The calcium isotope evolution of Lake Lisan, the Dead Sea glacial precursor

Calcium is a stoichiometric component of carbonate minerals whose calcium isotopic composition reflects changes in the calcium isotope composition of the water from which it precipitates as well as the calcium isotope fractionation factor during precipitation. The lacustrine deposits of the last glacial Dead Sea (Lisan Formation) are dominated by carbonate minerals (aragonite) that record the geochemical history of the lake. The sediment sequence comprises alternating laminae of aragonite and clay-rich marls, interspersed with primary gypsum beds and disseminated secondary gypsum crystals. The aragonite precipitated annually during high lake stands associated with wet periods, while the primary gypsum precipitated during low lake conditions (arid periods). We report the calcium isotopic composition (δ44Ca in ‰ relative to bulk silicate earth) of primary aragonite laminae, primary gypsum and secondary gypsum at 1-5kyr resolution throughout the Lisan Formation sampled at the Masada section (70 - 14.5 ka). The δ44Ca of the primary gypsum averages +0.29‰, and displays smaller temporal variations than the aragonite, which averages -0.35‰ but ranges between +0.18‰ and -0.68‰. The aragonite δ44Ca changes temporally in sync with the previously reconstructed lake level suggesting the aragonite δ44Ca reflects changes in the lake calcium balance during lake level changes. The secondary gypsum composition (-0.3‰) corresponds to coeval aragonite samples. For the secondary gypsum to have a similar δ44Ca to the aragonite it is likely that the calcium derived from the aragonite in a near quantitative fashion through recrystallization of the aragonite to gypsum. A numerical box model is used to explore the effect of changing lake water levels on the calcium isotope composition of the aragonite and gypsum over the time interval studied.