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Minerals 2019, 9, 766 4 of 21 In Morsleben, at the rim of the basin, the main components of the z3GT are quartz, muscovite-illite (ca. 30 wt. % each), with additional trace amounts of tourmaline, chlorite, serpentine and halite [39]. The z3LK consists of magnesite (ca. 56 wt. %), anhydrite (ca. 20 wt. %) and minor amounts of quartz, muscovite-illite, koenenite, chlorite and calcite [39]. The transition between the Leine- and the Aller-Series is characterised by the Tonmittelsalz (z3TM) and the Roter Salzton (z4RT). Close to the top of the Aller-Series, the Tonbockensalz (z4TS) is developed. These units are characterized by a high amount of halite of ca. 80–90 wt. % [39], with minor amounts of quartz, anhydrite, muscovite, chlorite-smectite, kaolinite and magnesite [28]. Clay rock occurrences are interrupted by intercalations of anhydrite and halite layers. The z4TS could not be observed in the Morsleben salt structure. Organic matter is contained in all stratigraphic units described, often enriched in thin layers associated with carbonate and quartz/phyllosilicates. Depending on the lithology of the samples, Li concentrations are highly variable [28]. Potentially Li-bearing minerals within phyllosilicate-containing strata are muscovite and chlorites. Due to relatively low Li concentrations in seawater (0.17 μg/g; [40]) and evaporated seawater, from which the salts originate, it is unclear where the high Li concentrations derive from. The Li concentrations of brines detected in salt deposits are in the range of bulk rock analyses of Upper Permian (Zechstein) phyllosilicate-bearing strata [28], both of which are some magnitudes higher than the Li concentrations of the most strongly evaporated seawater. Lepidolite was used to investigate leaching effects between brines and phyllosilicates because lepidolite is comparable with muscovites and chlorites that are common components of the phyllosilicate-bearing strata. Another advantage of using lepidolite is its very high Li content, advantageous for getting a measurable leaching effect in a manageable timescale for laboratory experiments. Experimental studies on the leaching behaviour were performed by exposing lepidolite to 18 saline solutions of different composition for the duration of ca. three years. 2. Analytical Methods and Experimental Setup 2.1. Sampling of Natural Brines In the Gorleben salt dome, the inflow of solutions was linked to mining activity. During excavation of galleries, at certain points, connected to changes in lithology and lithostratigraphic boundaries, saline solutions entered the mine. However, most solution influxes had a limited volume of few dm3 to several m3 [5]. Brine that originated from more extensive and long-lasting solution influx were collected by a system of tailraces, tubes and accumulation bins. The gathered brine was sampled on a regular basis. In the Morsleben mine, a similar construction is used to collect brine at mining claim 1A. The volume of inflowing brine is ca. 1.4 m3/a [35]. The influx rate has been sporadically analysed since 1962, and systematic analyses of the composition and trace element content have been carried out in monthly intervals since 1991. At the second solution influx, mining claim H, the brine inflow started in 1907 due to extensive mining activities. Consequently, a protection embankment was built, thus the exact position of the influx is not clear. Furthermore, the volume is higher (ca. 10 m3/a, [35]), therefore the brine is collected in a pool. The influx rate has been monitored since 1907, and systematic analyses of the composition and trace element content have also been carried out since 1991. 2.2. Experimental Setup For each experimental run, 8 g of lepidolite (from Minas Gerais, Brazil; stoichiometric formula: K(Li,Al)2–3 ((OH,F)2 /Si3 AlO10 )) with a lithium concentration of 2.42 wt. % (for more details see Section 3.2.1) was ground to a grain size <200 μm and added to 100 g solution (mass ratio 1(rock):12.5(solution)). The compositions of the solutions vary from double distilled H2O, NaCl, KCl, MgCl2 solutions, modern seawater to artificial solutions (Table 1), approximately comparable to the composition of the so-called solutions Q, R and Z (according to References [10,41]). These solutions are basically halite, anhydrite and partly polyhalite saturated. Solution Q is saturated with respect to sylvite,PDF Image | Lithium Occurrences in Brines from Two German Salt Deposits
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