Characterization of iron diagenesis in marine sediments using refined iron speciation and quantized iron(III)-oxide reactivity: a case study in the Jiaozhou Bay, China

Abstract

As a case study, refined iron (Fe) speciation and quantitative characterization of the reductive reactivity of Fe (III) oxides are combined to investigate Fe diagenetic processes in a core sediment from the eutrophic Jiaozhou Bay. The results show that a combination of the two methods can trace Fe transformation in more detail and offer nuanced information on Fe diagenesis from multiple perspectives. This methodology may be used to enhance our understanding of the complex biogeochemical cycling of Fe and sulfur in other studies. Microbial iron reduction (MIR) plays an important role in Fe(III) reduction over the upper sediments, while a chemical reduction by reaction with dissolved sulfide is the main process at a deeper (> 12 cm) layer. The most bioavailable amorphous Fe(III) oxides [Fe(III)am] are the main source of the MIR, followed by poorly crystalline Fe(III) oxides [Fe(III)pc)] and magnetite. Well crystalline Fe(III) oxides [Fe (III)wc] have barely participated in Fe diagenesis. The importance of the MIR over the upper layer may be a combined result of the high availability of highly reactive Fe oxides and low availability of labile organic matter, and the latter is also the ultimate factor limiting sulfate reduction and sulfide accumulation in the sediments. Microbially reducible Fe(III) [MR-Fe(III)], which is quantified by kinetics of Fe(II)-oxide reduction, mainly consists of the most reactive Fe(III)am and less reactive Fe(III)pc. The bulk reactivity of the MR-Fe(III) pool is equivalent to aged ferrihydrite, and shows down-core decrease due to preferential reduction of highly reactive phases of Fe oxides.