科研之友
微信
新浪微博
Facebook
分享链接
摘要
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 similar to 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 %26gt;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 %26lt;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.
- 出版日期2013-9-15
