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Dissolved sulfide, iron (Fe), and phosphorus (P) concentrations in sediments of the East China Sea were simultaneously measured in situ by diffusive gradients in thin films (DGT) technique. The results, by combination with solid-phase Fe speciation, were used to characterize the interplays of Fe, S and P. Diverse distributions of dissolved sulfide among the sites are attributable to highly dynamic diagenetic regimes and varying availability of labile organic carbon (OC). The DGT technique provided high-resolution evidence for coexistence of microbial iron reduction (MIR) and sulfate reduction in localized zones, and for Fe-coupled P mobilization. Measured Fe 2 + /P ratios suggest that Fe 2 + reoxidatiion at the oxic zones can serve as an efficient scavenger of P. Empirical estimation indicates that MIR plays an important role in anaerobic OC mineralization in the sediments, which is a combined result of low availability of labile OC, high reactive Fe content, and unsteady diagenetic regimes. [ABSTRACT FROM AUTHOR]

In marine sediments factors that influence iron (Fe) geochemistry and its interactions with other elements are diverse and remain poorly understood. Here we comparatively study Fe speciation and reactive Fe-bound organic carbon (Fe-OC) in surface sediments of the East China Sea (ECS) and the south Yellow Sea (SYS). The objectives are to better understand the potential impacts of geochemically distinct sediment sources and depositional/diagenetic settings on Fe geochemistry and OC preservation by Fe (hydr)oxides in sediments of the two extensive shelf seas around the world. Contents of carbonate- and acid-volatile-sulfide (AVS)-associated Fe(II) (Fe AVS + carb ) and magnetite (Fe mag ) in the ECS sediments are about 5 and 9 times higher, respectively, than in the SYS. This could be ascribed to the ferruginous conditions of the ECS sediments that favor the formation/accumulation of Fe carb and Fe mag , a unique feature of marine unsteady depositional regimes. Much lower total Fe(II) contents in the SYS than in the ECS suggest that lower availability of highly reactive Fe (Fe HR ) and/or weak Fe reduction is a factor limiting Fe(II) formation and accumulation in the SYS sediments. The ratio of Fe HR to total Fe is, on average, markedly higher (2.4 times) in the ECS sediments than in the SYS, which may be a combined result of several factors relevant to different sediment sources and depositional/diagenetic settings. In comparison with many other marine sediments, the percent fractions ( f Fe-OC ) of Fe-OC to total organic carbon (TOC) in the ECS and the SYS are low, which can be ascribed to surface adsorption of OC rather than coprecipitation or organic complexation as the dominant binding mechanisms. Based on the f Fe-OC in this study, total Fe-OC estimated for global continental shelves is equivalent to 38% of the atmospheric CO 2 pool, which indicates the important role of sorptive stabilization of Fe-OC in continental shelf sediments for buffering CO 2 release to the atmosphere. In the SYS, consistently less 13 C-depleted Fe-OC relative to 13 C of non-Fe-bound OC ( 13 C non-Fe-OC ) suggests selective sequestration of labile marine OC in the marine OC-dominated sediments of the central SYS. In the ECS, however, efficient oxidation of OC and frequent redox cycling of Fe in the unsteady depositional regimes may complicate the isotopic compositions of Fe-OC. A combination of our results and literature data demonstrates that Fe-OC contents are strongly dependent on the availability of TOC and reactive Fe, but the f Fe-OC is primarily controlled by the processes of Fe redox cycling in the sediments. [ABSTRACT FROM AUTHOR]

Highlights: [•] Reactivity of Fe oxides was quantified by the reactive continuum model. [•] Factors influencing Fe oxide reactivity and its variation were documented. [•] Spatial pattern of reactive Fe oxides is generally controlled by clay fraction. [•] Redox cycles caused a decrease in amount and reactivity of reactive Fe oxides. [Copyright &y& Elsevier]

Abstract: Speciation and reactivity characterization of solid-phase Fe in marine sediments are of significance to understanding its heterogeneous mineralogy and crystallinity, the diagenetic cycling of Fe and its regulating roles on many other elements in sediments. In this study, a combination of sequential and single-step extractions was used for the determination of seven Fe pools in surface sediments of the East China Sea (ECS) continental shelf: (1) carbonate associated Fe (Fe(II)carb) plus acid volatile sulfide-Fe (Fe(II)AVS), (2) easily reducible amorphous/poorly crystalline Fe oxides (Feox1), (3) reducible crystalline Fe oxides (Feox2), (4) magnetite (Femag), (5) poorly reactive sheet silicate Fe (FePRS), (6) pyrite-Fe (Fepy), and (7) unreactive silicate Fe (FeU). Total Fe (FeT) in the sediments is largely determined by terrestrial aluminosilicate particles as indicated by a great similarity of the FeT with that of the Yangtze River and global riverine particulates. The size of FePRS is found to be the largest pool, followed by FeU, Feox2, Femag, Fe(II)AVS+carb, Feox1 and Fepy. The large FePRS may result from neoformation of Fe-rich clay minerals via reverse weathering and subsequent ageing. The small sizes of Fe(II)AVS+carb and Fepy pools is believed to be the result of low SO4 reduction due to generally low labile organic matter together with the oxic/suboxic, dynamic environments of the surface sediments. The occurrence of Feox1, Feox2 and FePRS in the sediments is closely associated with the clay fraction as indicated by a high spatial correlation between the former and the latter. Highly reactive Fe(FeHR) in the sediments is comparable to that in global marine sediments, but apparently lower than in the Yangtze River and global riverine particulates due probably to sequestration in the Yangtze Estuary. The ratios of FeHR/FeT, FePR/FeT and FeU/FeT in the ECS surface sediments consistently show more similarity to those in the Yangtze River particulates than in the global continental margin or deep-sea sediments. The surface sediments maintain a high level of buffering capacity toward sulfidation suggested by a large fraction of highly reactive Fe(III) oxides (Fe(III)HR) in FeHR. [Copyright &y& Elsevier]