A magnetic chitosan for efficient adsorption of vanadium (V) from aqueous solution.

The all-vanadium redox flow battery (VRFB) is becoming a promising technology for large-scale energy storage due to its advantages such as scalability and flexibility. In recent years, the VRFB has been successfully developed and put into use in many countries. It is expected that the abandoned VRFB will generate a large amount of vanadium waste. To our knowledge, there are few reports on the disposal of spent VRFBs. Herein, chitosan-coated nano-zero-valent iron (CS-Fe0) is proposed for the first time as adsorbents for the treatment of spent VRFBs. It can provide a new approach to deal with the upcoming large number of spent VRFBs. The calculated maximum adsorption capacity for V(V) of chitosan and CS-Fe0 reached 209.5 and 511.3 mg/g at 288 K, respectively. CS-Fe0 showed better adsorption performance than chitosan under different pH conditions and is easy to be separated from the liquid phase. The Freundlich isotherm was suitable for the adsorption process of chitosan, and CS-Fe0 was more consistent with the Langmuir isotherm. Ionic strength (0.05-0.5 M) had a positive effect on the adsorption capacity of CS-Fe0, and the influence of coexisting anions on CS-Fe0 could be negligible. FTIR and XPS analyses revealed that the primary mechanisms were the electrostatic attraction of chitosan and redox of Fe0. The present study confirmed that CS-Fe0 could be a potential material to efficiently trap V(V) from the VRFB electrolyte.

Mechanism of surfactant in trichloroethene degradation in aqueous solution by sodium persulfate activated with chelated-Fe(II).

The mechanism of surfactants in surfactant-in situ chemical oxidation (S-ISCO) coupled process for trichloroethene (TCE) degradation was firstly reported. The performance of TCE solubilization and inhibition of TCE degradation in three nonionic surfactants (TW-80, Brij-35, TX-100) in PS/Fe(II)/citric acid (CA) system was compared and TW-80 was evaluated to be the optimal surfactant in S-ISCO coupled process due to the best TCE solubilizing ability and minimal inhibition for TCE degradation (only 31.8% TCE inhibition in the presence of 1 g L-1 TW-80 surfactant). The inhibition mechanism in TCE degradation was also demonstrated by comparing the strength of ROSs and PS utilization. In the presence of TW-80 (1 g L-1), over 97.5% TCE was removed at the PS/Fe(II)/CA/TCE molar ratio of 30/4/4/1, in which more than 86.7% TCE was dechlorinated. The result of scavenger experiments revealed that the dominant radicals were HO• and SO4-• in PS/Fe(II)/CA system in TW-80 containing aqueous solution, among which SO4-• performed a greater role in TCE removal. Moreover, over 85.3% TCE degradation in actual groundwater revealed the potential of PS/Fe(II)/CA process for actual groundwater remediation in containing TW-80 of TCE contaminant. This research provided a novel alternative technology for groundwater remediation with TCE contaminant when containing surfactants.

Enhancement of benzene degradation by persulfate oxidation: synergistic effect by nanoscale zero-valent iron (nZVI) and thermal activation.

The feasibility of an advanced oxidation process based upon sodium persulfate (SPS) activated simultaneously by heat (50 °C) and nanoscale zero-valent iron (nZVI) on benzene removal was investigated. The experimental results strongly showed the synergistic effect of thermal and nZVI activation to SPS and benzene removal was enhanced with the increase of SPS/nZVI/benzene molar ratio. Specifically, 94% of benzene could be removed in 1 hr at 50 °C at the SPS/nZVI/benzene molar ratio of 10/5/1. The radical scavenger tests and electron paramagnetic resonance (EPR) analysis confirmed that SO4•- was the predominant species contributing to benzene degradation. Further, the effects of the solution matrix on benzene elimination were investigated. The results indicated that benzene destruction in the thermally activated SPS/nZVI system performed better under acidic conditions, and the high concentration of both Cl- and HCO3 - had adverse effects on benzene elimination. The test for the performance of benzene degradation in the actual groundwater demonstrated that benzene could be degraded entirely at SPS/nZVI/benzene molar ratio of 40/40/1 at 50 °C, indicating that the synergistic catalysis of thermal and nZVI activation to SPS is exploitable and the thermally activated SPS/nZVI system can be applicable to the remediation of benzene contaminated groundwater.

