Insights into the origins, molecular characteristics and distribution of iron-binding ligands in the Arctic Ocean

Tatiana Williford*, Rainer M.W. Amon*, Ronald Benner, Karl Kaiser, Dorothea Bauch, Colin Stedmon, Ge Yan, Sally A. Walker, Michiel Rutgers van der Loeff, Maarten B. Klunder

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

Dissolved lignin phenols, chromophoric dissolved organic matter (DOM), and in situ fluorescence were determined in waters of the Laptev Sea and major Arctic basins, and they were compared with dissolved iron (dFe) distributions to elucidate the sources, molecular characteristics and distributions of iron-binding ligands in the Arctic Ocean. In the Transpolar Drift region (TPD), concentrations of dFe were positively correlated with concentrations of lignin phenols and multiple optical proxies of DOM composition and source. Strong relationships between dFe and visible and ultraviolet wavelength fluorescent DOM indicated that vascular plant and algal-derived DOM contributed to the dFe-ligand pool. These observations are consistent with previous studies suggesting the association of dFe with humic terrigenous and marine organic ligands. The primary sources of iron-binding ligands appear to be the riverine discharge of terrigenous DOM, marine organic matter produced on the shelves, and degradation products of plankton-derived organic matter in the shelf sediments. A stronger relationship between dFe and visible wavelength CDOM fluorescence than with lignin phenols suggested the presence of multiple terrigenous ligands, such as aromatic tannins. The aromatic nature of these terrigenous ligands was indicated by a strong relationship between dFe and the absorption coefficient at 254 nm. A strong negative correlation between the p-hydroxyl to vanillyl lignin phenols ratio and dissolved iron concentrations indicated recently-discharged terrigenous DOM (tDOM) was an important source of iron-binding ligands. Given the strong relationships of marine and terrigenous DOM with dissolved iron, iron-binding functional groups appear to occur in diverse molecules of multiple sources. Examples of such iron-binding functional groups included catechols and carboxylates found in lignins and tannins of terrigenous origins and carboxyl-rich alicyclic molecules (CRAM) of terrigenous and marine origins. The observed dFe distributions in the Arctic Ocean could not be explained by the presence of a single ligand type, but rather by a potpourri of ligand molecules of varying concentrations and binding strengths. This molecular diversity of ligands and associated binding strengths ultimately controls the distribution and transport of dFe in the Arctic Ocean and beyond.
Original languageEnglish
Article number103936
JournalMarine Chemistry
Volume231
Number of pages14
ISSN0304-4203
DOIs
Publication statusPublished - 2021

Keywords

  • Dissolved organic matter
  • Iron
  • Organic ligands
  • Complexation
  • Biomarkers
  • Optical properties
  • CDOM
  • Arctic ocean

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