Enhanced uranium removal from aqueous solution by core-shell Fe0@Fe3O4: Insight into the synergistic effect of Fe0 and Fe3O4.

In this study, Fe0@Fe3O4 was synthesized and used to remove U(VI) from groundwater. Different experimental conditions and cycling experiments were used to investigate the performance of Fe0@Fe3O4 in the U(VI) removal, and the XRD, TEM, XPS and XANES techniques were employed to characterize the Fe0@Fe3O4. The results showed that the U(VI) removal efficiency of Fe0@Fe3O4 was 48.5 mg/g that was higher than the sum of removal efficiency of Fe0 and Fe3O4. The uranium on the surface of Fe0@Fe3O4 mainly existed as U(IV), followed by U(VI) and U(V). The Fe0 content decreased after reaction, while the Fe3O4 content increased. Based on the results of experiments and characterization, the enhanced removal efficiency of Fe0@Fe3O4 was attributed to the synergistic effect of Fe0 and Fe3O4 in which Fe3O4 accelerated the Fe0 corrosion that promoted the progressively formation of Fe(II) that promoted the reduction of adsorbed U(VI) to U(IV) and incorporated U(VI) to U(V). The performance of Fe0@Fe3O4 at near-neutrality condition was better than at acidic and alkalic conditions. The chloride ions, sulfate ions and nitrate ions showed minor effect on the Fe0@Fe3O4 performance, while carbonate ions exhibited significant inhibition. The metal cations showed different effect on the Fe0@Fe3O4 performance. The removal efficiency of Fe0@Fe3O4 decreased with the number of cycling experiment. Ionizing radiation could regenerate the used Fe0@Fe3O4. This study provides insight into the U(VI) removal by Fe0@Fe3O4 in aqueous solution.

The correlation between electron exchange capacity of Fenton-like heterogeneous catalyst and catalytic activity.

Electron transfer played key role in peroxymonosulfate (PMS) activation for heterogeneous Fenton-like catalysts (HFCs). However, the relationship between electron exchange capacity (EEC) and catalytic activity of HFCs has not been elucidated. Herein, thirteen HFCs reported in our previous studies were selected to measure their EEC via electrochemical methods and to investigate the correlation between EEC and catalytic activity for PMS. The results show that nitrogen-doped graphene oxide had much higher EEC (5.299 mM(e) g-1), followed by reduced graphene oxide (3.23 mM(e) g-1), nitrogen-doped biochar-700 (2.032 mM(e) g-1), graphene oxdie (1.789 mM(e) g-1), nitrogen-doped biochar-300 (1.15 mM(e) g-1), g-C3N4 (0.752 mM(e) g-1) and biochar (0.351 mM(e) g-1). For carbon materials, their catalytic activity was not determined by electron donor capacity (EDC), electron acceptor capacity (EAC) and EEC (EDC + EAC), but was linear correlation with |EDC-EAC| that can characterize the extent of HFCs reacting with PMS. The higher the |EDC-EAC| is, the higher the catalytic activity of HFCs is. For carbonaceous materials, their catalytic activity was not proportional to EAC, but had good linear correlation with EDC and |EDC-EAC|. The discrepancy between carbon materials and carbonaceous materials could be due to the different activation mechanisms. Further analysis found that there was no correlation between EEC and the reactive species derived from PMS, indicating that the produced reactive species was not only controlled by EEC. This study firstly elucidated the correlation between EEC and catalytic activity of HFCs, and |EDC-EAC| could be used as an index for evaluating the catalytic activity of HFCs.

Peroxymonosulfate activation by nanocomposites towards the removal of sulfamethoxazole: Performance and mechanism.

