Stable Ca and Sr isotopes support volcanically triggered biocalcification crisis during Oceanic Anoxic Event 1a

Large igneous province (LIP) eruptions are hypothesized to trigger biocalcification crises. The Aptian nannoconid crisis, which correlates with emplacement of the Ontong Java Plateau and Oceanic Anoxic Event 1a (OAE 1a, ca. 120 Ma), represents one such example. The Ca isotope (δ^44/40Ca) system offers potential to detect biocalcification fluctuations in the rock record because Ca isotope fractionation is sensitive to precipitation rate. However, other primary and secondary processes, such as input-output flux perturbations and early diagenesis, can produce similar signals. Here, we exploit emergent properties of the stable Sr isotope (δ^88/86Sr) system to resolve the origin of δ^44/40Ca variability during OAE 1a. This study reports high-precision thermal ionization mass spectrometry (TIMS) δ^44/40Ca, δ^88/86Sr, and ⁸⁷Sr/⁸⁶Sr records for Hole 866A of Ocean Drilling Program Leg 143 drilled in Resolution Guyot, mid-Pacific Ocean. The samples span ~27 m.y. from the Barremian (ca. 127 Ma) to the Albian (ca. 100 Ma). The δ^44/40Ca and δ^88/86Sr secular trends differ from the ⁸⁷Sr/⁸⁶Sr record but mimic each other. δ^44/40Ca and [Sr], as well as δ^44/40Ca and δ^88/86Sr, strongly correlate and yield slopes predicted for kinetic control, which demonstrates that variable mass-dependent fractionation rather than end-member mixing dominated the isotopic relationship between carbonates and seawater. Positive δ^44/40Ca and δ^88/86Sr shifts that begin before OAE 1a and peak within the interval are consistent with reduced precipitation rates. All results combined point to a cascade of effects on rate-dependent Ca and Sr isotope fractionation, which derive from the dynamic interplay between LIP eruptions and biocalcification feedbacks.