Trace metal evolution of the Late Cretaceous Ocean

The Cenomanian-Turonian boundary (Late Cretaceous) witnessed the last spectacular manifestation of Mesozoic Anoxic Events (OAE 2, $\sim$94 Ma), marked by a prominent carbon isotope excursion (CIE) and burial of organic-matter-rich sediments under high atmospheric CO₂ concentrations. But the Late Cretaceous generally was a time of profound environmental change. OAE 2 was preceded by other CIEs, including the Mid-Cenomanian Event (MCE), and was punctuated by a short re‑oxygenation and cooling event (the Plenus Cold Event, PCE). Extensive previous studies, including many trace metal studies, have focused on OAE 2, but there is still debate concerning the degree of drawdown of oceanic trace metal reservoirs during OAE 2, whether this drawdown is global or local, its causes and consequences for ocean ecology. Here, we present records of eight trace metals, over about 5 Myr of the Late Cretaceous, from the Tarfaya Basin in the proto-North Atlantic. The long records from a core preserving a continuous sedimentary succession allow us to set changes occurring across OAE 2 in the broader context of Late Cretaceous, including the lead up to OAE 2. Moreover, the multiple trace metal dataset allows us to broadly investigate the oceanographic setting in the context of recent studies of multiple trace metals in modern organic-rich sediments aimed at refining the proxies.

Trace metal enrichments in these organic-rich sediments are discussed on three different timescales. Firstly, comparison of these Late Cretaceous sediments with modern organic-rich sediments are consistent with deposition in an open ocean upwelling margin in the Late Cretaceous, very like the modern Peru or Namibian Margin, although the deep proto-North Atlantic was probably partially restricted. Secondly, in common with previous studies, metal/TOC ratios often show sharp drops in the early part of OAE 2. Thirdly, however, this sharp drop occurs within a framework of pseudo-cyclical variations in metal/TOC, with a period of about 143 $\pm$19 kyr (1 SD), that is a feature of these long records well before OAE 2, including across the MCE. Different metals respond differently to the perturbation in the early part of OAE 2 itself. Simple mass balance considerations suggest that trace metal drawdown with organic carbon must be at least partially compensated by changes in the rate of chemical weathering on the continents, as previously inferred from Li and Ca isotopes. Moreover, changes in the patterns of variation between different metals, as well as covariation of metal/TOC ratios and Os isotopes, hint at changes in the pattern of chemical weathering, most prominently in the contribution of mafic rocks to the chemical weathering flux.