Methane production from the biodegradation of lignite with different sizes by mixed fungi-methanogen microflora.

Biogenic coalbed methane (CBM) is a developing clean energy source. However, it is unclear how the mechanisms of bio-methane production with different sizes of coal. In this work, pulverized coal (PC) and lump coal (LC) were used for methane production by mixed fungi-methanogen microflora. The lower methane production from LC was observed. The aromatic carbon of coal was degraded slightly by 2.17% in LC, while 11.28% in PC. It is attributed to the proportion of lignin-degrading fungi, especially Penicillium, which was reached 67.57% in PC on the 7th day higher than that of 11.38% in LC. The results suggested that the limited interaction area in lump coal led to microorganisms hardly utilize aromatics. It also led the accumulation of aromatic organics in the fermentation broth in PC. Increasing the reaction area of coal and facilitating the conversion of aromatic carbon are suggested means to increase methane production in situ.

Comparative analysis of UV-initiated ARPs for degradation of the emerging substitute of perfluorinated compounds: Does defluorination mean the sole factor?

Due to the increasing attention for the residual of per- and polyfluorinated compounds in environmental water, Sodium p-Perfluorous Nonenoxybenzenesulfonate (OBS) have been considered as an alternative solution for perfluorooctane sulfonic acid (PFOS). However, recent detections of elevated OBS concentrations in oil fields and Frontal polymerization foams have raised environmental concerns leading to the decontamination exploration for this compound. In this study, three advanced reduction processes including UV-Sulfate (UV-SF), UV-Iodide (UV-KI) and UV-Nitrilotriacetic acid (UV-NTA) were selected to evaluate the removal for OBS. Results revealed that hydrated electrons (eaq-) dominated the degradation and defluorination of OBS. Remarkably, the UV-KI exhibited the highest removal rate (0.005 s-1) and defluorination efficiency (35 %) along with the highest concentration of eaq- (K = -4.651). Despite that nucleophilic attack from eaq- on sp2 carbon and H/F exchange were discovered as the general mechanism, high-performance liquid chromatography-quadrupole time-of-flight mass spectrometry (HPLC/Q-TOF-MS) analysis with density functional theory (DFT) calculations revealed the diversified products and routes. Intermediates with lowest fluorine content for UV-KI were identified, the presence nitrogen-containing intermediates were revealed in the UV-NTA. Notably, the nitrogen-containing intermediates displayed the enhanced toxicity, and the iodine poly-fluorinated intermediates could be a potential-threat compared to the superior defluorination performance for UV-KI.

Unraveling the Role of Humic Acid in the Oxidation of Phenolic Contaminants by Soluble Manganese Oxo-Anions.

Humic acid (HA) is ubiquitous in natural aquatic environments and effectively accelerates decontamination by permanganate (Mn(VII)). However, the detailed mechanism remains uncertain. Herein, the intrinsic mechanisms of HA's impact on phenolics oxidation by Mn(VII) and its intermediate manganese oxo-anions were systematically studied. Results suggested that HA facilitated the transfer of a single electron from Mn(VII), resulting in the sequential formation of Mn(VI) and Mn(V). The formed Mn(V) was further reduced to Mn(III) through a double electron transfer process by HA. Mn(III) was responsible for the HA-boosted oxidation as the active species attacking pollutants, while Mn(VI) and Mn(V) tended to act as intermediate species due to their own instability. In addition, HA could serve as a stabilizer to form a complex with produced Mn(III) and retard the disproportionation of Mn(III). Notably, manganese oxo-anions did not mineralize HA but essentially changed its composition. According to the results of Fourier-transform ion cyclotron resonance mass spectrometry and the second derivative analysis of Fourier-transform infrared spectroscopy, we found that manganese oxo-anions triggered the decomposition of C-H bonds on HA and subsequently produced oxygen-containing functional groups (i.e., C-O). This study might shed new light on the HA/manganese oxo-anion process.

Effect of Tb3+ and Ce3+ Co-doping on the Structure and Photoluminescence Properties of Hexagonal Boron Nitride Phosphors.

