Dynamic Fe-precipitate formation induced by Fe(II) oxidation in aerated phosphate-containing water

We studied the effect of phosphate on the precipitation of Fe during the oxidation of 1 mM Fe(II) in aerated 8 mM NaHCO3–CO2 buffered aqueous solutions at near-neutral pH. The structure and morphology of the precipitates were analyzed by X-ray diffraction (XRD), extended X-ray absorption fine structure (EXAFS) spectroscopy at the Fe K-edge, and transmission electron microscopy (TEM). Up to an initial dissolved P/Fe ratio of ∼0.55, most phosphate was incorporated into the fresh Fe(III)-precipitates. At dissolved P/Fe ratios from 0.55 to 1.91, the precipitate P/Fe ratios only exhibited a minor increase from 0.56 to 0.72. XRD patterns and Fe EXAFS spectra indicated a shift in precipitate type from mostly poorly-crystalline lepidocrocite in the absence of phosphate to amorphous Fe(III)–phosphate (mostly monomeric and oligomeric Fe(III) coordinated with phosphate) at dissolved P/Fe ratios >0.55. A time-resolved oxidation experiment at an initial dissolved P/Fe ratio of 0.29 revealed that amorphous Fe(III)–phosphate formed during Fe(II) oxidation until phosphate was nearly depleted from solution. During continuing Fe(II) oxidation, about half of the newly formed Fe(III) contributed to the polymerization of Fe–phosphate into phosphate-rich hydrous ferric oxide with a maximum P/Fe ratio of 0.25 (HFO-P; edge-sharing linkage of Fe(III) octahedra) and about half precipitated as poorly-crystalline lepidocrocite in the phosphate-depleted solution. At initial P/Fe ratios <0.2, initially formed Fe(III)–phosphate was fully transformed into HFO-P during continuing Fe(II) oxidation. The dynamic interactions between phosphate and Fe described in this study impact the structure of fresh Fe(III)-precipitates at redox transitions in environmental and technical systems. The modulating effects of other dissolved species such as silicate and Ca on Fe precipitate formation and implications for co-transformed trace elements require further study.