Heterogeneous activation of peroxomonosulfate (PMS) has been extensively studied for the degradation of antibiotics. The cobalt ferrite spinel exhibits good activity in the PMS activation, but suffers from the disadvantage of low PMS utilization efficiency. Herein, the nanocomposites including FeS, CoS2, CoFe2O4 and Fe2O3 were synthesized by hydrothermal method and used for the first time to activate PMS for the removal of sulfamethoxazole (SMX). The nanocomposites showed superior catalytic activity in which the SMX could be completely removed at 40 min, 0.1 g L-1 nanocomposites and 0.4 mM PMS with the first order kinetic constant of 0.2739 min-1. The PMS utilization efficiency was increased by 29.4% compared to CoFe2O4. Both radicals and non-radicals contributed to the SMX degradation in which high-valent metal oxo dominated. The mechanism analysis indicated that sulfur modification, on one hand, enhanced the adsorption of nanocomposites for PMS, and promoted the redox cycles of Fe2+/Fe3+ and Co2+/Co3+ on the other hand. This study provides new way to enhance the catalytic activity and PMS utilization efficiency of spinel cobalt ferrite.

Uranium removal in groundwater by Priestia sp. isolated from uranium-contaminated mining soil.

Priestia sp. WW1 was isolated from a uranium-contaminated mining soil and identified. The uranium removal characteristics and mechanism of Priestia sp. WW1 were investigated. The results showed that the removal efficiency of uranium decreased with the increase of initial uranium concentration. When the uranium initial concentration was 5 mg/L, the uranium removal efficiency achieved 92.1%. The increase of temperature could promote the uranium removal. Carbon source could affect the removal rate of uranium, which was the fastest when the methanol was used as carbon source. The solution pH had significant effect on the uranium removal efficiency, which reached the maximum under solution pH 5.0. The experimental results and FTIR as well as XPS demonstrated that Priestia sp. WW1 could remove uranium via both adsorption and reduction. The common chloride ions, sulfate ions, Mn(II) and Cu(II) enhanced the uranium removal, while Fe(III) depressed the uranium removal. The Priestia sp. WW1 could effectively remove the uranium in the actual mining groundwater, and the increase of initial biomass could improve the removal efficiency of uranium in the actual mining groundwater. This study provided a promising bacterium for uranium remediation in the groundwater.

Advanced treatment of coking wastewater: Recent advances and prospects.

Advanced treatment of refractory industrial wastewater is still a challenge. Coking wastewater is one of coal chemical wastewater, which contains various refractory organic pollutants. To meet the more and more rigorous discharge standard and increase the reuse ratio of coking wastewater, advanced treatment process must be set for treating the biologically treated coking wastewater. To date, several advanced oxidation processes (AOPs), including Fenton, ozone, persulfate-based oxidation, and iron-carbon micro-electrolysis, have been applied for the advanced treatment of coking wastewater. However, the performance of different advanced treatment processes changed greatly, depending on the components of coking wastewater and the unique characteristics of advanced treatment processes. In this review article, the state-of-the-art advanced treatment process of coking wastewater was systematically summarized and analyzed. Firstly, the major organic pollutants in the secondary effluents of coking wastewater was briefly introduced, to better understand the characteristics of the biologically treated coking wastewater. Then, the performance of various advanced treatment processes, including physiochemical methods, biological methods, advanced oxidation methods and combined methods were discussed for the advanced treatment of coking wastewater in detail. Finally, the conclusions and remarks were provided. This review will be helpful for the proper selection of advanced treatment processes and promote the development of advanced treatment processes for coking wastewater.

Treatment of tributyl phosphate by fenton oxidation: Optimization of parameter, degradation kinetics and pathway.

In nuclear industry, tributyl phosphate (TBP) is used as organic extracting solvent to separate uranium and plutonium. The spent TBP is finally discarded as the radioactive organic waste, which should be treated due to its potential risk. In this study, TBP degradation by Fenton oxidation was investigated in detail, including the optimization of operational conditions, degradation kinetics and degradation products. The optimal conditions for TBP degradation (per 10 ml) by Fenton oxidation was: 95 °C, pH 2, 150 ml 30% H2O2, and 105 ml 0.2 M Fe(II). H2O2 was continuously added with the flow rate of 0.5 ml/min, Fe(II) was intermittently added with the flow rate of 3 ml/10 min. The oil phase volume decreased with time and completely disappeared at the third hour. In contrast, the COD in water phase increased firstly and then decreased. At the end of the experiments, the COD achieved 23.8 g/L. The detection of phosphorus in water phase further confirmed the decomposition of TBP. Mono-butyl phosphate and di-butyl phosphate were identified as the intermediate products of TBP degradation. In addition, other four degradation products with the same m/z of 154 were identified, which may be derived from the hydroxylation of mono-butyl phosphate and di-butyl phosphate. Based on the degradation products, the degradation pathway of TBP was proposed. This study could provide an insight into the TBP degradation by Fenton oxidation, and an potential strategy for treating the spent radioactive organic solvent.