In the paper, we have successfully prepared hexagonal boron nitride (h-BN:Tb3+, Ce3+) phosphors with melamine as the nitrogen source. The X-ray powder diffraction patterns confirm that the sample possesses a hexagonal crystal structure within the P 6 ¯ m2 space group. It is interesting that the co-doping combination of Tb3+ and Ce3+ can markedly enhance the threshold concentration of doped activators within the limited solid solution of h-BN phosphors. Under 302 nm excitation, the h-BN:Ce3+ phosphors exhibit broadband blue light emission at 406 nm. In h-BN:Tb3+, Ce3+ phosphors, the co-doping of Ce3+ not only ensures high phase purity but also results in strong green light emission. The energy transfer efficiency from Ce3+ to Tb3+ is about 55%. The fluorescence lifetime increases with the increase of Ce3+ and Tb3+ concentration, and the fluorescence lifetime of h-BN:0.025Tb3+, 0.05Ce3+ phosphor reached 2.087 ms. Additionally, the h-BN:0.025Tb3+, 0.05Ce3+ phosphor exhibits excellent thermal performance with an activation energy value of 0.2825 eV. Moreover, the photoluminescence quantum yield of the sample exceeds 52%. Therefore, the h-BN:Tb3+, Ce3+ samples can be used as green phosphors for solid state lighting and fluorescent labeling.

Synergy between UV light and trichloroisocyanuric acid on methylisothiazolinone degradation: Performance, kinetics and degradation pathway.

Methylisothiazolinone (MIT) is widely used in daily chemicals, fungicides, and other fields and its toxicity has posed a threat to water system and human health. In this study, ultraviolet (UV)/trichloroisocyanuric acid (TCCA), which belongs to advanced oxidation processes (AOP), was adopted to degrade MIT. Total chlorine attenuation detection proved that TCCA has medium UV absorption and a strong quantum yield (0.49 mol E-1). At a pH of 7.0, 93.5% of MIT had been decontaminated after 60 min in UV/TCCA system (kobs = 4.4 × 10-2 min-1, R2 = 0.978), which was much higher than that in the UV alone system and TCCA alone system, at 65% (1.7 × 10-2 min-1, R2 = 0.995) and 10% (1.8 × 10-3 s-1, R2 = 0.915), respectively. This system also behaved well in degrading other five kinds of contaminants. Tert-butanol (TBA) and carbonate (CO32-) were separately used in quenching experiments, and the degradation efficiency of MIT decreased by 39.5% and 46.5% respectively, which confirmed that HO• and reactive chlorine species (RCS) were dominant oxidants in UV/TCCA system. With TCCA dosage increasing in a relatively low concentration range (0.02-0.2 mM) and pH decreasing, the effectiveness of this AOP system would be strengthened. The influences of coexisting substances (Cl-, SO42-, CO32-, NO2- and NO3-) were explored. MIT degradation pathways were proposed and sulfur atom oxidation and carboxylation were considered as the dominant removal mechanisms of MIT. Frontier orbital theory and Fukui indexes of MIT were employed to further explore the degradation mechanism.

Reevaluation for UV photolysis of Fe(III) inducing tetracycline abatement: Overlooked significance of complexation-assistance in environmental fates of antibiotics.

Interaction of antibiotics with metal ions in aquatic environments, commonly occurring to form complexes, may affect the migration, transformation and reactivity of residual antibiotics. This study demonstrates the photolysis of Fe(III) by UV irradiation at pH 3.5, as an advanced oxidation process, to produce •OH for the abatement of a common broad-spectrum antibiotic compound, tetracycline (TET). The dimethylamino (-N(CH3)2) and hydroxyl (-OH) groups of TET were determined as the binding sites for the complexation with Fe(III) via a series of novel characterization approaches. The complexation stoichiometry of Fe(III)-TET complexation, including the complexation ratio, constants and percentages, was determined via a complexometric titration based on the UV differential spectroscopy. The complexation constant was determined to be 21,240 ± 1745 L·mol-1 under the designed conditions. Complexation of TET with Fe(III) enhanced its degradation in the UV/Fe(III) process, through the promotion of the •OH generation by inhibiting hydrolysis-precipitation process of Fe(III) and enhancing Fe(III)/Fe(II) cycle and the acceleration of mass transfer between •OH and TET. This finding provides new insights into the role of complexation in the fate of residual antibiotics in the UV/Fe(III) process. The reduced overall ecotoxicity during the TET abatement, evaluated by the toxicity variation through ECOSAR program, provides the UV/Fe(III) process with a theoretical feasibility for water decontamination in actual applications.

