Calcium isotopes reveal shelf acidification on southern Neotethyan margin during the Smithian-Spathian boundary cooling event

Abstract

The Smithian-Spathian transition of the late Early Triassic was a critical period of environmental and biological upheavals, following the end-Permian mass extinction. Changes in carbonate deposition during this period have been attributed to intensified upwelling along shelf margins, but relevant studies are scarce. Here, we present calcium isotopes of bulk marine carbonate (δ44/40Cacarb) from a Smithian–Spathian boundary (SSB) succession (Guryul Ravine section, Kashmir) on the southern margin of the Neo-Tethys. Our smoothed δ44/40Cacarb curve reveals a ∼ 0.2‰ negative shift (from ∼ − 1.1‰ to ∼ − 1.3‰) across the SSB, concurrent with a ∼ +10‰ shift in δ13Ccarb. While increased Ca isotopic fractionation could play a role, we specifically examine potential impacts due to changes in marine Ca fluxes. Using a Ca-cycle mass balance model, we explore scenarios of decreased carbonate burial flux (Fcarb), decreased riverine flux (Friv), and a combination of these processes. The modeling suggest that a pulse decrease in Fcarb by 40% over ∼0.06 Myr match the negative shift in δ44/40Cacarb at Guryul Ravine. We infer that this decrease was likely related to intensified upwelling of acidic deep seawater due to invigorated global-oceanic circulation during the SSB cooling event. We suggest that the regionally diverse excursions in δ44/40Cacarb in the Tethyan region could be attributed to spatially varied upwellings in the shelf margin. The upwelling of acidic and anoxic deep seawater may have driven the second-order extinction of ammonoids and conodonts at the beginning of the SSB cooling event.