Carbonate lithium isotope systematics indicate cooling triggered mass extinction during the Frasnian-Famennian transition

We present comprehensive Li-C-Sr isotopic studies on two classic marine carbonate sections (Yangdi and Dongcun) transecting the Late Devonian Frasnian-Famennian (FF) boundary from South China to constrain the causes of the FF mass extinction. Both sections show positive Li and C isotopic excursions in carbonate and unchanged conodont 87Sr/86Sr ratios across the FF boundary. Low Li/Ca and Sr/Ca ratios, but heavy Li isotope composition (δ7Li) of the Dongcun section indicate possible diagenetic alteration on carbonate Li isotopic records. By contrast, the Yangdi section records more primary seawater δ7Li signal, showing a ∼ 2 ‰ positive excursion before the FF boundary, although reconstructed paleo-seawater δ7Li values (from 11.8 ± 1.4‰ to 13.8 ± 1.4‰) are lower than modern times. Combined box model with Monte Carlo simulation demonstrates that low seawater δ7Li requires low riverine δ7Li and small effective Li isotopic fractionation by marine sinks (Δ7Lisw-ms). The latter is likely due to high silicon concentration in the paleo-seawater and rapid formation of clay minerals. Positive δ7Li excursion but invariant 87Sr/86Sr ratios in the seawater are related to attenuated continental weathering (reduced riverine fluxes but increased riverine δ7Li), and enlarged effective Δ7Lisw-ms. Based on the present data we suggest that rapid climate cooling is responsible for the weathering transition and must have exerted significant influence on the marine environment. Global climate cooling weakens seawater stratification while intensifying oceanic circulation and upwelling, resulting in enhanced primary productivity, precipitation of the Kellwasser black shales and a remarkable positive C isotopic excursion in carbonate. Additionally, rapid climate cooling around the FF boundary has significantly threatened the ecological system and finally triggered mass extinction especially for the faunas adapted to warm temperatures.