Self-Enhanced Selective Oxidation of Phosphonate into Phosphate by Cu(II)/H2O2: Performance, Mechanism, and Validation.

Phosphonate is an important category of highly soluble organophosphorus in contaminated waters, and its oxidative transformation into phosphate is usually a prerequisite step to achieve the in-depth removal of the total phosphorus. Currently, selective oxidation of phosphonate into phosphate is urgently desired as conventional advanced oxidation processes suffer from severe matrix interferences. Herein, we employed 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) as a model phosphonate and demonstrated its efficient and selective oxidation by the Cu(II)/H2O2 process at alkaline pH. In the presence of trace Cu(II) (0.020 mM), 90.8% of HEDP (0.10 mM) was converted to phosphate by H2O2 in 30 min at pH 9.5, whereas negligible conversion was observed by UV/H2O2 or a Fenton reaction (pH = 3.0). The oxidation of HEDP by Cu(II)/H2O2 was insignificantly affected by natural organic matters (10.0 mg TOC/L) and various anions including chloride, sulfate, and nitrate (10.0 mM). The complexation of Cu(II) with HEDP coupling Cu(III) produced in situ enabled an intramolecular electron transfer process, which features high selective oxidation. Selective degradation of HEDP was further validated by adding stoichiometric H2O2 into an industrial effluent, where the existing Cu(II) could serve as the catalyst. This study also provides a successful case to trigger selective oxidation of trace pollutants of concern upon synergizing with the nature of the contaminated water.

Photochemical Synthesis of Selenium Nanospheres of Tunable Size and Colloidal Stability with Simple Diketones.

Temporal and spatial segregations are two fundamental requirements for the successful synthesis of nanoparticles (NPs). To obtain colloidally stable selenium nanospheres (SeNSs), surfactants or polymers are generally needed as structure-directing agents or stabilizers in the reduction approaches for SeNP synthesis. The addition of such chemicals sacrifices the purity of the obtained SeNPs and, therefore, is detrimental to the applications. Here, for the first time, we report that low-molecular weight (less than six carbons) diketones are excellent photoreductants for green and tunable synthesis of SeNPs, owing to their merits in temporal and spatial control. With simple diketones as the photoreductants, the resultant SeNPs were pure and colloidally stable with nice photoelectronic properties. This finding not only provides a useful strategy for the synthesis of SeNPs but also might be a milestone in the development of ketone photochemistry.

A novel combined process for efficient removal of Se(VI) from sulfate-rich water: Sulfite/UV/Fe(III) coagulation.

The efficient removal of Se(VI) from sulfate-rich water is challenging as most reported processes last for hours to days. In this study, a combined sulfite/UV/Fe(III) coagulation process was proposed for efficient Se(VI) removal from sulfate-rich water within a short time (∼1 h). In the presence of sulfate (1000 mg L-1), over 99% of Se(VI) (initially at 10 mg L-1) could be reduced by sulfite (5.0 mM) with a UV dose of 16 J cm-2 (within 20 min) into Se(IV) as the sole observed product. An alkaline pH (>9) was required for the reduction process, which was naturally obtained with the addition of sulfite. Scavenging experiments with N2O and NO3- both indicated that hydrated electrons (eaq-) were responsible for Se(VI) reduction by sulfite/UV. The presence of chloride, sulfate, phosphate, and carbonate (up to 10 mM) showed negligible influence on Se(VI) reduction, whereas nitrate and humic acid inhibited Se(VI) reduction to different extents depending on their concentrations. By Fe(III) coagulation, Se(IV) in the co-presence of sulfite and sulfate was efficiently removed at an OH-/Fe molar ratio of 1.8-2.8. The removal of Se(IV) by Fe(III) coagulation responded insignificantly to chloride, nitrate, or sulfate (up to 10 mM), whereas it was adversely affected at high levels of carbonate (10 mM) and phosphate (1 mM). The combined sulfite/UV/Fe(III) coagulation process was validated for the efficient removal of Se(VI) from synthetic sulfate-rich solution, simulated wastewater, and authentic smelting wastewater (in 1.1 h). The introduced sulfite underwent minor consumption during UV irradiation and was almost (∼90%) removed after coagulation.

Enhanced removal of Se(VI) from water via pre-corrosion of zero-valent iron using H2O2/HCl: Effect of solution chemistry and mechanism investigation.