Efficient removal of trichloroethene in oxidative environment by anchoring nano FeS on reduced graphene oxide supported nZVI catalyst: The role of FeS on oxidant decomposition and iron leakage.

The performance of trichloroethene (TCE) removal was initially investigated in sodium persulfate (SPS) or potassium monopersulfate triple salt (PMS) oxidative environment by reduced graphene oxide (rGO) supported nZVI (nZVI-rGO) catalyst and further the role of sulphur by anchoring nano FeS on nZVI-rGO (FeS@nZVI-rGO) was evaluated. The high usage of oxidants and stability of FeS@nZVI-rGO catalyst were significantly improved due to the insoluble nature of this innovative catalyst by involvement of nano FeS which limited the rapid iron loss caused by the corrosion of active sites and mitigated rapid oxidants decomposition in FeS@nZVI-rGO/SPS and FeS@nZVI-rGO/PMS systems. The tests for target contaminant removal showed that over 95 % TCE could be removed at 100 mg L-1 FeS@nZVI-rGO and 1.2 mM SPS or 0.3 mM PMS dosages, in which over 85 % TCE could be dechlorinated. The reactive oxygen radicals (ROSs) generation mechanisms and their contribution to TCE removal were investigated through radical scavenge tests in both systems, indicating that both HO and SO4- were the major ROSs rather than O2-. In conclusion, this study revealed the well function and fundamental mechanism of this innovative catalyst by anchoring nano FeS and worth of further demonstration of this technique in TCE contaminated groundwater remediation application.

Trichloroethylene degradation performance in aqueous solution by Fe(II) activated sodium percarbonate in the presence of surfactant sodium dodecyl sulfate.

The performance of trichloroethylene (TCE) degradation by sodium percarbonate (SPC) activated with Fe(II) in the presence of 3.0 g/L sodium dodecyl sulfate (SDS) as well as the role of SDS in the SPC/Fe(II) system was investigated since SDS is a common surfactant used in groundwater remediation for improving TCE dissolution to the aqueous phase. The results showed that though the introduction of SDS could inhibit the TCE degradation, the inhibiting effect was less with the increasing SDS dose. In the presence of SDS, TCE could be completely removed with the SPC/Fe(II)/TCE molar ratio of 40/80/1. Experiments with free radical probe compounds and radical scavengers elucidated that TCE was mainly oxidized by both HO· and O 2 - · . A weakly acidic environment was more favorable to TCE degradation. Nevertheless, HCO 3 - at a high concentration had a strongly inhibitive effect on the TCE degradation but the influence of Cl- was negligible. Finally, the excellent TCE degradation achieved in actual groundwater demonstrated that Fe(II) activated SPC technique was applicable in the remediation of TCE contaminated groundwater in the presence of SDS. PRACTITIONER POINTS: The effects of SDS were evaluated SPC/Fe(II)/SDS system applied to remediate TCE The mechanism of HO· and O 2 - · generation had been investigated Cl- and HCO 3 - affected TCE degradation at different levels The performance of TCE removal in actual groundwater had been studied.

The performance of nCaO2 for BTEX removal: Hydroxyl radical generation pattern and the influences of co-existing environmental pollutants.

