Formation and chemical evolution of magnesium chloride brines by evaporite dissolution processes—Implications for evaporite geochemistry |
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| Authors: | Ralf E Krupp |
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| Institution: | Flachsfeld 5, D-31303 Burgdorf, Germany |
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| Abstract: | The evolution of magnesium chloride brines with high bromide contents via a multistage reaction and dissolution process has been studied in brine seeps of a German potash mine. The observed chemical trends and phase equilibria can be modeled and interpreted in terms of a NaCl solution (cap rock brine) infiltrating into a potash zone characterized by the metamorphic mineral assemblage kieserite + sylvite + halite + anhydrite. Establishment of a persistent, stable equilibrium assemblage and constant fluid composition in the invariant point IP1 of the six component (Na-K-Mg-Ca-Cl-SO4-H2O) system of oceanic salts is prevented by the perpetually renewed input of NaCl-brine and by the intermittent exposure of incompatible kieserite. Instead, the solutions develop towards the metastable invariant point IP1(gy), with the mineral assemblage carnallite + polyhalite + sylvite + halite + gypsum, where gypsum takes the place of anhydrite (stage I). The temporary exposure of kieserite and the ensuing formation of polyhalite effectively buffer the solutions along the metastable polyhalite phase boundary during stages II and III. Eventually, in stage IV, polyhalite becomes depleted and admixture of more NaCl brine leads to low sulfate solution compositions, which are now only constrained by carnallite + sylvite + halite, and the once hexary system degenerates to a quaternary one (Na-K-Mg-Cl-H2O) in point E. Bromide in brines shows equilibrium partitioning with respect to the wall rock minerals. The pattern of evolving brine compositions may serve as a model for similar brine occurrences, which in some cases may have been misinterpreted as remains of fossil, highly concentrated and chemically modified seawater. Similar magnesium chloride brines of salt lakes (e.g., Dead Sea, Dabusun Lake) show subtle differences and are constrained by fewer mineral equilibria (more degrees of freedom), and their low sulfate contents are due to gypsum precipitation, driven by calcium chloride input from dolomitization reactions. Finally, the observed reaction sequence is generalized, and a model for the formation of magnesium sulfate depleted, chloride-type potash salts and bischofite deposits by leaching of sulfate-type evaporites is proposed. |
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