Radiation-induced preparation of nanoscale CoO@graphene oxide for activating peroxymonosulfate to degrade emerging organic pollutants.

In this study, ionizing radiation was used to induce the in-situ formation of highly dispersed nanosized cobalt oxide on the surface of graphene oxide (R-Co-GO), which was highly effective for activating PMS to degrade sulfamethoxazole (SMX). R-Co-GO had the highest catalytic activity when 150 µL cobalt chloride hexahydrate solution was used in the precursor, and the pseudo first-order kinetic constant of SMX degradation was 0.07 min-1 with high mineralization efficiency (63.1 %) and high PMS utilization efficiency. The sulfate radicals and high-valent cobalt oxo were mainly responsible for SMX degradation. Mechanism analysis showed that cobalt active site dominated in PMS activation, which was responsible for the formation of sulfate radicals and high-valent cobalt oxo; while the carbon framework contributed to the formation of singlet oxygen. The R-Co-GO-150 had good catalytic activity and stability in five cycling experiments, in which SMX was completely degraded and the concentration of dissolved Co was below 0.1 mg/L. In addition, the R-Co-GO-150/PMS system could also degrade phenol, bisphenol A, atrazine and nitrobenzene effectively, confirming its wide applicability. This study provided a facile method to uniformly disperse the metal oxides on the surface of carbon materials, and an effective system for the removal of emerging organic pollutants from the actual 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.

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 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.

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.

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.

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.

Oxidative removal of carbamazepine by peroxymonosulfate (PMS) combined to ionizing radiation: Degradation, mineralization and biological toxicity.

Carbamazepine is one of pharmaceutical and personal care products (PPCPs) and has been widely used to treat depression and seizures, and it cannot be effectively removed during the conventional wastewater treatment processes. In this study, three processes were used for the carbamazepine degradation, including single radiation, radiation in the presence of peroxymonosulfate (PMS) and radiation followed by PMS oxidation. The results show that radiation in the presence of PMS could enhance the degradation and mineralization of carbamazepine, decreasing the absorbed dose required for completely degrading carbamazepine from 800 Gy to 300 Gy, no matter what the molar ratio of PMS to carbamazepine was. The radiation followed by PMS oxidation significantly increased the mineralization, and the maximum mineralization achieved 46.5% at the dose of 600 Gy. Eight intermediates were tentatively identified. Compared to single radiation process, the radiation in the presence of PMS enhanced the transformation of intermediates and the release of ammonium ion. In real wastewater, the radiation in the presence of PMS could effectively remove carbamazepine and considerably decreased the biological toxicity of the wastewater containing carbamazepine.

Acclimation of aerobic-activated sludge degrading benzene derivatives and co-metabolic degradation activities of trichloroethylene by benzene derivative-grown aerobic sludge.

The acclimation of aerobic-activated sludge for degradation of benzene derivatives was investigated in batch experiments. Phenol, benzoic acid, toluene, aniline and chlorobenzene were concurrently added to five different bioreactors which contained the aerobic-activated sludge. After the acclimation process ended, the acclimated phenol-, benzoic acid-, toluene-, aniline- and chlorobenzene-grown aerobic-activated sludge were used to explore the co-metabolic degradation activities of trichloroethylene (TCE). Monod equation was employed to simulate the kinetics of co-metabolic degradation of TCE by benzene derivative-grown sludge. At the end of experiments, the mixed microbial communities grown under different conditions were identified. The results showed that the acclimation periods of microorganisms for different benzene derivatives varied. The maximum degradation rates of TCE for phenol-, benzoic acid-, toluene-, aniline- and chlorobenzene-grown aerobic sludge were 0.020, 0.017, 0.016, 0.0089 and 0.0047 mg g SS(-1) h(-1), respectively. The kinetic of TCE degradation in the absence of benzene derivative followed Monod equation well. Also, eight phyla were observed in the acclimated benzene derivative-grown aerobic sludge. Each of benzene derivative-grown aerobic sludge had different microbial community composition. This study can hopefully add new knowledge to the area of TCE co-metabolic by mixed microbial communities, and further the understanding on the function and applicability of aerobic-activated sludge.

Kinetics of the aerobic co-metabolism of 1,1-dichloroethylene by Achromobacter sp.: a novel benzene-grown culture.

Batch experiments were performed for the aerobic co-metabolism of 1,1-dichloroethylene (1,1-DCE) by Achromobacter sp., identified by gene sequencing of 16S rRNA and grown on benzene. Kinetic models were employed to simulate the co-metabolic degradation of 1,1-DCE, and relevant parameters were obtained by non-linear least squares regression. Benzene at 90 mg L(-1) non-competitively inhibited degradation of 1,1-DCE (from 125 to 1,200 µg L(-1)). The maximum specific utilization (kc) rate and the half-saturation constant (Kc) for 1,1-DCE were 54 ± 0.85 µg h(-1) and 220 ± 6.8 µg L(-1), respectively; the kb and Kb for benzene were 13 ± 0.18 mg h(-1) and 28 ± 0.42 mg L(-1), respectively. This study provides a theoretical basis to predict the natural attenuation when benzene and 1,1-DCE occur as co-contaminants.