Treatment of hospital wastewater by electron beam technology: Removal of COD, pathogenic bacteria and viruses.

The effective treatment of hospital sewage is crucial to human health and eco-environment, especially during the pandemic of COVID-19. In this study, a demonstration project of actual hospital sewage using electron beam technology was established as advanced treatment process during the outbreak of COVID-19 pandemic in Hubei, China in July 2020. The results indicated that electron beam radiation could effectively remove COD, pathogenic bacteria and viruses in hospital sewage. The continuous monitoring date showed that the effluent COD concentration after electron beam treatment was stably below 30 mg/L, and the concentration of fecal Escherichia coli was below 50 MPN/L, when the absorbed dose was 4 kGy. Electron beam radiation was also an effective method for inactivating viruses. Compared to the inactivation of fecal Escherichia coli, higher absorbed dose was required for the inactivation of virus. Absorbed dose had different effect on the removal of virus. When the absorbed dose ranged from 30 to 50 kGy, Hepatitis A virus (HAV) and Astrovirus (ASV) could be completely removed by electron beam treatment. For Rotavirus (RV) and Enterovirus (EV) virus, the removal efficiency firstly increased and then decreased. The maximum removal efficiency of RV and EV was 98.90% and 88.49%, respectively. For the Norovirus (NVLII) virus, the maximum removal efficiency was 81.58%. This study firstly reported the performance of electron beam in the removal of COD, fecal Escherichia coli and virus in the actual hospital sewage, which would provide useful information for the application of electron beam technology in the treatment of hospital sewage.

Removal of ammonia and phenol from saline chemical wastewater by ionizing radiation: Performance, mechanism and toxicity.

Saline chemical wastewater containing ammonia and toxic organic pollutants has been a challenge for conventional wastewater treatment technology. Advanced treatment is thus required. In this study, the removal of ammonia and phenol in saline chemical wastewater by radiation was investigated in detail. The results showed that chloridion in saline chemical wastewater could be transferred to •Cl and •ClO by radiation, which promoted ammonia oxidation, but inhibited phenol degradation. Solution pH affected the types of reactive species, which further affected the removal of ammonia and phenol. When ammonia and phenol co-existed in saline chemical wastewater, the removal efficiency of ammonia was depressed compared to that in the absence of phenol. Similarly, the phenol removal efficiency was also depressed in the presence of ammonia when the solution pH was lower than 7.0. Interestingly, the phenol removal efficiency was improved with increase of either chloridion concentration (2-8 g/L) or dose (2-5 kGy), which was attributed to the formation of intermediate nitrogen-centered radicals that can react with phenol. In addition, the intermediate products of phenol degradation under different conditions were identified. The acute toxicity of saline chemical wastewater after radiation treatment was evaluated. The results of this study could provide an insight into the removal of ammonia and phenol from saline chemical wastewater by radiation technology.

Degradation of sulfamethoxazole using PMS activated by cobalt sulfides encapsulated in nitrogen and sulfur co-doped graphene.

In this study cobalt sulfides (Co9S8) coated on the nitrogen and sulfur co-doped graphene (Co9S8@S-N-RG) was firstly prepared and used for degradation of antibiotic sulfamethoxazole (SMX). The results showed that SMX could be completely degraded by Co9S8@S-N-RG-activated peroxymonosulfate (PMS) within 20 min with its mineralization efficiency of 38.7%. The SMX degradation rate followed pseudo first-order kinetics with kinetic constant of 0.377 min-1 that was higher than that induced by Co9S8, N-RG, S-N-RG and Co9S8@S-RG, indicating Co9S8@S-N-RG had superior catalytic activity. Co9S8@S-N-RG can activate PMS to produce sulfate radicals and hydroxyl radicals, while sulfate radicals played major role. Co9S8 participated in PMS activation in which Co2+ was involved in sulfate radicals formation, while sulfur species facilitated the conversion of Co3+ to Co2+. In addition, carbon defects, CO, pyridinic N and pyrrolic N also contributed to PMS activation.The superior catalytic activity was attributed to the synergistic effect of Co9S8 and S-N-RG. This study could provide an efficient and stable PMS activator, and insight into the PMS activation mechanism by Co9S8@S-N-RG.