In this study, nano-CaO2 (nCaO2 ) was successfully synthesized and constituted the nCaO2 /Fe(II) system applying to remediate BTEX, which are typical mixed pollutants in contaminated groundwater. The particle size of the synthesized nCaO2 was 108.91 nm, and it displayed better BTEX remediation performance than that of commercial CaO2 . The innovative generation pattern of hydroxyl radicals ( HO · ) in the nCaO2 /Fe(II) system has been investigated using benzoic acid as the HO · probe, and the proper molar ratio of nCaO2 /Fe(II) was optimized as 1/1. Over 90% of BTEX was removed in 180 min with the nCaO2 /Fe(II)/BTEX molar ratio of 40/40/1. Further experiments evaluated the influence of co-existence of mixed pollutants chlorinated hydrocarbon compounds (CHCs) or surfactant constituents on BTEX remediation performance. The experimental results suggested that CHCs have limited influence on BTEX removal rate and surfactants have negative effects on BTEX remediation performance in the experimental conditions. In conclusion, the findings in this study could give some inspirations to apply the nCaO2 /Fe(II) process in remediating co-existing pollutants in contaminated groundwater. PRACTITIONER POINTS: nCaO2 /Fe(II) system applied to remediate mixed contaminants. HO · generation pattern of the nCaO2 /Fe(II) system has been investigated. The influence of chloride hydrocarbon compounds have been studied. The effects of surfactants were evaluated.

Mechanism of carbon tetrachloride reduction in ferrous ion activated calcium peroxide system in the presence of methanol.

This study investigated the reductive initiation for the depletion of highly oxidized/perhalogenated pollutants, specifically the degradation of carbon tetrachloride (CT) was induced by adding methanol (MeOH) into a ferrous ion (Fe(II)) activated calcium peroxide (CaO2) system. The results indicated that CT could be completely degraded within 20 min at CaO2/Fe(II)/MeOH/CT molar ratio of 30/40/10/1 in this system. Scavenging tests suggested that both superoxide radical anion (O2 •-) and carbon dioxide radical anion (CO2 •-) were predominant reactive species responsible for CT destruction. Hydroxymethyl radicals (•CH2OH), an intermediate in the transformation of MeOH, could also initiate CT degradation by reducing C-Cl bond. GC/MS analysis identified CHCl3, C2Cl4, and C2Cl6 as the intermediates accompanied by CT destruction, and a reduction mechanism for CT degradation was proposed accordingly. In addition, the impact of solution matrix and initial solution pH were evaluated, and the results showed that Cl-, NO3 -, and HCO3 - had adverse effects on CT degradation. Moreover, the alkaline condition was unfavorable to CT depletion. In conclusion, the results obtained in the actual groundwater tests encouragingly demonstrated that the CaO2/Fe(II)/MeOH process is a highly promising technique for the remediation of CT-contaminated groundwater.

Enhanced redox degradation of chlorinated hydrocarbons by the Fe(II)-catalyzed calcium peroxide system in the presence of formic acid and citric acid.

Two carboxylic acids (formic acid (FA) and citric acid (CIT)) enhanced the Fenton process using Fe(II)-activated calcium peroxide (CP) to develop a hydroxyl (HO) and carbon dioxide radical (CO2-) coexistence process for the simultaneous redox-based degradation of three chlorinated hydrocarbons (CHs), namely carbon tetrachloride (CT), tetrachloroethene (PCE), and trichloroethene (TCE), was investigated. The experimental results showed that CT removal was increased while PCE and TCE degradation were decreased with the addition of FA to the Fe(II)/CP system. However, addition of CIT to the Fe(II)/CP/FA system enhanced the removal efficiency of all three contaminants. For example, 81.7%, 79.4%, and 96.1% of CT, PCE, and TCE, respectively, were removed simultaneously under the optimal molar ratio of 12/12/12/12/1 of CIT/CP/Fe(II)/FA/CHs. Mechanism study confirmed the specific roles of HO and secondarily generated CO2- radical. PCE and TCE were degraded oxidatively by HO while CT was degraded via reductive dechlorination by CO2-. Carbonate reduced PCE and TCE degradation in actual groundwater as it consumed reactive oxygen species, whereas humic acid and neutral pH had minimal impact on contaminant removal. These results can help us better understand the synergistic effects of carboxylic acids in the modified Fenton process for the redox degradation of refractory chlorinated hydrocarbons.

Enhanced degradation of carbon tetrachloride by sodium percarbonate activated with ferrous ion in the presence of ethyl alcohol.

