An efficient catalytic degradation of trichloroethene in a percarbonate system catalyzed by ultra-fine heterogeneous zeolite supported zero valent iron-nickel bimetallic composite.

Zeolite supported nano iron-nickel bimetallic composite (Z-nZVI-Ni) was prepared using a liquid-phase reduction process. The corresponding surface morphologies and physico-chemical properties of the Z-nZVI-Ni composite were determined using scanning electron microscopy (SEM), transmission electron microscopy (TEM), Energy dispersive X-ray spectra (EDS), Brunauer Emmett Teller (BET) adsorption, wide angle X-ray diffractometry (WA-XRD), and Fourier transform infrared spectroscopy (FTIR). The results indicated high dispersion of iron and nickel nano particles on the zeolite sheet with an enhanced surface area. Complete destruction of trichloroethene (TCE) and efficient removal of total organic carbon (TOC) were observed by using Z-nZVI-Ni as a heterogeneous catalyst for a Fenton-like oxidation process employing sodium percarbonate (SPC) as an oxidant. The electron spin resonance (ESR) of Z-nZVI-Ni verified the generation and intensity of hydroxyl radicals (OH•). The quantification of OH• elucidated by using p-chlorobenzoic acid, a probe indicator, confirmed the higher intensity of OH•. The transformation products were identified using GC-MS. The slow iron and nickel leaching offered higher stability and better catalytic activity of Z-nZVI-Ni, demonstrating its prospective long term applications in groundwater for TCE degradation.

Application of calcium peroxide activated with Fe(II)-EDDS complex in trichloroethylene degradation.

This study was conducted to assess the application of calcium peroxide (CP) activated with Fe(II) chelated by (S,S)-ethylenediamine-N,N'-disuccinic acid (EDDS) to enhance trichloroethylene (TCE) degradation in aqueous solution. It was indicated that EDDS prevented soluble iron from precipitation, and the optimum molar ratio of Fe(II)/EDDS to accelerate TCE degradation was 1/1. The influences of initial TCE, CP and Fe(II)-EDDS concentration were also investigated. The combination of CP and Fe(II)-EDDS complex rendered the efficient degradation of TCE at near neutral pH range. Chemical probe and scavenger tests identified that TCE degradation mainly owed to the oxidation of HO while O2(-) promoted HO generation. Cl(-), HCO3(-) and humic acid were found to inhibit CP/Fe(II)-EDDS performance on different levels. In conclusion, the application of CP activated with Fe(II)-EDDS complex is a promising technology in chemical remediation of groundwater, while further research in practical implementation is needed.

Enhanced degradation of benzene by percarbonate activated with Fe(II)-glutamate complex.

Effective degradation of benzene was achieved in sodium percarbonate (SPC)/Fe(II)-Glu system. The presence of glutamate (Glu) could enhance the regeneration of Fe(III) to Fe(II), which ensures the benzene degradation efficiency at wider pH range and eliminate the influence of HCO3 (-) in low concentration. Meanwhile, the significant scavenging effects of high HCO3 (-) concentration could also be overcome by increasing the Glu/SPC/Fe(II)/benzene molar ratio. Free radical probe compound tests, free radical scavenger tests, and electron paramagnetic resonance (EPR) analysis were conducted to explore the reaction mechanism for benzene degradation, in which hydroxyl radical (HO•) and superoxide anion radical (O2 (•-)) were confirmed as the predominant species responsible for benzene degradation. In addition, the results obtained in actual groundwater test strongly indicated that SPC/Fe(II)-Glu system is applicable for the remediation of benzene-contaminated groundwater in practice.

The destruction of benzene by calcium peroxide activated with Fe(II) in water.

