Dynamic oceanic redox conditions across the late Cambrian SPICE event constrained by molybdenum and uranium isotopes

The Steptoean Positive Carbon Isotope Excursion Event (SPICE) represents one of the largest carbon cycle perturbations in the Cambrian, which coincided with climatic changes and dramatic extinction of shallow-shelf faunas. This carbon perturbation has been linked to a global expansion of marine euxinia (SPICE-OAE), but the precise timing, duration and extent of changing redox conditions across the SPICE event, as well as its influences on the coeval biotic evolution, remain unclear. Here, we report paired δ98Mo–δ238U data across this event, constrained by a radioisotopically anchored astrochronology, based on Alum Shale samples from the Albjära-1 and Billegrav-2 drill-cores in Scandinavia. The δ98Mo profiles are largely invariant around 1.08±0.21‰ with short-term fluctuations parallelling changes in pyritization of iron, possibly as a result of locally varying [H2S]aq in the water column and/or fluctuating reactive iron delivery. The bottom water is interpreted to have been primarily anoxic, but with frequent local variations between oxic and sulfidic conditions in a moderately restricted basin. A novel analytic method based on variation of Mo concentrations at millimeter scale stratigraphic resolution was applied to distinguish between local and global redox signatures, revealing that cyclic redox changes are recorded in the Alum Shale sea with periods of ∼0.3 Myr, ∼0.9 Myr and ∼0.15 Myr before, during and after the SPICE-OAE, respectively. Stratigraphic profiles of Mo, U, Mo/TOC ratios and δ238U in the two cores show comparable trends, facilitating recognition of three chemically distinct stages across the SPICE event: 1) global expansion of marine euxinia (SPICE-OAE; 497.9–496.6 Ma), 2) global contraction of euxinia accompanied by enhanced carbonate weathering inputs (496.6–495.8 Ma) and 3) general global oxygenation (495.8–494.4 Ma). The first in situ correlation between the onset of the SPICE-OAE and the end-Miaolingian extinctions in Baltica corroborates that expansive anoxic and sulfidic water masses likely contributed to the biotic crisis. The time gap between the start of the extinction and the appearance of the new fauna in Baltoscandia is estimated to be ∼600 kyr.