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Adsorption of (Poly)vanadate onto Ferrihydrite and Hematite: An In Situ ATR–FTIR Study

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dc.contributor.authorVessey, Colton
dc.contributor.authorSchmidt, Michael P.
dc.contributor.authorAbdolahnezhad, Mojtaba
dc.contributor.authorPeak, Derek
dc.contributor.authorLindsay, Matthew B. J.
dc.date.accessioned2022-10-25T20:24:25Z
dc.date.available2022-10-25T20:24:25Z
dc.date.issued2020-03-25
dc.descriptionCopyright © 2020 American Chemical Societyen_US
dc.description.abstractVanadium (V) has been a useful trace metal in describing Earth’s biogeochemical cycling and development of industrial processes; however, V has recently been recognized as a potential contaminant of concern. Although Fe (oxyhydr)oxides are important sinks for aqueous V in soils and sediments, our understanding of adsorption mechanisms is currently limited to mononuclear species (i.e., HxVO4(3–x)–). Here we use in situ attenuated total reflectance – Fourier transform infrared spectroscopy to examine sorption mechanisms and capacity for (poly)vanadate attenuation by ferrihydrite and hematite from pH 3 to 6. Adsorption isotherms illustrate the low affinity of polyvanadate species for ferrihydrite surfaces compared to hematite. Mononuclear V species (i.e., [HxVO4](3−x)− and VO2+) were present at all experimental conditions. At low surface loadings and pH 5 and 6, H2VO4− adsorption onto ferrihydrite and hematite surfaces results from formation of inner sphere complexes. At [V]T above 250 µM, adsorbed polynuclear V species in this study include H2V2O72− and V4O124−. Whereas, HV10O286−, H3V10O285−, and NaHV10O284− are the predominant adsorbed species at pH 3 and 4 and elevated [V]T. Surface polymers were identified on hematite at all experimental pH values, whereas polymeric adsorption onto ferrihydrite was limited to pH 3 and 4. These results suggest that hematite offers a more suitable substrate for polymer complexation compared to ferrihydrite. Our results demonstrate the pH and concentration dependant removal of (poly)vanadate species by Fe(III) (oxyhydr)oxides, which has implications for understanding V mobility, behaviour, and fate in the environment.en_US
dc.description.sponsorshipFunding was provided by the Natural Sciences and Engineering Council of Canada (NSERC) through the Discovery Grants program (Grant no. RGPIN-2014-06589). Additional support awarded to C.J.V. was through the NSERC-Canada Graduate Scholarship-Master’s (NSERC CGS-M) Program. M.P.S. would like to acknowledge the Natural Sciences and Engineering Research Council Collaborative Research and Training Experience Sustainable Applied Fertilizer and Environmental Remediation (NSERC CREATE SAFER) program, as well as the NSERC Research and Development grant supported by Federated Cooperatives Limited for financial support.en_US
dc.description.versionPeer Revieweden_US
dc.identifier.citationVessey, C.J., Schmidt, M. P., Abdolahnezhad, M., Peak, D. & Lindsay, M. B. J. (2020). Adsorption of (Poly)vanadate onto Ferrihydrite and Hematite: An In Situ ATR–FTIR Study. ACS Earth and Space Chemistry, 4(4): 641–649. https://doi.org/10.1021/acsearthspacechem.0c00027en_US
dc.identifier.doi10.1021/acsearthspacechem.0c00027
dc.identifier.urihttps://hdl.handle.net/10388/14268
dc.language.isoenen_US
dc.publisherAmerican Chemical Society (ACS) Publicationsen_US
dc.subjectvanadiumen_US
dc.subjectpolymerizationen_US
dc.subjectferrihydriteen_US
dc.subjecthematiteen_US
dc.subjectadsorptionen_US
dc.subjectATR−FTIRen_US
dc.subjectsurface complexationen_US
dc.titleAdsorption of (Poly)vanadate onto Ferrihydrite and Hematite: An In Situ ATR–FTIR Studyen_US
dc.typeArticleen_US

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