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Minerals 2019, 9, 766 10 of 21 Minerals 2019, 9, x FOR PEER REVIEW 11 of 22 Figure 6. K, Si, Li, Rb and Cs concentrations and pH of initial solutions, after one year (red) and after Figure 6. K, Si, Li, Rb and Cs concentrations and pH of initial solutions, after one year (red) and after three years of reaction (blue). The K content is displayed in logarithmic scale; DI H2O = double three years of reaction (blue). The K content is displayed in logarithmic scale; DI H2O = double distilled distilled H2O. The K, Si, Li, Rb and Cs content of the initial lepidolite is displayed for comparison. H2O. The K, Si, Li, Rb and Cs content of the initial lepidolite is displayed for comparison. The Si content in the reacting solution increased after one year in seawater up to 16.37 μg/g and TheaSfitecrotnhrteenyteianrst,htheerheiagchteisntgSiscolnucteinotnratiinocnr,ewaisthed72a.7f9teμrgo/gn,ewyaseadretienctesdeainwsaotleurtiounpZto(re1a6c.t3io7nμg/g and after three years, the highest Si concentration, with 72.79 μg/g, was detected in solution Z (reaction The highest Rb content in the reaction solution was detected in the KCl solution with the very likely not finished). very likely not finished). highest concentration. The Rb value increased from 39.69 μg/g (sample 28) after one year, to 84.93 The highest Rb content in the reaction solution was detected in the KCl solution with the highest μg/g (sample 46) after three years of reaction. concentration. The Rb value increased from 39.69 μg/g (sample 28) after one year, to 84.93 μg/g The highest Cs content was also detected in the KCl solution with the highest concentration (sample 4(6sa)mapftler10t)h,reperyeseanrtisnogfanreiancrteioasne.from a maximum of 5.80 μg/g after one year to 13.65 μg/g after three years of reaction. The highest Cs content was also detected in the KCl solution with the highest concentration Potassium is leached by double distilled H2O, NaCl (Figure 6), MgCl2 solutions (with the (sample 10), representing an increase from a maximum of 5.80 μg/g after one year to 13.65 μg/g after exception of sample 12–30, 48) and some potassium solutions that reacted for three years (samples 7, three years of reaction. 8, 9,10–43, 44, 45, 46; Table 1, not noticeable in Figure 5 due to logarithmic scale). The largest release Potafsrsoimumtheislleepaidcohleitde bwyasddoeutbecltediwstiitlhle0d.7H99 wOt,.N%aKClin(Fsiagmuprele64)6,.MVgirCtulallsyolnuotidoinffesr(ewnciethinththeeexception 22 dynamic of leaching in relation to K between one and three years was observed with the exception of of sample 12–30, 48) and some potassium solutions that reacted for three years (samples 7, 8, 9,10–43, the higher concentrated K solutions (Table 1). 44, 45, 46; Table 1, not noticeable in Figure 5 due to logarithmic scale). The largest release from the lepidolite was detected with 0.799 wt. % K in sample 46. Virtually no difference in the dynamic of 4. Discussion leaching in relation to K between one and three years was observed with the exception of the higher North Sea, which show a mean value of 0.167 μg/g. During evaporation of seawater, the Li content 4.1. NatuirnalthOecrceusirdruenalcbesrine increases continuously (Figure 7), because the precipitating evaporites neither form Li minerals nor incorporate Li in the minerals in detectable concentrations. Theoretical Published data for Li concentrations in seawater vary between 0.166 μg/g [45], 0.17 μg/g [40] and considerations and experimental investigations of seawater evaporation suggest that the Li 4.1. Natural Occurrences concentrated K solutions (Table 1). Published data for Li concentrations in seawater vary between 0.166 μg/g [45], 0.17 μg/g [40] 4. Discussion and 0.176 μg/g [46]. These data are in good agreement with analyses of surface seawater from the 0.176μg/cgon[4ce6n].traTthioenseridseastainartheeinregsiodoudalasgorlueteiomnefnrtomwi0t.h17anμagl/ygsteos1o.f37suμrgf/agcewsheanwhatleitrefirsomfirstheNorth precipitated. The Li concentration in the solution when the first polyhalite is formed is 4.57 μg/g, at Sea, which show a mean value of 0.167 μg/g. During evaporation of seawater, the Li content in the the first kieserite precipitation 11.49 μg/g and at the first kainite crystallization 13.25 μg/g (Figure 7, residual brine increases continuously (Figure 7), because the precipitating evaporites neither form Li Table 2, Appendix A, Table A5). minerals nor incorporate Li in the minerals in detectable concentrations. Theoretical considerations and experimental investigations of seawater evaporation suggest that the Li concentration rises in the residual solution from 0.17 μg/g to 1.37 μg/g when halite is first precipitated. The Li concentration in the solution when the first polyhalite is formed is 4.57 μg/g, at the first kieserite precipitation 11.49 μg/g and at the first kainite crystallization 13.25 μg/g (Figure 7, Table 2, Appendix A, Table A5).PDF Image | Lithium Occurrences in Brines from Two German Salt Deposits
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