystal lattice of naturally salt minerals. formed salt minerals. In brines and rocks of the Upper Permian salt deposits of the Gorleben salt dome and the In brines and rocks of the Upper Permian salt deposits of the Gorleben salt dome and the Morsleben salt structure, both located in the Southern Permian Basin, northern Germany (Figure 1), Morsleben salt structure, both located in the Southern Permian Basin, northern Germany (Figure 1), high Li concentrations of up to 401 μg/g in brines [27] and 161 μg/g in bulk rock samples [28] were high Li concentrations of up to 401 μg/g in brines [27] and 161 μg/g in bulk rock samples [28] were measured. The Gorleben salt dome consists of Upper Permian (Zechstein) rock salt formations. The measured. The Gorleben salt dome consists of Upper Permian (Zechstein) rock salt formations. The salt dome is aligned in the NE–SW direction and is ca. 14 km long. The salt table is located ca. salt dome is aligned in the NE–SW direction and is ca. 14 km long. The salt table is located ca. 250 m 250 m below ground level [5]. The salt movement started in the Early Triassic and during Upper below ground level [5]. The salt movement started in the Early Triassic and during Upper Jurassic Jurassic periods to the Lower Cretaceous period, and the salt rocks penetrated the overburden and periods to the Lower Cretaceous period, and the salt rocks penetrated the overburden and created a created a salt dome. The final stages of salt rise occurred during the Upper Cretaceous and Paleogen salt dome. The final stages of salt rise occurred during the Upper Cretaceous and Paleogen periods periods [29,30]. The Gorleben salt dome was investigated for its suitability to construct a repository for [29,30]. The Gorleben salt dome was investigated for its suitability to construct a repository for high-level radioactive waste between 1979–2000 and 2010–2012. In the Gorleben exploration mine, high-level radioactive waste between 1979–2000 and 2010–2012. In the Gorleben exploration mine, saline solutions were collected continuously at different sites between ca. 1996 and 2012, all of the saline solutions were collected continuously at different sites between ca. 1996 and 2012, all of the solutions originating from anhydrite rocks [5,31]. solutions originating from anhydrite rocks [5,31]. Figure 1.. Distriibuttiion off the Zechstein rocks (Upper Permian) in Northern Europe showing the investigated salt deposits of Gorleben and Morsleben, (map from Reference [[32]];;modiififieed)).. The Morsleben salt structure is located in the northeastern part of the Subherzynian basin, at the southern rim of the Zechstein basin. In this region, Zechstein salt migrated into the NW–SE trendingPDF Image | Lithium Occurrences in Brines from Two German Salt Deposits
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