Oxygen minimum zone-type biogeochemical cycling in the Cenomanian-Turonian Proto-North Atlantic across Oceanic Anoxic Event 2

Oceanic Anoxic Events (OAEs) in Earth's history are regarded as analogues for current and future ocean deoxygenation, potentially providing information on its pacing and internal dynamics. In order to predict the Earth system's response to changes in greenhouse gas concentrations and radiative forcing, a sound understanding of how biogeochemical cycling differs in modern and ancient marine environments is required. Here, we report proxy records for iron (Fe), sulfur and nitrogen cycling in the Tarfaya upwelling system in the Cretaceous Proto-North Atlantic before, during and after OAE2 (similar to 93 Ma). We apply a novel quantitative approach to sedimentary Fe speciation, which takes into account the influence of terrigenous weathering and sedimentation as well as authigenic Fe (non-terrigenous, precipitated onsite) rain rates on Fe-based paleo-redox proxies. Generally elevated ratios of reactive Fe (i.e., bound to oxide, carbonate and sulfide minerals) to total Fe (Fe-HR/Fe-T) throughout the 5 million year record are attributed to transport-limited chemical weathering under greenhouse climate conditions. Trace metal and nitrogen isotope systematics indicate a step-wise transition from oxic to nitrogenous to euxinic conditions over several million years prior to OAE2. Taking into consideration the low terrigenous sedimentation rates in the Tarfaya Basin, we demonstrate that highly elevated Fe-HR/Fe-T from the mid-Cenomanian through OAE2 were generated with a relatively small flux of additional authigenic Fe. Evaluation of mass accumulation rates of reactive Fe in conjunction with the extent of pyritization of reactive Fe reveals that authigenic Fe and sulfide precipitation rates in the Tarfaya Basin were similar to those in modern upwelling systems. Because of a smaller seawater nitrate inventory, however, chemolithoautotrophic sulfide oxidation with nitrate was less efficient in preventing hydrogen sulfide release into the water column. As terrigenous weathering and sediment flux determine how much authigenic Fe is required to generate an anoxic euxinic or ferruginous proxy signature, we emphasize that both have to be taken into account when interpreting Fe-based paleo-redox proxies. (C) 2019 Elsevier B.V. All rights reserved.