In this study, the degradation performance of carbon tetrachloride (CT) by sodium percarbonate (SPC) activated with Fe(II) in the presence of ethyl alcohol (EA) was investigated. The experimental results showed that CT could be readily degraded and the optimal EA/Fe(II)/SPC/CT molar ratio for CT reduction was 100/50/20/1. Superoxide radical anion ( ) and hydroxyethyl radical (•CHCH3OH, HER) were the predominant radical species responsible for CT degradation and EA could regulate the generation of and HER in the system. Further investigation for the solution matrix effects suggested that Cl-, , , and humic acid had negligible influences on CT degradation, while had negative effect in EA/Fe(II)/SPC system. On the other hand, the application of SPC/Fe(II)/EA technique is favorable to acidic condition is effective at a wide pH range of 3.0-7.0. In summary, CT degradation in Fe(II)-activated SPC system can be significantly promoted by addition of solvents, and these findings provide an innovative technology for the degradation of highly oxidized organic contaminants.

Degradation of trichloroethylene in aqueous solution by nanoscale calcium peroxide in the Fe(II)-based catalytic environments.

In this study, nCaO2 was synthesized successfully and applied in the Fe(II)-based catalytic environments in investigating trichloroethylene (TCE) removal performance. nCaO2 with the particle sizes in the range of 50-200 nm was prepared, and it performed better for TCE removal when compared to the conventional CaO2. Further experimental results showed that 70.4% of TCE could be removed in 180 min at the nCaO2/Fe(II)/TCE molar ratio of 1/2/1, while this data was elevated to 86.1% in the presence of citric acid (CA) at the nCaO2/Fe(II)/CA/TCE molar ratio of 1/2/2/1 in the same test period. Probe compound tests, specifically designed for free radicals confirmation, demonstrated the presence of HO• and O2 -•. Moreover, scavenging tests indicated that HO• was the major radical responsible for TCE degradation but O2 -• promoted the removal of TCE in both nCaO2/Fe(II) and nCaO2/Fe(II)-CA system. In addition, the effects of initial solution pH and anions (Cl-, HCO3 -) were also evaluated. The performance of TCE degradation in actual groundwater demonstrated that both nCaO2/Fe(II) and nCaO2/Fe(II)-CA systems can be applicable for TCE removal in ISCO practice and the nCaO2/Fe(II)-CA system is much promising technique. These fundamental data strongly confirmed the feasibility and potential of nCaO2 based technique in the remediation of TCE contaminated groundwater.

Insight into CaO2-based Fenton and Fenton-like systems: strategy for CaO2-based oxidation of organic contaminants.

This study conducted a comparison of the CaO2-based Fenton (CaO2/Fe(II)) and Fenton-like (CaO2/Fe(III)) systems on their benzene degradation performance. The H2O2, Fe(II), Fe(III), and HO● variations were investigated during the benzene degradation. Although benzene has been totally removed in the two systems, the variation patterns of the investigated parameters were different, leading to the different benzene degradation patterns. In terms of the Fe(II)/Fe(III) conversion, the CaO2/Fe(II) and CaO2/Fe(III) systems were actually inseparable and had the inherent mechanism relationships. For the CaO2/Fe(III) system, the initial Fe(III) must be converted to Fe(II), and then the consequent Fenton reaction could be later developed with the regenerated Fe(II). Moreover, some benzene degradation intermediates could have the ability to facilitate the transformation of the Fe(III) to Fe(II) without the classic H2O2-associated propagation reactions. By varying the Fe(II) dosing method, an effective degradation strategy has been developed to take advantage of the two CaO2-based oxidation systems. The proposed strategy was further successfully tested in TCE degradation, therefore extending the potential for the application of this technique.

Adsorption and mechanistic study for phosphate removal by magnetic Fe3O4-doped spent FCC catalysts adsorbent.

