Ca isotopic gradients in epeiric marine carbonates: Diagenetic origins of and significance for Ca cycle reconstructions

Abstract

Marine carbonates record geochemical information on the state of Earth’s surface environment in the geological past, but recrystallization during burial can make the records difficult to interpret. Here, we report shore to basin gradients in δ44Ca values in matrix limestone and burrow dolomite across a sequence of Late Ordovician (Katian Stage) burrow-mottled carbonates in the Williston Basin, an intracratonic epeiric marine basin in North America. Both gradients are interpreted to have diagenetic origins. The gradient in limestone δ44Ca values developed in a bathymetrically controlled sediment- to fluid-buffered diagenetic system operating between the center and the edges of the basin. Two dolomitizing events formed the gradient in dolomite δ44Ca values. The sediment-buffered end of the limestone gradient preserves the δ44Ca value of the original carbonate mud (∼–1.28 ± 0.10 ‰). The fluid-buffered end of the gradient conserves the δ44Ca value of contemporaneous seawater (–0.47 ± 0.10 ‰), because: (1) pore water exchange drivers operated with greater variety and intensity in shallow water settings, (2) shallow nearshore deposits exchanged more Ca with seawater during recrystallization to diagenetic calcite than deeper offshore deposits, and (3) diagenetic calcite formed with negligible fractionation under equilibrium conditions. The gradient conserves the local value of Δsed (–0.81 ± 0.20 ‰) despite its diagenetic origin, and the magnitude of Δsed is consistent with primary calcite precipitation in a ‘calcite sea’. Field assessment of the equilibrium Ca isotope fractionation factor between calcite and dolomite of –0.41 ± 0.17 ‰ at ambient temperature is applied to correct basin-centered dolomite for fractionation, yielding –1.62 ± 0.27 ‰, which is very different from the –0.25 ± 0.07 ‰ value of Ca in evaporatively concentrated seawater from which the dolomite originally formed. Applying the same fractionation factor to correct literature data on early diagenetic dolomite in the Great Basin, North America, yields –0.69 ± 0.22 ‰ for the δ44Ca value of seawater, which is ∼0.2 ‰ lower than ‘normal marine’ waters in stratigraphically equivalent deposits in the Willison Basin, and 0.44 ‰ lower than evaporatively concentrated seawater during a brief period of basin restriction and anhydrite deposition. The nearly 0.5 ‰ variation in the δ44Ca value of Katian seawater falls within the range of scatter in the brachiopod reconstruction of seawater Ca isotopes. Here, we propose that the true ocean record of secular change lies towards the bottom of the range of scatter, and that the higher values in the record reflect local Ca cycling and circulation restriction in epeiric seas. Epeiric seas cultivate the fluid-buffered diagenetic conditions required to promote Ca isotope exchange between reactive carbonate sediments and seawater through carbonate mineral dissolution/recrystallization, crystal coarsening by way of Ostwald ripening, and replacive dolomitization. It is not the apportioning of kinetically fractionated aragonite and calcite in the carbonate deposition flux that drove secular changes in global value of Δsed between ‘calcite’ and ‘aragonite’ seas, but rather the replacement of kinetic fractionations with equilibrium fractionations during fluid-buffered diagenesis with seawater.