Perturbation of the marine nitrogen cycle during the Late Ordovician glaciation and mass extinction

• δ15N of bulk and organic nitrogen during the O–S transition at two sections in South China were analyzed.
• δ15N underwent significant positive shift during the Hirnantian glaciation.
• Nitrogen fixation was the main source of marine biologically available nitrogen pre- and post Hirnantian glaciation.
• Denitrification decreased during the Hirnantian glaciation.
• Perturbations of nitrogen cycle might contribute to the wax and wane of the Hirnantian glaciation.

The Late Ordovician was a critical interval in geologic history, during which both the biosphere and marine environments underwent severe perturbations, including one of the ‘Big Five’ Phanerozoic mass extinctions and the massive but short-term (~ 0.5-Myr) Hirnantian glaciation. The onset and termination of the Hirnantian glaciation have been widely accepted as the triggers for the two extinction pulses that comprise the Late Ordovician biocrisis, but the mechanisms that caused the Hirnantian glaciation itself remain poorly known. Here, we analyze the nitrogen isotope composition (δ15N) of two sections in South China (Wangjiawan and Nanbazi) in order to better understand nitrogen cycle perturbations in the Late Ordovician ocean and their relationship to contemporaneous climatic and biogeochemical changes. Low δ15N (~ 1‰) in the upper Katian and lower Rhuddanian of both sections suggests intensive (i.e., near-quantitative) denitrification and, thus, nitrogen fixation as the main source of biologically available nitrogen for primary producers. A positive δ15N excursion in both sections during the Hirnantian indicates weaker (i.e., non-quantitative) denitrification, possibly as a result of more vigorous thermohaline circulation and improved ocean ventilation. Weaker denitrification would have reduced the flux of N2O, an intermediate product of denitrification, to the atmosphere. N2O is a potent greenhouse gas, and a major decline in its production would have led to cooler climatic conditions and, ultimately, the Hirnantian glaciation. A global survey of published nitrogen isotope records suggests that similar processes operated broadly within the Late Ordovician global ocean.