Insights into the electron transfer regime of permanganate activation on carbon nanomaterial reduced from carbon dioxide.

Simultaneously eliminating novel contaminants in the water environment while also achieving high-value utilization of CO2 poses a significant challenge in water purification. Herein, a CO2-reduced carbon catalyst (CRC) was synthesized via the chemical vapor deposition method for permanganate (PM) activation, fulfilling the ultra-efficient removal of bisphenol A (BPA). The primary mechanism responsible for the BPA degradation in the CRC/PM process is electron transfer. Hydroxyl groups and defect structures on CRC act as electron mediators, facilitating the transfer of electrons from contaminants to PM. On the basis of the quantitative structure-activity relationship, the elimination performance of the CRC/PM process exhibited variability in accordance with the inherent characteristics of pollutants. In addition, the yield of manganese intermediates was also observed in the CRC/PM process, which only serve as redox intermediates rather than active species attacking organics. Ascribed to nonradical mechanisms, the CRC/PM system exhibited remarkable stability and demonstrated significant resistance to the presence of background substances. Moreover, BPA degradation pathways were clarified via mass spectrometry analysis and density functional theory calculations, with intermediate products exhibiting lower toxicity. This study provided new insights into the employment of carbon catalysts derived from CO2 for PM nonradical activation to degrade contaminants in various water matrices.

Insights into the carbon nanotubes-mediated activation of permanganate for decontamination under high salinity.

Radical-based advanced oxidation process (AOPs) has attracted great interests in wastewater treatment field. However, by the traditional radical-based method, the degradation of organic pollution is greatly suppressed when radicals react with the co-existing anions in the solution. Herein, an efficient method for degrading of contaminant under high salinity conditions is discussed through a non-radical pathway. Carbon nanotubes (CNTs) was employed as an electron transfer medium to facilitate the electron conversion from contaminants to potassium permanganate (PM). Based the results of quenching experiments, probe experiments, and galvanic oxidation process experiments, the degradation mechanism of CNTs/PM process was demonstrated to be electron transfer, rather than reactive intermediate Mn species. As a result, typical influencing factors including salt concentration, cations, and humic acid have less of an impact on degradation during CNTs/PM processes. In addition, the CNTs/PM system exhibits superior reusability and universality of pollutants, which has the potential to be applied as a non-radical pathway for the purification of contaminant in the large-scale high salinity wastewater treatment.

The effect of organics transformation and migration on pore structure of bituminous coal and lignite during biomethane production.

Biomethane generation by coal degradation not only can increase coalbed methane (CBM) reserves, namely, microbially enhanced coalbed methane (MECBM), but also has a significant effect on the pore structure of coal which is the key factor in CBM extraction. The transformation and migration of organics in coal are essential to pore development under the action of microorganisms. Here, the biodegradation of bituminous coal and lignite to produce methane and the cultivation with inhibition of methanogenic activity by 2-bromoethanesulfonate (BES) were performed to analyze the effect of biodegradation on coal pore development by determining the changes of the pore structure and the organics in culture solution and coal. The results showed that the maximum methane productions from bituminous coal and lignite were 117.69 µmol/g and 166.55 µmol/g, respectively. Biodegradation mainly affected the development of micropore whose specific surface area (SSA) and pore volume (PV) decreased while the fractal dimension increased. After biodegradation, various organics were generated which were partly released into culture solution while a large number of them remained in residual coal. The content of newly generated heterocyclic organics and oxygen-containing aromatics in bituminous coal was 11.21% and 20.21%. And the content of heterocyclic organics in bituminous coal was negatively correlated with SSA and PV but positively correlated with the fractal dimension which suggested that the retention of organics contributed greatly to the decrease of pore development. But the retention effect on pore structure was relatively poor in lignite. Besides, microorganisms were observed around fissures in both coal samples after biodegradation which would not be conducive to the porosity of coal on the micron scale. These results revealed that the effect of biodegradation on pore development of coal was governed by the combined action of organics degradation to produce methane and organics retention in coal whose contributions were antagonistic and determined by coal rank and pore aperture. The better development of MECBM needs to enhance organics biodegradation and reduce organics retention in coal.