The performance and pathway of indole degradation by ionizing radiation.

Indole is a typical recalcitrant aromatic nitrogen heterocyclic compound, which usually exists in coal chemical wastewater, and cannot be effectively removed by conventional wastewater treatment process. In this study, ionizing radiation was applied for the degradation of indole in aqueous solution. The effect of absorbed dose (1, 2, 3 and 5 kGy), initial concentration of indole (10, 20, 40 and 100 mg/L) and pH (3, 5, 7 and 9) on the degradation of indole was investigated. The results showed that the removal efficiency of indole was 99.2% at its initial concentration of 10 mg/L, absorbed dose of 2 kGy, and pH of 5. In addition, quenching experiments confirmed that three reactive species, including hydroxyl radical, hydrated electron and hydrogen radical, contributed to indole degradation. Five intermediate products were identified during indole degradation, including 3-methylindole, 3-methylinodle radicals, hydroxylation inodole, anilinoethanol and isatoic acid. The possible pathway of indole degradation was proposed. The acute toxicity and chronic toxicity of intermediate products of indole degradation were significantly reduced, except for 3-methylindole. In summary, ionizing radiation is alternative technology for the degradation of indole in coal chemical wastewater.

Degradation of chloroaniline in chemical wastewater by ionizing radiation technology: Degradation mechanism and toxicity evaluation.

Chloroaniline is a typical organic pollutant in chemical wastewater, which cannot be effectively removed in conventional wastewater treatment processes. In this study, ionizing radiation was used as advanced treatment process to degrade 2-chloroaniline (2-CA). The results showed that 10 mg/l of 2-CA could be completely degraded at 1 kGy. The required dose for completely degrading 2-CA by radiation increased when its initial concentration increased. Solution pH affected 2-CA degradation by changing the radiation-chemical yield of reactive species. Chloride ions (10 and 100 mM) had not obvious influence on 2-CA degradation. Hydrogen radicals, hydrated electrons and hydroxyl radicals, all contributed to the degradation of 2-CA, but with different degradation mechanisms. Hydrogen radicals and hydrated electrons could initiate reductive dechlorination of 2-CA, while hydroxyl radicals can degrade 2-CA by hydroxylation. 6-amino-1,4-cyclohexadiene and chlorobenzene were the main intermediate products of 2-CA degradation in the hydrogen radicals or hydrated electrons dominant process; while o-hydroxyaniline and nitroso-chlorobenzene were the main intermediate products in the hydroxyl radicals dominant process. The solution toxicity after radiation treatment varied with the initial concentration of 2-CA and the absorbed dose. In the actual chemical wastewater, 2-CA can be effectively removed by radiation, even in the presence of high concentration of chloride ions (about 2800 mg/l). The solution toxicity of actual wastewater decreased with the increase of adsorbed dose. This study provided an insight into the 2-CA degradation by radiation, and demonstrated that radiation could be an alternative option for the treatment of chloroaniline-containing chemical wastewater.

Magnetic 2D/2D oxygen doped g-C3N4/biochar composite to activate peroxymonosulfate for degradation of emerging organic pollutants.

Herein, magnetic 2D/2D oxygen-doped graphite carbon nitride/ biochar (γ-Fe2O3/O-g-C3N4/BC) composite was rationally fabricated and used to activate peroxymonosulfate (PMS) for the degradation of emerging organic pollutants. O-g-C3N4 or coconut-derived biochar (BC) displayed low catalytic activity to PMS, while γ-Fe2O3/O-g-C3N4/BC composite showed superior catalytic activity, in which complete degradation of antibiotic sulfamethoxazole (SMX) was quickly achieved, with the mineralization ratio of 62.3%. The surface-bound reactive species (dominant) and sulfate radicals as well as hydroxyl radicals contributed to SMX degradation. Visible light could accelerate SMX degradation and enhance SMX mineralization, suggesting that γ-Fe2O3/O-g-C3N4/BC composite had good photocatalytic activity. The superior catalytic activity of γ-Fe2O3/O-g-C3N4/BC composite to activate PMS and visible light was attributed to the enhanced interfacial charge transfer and adsorption capacity. In addition to antibiotic SMX, other typical emerging organic pollutants, including atrazine, phenol, nitrobenzene and carbamazepine could also be degraded and mineralized in the system of visible light/O-g-C3N4/BC/PMS, indicating its wide applicability for degradation of various toxic organic pollutants in water and wastewater.

