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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]
Copyright of Geochimica et Cosmochimica Acta is the property of Pergamon Press - An Imprint of Elsevier Science and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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DbLabel: Engineering Source
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Items – Name: Title
  Label: Title
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  Data: Phosphate coprecipitation affects reactivity of iron (oxyhydr)oxides towards dissolved iron and sulfide.
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  Data: <searchLink fieldCode="AR" term="%22Kraal%2C+Peter%22">Kraal, Peter</searchLink><relatesTo>1,2</relatesTo> (AUTHOR)<i> peter.kraal@nioz.nl</i><br /><searchLink fieldCode="AR" term="%22van+Genuchten%2C+Case+M%2E%22">van Genuchten, Case M.</searchLink><relatesTo>2,3</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Behrends%2C+Thilo%22">Behrends, Thilo</searchLink><relatesTo>2</relatesTo> (AUTHOR)
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  Data: <searchLink fieldCode="JN" term="%22Geochimica+et+Cosmochimica+Acta%22">Geochimica et Cosmochimica Acta</searchLink>. Mar2022, Vol. 321, p311-328. 18p.
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  Data: <searchLink fieldCode="DE" term="%22Iron+sulfides%22">Iron sulfides</searchLink><br /><searchLink fieldCode="DE" term="%22Iron%22">Iron</searchLink><br /><searchLink fieldCode="DE" term="%22Goethite%22">Goethite</searchLink><br /><searchLink fieldCode="DE" term="%22X-ray+absorption%22">X-ray absorption</searchLink><br /><searchLink fieldCode="DE" term="%22X-ray+spectroscopy%22">X-ray spectroscopy</searchLink><br /><searchLink fieldCode="DE" term="%22Pollutants%22">Pollutants</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: 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]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Geochimica et Cosmochimica Acta is the property of Pergamon Press - An Imprint of Elsevier Science and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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RecordInfo BibRecord:
  BibEntity:
    Identifiers:
      – Type: doi
        Value: 10.1016/j.gca.2021.12.032
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      – Code: eng
        Text: English
    PhysicalDescription:
      Pagination:
        PageCount: 18
        StartPage: 311
    Subjects:
      – SubjectFull: Iron sulfides
        Type: general
      – SubjectFull: Iron
        Type: general
      – SubjectFull: Goethite
        Type: general
      – SubjectFull: X-ray absorption
        Type: general
      – SubjectFull: X-ray spectroscopy
        Type: general
      – SubjectFull: Pollutants
        Type: general
    Titles:
      – TitleFull: Phosphate coprecipitation affects reactivity of iron (oxyhydr)oxides towards dissolved iron and sulfide.
        Type: main
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      – PersonEntity:
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            NameFull: Kraal, Peter
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            NameFull: van Genuchten, Case M.
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            NameFull: Behrends, Thilo
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            – D: 15
              M: 03
              Text: Mar2022
              Type: published
              Y: 2022
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              Value: 321
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