The Modern Marine Ca-isotope Budget and its Application to the Phanerozoic Ca-isotope Record

Variations in the calcium-isotope ratio (δ^44/40Ca) of ancient seawater have been recorded in several studies using marine carbonate, barite, or apatite, but the causes of these variations have not been explored quantitatively. Seawater Ca-isotope ratios are affected by the average fractionation factor between seawater and the carbonate that precipitates from it, which is defined by the composition of the marine carbonate sink. To investigate possible changes in the fractionation factor of marine carbonate over the Phanerozoic, a Ca-isotope budget has been constructed for the modern oceans. Over 250 Ca-isotope measurements have been compiled from a wide variety of carbonate sources to describe the modern marine Ca-isotope budget. This dataset includes over 50 new measurements to characterize several components of the carbonate system, such as coral reefs, which are quantitatively important but have been undersampled, for example, relative to planktic foraminifera. δ^44/40Ca values have been temperature-normalized using the relationship of +0.02% per °C, which permits observations and comparisons based on mineralogy, taxonomy, and locus of carbonate precipitation. A general offset of ~0.25%, increasing up to ~0.8% for certain taxa, is observed between subsets of aragonite and calcite samples; no statistical difference is observed between high-Mg calcite and low-Mg calcite. Additionally, within the data for calcite skeletons, two broad groups appear based on taxonomic patterns. Taxa with generally weak control over their biomineralization, such as sclerosponges, brachiopods, and calcareous red algae, are 0.4-0.5% heavier than organisms with more controlled calcification mechanisms, such as coccolithophores and planktic foraminifera. The patterns that emerge from this dataset for different clades demonstrate the usefulness of fossil carbonate for reconstructing the Ca-isotope ratio of ancient seawater. The composition of the modern Ca-isotope budget provides a basis for estimating changes to the Ca-isotope budget in the past. Quantitative estimates about the dominant calcifying organisms and the areal extent of environments can be interpreted as Ca-isotope signatures. These estimates can then be used to reexamine the Phanerozoic Ca-isotope record through the evolution of marine carbonate precipitation, including factors such as changes in seawater composition (e.g. calcite sea-aragonite sea transitions), the development of reefs, and the evolution of pelagic calcification.