Millennial-scale growth of (proto)dolomite in Lake Neusiedl (Austria) is consistent with Ostwald's step rule

Authigenic Mg-calcite and dolomite are currently forming in Lake Neusiedl (Neuhuber et al. 2024), an episodically evaporative shallow lake in eastern Austria (Draganits et al., 2022). Radiocarbon dating by Neuhuber et al. (2024) revealed average ages of 200 to 3700 cal yr BP, reflecting extremely slow precipitation rates. The relatively high ages of fine-grained crystals agree with high radiocarbon ages of dolomite from Deep Springs Lake (California; Peterson et al., 1963). Such comparably high ages are commonly explained by the slow formation of dolomite due to its high kinetic barrier. Close examination by transmission electron microscopy (Meister et al., 2023) revealed concentric zones of Mg-rich carbonate replacing less Mg-rich precursors. However, no considerable progress in ripening has been noticed in older layers buried below 30 cm depth, which are no longer affected by sediment reworking (Fussmann et al., 2023). It appears that ripening of the metastable phase to the stable phase does not occur as long as the porewater remains supersaturated with respect to a metastable Mg-calcite phase. Ripening of Mg-calcite to protodolomite and ordered dolomite may however occur at the sediment-water interface, where the bottom water becomes episodically undersaturated with respect to Mg-calcite. Fussmann et al. (2023) observed a drop in pH in the benthic boundary layer, which can be caused by the release of acidic fermentation products and aerobic respiration. Ripening due to episodic undersaturation of water with respect to a metastable Mg-calcite phase is consistent with a model of dolomite formation under conditions fluctuating between supersaturation and undersaturation with respect to the metastable phase, conforming to Ostwalds step rule. This effect has recently been reproduced using density function theory (Kim et al., 2023). This model could also explain the formation of nano-domains of ordered dolomite in coherent crystallographic orientation within the protodolomite due to oscillating conditions at the recrystallization front (Meister et al., 2023). The case of authigenic carbonate formation in Lake Neusiedl exemplifies that the model of dolomite formation under fluctuating hydrochemical conditions is well applicable to natural conditions in modern, as well as ancient, environments. Draganits, E. et al. (2022) Lake Neusiedl Area: A Particular Lakescape at the Boundary Between Alps and Pannonian Basin. In: Embleton-Hamann, C. (ed.), Landscapes and Landforms of Austria. World Geomorphological Landscapes. Springer, Cham, pp. 207-222. Fussmann, D. et al. (2020) Authigenic formation of Mg-Ca-carbonates in shallow alkaline water in Lake Neusiedl, Austria. Biogeosciences 17, 20852106. Kim, J. et al. (2023) Dissolution enables dolomite crystal growth near ambient conditions. Science 382, 915920. Meister, P. et al. (2023) Nanoscale pathway of modern dolomite formation in a shallow, alkaline lake. Cryst. Growth Des. 23, 32023212. Neuhuber, S. et al. (2024) Radiocarbon ages of microcrystalline authigenic carbonate in Lake Neusiedl (Austria) suggest millennial-scale growth of Mg-calcite and protodolomite. Sedimentology in press. Peterson, M.N.A. et al. (1963) Radiocarbon studies of recent dolomite from Deep Spring Lake, California. J. Geophys. Res. 68, 64936505.