Unraveling the Sulfate Sources of (Giant) Gypsum Crystals Using Gypsum Isotope Fractionation Factors

Abstract

We combine newly determined isotope fractionation factors of gypsum precipitated in the laboratory with the isotopic compositions of natural anhydrite and gypsum to unravel the sulfate sources of the giant selenite crystals in the Naica mine (Chihuahua, Mexico). Gypsum was precipitated in the laboratory from CaSO4-NaCl-H2O solutions across a broad temperature range to establish the isotopic fractionation behavior of the sulfate molecule between the solid and dissolved phase. Oxygen isotopes show a significant fractionation dependence on temperature, with the solid phase more depleted in light isotopes with decreasing temperature. Sulfur isotopes display only a weak but similar dependence on temperature. At high salinity (4.5 M NaCl) no temperature dependence was found for the isotope composition. Based on this fractionation behavior, we attempt to elucidate the origin of the sulfate source(s) responsible for the formation of the (giant) gypsum crystals in the Naica mine. Detailed analysis of the isotopic composition of anhydrite, gypsum, and water samples strongly suggests that different types of anhydrite (of hypogenic and sedimentary origin) were dissolved to form these unique gypsum formations. The homogeneous isotopic composition of most gypsum crystals analyzed reveals an effective hydrodynamic mixing and a slow kinetics of precipitation fed by solutions of calcium sulfate from different anhydrite sources.