New Insights into the Role of Humic Acid in Permanganate Oxidation of Diclofenac: A Novel Electron Transfer Mechanism.

Humic acid (HA) ubiquitously existing in aquatic environments has been reported to significantly impact permanganate (KMnO4) decontamination processes. However, the underlying mechanism of the KMnO4/HA system remained elusive. In this study, an enhancing effect of HA on the KMnO4 oxidation of diclofenac (DCF) was observed over a wide solution pH range of 5-9. Surprisingly, the mechanism of HA-induced enhancement varied with solution pH. Quenching and chemical probing experiments revealed that manganese intermediates (Mn(III)-HA and MnO2) were responsible for the enhancement under acidic conditions but not under neutral and alkaline conditions. By combining KMnO4 decomposition, galvanic oxidation process experiments, electrochemical tests, and FTIR and XPS analysis, it was interestingly found that HA could effectively mediate the electron transfer from DCF to KMnO4 in neutral and alkaline solutions, which was reported for the first time. The formation of an organic-catalyst complex (i.e., HA-DCF) with lower reduction potential than the parent DCF was proposed to be responsible for the accelerated electron transfer from DCF to KMnO4. This electron transfer likely occurred within the complex molecule formed through the interaction between HA-DCF and KMnO4 (i.e., HA-DCF-KMnO4). These results will help us gain a more comprehensive understanding of the role of HA in the KMnO4 oxidation processes.

Removal of trace mercury (II) from aqueous solution by in situ MnO(x) combined with poly-aluminum chloride.

Removal of trace mercury from aqueous solution by Mn (hydr)oxides formed in situ during coagulation with poly-aluminum chloride (PAC) (in situ MnO(x) combined with PAC) was investigated. The efficiency of trace mercury removal was evaluated under the experimental conditions of reaction time, Mn dosage, pH, and temperature. In addition, the ionic strength and the initial mercury concentration were examined to evaluate trace mercury removal for different water qualities. The results clearly demonstrated that in situ MnO(x) combined with PAC was effective for trace mercury removal from aqueous solution. A mercury removal ratio of 9.7 µg Hg/mg Mn was obtained at pH 3. Furthermore, at an initial mercury concentration of 30 µg/L and pH levels of both 3 and 5, a Mn dosage of 4 mg/L was able to lower the mercury concentration to meet the standards for drinking water quality at less than 1 µg/L. Analysis by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy suggests that the hydroxyls on the surface of Mn (hydr)oxides are the active sites for adsorption of trace mercury from aqueous solution.

High efficient removal of molybdenum from water by Fe2(SO4)3: Effects of pH and affecting factors in the presence of co-existing background constituents.

Comparatively investigated the different effects of Fe2(SO4)3 coagulation-filtration and FeCl3 coagulation-filtration on the removal of Mo (VI). And the influence of calcium, sulfate, silicate, phosphate and humic acid (HA) were also studied. The following conclusions can be obtained: (1) compared with the case of FeCl3, Fe2(SO4)3 showed a higher Mo (VI) removal efficiency at pH 4.00-5.00, but an equal removal efficiency at pH 6.00-9.00. (2) The optimum Mo (VI) removal by Fe2(SO4)3 was achieved at pH 5.00-6.00; (3) The presence of calcium can reduce the removal of Mo (VI) over the entire pH range in the present study; (4) The effect of co-existing background anions (including HA) was dominated by three factors: Firstly the influence of co-existing background anions on the content of Fe intercepted from water (intercepted Fe). Secondly the competition of co-existing anions with Mo (VI) for adsorption sites. Thirdly the influence of co-existing background anions on the Zeta potential of the iron flocs.

Removal of trace mercury(II) from aqueous solution by in situ formed Mn-Fe (hydr)oxides.

The efficiency and mechanism of trace mercury (Hg(II)) removal by in situ formed manganese-ferric (hydr)oxides (in situ Mn-Fe) were investigated by reacting KMnO4 with Fe(II) in simulated solutions and natural water. In the simulated solutions, the impact of coagulant dosage, pH, and temperature on mercury removal was studied. Experimental results showed that in situ Mn-Fe more effectively removed mercury compared with polyaluminum chloride (PAC) and iron(III) chloride (FeCl3), and that mercury existed in the form of uncharged species, namely Hg(OH)2, HgClOH(aq), and HgCl2(aq). Fourier transform infrared spectroscopy demonstrated that in situ Mn-Fe contained hydroxyl groups as the surface active sites, while X-ray photoelectron spectroscopy (XPS) measurements revealed that MnO2 or MnOOH and FeOOH were the dominant species in the precipitates. XPS analysis indicated that an Hg-Mn-Fe mixture was formed in the precipitates, suggesting that mercury was removed from solutions via transfer from the liquid phase to solid phase. These results indicated that the primary mercury removal mechanisms in in situ Mn-Fe were surface complexation and flocculation-precipitation processes. Satisfactory removal efficiency of mercury was also observed following in situ Mn-Fe in natural waters.

Strong enhancement of trace mercury removal from aqueous solution with sodium thiosulfate by in situ formed Mn-(hydr)oxides.

The effect of sodium thiosulfate (Na2S2O3) on trace mercury removal from aqueous solution by in situ MnOx was investigated. Removal efficiency was studied at different molar ratios of Na2S2O3/Mn (0, 0.264, 0.593 and 1.582) and under changes in Mn dosage, reaction time and pH conditions. Additionally, the ionic strength and the mercury removal amount were examined to evaluate the efficiency of trace mercury removal. The results indicated that the presence of thiosulfate clearly improved removal of mercury from solution, and that increases in the ionic strength enhanced removal in a certain range of thiosulfate concentration. At neutral conditions, the mercury removal amount reached to maximum of 64 µg/mg. It is proposed that the ability of thiosulfate to reduce some MnOx to Mn(2+) as well as transfer the uncharged mercury species to a negatively charged species [Formula: see text] improved trace mercury removal. The mechanism analysis revealed that ternary complexes or large aggregations may be formed because of surface complexation or electrostatic attraction.