Increased Oxygenation of the Oceans Since the Mid-Cenozoic as Constrained by Cr/Co and Os/Ir Ratios in Oxic Pelagic Sediments

In terms of redox, the marine sediments can be roughly divided into anoxic to suboxic sediments on the margins and oxic sediments in pelagic (open ocean) environments. The relative amounts of anoxic/suboxic sediments being deposited at any given time could be related to biological productivity and/or the efficiency of the ocean circulation system. How the depositional area of anoxic/suboxic deposition has changed through time is thus of concern. One way to track redox conditions is to investigate variations in the concentrations of redox sensitive trace metals. Most studies along these lines have focused on anoxic sediments. However, one problem with using anoxic sediments to study the global oceans is that such sediments are typically deposited in somewhat isolated basins, whose redox conditions may vary from basin to basin. An alternative approach, taken here, is to examine redox-sensitive elemental ratios in oxic pelagic sediments. This is motivated by the fact that pelagic sediments are more likely to reflect average ocean chemistry. In addition, the redox-sensitive metal contents of oxic sediments represent the complement to anoxic sediments. Choosing an appropriate redox-sensitive elemental ratio which eliminates dilution/concentration effects, requires the identification of trace metals that are preferentially precipitated in oxic conditions and those precipitated in more reducing conditions. Overall elemental behaviors were estimated by comparing hydrogenous or authigenic burial fluxes of various trace metals at given pelagic ODP sites to global riverine input fluxes. If the pelagic burial fluxes of a given element are significantly smaller than the riverine input flux, other burial outputs are implied, and it is hypothesized here that this element may precipitate in reducing conditions, such as in oceanic margin. If, on the other hand, the pelagic burial flux is equal to or greater than the riverine input flux, the implication is that oxic pelagic sediments must account for a significant proportion of the burial output of that element. In this case, we assume that this element is oxic-loving. Results of this work reveal that V, Cr, and Co may be particularly redox-sensitive: V and Cr precipitate in reducing environments while Co precipitates in more oxidizing environments. Results of our study, combined with existing data from the literature, show that Cr/Co ratios decrease with depth in DSDP596, 39, 801A, 319, 321, 465A, 577 in the N and S Pacific. After correcting for sedimentation rate, it is shown that the variation of Cr/Co versus time in all of these cores converge, which suggests that the variations in Cr/Co reflect a true variation in seawater composition. This also supported by the lack of sedimentation constrained by Cr/Co and Ce flux. Cr/Co remains low during the Cretaceous but begins to rise at ~25Ma across the entire Pacific. If the Cr/Co and Os/Ir ratio of inputs to the ocean have not changed much, this trend also matches that Os/Ir in the DSDP 596 site in the south Pacific. One interpretation of these results is that there has been a decrease in the area of anoxic/suboxic sedimentation beginning at this time. If correct, the implication is that there was a fundamental change in the redox conditions of the ocean in the mid-Cenozoic. We speculate that this might have been related to mid-Cenozoic global cooling, which may have increased the efficiency of the oceanic circulation system.