<p>Iron(III) (oxyhydr)oxides are the major sink for PO<sub>4</sub><sup>3−</sup> in freshwater sediments, helping to control the onset of eutrophic conditions when PO<sub>4</sub><sup>3−</sup> is in excess; however, this sink is transient as ferrous iron and PO<sub>4</sub><sup>3−</sup> are typically released when sediments become anoxic, triggering a self-sustaining reversible cycle as sediments become an internal source of phosphate. Ferrous iron can then react with dissolved sulfides to form iron sulfide minerals such as mackinawite (FeS), whose interactions with PO<sub>4</sub><sup>3−</sup> remain largely unexplored. We investigate the role of FeS in the sequestration of PO<sub>4</sub><sup>3−</sup> under anoxic conditions, with or without natural organic carbon (OC). We show that Fes has a high affinity for PO<sub>4</sub><sup>3−</sup>, with a maximum sorption capacity comparable to moderately crystalline FeO<sub>x</sub> minerals. The presence of sorbed OC decreases the FeS affinity toward the PO<sub>4</sub><sup>3−</sup> by ~ 75%, which is attributed to the lower surface area of FeS-OC compared to FeS, electrostatic repulsion, and the reduced accessibility to reactive Fe(II) sites. Moreover, we show that upon exposure of FeS to oxic conditions, PO<sub>4</sub><sup>3−</sup> is efficiently recaptured by the FeS oxidation products (FeOx), hence highlighting a parallel self-sustaining reversible cycle resulting in the permanent sequestration of a small fraction of PO<sub>4</sub><sup>3−</sup>. Overall, these findings highlight FeS as a potentially important phosphate sink in anoxic freshwater sediments.</p>

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Phosphate immobilization by mackinawite in freshwater sediments and the competitive role of organic carbon

  • Milad Ezzati,
  • Yves Gélinas

摘要

Iron(III) (oxyhydr)oxides are the major sink for PO43− in freshwater sediments, helping to control the onset of eutrophic conditions when PO43− is in excess; however, this sink is transient as ferrous iron and PO43− are typically released when sediments become anoxic, triggering a self-sustaining reversible cycle as sediments become an internal source of phosphate. Ferrous iron can then react with dissolved sulfides to form iron sulfide minerals such as mackinawite (FeS), whose interactions with PO43− remain largely unexplored. We investigate the role of FeS in the sequestration of PO43− under anoxic conditions, with or without natural organic carbon (OC). We show that Fes has a high affinity for PO43−, with a maximum sorption capacity comparable to moderately crystalline FeOx minerals. The presence of sorbed OC decreases the FeS affinity toward the PO43− by ~ 75%, which is attributed to the lower surface area of FeS-OC compared to FeS, electrostatic repulsion, and the reduced accessibility to reactive Fe(II) sites. Moreover, we show that upon exposure of FeS to oxic conditions, PO43− is efficiently recaptured by the FeS oxidation products (FeOx), hence highlighting a parallel self-sustaining reversible cycle resulting in the permanent sequestration of a small fraction of PO43−. Overall, these findings highlight FeS as a potentially important phosphate sink in anoxic freshwater sediments.