Stable chlorine isotopes in arid non-marine basins: Instances and possible fractionation mechanisms

• δ37Cl in halite from arid, non-marine sedimentary basins ranges from −3 to +5.5‰.
• Cl− in vadose playas may develop large isotope fractionation through cyclic wetting and drying.
• Cl− in phreatic playas undergoes no fractionation as a result of cyclic wetting and drying.
• Cl− in weathered crusts may fractionate through cyclic wetting and drying with outward diffusion of low- δ37Cl chloride.

Stable chlorine isotopes are useful geochemical tracers in processes involving the formation and evolution of evaporitic halite. Halite and dissolved chloride in groundwater that has interacted with halite in arid non-marine basins has a δ37Cl range of 0 ± 3‰, far greater than the range for marine evaporites. Basins characterized by high positive (+1 to +3‰), near-0‰, and negative (−0.3 to −2.6‰) are documented. Halite in weathered crusts of sedimentary rocks has δ37Cl values as high as +5.6‰. Salt-excluding halophyte plants excrete salt with a δ37Cl range of −2.1 to −0.8‰. Differentiated rock chloride sources exist, e.g. in granitoid micas, but cannot provide sufficient chloride to account for the observed data. Single-pass application of known fractionating mechanisms, equilibrium salt-crystal interaction and disequilibrium diffusive transport, cannot account for the large ranges of δ37Cl. Cumulative fractionation as a result of multiple wetting-drying cycles in vadose playas that produce halite crusts can produce observed positive δ37Cl values in hundreds to thousands of cycles. Diffusive isotope fractionation as a result of multiple wetting-drying cycles operating at a spatial scale of 1–10 cm can produce high δ37Cl values in residual halite. Chloride in rainwater is subject to complex fractionation, but develops negative δ37Cl values in certain situations; such may explain halite deposits with bulk negative δ37Cl values. Future field studies will benefit from a better understanding of hydrology and rainwater chemistry, and systematic collection of data for both Cl and Br.