No abstract

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 (δ44/40Ca) 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 (δ88/86Sr) system to resolve the origin of δ44/40Ca variability during OAE 1a. This study reports high-precision thermal ionization mass spectrometry (TIMS) δ44/40Ca, δ88/86Sr, 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 δ44/40Ca and δ88/86Sr secular trends differ from the 87Sr/86Sr record but mimic each other. δ44/40Ca and [Sr], as well as δ44/40Ca and δ88/86Sr, 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 δ44/40Ca and δ88/86Sr 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.

Carbon dioxide release during Deccan Traps volcanism and the Chicxulub impact likely contributed to the Cretaceous-Paleogene (K-Pg) mass extinction; however, the intensity and duration of CO2 input differed between the two events. Large and rapid addition of CO2 to seawater causes transient decreases in pH, [CO32–], and carbonate mineral saturation states. Compensating mechanisms, such as dissolution of seafloor sediment, reduced biomineralization, and silicate weathering, mitigate these effects by increasing the same parameters. The calcium isotope ratios (δ44/40Ca) of seawater and marine carbonates are hypothesized to respond to these perturbations through weathering/carbonate deposition flux imbalances and/or changes in fractionation between carbonate minerals and seawater. We used a high-precision thermal ionization mass spectrometry method to measure δ44/40Ca values of aragonitic bivalve and gastropod mollusk shells from the K-Pg interval of the López de Bertodano Formation on Seymour Island, Antarctica. Well-preserved shells spanning the late Maastrichtian (ca. 67 Ma) to early Danian (ca. 65.5 Ma) have δ44/40Ca values ranging from −1.89‰ to −1.57‰ (seawater [sw]). Shifts in δ44/40Ca inversely correlate with sedimentological indicators of saturation state. A negative excursion begins before and continues across the K-Pg boundary. According to a simple mass-balance model, neither input/output flux imbalances nor change in the globally integrated bulk carbonate fractionation factor can produce variations in seawater δ44/40Ca sufficient to explain the measured trends. The data are consistent with a dynamic molluscan Ca isotope fractionation factor sensitive to the carbonate geochemistry of seawater. The K-Pg extinction appears to have occurred during a period of carbonate saturation state variability caused by Deccan volcanism.

No abstract

No abstract