Additive effects of acidification and mineralogy on calcium isotopes in Triassic/Jurassic boundary limestones

The end-Triassic mass extinction coincided with a negative δ13C excursion, consistent with release of 13C-depleted CO2 from the Central Atlantic Magmatic Province. However, the amount of carbon released and its effects on ocean chemistry are poorly constrained. The coupled nature of the carbon and calcium cycles allows calcium isotopes to be used for constraining carbon cycle dynamics and vice versa. We present a high-resolution calcium isotope (δ44/40Ca) record from 100 m of marine limestone spanning the Triassic/Jurassic boundary in two stratigraphic sections from northern Italy. Immediately above the extinction horizon and the associated negative excursion in δ13C, δ44/40Ca decreases by ∼0.8‰ in 20 m of section and then recovers to preexcursion values. Coupled numerical models of the geological carbon and calcium cycles demonstrate that this δ44/40Ca excursion is too large to be explained by changes to seawater δ44/40Ca alone, regardless of CO2 injection volume and duration. Less than 20% of the δ44/40Ca excursion can be attributed to acidification. The remaining 80% likely reflects a higher proportion of aragonite in the original sediment, based largely on high concentrations of Sr in the samples. Our study demonstrates that coupled models of the carbon and calcium cycles have the potential to help distinguish contributions of primary seawater isotopic changes from local or diagenetic effects on the δ44/40Ca of carbonate sediments. Differentiating between these effects is critical for constraining the impact of ocean acidification during the end-Triassic mass extinction, as well as for interpreting other environmental events in the geologic past