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Influence of contrasting redox conditions on iron (oxyhydr)oxide transformation and associated phosphate sorption

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Abstract

Iron (oxyhydr)oxides strongly adsorb phosphate and limit its bioavailability, but interactions between phosphate and various Fe (oxyhydr)oxides are poorly constrained in natural systems. An in-situ incubation experiment was conducted to explore Fe (oxyhydr)oxide transformation and effects on phosphate sorption in soils with contrasting saturation and redox conditions. Synthetic Fe (oxyhydr)oxides (ferrihydrite, goethite and hematite) were coated onto quartz sand and either pre-sorbed with phosphate or left phosphate-free. The oxide-coated sands were mixed with natural organic matter, enclosed in mesh bags, and buried in and around a vernal pond for up to 12 weeks. Redox conditions were stable and oxic in the upland soils surrounding the vernal pond but largely shifted from Fe reducing to Fe oxidizing in the lowland soils within the vernal pond as it dried during the summer. Iron (oxyhydr)oxides lost more Fe (− 41% ± 10%) and P (− 43 ± 11%) when incubated in the redox-dynamic lowlands compared to the uplands (− 18% ± 5% Fe and − 24 ± 8% P). Averaged across both uplands and lowlands, Fe losses from crystalline goethite and hematite (− 38% ± 6%) were unexpectedly higher than losses from short range ordered ferrihydrite (− 12% ± 10%). We attribute losses of Fe and associated P from goethite and hematite to colloid detachment and dispersion but losses from ferrihydrite to reductive dissolution. Iron losses were partially offset by retention of solubilized Fe as organic-bound Fe(III). Iron (oxyhydr)oxides that persisted during the incubation retained or even gained P, indicating low amounts of phosphate sorption from solution. These results demonstrate that hydrologic variability and Fe (oxyhydr)oxide mineralogy impact Fe mobilization pathways that may regulate phosphate bioavailability.

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Acknowledgements

We would like to thank Shannon Joseph for field and lab work assistance, as well as Lindsey Yazbek, Raihan Chowdhury, and Mallory Klein for help with mesh bag assembly.

Funding

This work was supported by grants from the National Science Foundation (EAR-1609027 and OPP-2006194) and the Kent State Environmental Science and Design Research Initiative to Herndon and Kinsman-Costello. Portions of this work were performed at GeoSoilEnviroCARS (Sector 13) and 12-BMB (Sector 12), Advanced Photon Source (APS), Argonne National Laboratory. GeoSoilEnviroCARS is supported by the National Science Foundation – Earth Sciences (EAR-1128799) and Department of Energy – GeoSciences (DE-FG02-94ER14466). Use of the Advanced Photon Source was supported by the U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.

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Authors and Affiliations

  1. Department of Earth Sciences, Kent State University, Kent, OH, USA

    Maximilian Barczok, Nicolle Di Domenico & David Singer

  2. Department of Biological Sciences, Kent State University, Kent, OH, USA

    Chelsea Smith & Lauren Kinsman-Costello

  3. Earth and Planetary Sciences, The University of Tennessee Knoxville, Knoxville, TN, USA

    Elizabeth Herndon

  4. Environmental Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN, USA

    Elizabeth Herndon

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  1. Maximilian Barczok
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  2. Chelsea Smith
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Contributions

MB developed methodologies, conducted the experiments, performed data analyses, and wrote the manuscript. CS and ND contributed to conceptualization, methodology, and experimentation. LKC contributed to conceptualization, funding acquisition, and review and editing of the manuscript. DS contributed to project supervision and review and editing of the manuscript. EH provided funding, supervised the project, and contributed to conceptualization, methodology, and writing.

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Correspondence to Elizabeth Herndon.

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Barczok, M., Smith, C., Di Domenico, N. et al. Influence of contrasting redox conditions on iron (oxyhydr)oxide transformation and associated phosphate sorption. Biogeochemistry 166, 87–107 (2023). https://doi.org/10.1007/s10533-023-01094-z

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