Effects of oxygen and weak magnetic field on Fe(0)/bisulfite system: performance and mechanisms.

The performance and mechanisms of 4-nitrophenol (4-NP) degradation by the Fe(0)/bisulfite system were systematically investigated for the first time. The evidences presented in this study verified that O2 was a crucial factor that affected the mechanism of Fe(0)/bisulfite-driven 4-NP degradation. In the Fe(0)/bisulfite/O2 system, Fe(0) acted as a supplier of Fe(2+) to catalyze bisulfite oxidation that induced a chain reaction to produce reactive radicals for 4-NP degradation. While under N2 purging condition, bisulfite worked as a specified reductant that facilitated the transformation of Fe(3+) to nascent Fe(2+) ions, which principally accounted for the reductive removal of 4-NP. The application of a weak magnetic field (WMF) efficiently improved the removal rate of 4-NP and did not alter the mechanisms in both Fe(0)/bisulfite/O2 and Fe(0)/bisulfite/N2 processes. The secondary radicals, HO(·), SO4 (·-), and SO5 (·-), were considered as the most possible active oxidants contributing to the oxidative removal of 4-NP and even partial mineralization under an oxic condition. Compared with anoxic conditions, the performance removal of 4-NP by the WMF-Fe(0)/bisulfite/O2 system showed less pHini dependence. To facilitate the application of WMF-Fe(0)/bisulfite/O2 technology in real practice, premagnetization of Fe(0) was employed to combine with bisulfite/O2 and proved to be an effective and applicable method for 4-NP removal.

Predicting heavy metals' adsorption edges and adsorption isotherms on MnO2 with the parameters determined from Langmuir kinetics.

Although surface complexation models have been widely used to describe the adsorption of heavy metals, few studies have verified the feasibility of modeling the adsorption kinetics, edge, and isotherm data with one pH-independent parameter. A close inspection of the derivation process of Langmuir isotherm revealed that the equilibrium constant derived from the Langmuir kinetic model, KS-kinetic, is theoretically equivalent to the adsorption constant in Langmuir isotherm, KS-Langmuir. The modified Langmuir kinetic model (MLK model) and modified Langmuir isotherm model (MLI model) incorporating pH factor were developed. The MLK model was employed to simulate the adsorption kinetics of Cu(II), Co(II), Cd(II), Zn(II) and Ni(II) on MnO2 at pH3.2 or 3.3 to get the values of KS-kinetic. The adsorption edges of heavy metals could be modeled with the modified metal partitioning model (MMP model), and the values of KS-Langmuir were obtained. The values of KS-kinetic and KS-Langmuir are very close to each other, validating that the constants obtained by these two methods are basically the same. The MMP model with KS-kinetic constants could predict the adsorption edges of heavy metals on MnO2 very well at different adsorbent/adsorbate concentrations. Moreover, the adsorption isotherms of heavy metals on MnO2 at various pH levels could be predicted reasonably well by the MLI model with the KS-kinetic constants.

Removal of emerging pollutants by Ru/TiO2-catalyzed permanganate oxidation.

TiO2 supported ruthenium nanoparticles, Ru/TiO2 (0.94‰ as Ru), was synthesized to catalyze permanganate oxidation for degrading emerging pollutants (EPs) with diverse organic moieties. The presence of 1.0 g L(-1) Ru/TiO2 increased the second order reaction rate constants of bisphenol A, diclofenac, acetaminophen, sulfamethoxazole, benzotriazole, carbamazepine, butylparaben, diclofenac, ciprofloxacin and aniline at mg L(-1) level (5.0 µM) by permanganate oxidation at pH 7.0 by 0.3-119 times. The second order reaction rate constants of EPs with permanganate or Ru/TiO2-catalyzed permanganate oxidation obtained at EPs concentration of mg L(-1) level (5.0 µM) underestimated those obtained at EPs concentration of µg L(-1) level (0.050 µM). Ru/TiO2-catalyzed permanganate could decompose a mixture of nine EPs at µg L(-1) level efficiently and the second order rate constant for each EP was not decreased due to the competition of other EPs. The toxicity tests revealed that Ru/TiO2-catalyzed permanganate oxidation was effective not only for elimination of EPs but also for detoxification. The removal rates of sulfamethoxazole by Ru/TiO2-catalyzed permanganate oxidation in ten successive cycles remained almost constant in ultrapure water and slightly decreased in Songhua river water since the sixth run, indicating the satisfactory stability of Ru/TiO2. Ru/TiO2-catalyzed permanganate oxidation was selective and could remove selected EPs spiked in real waters more efficiently than chlorination. Therefore, Ru/TiO2-catalyzed permanganate oxidation is promising for removing EPs with electron-rich moieties.