Corrigendum: Contaminants from a former Croatian coal sludge dictate the structure of microbiota in the estuarine (Rasa Bay) sediment and soil.

[This corrects the article DOI: 10.3389/fmicb.2023.1126612.].

Trade-off effect of dissolved organic matter on degradation and transformation of micropollutants: A review in water decontamination.

The degradation of micropollutants by various treatments is commonly affected by the ubiquitous dissolved organic matter (DOM) in the water environment. To optimize the operating conditions and decomposition efficiency, it is necessary to consider the impacts of DOM. DOM exhibits varied behaviors in diverse treatments, including permanganate oxidation, solar/ultraviolet photolysis, advanced oxidation processes, advanced reduction process, and enzyme biological treatments. Besides, the different sources (i.e., terrestrial and aquatic, etc) of DOM, and operational circumstances (i.e., concentration and pH) fluctuate different transformation efficiency of micropollutants in water. However, so far, systematic explanations and summaries of relevant research and mechanism are rare. This paper reviewed the "trade-off" performances and the corresponding mechanisms of DOM in the elimination of micropollutants, and summarized the similarities and differences for the dual roles of DOM in each of the aforementioned treatments. Inhibition mechanisms typically include radical scavenging, UV attenuation, competition effect, enzyme inactivation, reaction between DOM and micropollutants, and intermediates reduction. Facilitation mechanisms include the generation of reactive species, complexation/stabilization, cross-coupling with pollutants, and electron shuttle. Moreover, electron-drawing groups (i.e., quinones, ketones functional groups) and electron-supplying groups (i.e., phenols) in the DOM are the main contributors to its trade-off effect.

Contaminants from a former Croatian coal sludge dictate the structure of microbiota in the estuarine (Rasa Bay) sediment and soil.

Introduction: Croatian superhigh-organic-sulfur Rasa coal had been mined for nearly 400 years. The release of hazardous trace elements (HTEs) and toxic organic pollutants (TOPs) into the local environment by coal mining, preparation, and combustion activities has resulted in pollution. Methods: In this study, the diversity and composition of microbial communities in estuarine sediment and soil samples as well as community function responses to the pollutants were investigated. Results: The results showed that PAH degradation does occur following 60 years of natural attenuation, the location is still heavily polluted by polycyclic aromatic hydrocarbons (PAHs) and HTEs. Microbial analyses have shown that high concentrations of PAHs have reduced the diversity and abundance of microbial communities. The pollution exerted an adverse, long-term impact on the microbial community structure and function in the brackish aquatic ecosystem. Microorganisms associated with the degradation of PAHs and sulfur-containing compounds have been enriched although the diversity and abundance of the microbial community have reduced. Fungi which are believed to be the main PAH degrader may play an important role initially, but the activity remains lower thereafter. It is the high concentrations of coal-derived PAHs, rather than HTEs, that have reduced the diversity and abundance of microbial communities and shaped the structure of the local microbiota. Discussion: This study could provide a basis for the monitoring and restoration of ecosystems impacted by coal mining activities considering the expected decommission of a large number of coal plants on a global scale in the coming years due to growing global climate change concerns.

A Novel Source of Radicals from UV/Dichloroisocyanurate for Surpassing Abatement of Emerging Contaminants Versus Conventional UV/Chlor(am)ine Processes.

