Diagenesis and iron paleo-redox proxies: New perspectives from magnetic and iron speciation analyses in the Santa Barbara Basin

Abstract

Sedimentary redox proxies are usually employed to reconstruct the paleo-redox conditions of bottom water environments, assuming that porewater and bottom water dissolved oxygen concentrations are similar. Using a combination of geochemical and magnetic techniques, we investigate the relationship between iron speciation and mineralogy in recent (~1760–2009 CE) sediments retrieved from the Santa Barbara Basin (SBB) – a modern silled basin with low-oxygen (dissolved O2 < 10 μmol/kg) and sporadically anoxic (no O2 detected) bottom waters. Magnetic analyses reveal that biogenic magnetite is preserved in SBB sulfidic porewaters on at least decadal to centennial time scales. Highly-reactive Fe (oxyhydr)oxides remain preserved despite observed sulfidic porewaters, indicating incomplete pyrite conversion, and producing low Fepy [pyrite Fe]/FeHR ratios. We attribute this observation to restricted porewater reaction kinetics under high sedimentation rates. Our results also reveal non-steady state diagenesis caused by instantaneous depositional events (e.g., turbidites and flood layers). The most reducing water column suggested by Fe speciation coincided with the Macoma layer, where in situ colonization of hypoxia-intolerant bivalve shells argues for the most oxygenated bottom water in the 250 year record. A turbidite potentially introduced fresh unsulfidized FeHR that buffered upward-diffusing sulfide from underlying sediments. Subsequent pyrite precipitation following re-establishment of sulfidic porewaters could have facilitated a “false positive” interpretation. In comparison, redox-sensitive metal enrichments (MoEF, UEF, and ReEF) were not obscured by post-depositional diagenesis and appear to accurately record redox geochemistry at the sediment-water interface.