Activating persulfate by Fe° coupling with weak magnetic field: performance and mechanism.

Weak magnetic field (WMF) and Fe(0) were proposed to activate PS synergistically (WMF-Fe(0)/PS) to degrade dyes and aromatic contaminants. The removal rates of orange G (OG) by WMF-Fe(0)/PS generally decreased with increasing initial pH (3.0-10.0) and increased with increasing Fe(0) (0.5-3.0 mM) or PS dosages (0.5-3.0 mM). Compared to its counterpart without WMF, the WMF-Fe(0)/PS process could induce a 5.4-28.2 fold enhancement in the removal rate of OG under different conditions. Moreover, the application of WMF significantly enhanced the decolorization rate and the mineralization of OG. The degradation rates of caffeine, 4-nitrophenol, benzotriazole and diuron by Fe(0)/PS were improved by 2.1-11.1 fold due to the superimposed WMF. Compared to many other sulfate radical-based advanced oxidation technologies under similar reaction conditions, WMF-Fe(0)/PS technology could degrade selected organic contaminants with much greater rates. Sulfate radical was identified to be the primary radical species responsible for the OG degradation at pH 7.0 in WMF-Fe(0)/PS process. This study unraveled that the presence of WMF accelerated the corrosion rate of Fe(0) and thus promoted the release of Fe(2+), which induced the increased production of sulfate radicals from PS and promoted the degradation of organic contaminants. Employing WMF to enhance oxidation capacity of Fe(0)/PS is a novel, efficient, promising and environmental-friendly method since it does not need extra energy and costly reagents.

Enhanced arsenite removal from water by Ti(SO4)2 coagulation.

Coagulation with the conventional coagulants such as ferric and aluminum salts is not efficient for As(III) removal. In this study Ti(SO4)2 was employed for enhanced As(III) removal and Fe2(SO4)3 was used as a reference. The removal efficiencies of As(III) by Ti(SO4)2 at pH 4.0-9.0 were greater than that by Fe2(SO4)3 by 7.39-32.8% and 3.14-48.1% for coagulants dosed at 8.0 mg/L and 12.0 mg/L, respectively. The advantage of Ti(SO4)2 over Fe2(SO4)3 for As(III) removal was more significant at lower pH, which may be ascribed to the more negatively charged surface of Ti(IV) hydroxides. To reduce As(III) from 0.2 mg/L to 10 µg/L, the necessary dosage of Ti(SO4)2 was only ≈ 50% of that of Fe2(SO4)3. The adsorption capacity of As(III) on Ti(IV) hydroxides formed in-situ was greater than that on Fe(III) hydroxides formed in-situ by ≈ 100 mg/g and several times higher than the adsorption capacities of TiO2 for As(III) reported in the literature. The presence of competing anions, silicate, phosphate and humic acid, did not alter the advantage of Ti(SO4)2 over Fe2(SO4)3 for arsenite removal. Replacing partial Ti(SO4)2 with Fe2(SO4)3 (same dosage) and applying them sequentially could achieve similar As(III) removal efficiency as single Ti(SO4)2, which could thus reduce the chemical cost. The extended X-ray absorption fine structure (EXAFS) spectroscopy indicated that As(III) form bidentate binuclear surface complexes with Ti(IV) hydroxides as evidenced by As(III)-Ti bond distances of 3.33-3.35 Å. This study revealed that Ti(SO4)2 may be an alternative coagulant for efficient As(III) removal.