The ability of Fe(II)-activated calcium peroxide (CaO2) to remove benzene is examined with a series of batch experiments. The results showed that benzene concentrations were reduced by 20 to 100% within 30 min. The magnitude of removal was dependent on the CaO2/Fe(II)/Benzene molar ratio, with much greater destruction observed for ratios of 4/4/1 or greater. An empirical equation was developed to quantify the destruction rate dependence on reagent composition. The presence of oxidative hydroxyl radicals (HO•) and reductive radicals (primarily O2•-) was identified by probe compound testing and electron paramagnetic resonance (EPR) tests. The results of the EPR tests indicated that the application of CaO2/Fe(II) enabled the radical intensity to remain steady for a relatively long time. The effect of initial solution pH was also investigated, and CaO2/Fe(II) enabled benzene removal over a wide pH range of 3.0~9.0. The results of radical scavenging tests showed that benzene removal occurred primarily by HO• oxidation in the CaO2/Fe(II) system, although reductive radicals also contributed. The intermediates in benzene destruction were identified to be phenol and biphenyl. The results indicate that Fe(II)-activated CaO2 is a feasible approach for treatment of benzene in contaminated groundwater remediation.

Enhanced degradation of trichloroethene by calcium peroxide activated with Fe(III) in the presence of citric acid.

Trichloroethene (TCE) degradation by Fe(III)-activated calcium peroxide (CP) in the presence of citric acid (CA) in aqueous solution was investigated. The results demonstrated that the presence of CA enhanced TCE degradation significantly by increasing the concentration of soluble Fe(III) and promoting H2O2 generation. The generation of HO• and O2-• in both the CP/Fe(III) and CP/Fe(III)/CA systems was confirmed with chemical probes. The results of radical scavenging tests showed that TCE degradation was due predominantly o direct oxidation by HO•, while O2-• strengthened the generation of HO• by promoting Fe(III) transformation in the CP/Fe(III)/CA system. Acidic pH conditions were favorable for TCE degradation, and the TCE degradation rate decreased with increasing pH. The presence of Cl-, HCO3-, and humic acid (HA) inhibited TCE degradation to different extents for the CP/Fe(III)/CA system. Analysis of Cl- production suggested that TCE degradation in the CP/Fe(III)/CA system occurred through a dechlorination process. In summary, this study provided detailed information for the application of CA-enhanced Fe(III)-activated calcium peroxide for treating TCE contaminated groundwater.

Enhancement effects of chelating agents on the degradation of tetrachloroethene in Fe(III) catalyzed percarbonate system.

The performance of Fe(III)-based catalyzed sodium percarbonate (SPC) for stimulating the oxidation of tetrachloroethene (PCE) for groundwater remediation applications was investigated. The chelating agents citric acid monohydrate (CIT), oxalic acid (OA), and Glutamic acid (Glu) significantly enhanced the degradation of PCE. Conversely, ethylenediaminetetraacetic acid (EDTA) had a negative impact on PCE degradation, which may due to its strong Fe chelation and HO• scavenging abilities. However, excessive SPC or chelating agent will retard PCE degradation. In addition, investigations using free radical probe compounds and radical scavengers revealed that PCE was primarily degraded by HO• radical oxidation in both the chelated and non-chelated systems, while O2•- also participated in the non-chelated system and the OA and Glu modified systems. According to the electron paramagnetic resonance (EPR) studies, the presence of HO• in the Fe(III)/SPC system was maintained much longer than that in the Fe(II)/SPC system. The results indicated that the addition of CIT, OA or Glu indeed enhanced the generation of HO• in the first 10 min and promoted degradation efficiency by increasing the amount of Fe(III) and maintaining the concentration of HO• radicals in solution. In conclusion, chelated Fe(III)-based catalyzed SPC oxidation is a promising method for the remediation of PCE-contaminated groundwater.

Enhancement effects of reducing agents on the degradation of tetrachloroethene in the Fe(II)/Fe(III) catalyzed percarbonate system.