Although the removal of Se(VI) from water by using zero-valent iron (ZVI) is a promising method, passivation of ZVI severely inhibits its performance. To overcome such issue, we proposed an efficient technique to enhance Se(VI) removal via pre-corrosion of ZVI with H2O2/HCl in a short time (15 min). The resultant pcZVI suspension was weakly acidic (pH 4.56) and contained abundant aqueous Fe2+. 57Fe Mössbauer spectroscopy showed that pcZVI mainly consisted of Fe0 (66.2%), hydrated ferric oxide (26.3%), and Fe3O4 (7.5%). Efficient removal of Se(VI) from sulfate-rich solution was achieved by pcZVI compared with ZVI (in the absence and presence of H2O2) and acid-pretreated ZVI. Moreover, the efficient removal of Se(VI) by pcZVI sustained over a broad pH range (3-9) due to its strong buffering power. The presence of chloride, carbonate, nitrate, and common cations (Na+, K+, Ca2+, and Mg2+) posed negligible influence on the removal of Se(VI) by pcZVI, while the inhibitory effect induced by sulfate, silicate, and phosphate indicated the significance of Se(VI) adsorption as a prerequisite step for its removal. The consumption of aqueous Fe2+ was associated with Se(VI) removal, and X-ray absorption near edge structure revealed that the main pathway for Se(VI) removal by pcZVI was a stepwise reduction of Se(VI) to Se(IV) and then Se0 as the dominant final state (78.2%). Moreover, higher electron selectivity of pcZVI was attributed to the enhanced enrichment of Se oxyanions prior to their reduction.

Struvite-based phosphorus recovery from the concentrated bioeffluent by using HFO nanocomposite adsorption: Effect of solution chemistry.

Here we reported struvite-based phosphorous recovery from the concentrated desorption effluent of a proprietary hydrated ferric oxide (HFO) nanocomposite (HFO-201) system, and the effect of solution chemistry (alkalinity, salinity, and dissolved organic matter (DOM)) on struvite formation was particularly focused on. The optimum P recovery rate (∼97%) and high quality struvite was obtained at 25°C, pH 9.0-9.5, and the molar Mg:NH4:P ratio of 1.4:4:1. The reaction reached equilibrium within ∼30min, much faster than the reported high purity struvite formation at neutral pH (several days required). It largely relied on the absence of Ca(2+) in the desorption effluent due to the Donnon co-ion effect exerted by HFO-201. Thermodynamic modelling with Stockholm humic model revealed that the presence of salinity and DOM resulted in a lower saturation index (SI) of struvite, thus inhibiting P recovery by struvite. Nevertheless, it is favorable to form struvite of large particle size. In addition, increasing the molar Mg:NH4:P ratio from 1:1:1 to 1.4:4:1 could significantly weaken the adverse effect of the high salinity and DOM. Direct addition of Ca(2+) could also result in phosphorous recovery, but the P content of the resultant solid (∼4.4%) is much lower than the formed struvite (∼17%). The results indicated that struvite process is a very attractive option to recover P from the desorption effluent, and the effect of solution chemistry is crucial to optimize the process.

Removal of selenium from water with nanoscale zero-valent iron: mechanisms of intraparticle reduction of Se(IV).

Increasing evidences suggest that nanoscale zero-valent iron (nZVI) is an effective agent for treatment and removal of selenium from water. For example, 1.3 mM selenite was quickly removed from water within 3 min with 5 g/L nZVI. In this work, reaction mechanisms of selenite [Se(IV)] in a single core-shell structured nanoscale zero-valent iron (nZVI) particle were studied with the method of spherical aberration corrected scanning transmission electron microscopy (Cs-STEM) integrated with X-ray energy dispersive spectroscopy (XEDS). This method was utilized to visualize solid phase translocation and transformation of Se(IV) such as diffusion, reduction, deposition and the effect of surface defects in a single nanoparticle. Se(IV) was reduced to Se(-II) and Se(0), which then formed a 0.5 nm layer of selenium at the iron oxide-Fe(0) interface at a depth of 6 nm from the surface. The results provided near atomic-resolution proof on the intraparticle diffusion-reduction of Se(IV) induced by nZVI. The STEM mapping also discovered that defects on the surface layer accelerate the diffusion of selenium and increase the capacity of nZVI for selenium sequestration.