Vanadate Retention by Iron and Manganese Oxides

Abernathy, Macon J.; Schaefer, Michael V.; Ramirez, Roxana; Garniwan, Abdi; Lee, Ilkeun; Zaera, Francisco; Polizzotto, Matthew L.; Ying, Samantha C.

doi:10.1021/acsearthspacechem.2c00116

Vanadate Retention by Iron and Manganese Oxides

Journal Article · Fri Aug 05 00:00:00 EDT 2022 · ACS Earth and Space Chemistry

DOI:https://doi.org/10.1021/acsearthspacechem.2c00116· OSTI ID:2471712

Abernathy, Macon J. ^[1]; Schaefer, Michael V. ^[2]; Ramirez, Roxana ^[3]; Garniwan, Abdi ^[3]; Lee, Ilkeun ^[3]; ^[3]; Polizzotto, Matthew L. ^[4]; ^[3]

SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
New Mexico Institute of Mining and Technology, Socorro, NM (United States)
University of California-Riverside, CA (United States)
University of Oregon, Eugene, OR (United States)

Anthropogenic emissions of vanadium (V) into terrestrial and aquatic surface systems now match those of geogenic processes, and yet, the geochemistry of vanadium is poorly described in comparison to other comparable contaminants like arsenic. In oxic systems, V is present as an oxyanion with a +5 formal charge on the V center, typically described as H_xVO₄^(3–x)–, but also here as V(V). Iron (Fe) and manganese (Mn) (oxy)hydroxides represent key mineral phases in the cycling of V(V) at the solid–solution interface, and yet, fundamental descriptions of these surface-processes are not available. Here, we utilize extended X-ray absorption fine structure (EXAFS) and thermodynamic calculations to compare the surface complexation of V(V) by the common Fe and Mn mineral phases ferrihydrite, hematite, goethite, birnessite, and pyrolusite at pH 7. Inner-sphere V(V) complexes were detected on all phases, with mononuclear V(V) species dominating the adsorbed species distribution. Our results demonstrate that V(V) adsorption is exergonic for a variety of surfaces with differing amounts of terminal –OH groups and metal–O bond saturations, implicating the conjunctive role of varied mineral surfaces in controlling the mobility and fate of V(V) in terrestrial and aquatic systems.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 2471712

Journal Information:: ACS Earth and Space Chemistry, Journal Name: ACS Earth and Space Chemistry Journal Issue: 8 Vol. 6; ISSN 2472-3452

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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