In this study, the effects of reducing agents on the degradation of tetrachloroethene (PCE) were investigated in the Fe(II)/Fe(III) catalyzed sodium percarbonate (SPC) system. The addition of reducing agents, including hydroxylamine hydrochloride, sodium sulfite, ascorbic acid and sodium ascorbate, accelerated the Fe(III)/Fe(II) redox cycle, leading to a relatively steady Fe(II) concentration and higher production of free radicals. This, in turn, resulted in enhanced PCE oxidation by SPC, with almost complete PCE removal obtained for appropriate Fe and SPC concentrations. The chemical probe tests, using nitrobenzene and carbon tetrachloride, demonstrated that HO was the predominant radical in the system and that O2(-) played a minor role, which was further confirmed by the results of electron spin resonance measurements. PCE degradation decreased significantly with the addition of isopropanol, a HO scavenger, supporting the hypothesis that HO was primarily responsible for PCE degradation. It is noteworthy that Cl(-) release was slightly delayed in the first 20 min, indicating that intermediate products were produced. However, these intermediates were further degraded, resulting in the complete conversion of PCE to CO2. In conclusion, the use of reducing agents to enhance Fe(II)/Fe(III) catalyzed SPC oxidation appears to be a promising approach for the rapid degradation of organic contaminants in groundwater.

Degradation of trichloroethylene in aqueous solution by calcium peroxide activated with ferrous ion.

The application of calcium peroxide (CaO2) activated with ferrous ion to stimulate the degradation of trichloroethylene (TCE) was investigated. The experimental results showed that TCE could be completely degraded in 5 min at a CaO2/Fe(II)/TCE molar ratio of 4/8/1. Probe compound tests demonstrated the presence of reactive oxygen species HO· and O2(-·) in CaO2/Fe(II) system, while scavenging tests indicated that HO· was the dominant active species responsible for TCE removal, and O2(-·) could promote TCE degradation in CaO2/Fe(II) system. In addition, the influences of initial solution pH and solution matrix were evaluated. It suggested that the elevation of initial solution pH suppressed TCE degradation. Cl(-) had significant scavenging effect on TCE removal, whereas HCO3(-) of high concentration showed favorable function. The influences of NO3(-) and SO4(2-) could be negligible, while natural organic matter (NOM) had a negative effect on TCE removal at a relatively high concentration. The results demonstrated that the technique of CaO2 activated with ferrous ion is a highly promising technique in in situ chemical oxidation (ISCO) remediation in TCE contaminated sites.

Perchloroethylene (PCE) oxidation by percarbonate in Fe(2+)-catalyzed aqueous solution: PCE performance and its removal mechanism.

The performance of Fe(2+)-catalyzed sodium percarbonate (SPC) stimulating the oxidation of perchloroethylene (PCE) in groundwater remediation was investigated. The experimental results showed that PCE could be completely oxidized in 5 min at 20 °C with a Fe(2+)/SPC/PCE molar ratio of 8/8/1, indicating the effectiveness of Fe(2+)-catalyzed SPC oxidation for PCE degradation. Fe(2+)-catalyzed SPC oxidation was suitable for the nearly neutral pH condition, which was superior to the conventional Fenton oxidation in acidic condition. In addition, the investigations by using hydroxyl radical scavengers and free radical probe compounds elucidated that PCE was degraded mainly by hydroxyl radical (HO) oxidation in Fe(2+)/SPC system. In conclusion, Fe(2+)-catalyzed SPC oxidation is a highly promising technique for PCE-contaminated groundwater remediation, but more complex constituents in groundwater should be carefully considered for its practical application.

Degradation of carbon tetrachloride in aqueous solution in the thermally activated persulfate system.