Iron-Based Dual Active Site-Mediated Peroxymonosulfate Activation for the Degradation of Emerging Organic Pollutants.

It is still a challenge to synthesize highly efficient and stable catalysts for the Fenton-like reaction. In this study, we constructed an integrated catalyst with highly dispersed iron-based dual active sites, in which Fe2N and single-atom Fe (SA-Fe) were embedded into nitrogen- and oxygen-co-doped graphitic carbon (Fe-N-O-GC-350). Extended X-ray absorption fine structure (EXAFS) confirmed the coordination structure of iron, and line combination fitting (LCF) demonstrated the coexistence of Fe2N and SA-Fe with percentages of 75 and 25%, respectively. Iron-based dual active sites endowed Fe-N-O-GC-350 with superior catalytic activity to activate peroxymonosulfate (PMS) as evidenced by the fast degradation rate of sulfamethoxazole (SMX) (0.24 min-1) in the presence of 0.4 mM PMS and 0.1 g/L Fe-N-O-GC-350. Unlike the reported singlet oxygen and high-valent iron oxo-mediated degradation induced by the SA-Fe catalyst, both surface-bound reactive species and singlet oxygen contributed to SMX degradation, while surface-bound reactive species dominated. Density functional theory (DFT) simulation indicated that Fe2N and SA-Fe enhanced the adsorption of PMS, which played a key role in PMS activation. The Fe-N-O-GC-350/PMS system had resistance to the interference of common inorganic anions and high oxidation capacity to recalcitrant organic contaminants. This study elucidated the important role of Fe2N in PMS activation and provide a clue to design rationally catalysts with iron-based dual active sites to activate PMS for the degradation of emerging organic pollutants.

Nitrogen doping sludge-derived biochar to activate peroxymonosulfate for degradation of sulfamethoxazole: Modulation of degradation mechanism by calcination temperature.

The surface property of biochar can be modulated through nitrogen doping and calcination temperature. In this study, nitrogen-doped sludge-derived biochar (NSDB) was prepared and applied to activate peroxymonosulfate (PMS) for sulfamethoxazole (SMX) degradation, focusing on the effect of calcination temperature on the degradation mechanism. The results showed that the contribution of free radicals to SMX degradation decreased gradually when calcination temperature increased from 300 to 800 °C. In contrast, the contribution of surface-bound reactive species increased gradually. However, the contribution of surface-bound reactive species to SMX degradation decreased for NSDB prepared at 900 °C. The change of physiochemical properties such as contact angle caused by calcination temperature was responsible for the shift of SMX degradation mechanism. NSDB prepared at 800 °C showed higher catalytic activity to PMS compared to NSDB prepared at other temperatures. Compared to sludge-derived biochar (SDB), NSDB had much higher catalytic activity, indicating that nitrogen doping could improve the catalytic activity of SDB. This study provided a way to modulate the degradation mechanism of SMX by calcination temperature of biochar to activate PMS for degradation of organic pollutants.

Successive non-radical and radical process of peroxymonosulfate-based oxidation using various activation methods for enhancing mineralization of sulfamethoxazole.

