Complexation and Redox Buffering of Iron(II) by Dissolved Organic Matter

Daugherty, Ellen E.; Gilbert, Benjamin; Nico, Peter S.; Borch, Thomas

doi:10.1021/acs.est.7b03152

Complexation and Redox Buffering of Iron(II) by Dissolved Organic Matter

Journal Article · Wed Aug 30 00:00:00 EDT 2017 · Environmental Science and Technology

DOI:https://doi.org/10.1021/acs.est.7b03152· OSTI ID:1476552

Daugherty, Ellen E. ^[1]; ^[2]; Nico, Peter S. ^[2]; ^[3]

Colorado State Univ., Fort Collins, CO (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Colorado State Univ., Fort Collins, CO (United States); Dept. of Soil and Crop Sciences, Fort Collins, CO (United States)

Iron (Fe) bioavailability depends upon its solubility and oxidation state, which are strongly influenced by complexation with natural organic matter (NOM). Despite observations of Fe(II)-NOM associations under conditions favorable for Fe oxidation, the molecular mechanisms by which NOM influences Fe(II) oxidation remain poorly understood. In this study, we used X-ray absorption spectroscopy to determine the coordination environment of Fe(II) associated with NOM (as-received and chemically reduced) at pH 7, and investigated the effect of NOM complexation on Fe(II) redox stability. Linear combination fitting of extended X-ray absorption fine structure (EXAFS) data using reference organic ligands demonstrated that Fe(II) was complexed primarily by carboxyl functional groups in reduced NOM. Functional groups more likely to preserve Fe(II) represent much smaller fractions of NOM-bound Fe(II). Fe(II) added to anoxic solutions of as-received NOM oxidized to Fe(III) and remained organically complexed. Iron oxidation experiments revealed that the presence of reduced NOM limited Fe(II) oxidation, with over 50% of initial Fe(II) remaining after 4 h. Furthermore, these results suggest reduced NOM may preserve Fe(II) by functioning both as redox buffer and complexant, which may help explain the presence of Fe(II) in oxic circumneutral waters.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1476552

Journal Information:: Environmental Science and Technology, Journal Name: Environmental Science and Technology Journal Issue: 19 Vol. 51; ISSN 0013-936X

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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