title: Spectroscopic evidence for ternary complex formation between arsenate and ferric iron complexes of humic substances.
abstract: Formation of ternary complexes between arsenic (As) oxyanions and ferric iron (Fe) complexes of humic substances (HS) is often hypothesized to represent a major mechanism for As-HS interactions under oxic conditions. However, direct evidence for this potentially important binding mechanism is still lacking. To investigate the molecular-scale interaction between arsenate, As(V), and HS in the presence of Fe(III), we reacted fulvic and humic acids with Fe(III) (1 wt %) and equilibrated the Fe(III)-HS complexes formed with As(V) at pH 7 (molar Fe/As ~10). The local (<5 Å) coordination environments of As and Fe were subsequently studied by means of X-ray absorption spectroscopy. Our results show that 4.5-12.5 μmol As(V)/g HS (25-70% of total As) was associated with Fe(III). At least 70% of this As pool was bound to Fe(III)-HS complexes via inner-sphere complexation. Results obtained from shell fits of As K-edge extended X-ray absorption fine structure (EXAFS) spectra were consistent with a monodentate binuclear ((2)C) and monodentate mononuclear ((1)V) complex stabilized by H-bonds (R(As-Fe) = 3.30 Å). The analysis of Fe K-edge EXAFS spectra revealed that Fe in Fe(III)-HS complexes was predominantly present as oligomeric Fe(III) clusters at neutral pH. Shell-fit results complied with a structural motif in which three corner-sharing Fe(O,OH)(6) octahedra linked by a single μ(3)-O bridge form a planar Fe trimer. In these complexes, the average Fe-C and Fe-Fe bond distances were 2.95 Å and 3.47 Å, respectively. Our study provides the first spectroscopic evidence for ternary complex formation between As(V) and Fe(III)-HS complexes, suggesting that this binding mechanism is of fundamental importance for the cycling of oxyanions such as As(V) in organic-rich, oxic soils and sediments.
authors: Institute of Biogeochemistry and Pollutant Dynamics, Department of Environmental Sciences, ETH Zurich, 8092 Zurich, Switzerland. christian.mikutta@env.ethz.ch
authors: Christian
authors: C
authors: Mikutta
authors: Ruben
authors: R
authors: Kretzschmar
mesh_terms: D001149:Arsenates / Q000737:chemistry*; D001665:Binding Sites; D005290:Ferric Compounds / Q000737:chemistry*; D006812:Humic Substances / Q000032:analysis*; D008958:Models, Molecular; D056928:X-Ray Absorption Spectroscopy
chemical_list: D001149:Arsenates; D005290:Ferric Compounds; D006812:Humic Substances; C025657:arsenic acid