The waste materials utilization has attained increasing attention due to the generation of a large number of spent materials. In the current study, a practical magnetic adsorbent (Fe3O4-doped spent Fluid Catalytic Cracking catalysts, abbreviated as FCCx@(Fe)y-O) was prepared, liable to be separated. The batch experiments were employed to investigate the phosphate removal behavior. The findings of this study demonstrated that FCC4@(Fe)1-O exhibited the best phosphate removal performance among the adsorbents (FCCx@(Fe)y-O), attributed to rough surface layer, i.e., composed of active sites. The various characterizations results revealed that the adsorption behavior of FCC4@(Fe)1-O followed the inner-sphere adsorption based on ligand exchanges mechanism. Furthermore, OH- played an important role in the adsorption process. Minor effects were showed on the phosphate removal in the experiments of commonly coexisting anions, except CO32- and SiO32-. The above findings affirmed that FCC4@(Fe)1-O was a suitable adsorbent for phosphate removal in the practical application.

The impact of surface properties and dominant ions on the effectiveness of G-nZVI heterogeneous catalyst for environmental remediation.

The surface properties of nanocomposites are influenced by the existence of inorganic species that may affect its performance for specific catalytic applications. The impact of different ionic species on particular catalytic activity had not been investigated to date. In this study, the surface charge (zeta potential) of graphene-oxide-supported nano zero valent iron (G-nZVI) was tested in definitive cationic (Na+, K+, Ca2+ and Mg2+) and anionic (Br-, Cl-, NO3-, SO42-, and HCO3-) environments. The efficiency of G-nZVI catalyst was inspected by measuring the generation of reactive oxygen species (ROS) for the degradation of 1,1,1-trichloroethane (TCA) in sodium percarbonate (SPC) system. Tests conducted using probe compounds confirmed the generation of OH and O2- radicals in the system. In addition, the experiments performed using scavenging agents certified that O2- were primary radicals responsible for TCA removal, along with prominent contribution from OH radicals. The study confirmed that G-nZVI catalytic capability for TCA degradation is notably affected by various cationic species. The presence of Ni2+ and Cu2+ significantly enhanced (94%), whereas Na+ and K+ had minor effects on TCA removal. Overall, the results indicated that groundwater ionic composition may have low impact on the effectiveness of G-nZVI-catalyzed peroxide TCA treatment.

Enhanced degradation of trichloroethylene in oxidative environment by nZVI/PDA functionalized rGO catalyst.

Nano zero-valent iron (nZVI) particles with higher reactivity have been recognized as more efficient catalysts than Fe(II) for the groundwater remediation. The rapid emergence of novel catalyst supports efficiently prevent the rapid aggregation of nZVI and further improve catalytic reactivity. However, the lack of ability to avoid the potential oxidation of bare nZVI-support structure in air environment hinders its wider application in the actual contaminated sites. In this study, nZVI on reduced graphene oxide (rGO) functionalized by polydopamine (PDA) (nZVI-PDA@rGO) was synthesized successfully and applied into sodium persulfate (SPS), potassium monopersulfate (PMS) and H2O2 oxidative environments to remove trichloroethylene (TCE). For comparison, nZVI supported on solely rGO was prepared. The XRD test displayed the stronger stability of α-Fe(0) in nZVI-PDA@rGO catalyst against oxidation exposed to air. Compared with nZVI-rGO, a core shell structure of nZVI-PDA@rGO was observed in TEM image obviously. The dosage tests showed nZVI-PDA@rGO had a better catalytic reactivity than nZVI-rGO for TCE removal at lower catalyst and oxidant dosages, i.e. PMS dosage: 0.3 mM, catalyst dosage: 50 mg L-1, TCE removal: 45.0% (nZVI-rGO) up to 99.6% (nZVI-PDA@rGO). TCE removal mechanisms were revealed through radical scavenger tests, demonstrating sulfate radicals played more important role in nZVI-PDA@rGO catalyzed-oxidant systems.

Enhanced effect of EDDS and hydroxylamine on Fe(II)-catalyzed SPC system for trichloroethylene degradation.

