$\delta^{44/40}$Ca-$\delta^{88/86}$Sr multi-proxy constrains primary origin of Marinoan cap carbonates

Abstract

The Neoproterozoic Earth experienced at least two global-scale glaciations termed Snowball Earth events. 'Cap carbonates' were widely deposited after the events, but controversy surrounds their origin. Here, we apply the novel $\delta^{44/40}$Ca-$\delta^{88/86}$Sr multi-proxy to two Marinoan (ca. 635 Ma) cap carbonate sequences from Namibia and show that the rocks archive primary environmental signals deriving from a combination of seawater-glacial meltwater mixing and kinetic isotope effects. In an outer platform section, dolostone $\delta^{44/40}$Ca and $\delta^{88/86}$Sr values define a line predicted for kinetic mass-dependent isotope fractionation. This dolostone mostly precipitated from meltwater. Moreover, stratigraphically higher samples exhibiting the fastest precipitation rates correlate with elevated 87Sr/86Sr ratios, consistent with long-held expectations that a rapid deglacial weathering pulse forced cap carbonate formation. An inner-platform dolostone shows greater effects from water-mass mixing but still reveals that precipitation rates increased up-section. Overlying limestones show the greatest Ca and Sr contributions from seawater. Amplification of local coastal processes during global ice sheet collapse offers a simple but sufficient proposition to explain the Ca isotope heterogeneity of cap carbonates. Detection of kinetic isotope effects in the rock record provides a basis for developing the $\delta^{44/40}$Ca-$\delta^{88/86}$Sr multi-proxy as an indicator of saturation state and $p$CO$_2$.