Thermal activation of persulfate (PS) has been identified to be effective in the destruction of organic pollutants. The feasibility of carbon tetrachloride (CT) degradation in the thermally activated PS system was evaluated. The experimental results showed that CT could be readily degraded at 50 °C with a PS concentration of 0.5M, and CT degradation and PS consumption followed the pseudo-first order kinetic model. Superoxide radical anion (O2(*-)) was the predominant radical species responsible for CT degradation and the split of CCl was proposed as the possible reaction pathways for CT degradation. The process of CT degradation was accelerated by higher PS dose and lower initial CT concentration. No obvious effect of the initial pH on the degradation of CT was observed in the thermally activated PS system. Cl(*-), HCO3(*-), and humic acid (HA) had negative effects on CT degradation. In addition, the degradation of CT in the thermally activated PS system could be significantly promoted by the solvents addition to the solution. In conclusion, the thermally activated PS process is a promising option in in-situ chemical oxidation/reduction remediation for degrading highly oxidized organic contaminants such as CT that is widely detected in contaminated sites.

Efficient dechlorination of chlorinated solvent pollutants under UV irradiation by using the synthesized TiO2 nano-sheets in aqueous phase.

Titanium dioxide (TiO2), which is the widely used photo-catalyst, has been synthesized by simple hydrothermal solution containing tetrabutyl titanate and hydrofluoric acid. The synthesized product has been applied to photo-degradation in aqueous phase of chlorinated solvents, namely tetrachloroethene (PCE), trichloroethene (TCE) and 1,1,1-trichloroethane (TCA). The photo-degradation results revealed that the degradation of these harmful chemicals was better in UV/synthesized TiO2 system compared to UV/commercial P25 system and UV only system. The photo-catalytic efficiency of the synthesized TiO2 was 1.4, 1.8 and 3.0 folds higher compared to the commercial P25 for TCA, TCE and PCE degradation, respectively. Moreover, using nitrobenzene (NB) as a probe of hydroxyl radical (·OH), the degradation rate was better over UV/synthesized TiO2, suggesting the high concentration of ·OH generated in UV/synthesized TiO2 system. In addition, ·OH concentration was confirmed by the strong peak displayed in EPR analysis over UV/synthesized TiO2 system. The characterization result using XRD and TEM showed that the synthesized TiO2 was in anatase form and consisted of well-defined sheet-shaped structures having a rectangular outline with a thickness of 4 nm, side length of 50 nm and width of 33 nm and a surface 90.3 m(2)/g. XPS analysis revealed that ≡Ti-F bond was formed on the surface of the synthesized TiO2. The above results on both photocatalytic activity and the surface analysis demonstrated the good applicability of the synthesized TiO2 nano-sheets for the remediation of chlorinated solvent contaminated groundwater.

Occurrence and removal of six pharmaceuticals and personal care products in a wastewater treatment plant employing anaerobic/anoxic/aerobic and UV processes in Shanghai, China.

The occurrence and removal of six pharmaceuticals and personal care products (PPCPs) including caffeine (CF), N, N-diethyl-meta-toluamide (DEET), carbamazepine, metoprolol, trimethoprim (TMP), and sulpiride in a municipal wastewater treatment plant (WWTP) in Shanghai, China were studied in January 2013; besides, grab samples of the influent were also taken every 6 h, to investigate the daily fluctuation of the wastewater influent. The results showed the concentrations of the investigated PPCPs ranged from 17 to 11,400 ng/L in the WWTP. A low variability of the PPCP concentrations in the wastewater influent throughout the day was observed, with the relative standard deviations less than 25 % for most samples. However, for TMP and CF, the slight daily fluctuation still reflected their consumption patterns. All the target compounds except CF and DEET, exhibited poor removal efficiencies (<40 %) by biological treatment process, probably due to the low temperature in the bioreactor, which was unfavorable for activated sludge. While for the two biodegradable PPCPs, CF, and DEET, the anaerobic and oxic tank made contributions to their removal while the anoxic tank had a negative effect to their elimination. The tertiary UV treatment removed the investigated PPCPs by 5-38 %, representing a crucial polishing step to compensate for the poor removal by the biologic treatment process in winter.