To enhance the mineralization of toxic organic pollutants is crucial for the alleviation of environmental pollution. In this study, the successive non-radicals and radicals process (SNRP) of peroxymonosulfate (PMS)-based oxidation was performed using various methods for PMS activation, including UV, ozone, gamma radiation and biochar and applied for enhancing the mineralization of sulfamethoxazole (SMX). The results showed that SNRP-UV could improve the mineralization of SMX, and both SNRP-UV and PMS/UV could completely mineralize SMX. For SNRP-Ozone, SNRP-Radiation and SNRP-Biochar, compared to the sole radical oxidation, all SNRPs could enhance the mineralization of SMX. The biochar-induced SNRP obtained the maximum mineralization increment, followed by gamma irradiation-induced SNRP and ozone-induced SNRP. Sulfate radicals were mainly responsible for SMX mineralization for SNRP-Biochar, while hydroxyl radicals for SNRP-Radiation, and the synergetic effect of ozone and sulfate radicals for SNRP-Ozone. Different degradation intermediate products were identified in different SNRP, further revealing that SNRP induced by different methods had different mineralization capacity. This study further demonstrated that SNRP could be a new strategy for enhancing the mineralization of SMX.

Peroxymonosulfate Activation by Fe-Co-O-Codoped Graphite Carbon Nitride for Degradation of Sulfamethoxazole.

Graphite carbon nitride (g-C3N4) has a stable structure but poor catalytic capability for activating peroxymonosulfate (PMS). In this study, the codoping of g-C3N4 with bimetallic oxides (iron and cobalt) and oxygen was investigated to enhance its catalytic capability. The results showed that iron, cobalt, and oxygen codoped g-C3N4 (Fe-Co-O-g-C3N4) was successfully prepared, which was capable of completely degrading sulfamethoxazole (SMX) (0.04 mM) within 30 min, with a reaction rate of 0.085 min-1, indicating the superior catalytic activity of Fe-Co-O-g-C3N4. The mineralization efficiency of SMX was 22.1%. Sulfate radicals and singlet oxygen were detected during the process of PMS activation. However, the role that singlet oxygen played in degrading SMX was not obvious. Surface-bound reactive species and sulfate radicals were responsible for SMX degradation, in which sulfate radicals contributed to 46.6% of SMX degradation. The superior catalytic activity was due to the synergistic effect of metal oxides and O-g-C3N4, in which O-g-C3N4 could act as a carrier and an activator as well as an electron mediator to promote the conversion of Fe(III) to Fe(II) and Co(III) to Co(II). Four main steps of SMX degradation were proposed, including direct oxidation of SMX, bond fission of N-C, bond fission of N-S, and bond fission of S-C. The effect of the pH, temperature, PMS concentration, chloridion, bicarbonate, and humic acids on SMX degradation was investigated. Cycling experiments demonstrated the good stability of Fe-Co-O-g-C3N4. This study first reported the preparation of bimetallic oxide and oxygen codoped g-C3N4, which was an effective PMS activator for degradation of toxic organic pollutants.

Kinetics of PMS activation by graphene oxide and biochar.

Carbon-based materials have been studied as metal-free catalyst for persulfate activation. At present, the activation performance of carbon materials for persulfate is usually characterized by the removal efficiency of organic pollutants. However, the kinetics of persulfate activation by carbon materials has not been investigated. In this study, the kinetics of peroxymonosulfate (PMS) activation by reduced graphene oxide (RGO) and sludge-derived biochar (BC) were investigated. The experimental results showed that the kinetics of PMS activation followed the two-phase kinetic model (fast phase (a1) and slow phase (a2)). In the absence of organic pollutants, the a1 and a2 were calculated to be 0.320 and 0.0471 min-1 for BC, respectively, and 0.322 and 0.0850 min-1 for RGO, respectively. Based on the characterization of BC and RGO, it can be concluded that the fast phase was mainly due to the formation of surface-bound active species. Competitive adsorption between PMS and targeted pollutants decreased the kinetic constant for the first phase (a1) and the kinetic constant for the second phase (a2) for both BC and RGO. The value of a1 and a2 increased for BC after the addition of phenol, due to the enhanced PMS activation by surface adsorbed phenol. The increase of phenol concentration decreased slightly the value of a1 and a2. The increase of PMS concentration increased significantly the value of a1 and a2. The decrease of a1 and a2 in repeated use of carbon materials could be due to the decrease of oxygen-containing functional groups and defect intensity.

A novel strategy of successive non-radical and radical process for enhancing the utilization efficiency of persulfate.

