Abstract Magnesium isotopic compositions of evaporite deposits may record information concerning brine evolution during deposition. We report Mg isotopic values (δ 26 Mg DSM3 ) measured from an evaporite deposit of langbeinite (K 2 Mg 2 (SO 4 ) 3 ) found in the Permian Salado Formation. We used these data to model Mg isotope fractionation between langbeinite and its parent brine. In addition, both measured and theoretical results are used to estimate precipitation temperature and interpret depositional environment. The Salado langbeinite δ 26 Mg values are relatively low and fall within a relatively narrow range (–4.12 ± 0.03‰ to −3.81 ± 0.07‰). Equilibrium fractionation factors between langbeinite and aqueous Mg 2+ solutions were calculated using quantum chemical density functional theory. All computations were performed at the B3LYP/6‐31 + G(d,p) level. Solvation effects were addressed using a solvent model (“water‐droplet” approach) and mineral structures were investigated using volume variable cluster models (VVCM). The equilibrium Mg isotopic fractionation factors α between langbeinite and model brine solution we obtained are 1.0005, 1.0004, and 1.0003 (Δ 26 Mg langb‐water ≈10 3 lnα = 0.473‰, 0.390‰, and 0.322‰) at 10°C, 25°C, and 40°C, respectively. These relatively large equilibrium fractionation factors indicate significant Mg isotope fractionation between langbeinite and its parent brine during precipitation, as langbeinite preferentially incorporates the heavier 26 Mg and 25 Mg isotopes. Rayleigh distillation modeling of the Salado langbeinite's relatively light Mg isotopic composition requires δ 26 Mg DSM3 values of −4‰ for the parent brine. Models favor a precipitation temperature as high as 40°C under equilibrium conditions. Potential disequilibrium precipitation conditions suggested by Mg isotopic data also imply rapid deposition in a hot, arid sedimentary environment prevailing in the southwestern U.S. during the Late Permian.
