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Phosphate coprecipitation affects reactivity of iron (oxyhydr)oxides towards dissolved iron and sulfide.

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Title: Phosphate coprecipitation affects reactivity of iron (oxyhydr)oxides towards dissolved iron and sulfide.
Authors: Kraal, Peter1,2 (AUTHOR) peter.kraal@nioz.nl, van Genuchten, Case M.2,3 (AUTHOR), Behrends, Thilo2 (AUTHOR)
Source: Geochimica et Cosmochimica Acta. Mar2022, Vol. 321, p311-328. 18p.
Subjects: Iron sulfides, Iron, Goethite, X-ray absorption, X-ray spectroscopy, Pollutants
Abstract: Iron (Fe) cycling exerts strong control on the mobility and bioavailability of the key nutrient phosphate (PO 4) in soils and sediments. Coprecipitation of PO 4 is known to alter the structure of Fe (oxyhydr)oxides (FeOx), however the environmental fate of PO 4 -bearing FeOx is not well-understood. Here, PO 4 -bearing FeOx with 9 mol% coprecipitated PO 4 were prepared by Fe(III) hydrolysis and Fe(II) oxidation in the presence of dissolved PO 4 , in addition to pure FeOx synthesized in PO 4 -free solutions. The pure and PO 4 -bearing FeOx were subsequently exposed to different concentrations of dissolved Fe(II) and sulfide (2 and 10 mmol L−1). Mineral transformations and the fate of PO 4 were tracked over 7–14 days with wet chemical techniques (including sequential Fe and S extraction) and synchrotron-based Fe K-edge X-ray absorption spectroscopy. Coprecipitation of PO 4 affected the rate and extent of FeOx transformation differently for Fe(II) and sulfide. Poorly-ordered PO 4 -bearing FeOx was preserved in the presence of dissolved Fe(II) while pure ferrihydrite was nearly completely transformed into goethite over 7 days. By contrast, coprecipitation of PO 4 rendered FeOx more reactive towards sulfide compared to pure FeOx. Reaction with dissolved sulfide resulted in the formation of non-sulfidized Fe(II) or Fe(II) sulfide under high and low Fe/sulfide ratio, respectively. Under low Fe/sulfide ratio, Fh and PO 4 -bearing, poorly-ordered FeOx were nearly completely sulfidized after 14 days. Sulfidation of FeOx led to efficient release of PO 4 into solution, and at low Fe/sulfide ratio more PO 4 was released than expected based on the extent of Fe sulfidation. The results suggest feedback mechanisms of environmental relevance: coprecipitation of strongly-sorbing species such as PO 4 disrupts FeOx structure, which affects FeOx reactivity and the overall nutrient or contaminant retention capacity of soils or sediments differently depending on the ambient redox conditions. Specifically, the switch from reducing to sulfidic conditions may be associated with the disproportionate release of nutrients and contaminants. [ABSTRACT FROM AUTHOR]
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Abstract:Iron (Fe) cycling exerts strong control on the mobility and bioavailability of the key nutrient phosphate (PO 4) in soils and sediments. Coprecipitation of PO 4 is known to alter the structure of Fe (oxyhydr)oxides (FeOx), however the environmental fate of PO 4 -bearing FeOx is not well-understood. Here, PO 4 -bearing FeOx with 9 mol% coprecipitated PO 4 were prepared by Fe(III) hydrolysis and Fe(II) oxidation in the presence of dissolved PO 4 , in addition to pure FeOx synthesized in PO 4 -free solutions. The pure and PO 4 -bearing FeOx were subsequently exposed to different concentrations of dissolved Fe(II) and sulfide (2 and 10 mmol L−1). Mineral transformations and the fate of PO 4 were tracked over 7–14 days with wet chemical techniques (including sequential Fe and S extraction) and synchrotron-based Fe K-edge X-ray absorption spectroscopy. Coprecipitation of PO 4 affected the rate and extent of FeOx transformation differently for Fe(II) and sulfide. Poorly-ordered PO 4 -bearing FeOx was preserved in the presence of dissolved Fe(II) while pure ferrihydrite was nearly completely transformed into goethite over 7 days. By contrast, coprecipitation of PO 4 rendered FeOx more reactive towards sulfide compared to pure FeOx. Reaction with dissolved sulfide resulted in the formation of non-sulfidized Fe(II) or Fe(II) sulfide under high and low Fe/sulfide ratio, respectively. Under low Fe/sulfide ratio, Fh and PO 4 -bearing, poorly-ordered FeOx were nearly completely sulfidized after 14 days. Sulfidation of FeOx led to efficient release of PO 4 into solution, and at low Fe/sulfide ratio more PO 4 was released than expected based on the extent of Fe sulfidation. The results suggest feedback mechanisms of environmental relevance: coprecipitation of strongly-sorbing species such as PO 4 disrupts FeOx structure, which affects FeOx reactivity and the overall nutrient or contaminant retention capacity of soils or sediments differently depending on the ambient redox conditions. Specifically, the switch from reducing to sulfidic conditions may be associated with the disproportionate release of nutrients and contaminants. [ABSTRACT FROM AUTHOR]
ISSN:00167037
DOI:10.1016/j.gca.2021.12.032