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

PLoS One. 2013 Nov 15;8(11):e80367. doi: 10.1371/journal.pone.0080367. eCollection 2013.

Abstract

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.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • China
  • Environmental Monitoring / methods
  • Ferric Compounds / chemistry*
  • Geologic Sediments / chemistry*
  • Hydrogen-Ion Concentration
  • Iron / chemistry*
  • Kinetics
  • Oxides / chemistry*
  • Solubility
  • Water Pollutants, Chemical / chemistry*

Substances

  • Ferric Compounds
  • Oxides
  • Water Pollutants, Chemical
  • Iron

Grants and funding

This research was financially supported by the Natural Science Foundation of China (grant No. 41076045, and 41030858), the Shandong Province Natural Science Foundation (grant No. ZR2011DM003), and the Taishan Scholars Programme of Shandong Province. The funders had no role in study design, data collection and analysis, decision to publish, or preparation of the manuscript.