To better understand the role of reactive Fe (Fe R ) in the preservation of sedimentary organic carbon (SOC) in estuarine sediments, we examined specific surface area, grain size composition, total OC (TOC), lignin phenols, Fe R , Fe R -associated OC (Fe-OC) and lignin phenols (Fe-lignin), and δ 13 C of Fe R -associated OC (δ 13 C Fe-OC ) in surface sediments of the Changjiang Estuary and adjacent shelf. An estimated 7.4 ± 3.5% of the OC was directly bound with Fe R in the Changjiang Estuary and adjacent shelf. Unusually low TOC/specific surface area loadings and Fe-OC/Fe ratios in mobile muds suggest that frequent physical reworking may reduce Fe R binding with OC, with selective loss of marine OC. More depleted 13 C Fe-OC relative to 13 C of TOC ( 13 C bulk ) in deltaic regions and mobile muds showed that Fe R was largely associated with terrestrial OC, derived from extensive riverine OC and Fe inputs. A higher proportion of hematite in the mobile muds compared to the offshore samples indicated that Fe oxides are likely subjected to selective sorting and/or become mature during long-term sediment transport. When considering the percentage of Fe-OC to SOC and SOC burial rates in different marine environments (e.g., nondeltaic shelf, anoxic basins, slope, and deep sea), our findings suggest that about 15.6 ± 6.5% of SOC is directly bound to Fe R on a global scale, which is lower than the previous estimation (~21.5%). This work further supports the notion of a Rusty Sink where, in this case, Fe R plays an important role in the preservation and potential transport of terrestrial OC in the marine environment.
Reactive Fe(III) oxides in gravity-core sediments collected from the East China Sea inner shelf were quantified by using three selective extractions (acidic hydroxylamine, acidic oxalate, bicarbonate-citrate buffered sodium dithionite). Also the reactivity of Fe(III) oxides in the sediments was characterized by kinetic dissolution using ascorbic acid as reductant at pH 3.0 and 7.5 in combination with the reactive continuum model. Three parameters derived from the kinetic method: m
0 (theoretical initial amount of ascorbate-reducible Fe(III) oxides), k′ (rate constant) and γ (heterogeneity of reactivity), enable a quantitative characterization of Fe(III) oxide reactivity in a standardized way. Amorphous Fe(III) oxides quantified by acidic hydroxylamine extraction were quickly consumed in the uppermost layer during early diagenesis but were not depleted over the upper 100 cm depth. The total amounts of amorphous and poorly crystalline Fe(III) oxides are highly available for efficient buffering of dissolved sulfide. As indicated by the m
0, k′ and γ, the surface sediments always have the maximum content, reactivity and heterogeneity of reactive Fe(III) oxides, while the three parameters simultaneously downcore decrease, much more quickly in the upper layer than at depth. Albeit being within a small range (within one order of magnitude) of the initial rates among sediments at different depths, incongruent dissolution could result in huge discrepancies of the later dissolution rates due to differentiating heterogeneity, which cannot be revealed by selective extraction. A strong linear correlation of the m
0 at pH 3.0 with the dithionite-extractable Fe(III) suggests that the m
0 may represent Fe(III) oxide assemblages spanning amorphous and crystalline Fe(III) oxides. Maximum microbially available Fe(III) predicted by the m
0 at pH 7.5 may include both amorphous and a fraction of other less reactive Fe(III) phases.
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