During the process of persulfate oxidation, side reactions such as the recombination of radicals can usually result in the low utilization efficiency of persulfate, which decreases the mineralization of target pollutants. In this study, the successive oxidation strategy was proposed based on successive non-radical and radical process (SNRP), to enhance the utilization efficiency of peroxymonosulfate (PMS), and further enhance the mineralization of sulfonamides. The results indicated that 0.04 mM of sulfonamide could be completely removed within 240 min at 1.2 mM PMS and initial pH 6.8 in the non-radical process, but the mineralization was very low (<2%). Moreover, the decomposition efficiency of PMS was less than 10% within 480 min. Fe(II) was added into the solution in which non-radicals process was performed, to initiate radical process by activating residual PMS. Compared to Fe(II)/PMS process, the SNRP process significantly increased the mineralization of sulfonamides, reaching 27.0%, 19.0%, 16.7% and 17.2%, respectively for sulfamethoxazole, sulfanilamide, sulfadiazine and sulfamerazine. The increased mineralization was due to the enhanced PMS utilization. Seven degradation products were identified in the SNRP process. Among them, hydrolyzed 3-amino-5-methyl isoxazole, (3-amino-5-methylisoxazole) sulfonic acid and 4-aminobenzenesulfinic acid produced in the non-radical oxidation process showed resistance to the subsequent radical oxidation. This study can provide a possible way to enhance the utilization efficiency of PMS as well as the mineralization of organic pollutants.

Nitrogen, sulfur and oxygen co-doped carbon-armored Co/Co9S8 rods (Co/Co9S8@N-S-O-C) as efficient activator of peroxymonosulfate for sulfamethoxazole degradation.

In this study, nitrogen, sulfur and oxygen co-doped carbon armored cobalt sulfide (Co/Co9S8@N-S-O-C) composite was synthesized, characterized and used to activate peroxymonosulfate (PMS) for the degradation of sulfamethoxazole (SMX). SMX (0.04 mM) can be completely degraded within 20 min in the presence of 0.8 mM PMS and 0.1 g/L Co/Co9S8@N-S-O-C composite. The first-order kinetics constant of SMX degradation was 0.307 min-1, and the mineralization of SMX was 30.1 %. The Quenching experiments of the free radicals and the identification of degradation products demonstrated that sulfate radicals played a dominant role in SMX degradation. The degradation rate of SMX increased with temperature, and activation energy was calculated to be 48.6 kJ/mol. The degradation rate of SMX increased firstly then decreased with increase of pH. Chloridion and humic acid decreased the degradation rate of SMX no matter what their initial concentration was. The effect of carbonate on SMX degradation depended on its initial concentration. Co/Co9S8@N-S-O-C composite showed good stability, the removal efficiency of SMX was 98.4 % in the fifth experiment. Based on the characterization results of the catalyst before and after use, it was concluded that cobalt, sulfur, pyridnic N and graphitic N were responsible for PMS activation.

Strategy of combining radiation with ferrate oxidation for enhancing the degradation and mineralization of carbamazepine.

In this study, the strategy of combining radiation with ferrate oxidation was proposed to decrease the adsorbed dosse and enhance the mineralization of carbamazepine in aqueous solution. Compared to single radiation (800 Gy), the combined process of ferrate pretreatment and radiation required lower dose (600 Gy) for totally removing carbamazepine. During the combined process, the removal efficiency of total organic carbon (TOC) reached 22.2%. However, the removal efficiencies of carbamazepine and TOC decreased when ferrate and radiation were used simultaneously, indicating that the addition of ferrate during the radiation process had negative effect on the removal of carbamazepine. In contrast, the radiation followed by ferrate oxidation presented the best performance in decreasing the absorbed dose and enhancing the mineralization of carbamazepine. Carbamazepine could be completely removed under all conditions. TOC removal efficiency reached 18.3%, 31.3%, 52.9% and 60.6%, respectively, at the adsorbed dose of 100, 300, 600 and 800 Gy when 0.4 mM ferrate was adopted. The enhanced TOC removal could be due to the enhanced oxidation capacity of ferrate caused by the pH decrease at the end of radiation and the further oxidation of intermediate products formed during the radiation process by ferrate. Seven degradation products were identified in total, and thus the degradation pathway of carbamazepine was proposed. This study provides a possible way to decrease the adsorbed dose and enhance the mineralization of carbamazepine by radiation.