This study presents a performance comparison of Fe(II)-catalyzed sodium percarbonate (SPC), Fe(II)-EDDS-catalyzed SPC, and of the innovative hydroxylamine hydrochloride (HA)-Fe(II)-EDDS-catalyzed SPC for the degradation of trichloroethylene (TCE) in water. TCE degradation was greater in the Fe(II)-EDDS-catalyzed SPC system compared to the Fe(II)-catalyzed SPC system, indicating the effectiveness of adding EDDS as an enhancement factor for the removal of TCE. Moreover, TCE degradation was faster in the HA-Fe(II)-EDDS-catalyzed SPC system compared to the Fe(II)-EDDS-catalyzed SPC system, illustrating that HA can play a synergistic role in TCE degradation. Analysis of iron distribution in the three systems demonstrated that EDDS addition maintained iron in soluble form, and that the generation of soluble ferrous from ferric iron was expedited with addition of HA. Studies using nitrobenzene and carbon tetrachloride probes provided insights on the generation of hydroxyl radical (HO•) and superoxide anion radical (O2•-) in the three systems. A gradual increasing contribution of O2•- to TCE removal in Fe(II)-catalyzed SPC, Fe(II)-EDDS-catalyzed SPC, and HA-Fe(II)-EDDS-catalyzed SPC systems was verified through free-radical scavenger tests. Finally, monitoring of Cl- concentrations manifested the complete dechlorination of TCE. A possible mechanism of TCE degradation involving two pathways of HO• oxidation and O2•- reaction was proposed.

Degradation of trichloroethylene in aqueous solution by rGO supported nZVI catalyst under several oxic environments.

The reduced graphene oxide (rGO) supported nano zero-valent iron (nZVI) (nZVI-rGO) was synthesized successfully and applied in the several oxic environments to remove trichloroethylene (TCE). The nZVI-rGO had a better catalytic performance than bare nZVI for the TCE removal. Both aggregation of nZVI and agglomeration of rGO were in part prevented by loading the nZVI nanoparticles on the rGO sheet. Among all the oxic environments, the better removal of TCE was followed as the order of PMS > SPS > H2O2. Chemical scavenger tests were carried out to identify the reactive oxygen species (ROSs) generated in the removal of TCE, showing that in PMS and SPS systems, SO4- and HO were main radicals responsible for TCE removal, while HO and O2- were main radicals in H2O2 system. The possible mechanisms were proposed with nZVI-rGO under several oxic environments. The recyclability of nZVI-rGO, dechlorination and mineralization of TCE were investigated. These fundamental data confirmed the effectiveness of nZVI-rGO to remove TCE and could help selecting the suitable oxidants to use with nZVI-rGO in the actual field groundwater remediation.

Insight on the generation of reactive oxygen species in the CaO2/Fe(II) Fenton system and the hydroxyl radical advancing strategy.

Calcium peroxide (CaO2) is a stable hydrogen peroxide (H2O2) carrier, and the CaO2/Fe(II) system has been applied for treatment of various pollutants. It is commonly reported in the literature that hydroxyl radical (HO●) and superoxide radical anions (O2 ●-) are the two main reactive oxygen species (ROSs) generated in the CaO2/Fe(II) system. However, many of the reported results were deduced from degradation performance rather than specific testing of radical generation. Thus, the specific generation of ROSs and the influence of system conditions on ROSs yield is still unclear. To our knowledge, this is the first study specifically focusing on the generation of HO● and O2 ●- in the CaO2/Fe(II) system. Experimental conditions were optimized to investigate the production of HO● and O2 ●-. The results showed the influences of CaO2, Fe(II), and solution pH on HO● and O2 ●- generation, and the HO● generation efficiency was reported for the first time. In addition, the ROSs generation pathways in the CaO2/Fe(II) system were elucidated. A strategy for enhancing HO● yield is developed, based on the continuously dosing Fe(II). This proposed strategy has implications for the effective application of in situ chemical oxidation employing CaO2/Fe(II) for groundwater remediation.

Investigation into the nitrate removal efficiency and microbial communities in a sequencing batch reactor treating reverse osmosis concentrate produced by a coking wastewater treatment plant.

