Spatial distribution of organic and pyritic sulfur in surface sediments of eutrophic Jiaozhou Bay, China: clues to anthropogenic impacts.

Anthropogenic perturbations exert important impacts on sulfur geochemistry in marine sediments. In the study, chemical extraction was used to quantify four sulfur pools, i.e., pyrite, humic-acid sulfur (HA-S), fulvic-acid sulfur (FA-S), and residual organic sulfur (ROS), in surface sediments of eutrophic Jiaozhou Bay. Results show that riverine inputs are the main control on organic matter (OM) distribution in the sediments. OM enrichment in the eastern coast is mainly due to discharges of anthropogenic wastes. Spatial coupling of pyrite and FA-S vs. TOC points to the impacts of OM enrichment on formation and preservation of pyrite and FA-S. Poor spatial coupling of HA-S vs. TOC is due to low fractions of diagenetic OS in the pool. ROS is mainly from riverine inputs and anthropogenic OS has been superimposed on this pool. Spatial coupling among TOC, pyrite-S and FA-S is a sensitive indicator of anthropogenic impacts on benthic processes of the bay.

Reductive reactivity of iron(III) oxides in the east china sea sediments: characterization by selective extraction and kinetic dissolution.

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.