Geochemistry of iron and sulfur in the Holocene marine sediments under contrasting depositional settings, with caveats for applications of paleoredox proxies

Abstract

Cycling and fates of iron (Fe) and sulfur (S) in marine sediments are influenced by depositional settings to differential extents. The information is crucial for addressing the responses of their benthic diagenesis to changing climates and environments and also for reconstructing paleo-depositional conditions, but has not been well constrained. Detailed chemical speciation was utilized to characterize geochemistry of Fe and S, and then to reveal the impacts of depositional settings on their diagenesis at three locations, representing contrasting depositional environments: (i) highly dynamic Yangtze River estuary (YRE), (ii) the depocenter of South Yellow Sea (SYS), which is only remotely impacted by large river, and (iii) the middle Okinawa trough (OT), a back-arc deep basin along the outer edge of the East China Sea (ECS) slope. Results show that the YRE sediments favor accumulation of total highly reactive Fe (FeHR), while the SYS sediments are poor in FeHR due to low FeHR in their source material and/or preferential trapping of FeHR during sediment transport through the semi-enclosed Bohai Sea. Ferruginous sediment regimes in the highly dynamic YRE system facilitate Fe(III) reduction and burial of unsulfidized Fe(II), while the SYS and OT sediments favor sulfate reduction and pyritization of Fe(II). Pyrite is always the main sink of reduced S that escapes reoxidation in the entire continental margin, regardless of depositional environments. Abundant reactive Fe(III) but low total reduced inorganic sulfide (TRIS) contents in the three sites suggest that TRIS burial is largely controlled by the availability of degradable OC and/or dynamic regimes of sediments. The applicability of two widely used Fe- and S-based proxies to distinguish bottom-water conditions, that is, OC/TRIS ratio and FeHR to total Fe (FeHR/FeT) ratio, were examined in the three contrasting environments, and caveats were given for future applications of the two proxies.