In this study, a biological denitrifying process using a sequencing batch reactor (SBR) was employed to treat reverse osmosis (RO) concentrate with high conductivity produced from a coking wastewater plant. From the results, the average removal efficiencies for chemical oxygen demand, total nitrogen, and nitrate were 79.5%, 90.5%, and 93.1%, respectively. Different microbial communities were identified after sequencing the V1-V3 region of the 16S rRNA gene using the MiSeq platform, and the major bacterial phyla in the SBR system were Proteobacteria and Bacteroidetes. The main microorganisms responsible for denitrification were from the genera Hyphomicrobium, Thauera, Methyloversatilis, and Rhodobacter. Quantitative real-time PCR was used to quantify the absolute levels of denitrifying genes, including narG, nirS, nirK, and nosZ, during the start-up and stable operation of the SBR. The abundances of narG, nirK, and nosZ were lower during stable operation than those in the start-up period. The abundance of nirS at a concentration of 104-105 copies/ng in DNA was much higher than that of nirK, making it the dominant functional gene responsible for nitrite reduction. The higher nitrate removal efficiency suggests that biological denitrification using SBR is an effective technique for treating RO concentrate produced from coking wastewater plants.

Application of ascorbic acid to enhance trichloroethene degradation by Fe(III)-activated calcium peroxide.

The enhancement effect of an environmentally friendly reducing agent, ascorbic acid (AA), on trichloroethene (TCE) degradation by Fe(III)-activated calcium peroxide (CP) was evaluated. The addition of AA accelerated the transformation of Fe(III) to Fe(II), and the complexation of Fe(III)/Fe(II) with AA and its products alleviated the precipitation of dissolved iron. These impacts enhanced the generation of reactive oxygen species (ROSs). Investigation of ROSs using chemical probe tests, electron paramagnetic resonance (EPR) tests, and radical scavenger tests strongly confirm large production of hydroxyl radicals (HO•) that is responsible for TCE degradation. The generation of Cl- from the degraded TCE was complete in the enhanced CP/Fe(III)/AA system. The investigation of solution matrix effects showed that the TCE degradation rate decreases with the increase in solution pH, while Cl-, SO42- and NO3- anions have minor impact. Conversely, HCO3- significantly inhibited TCE degradation due to pH elevation and HO• scavenging. The results of experiments performed using actual groundwater indicated that an increase in reagent doses are required for effective TCE removal. In summary, the potential effectiveness of the CP/Fe(III)/AA oxidation system for remediation of TCE contaminated groundwater has been demonstrated. Additional research is needed to develop the system for practical implementation.

Benzene oxidation by Fe(III)-catalyzed sodium percarbonate: matrix constituent effects and degradation pathways.

Complete degradation of benzene by the Fe(III)-activated sodium percarbonate (SPC) system is demonstrated. Removal of benzene at 1.0 mM was seen within 160 min, depending on the molar ratios of SPC to Fe(III). A mechanism of benzene degradation was elaborated by free-radical probe-compound tests, free-radical scavengers tests, electron paramagnetic resonance (EPR) analysis, and determination of Fe(II) and H2O2 concentrations. The degradation products were also identified using gas chromatography-mass spectrometry method. The hydroxyl radical (HO.) was the leading species in charge of benzene degradation. The formation of HO. was strongly dependent on the generation of the organic compound radical (R.) and superoxide anion radical (O.). Benzene degradation products included hydroxylated derivatives of benzene (phenol, hydroquinone, benzoquinone, and catechol) and aliphatic acids (oxalic and fumaric acids). The proposed degradation pathways are consistent with radical formation and identified products. The investigation of selected matrix constituents showed that the Cl and HCO3 had inhibitory effects on benzene degradation. Natural organic matter (NOM) had accelerating influence in degrading benzene. The developed system was tested with groundwater samples and it was found that the Fe(III)-activated SPC has a great potential in effective remediation of benzene-contaminated groundwater while more further studies should be done for its practical application in the future because of the complex subsurface environment.