Ultraviolet (UV)/chlor(am)ine processes are emerging advanced oxidation processes (AOPs) for water decontamination and raising continuous attention. However, limitations appear in the UV/hypochlorite and UV/monochloramine for removing specific contaminants ascribed to the differences in the sorts and yields of free radicals. Here, this study reports UV/dichloroisocyanurate (NaDCC) as a novel source of radicals. NaDCC was demonstrated to be a well-balanced compound between hypochlorite and monochloramine, and it had significant UV absorption and a medium intrinsic quantum yield. The UV/NaDCC produced more substantial hydroxyl radicals (·OH) and reactive chlorine species (RCSs, including Cl·, ClO·, and Cl2·-) than conventional UV/chlor(am)ine, thereby generating a higher oxidation efficiency. The reaction mechanisms, environmental applicability, and energy requirements of the UV/NaDCC process for emerging contaminants (ECs) abatement were further investigated. The results showed that ·OH and ·NH2 attacked ECs mostly through hydrogen atom transfer (HAT) and radical adduct formation, whereas Cl· destroyed ECs mainly through HAT and single electron transfer, with ClO· playing a certain role through HAT. Kinetic model analyses revealed that the UV/NaDCC outperformed the conventional UV/chlor(am)ine in a variety of water matrices with superior degradation efficiency, significantly saving up to 96% electrical energy per order. Overall, this study first demonstrates application prospects of a novel AOP using UV/NaDCC, which can compensate for the deficiency of the conventional UV/chlor(am)ine AOPs.

The variation of microorganisms and organics during methane production from lignite under an electric field.

OBJECTIVES: The succession of microbial communities and intermediates during methane production was determined by pyrosequencing and GC-MS to investigate the mechanism of biomethanation enhancement from coal. RESULTS: The maximum methane production at 1.2 V was significantly higher than that at 0 V. Bacterial flora have been changed as a result of the addition of an electric field, e.g., the abundance of Pseudomonas significantly increased to enhance the coal degradation which improved the methane yield by facilitating the electron transfer. The fungal structure was also found stabilized by the electric field when compared to the control after 7 days of cultivation. The predominance of Methanosarcina could also stimulate interspecies electron transfer. The GC-MS analysis revealed that the electric field can selectively promote the metabolism of refractory intermediates such as esters and aromatics during coal biodegradation. CONCLUSION: The application of an electric field could enhance methane production from coal by changing the structure and succession of microbial communities, improving electron transfer, and enhancing the fermentation of intermediates during coal biodegradation.

Determining Factors for Nitrite Accumulation in an Acidic Nitrifying System: Influent Ammonium Concentration, Operational pH, and Ammonia-Oxidizing Community.

Acidic nitrification is attracting wide attention because it can enable robust suppression of nitrite-oxidizing bacteria (NOB) in wastewater treatment. This study reports a comprehensive assessment of the novel acidic nitrification process to identify the key factors that govern stable nitrite accumulation. A laboratory-scale moving-bed biofilm reactor receiving low-alkalinity wastewater was continuously operated under acidic conditions (pH < 6) for around two years, including nine stages varying influent and operational conditions. The results revealed that nitrite accumulation was related to three factors, i.e., influent ammonium concentration, operating pH, and ammonia-oxidizing microbial community. These three factors impact nitrite accumulation by altering the in situ concentration of free nitrous acid (FNA), which is a potent inhibitor of NOB. The critical FNA concentration is approximately one part per million (ppm, ∼1 mg HNO2-N/L), above which nitrite accumulation is stably maintained in an acidic nitrifying system. The findings of this study suggest that stable nitrite accumulation via acidic ammonia oxidation can be maintained under a range of influent and operational conditions, as long as a ppm-level of FNA is established. Taking low-strength mainstream wastewater (40-50 mg NH4+-N/L) with limited alkalinity as an example, stable nitrite accumulation was experimentally demonstrated at a pH of 4.35, under which an in situ FNA of 2.3 ± 0.6 mg HNO2-N/L was attained. Under these conditions, Candidatus Nitrosoglobus became the only ammonia oxidizer detectable by 16S rRNA gene sequencing. The results of this study deepen our understanding of acidic nitrifying systems, informing further development of novel wastewater treatment technologies.

Enhancing Biomethane Production From Lignite by an Anaerobic Polycyclic Aromatic Hydrocarbon Degrading Fungal Flora Enriched From Produced Water.

The coal-degrading ability of microorganisms is essential for the formation of biogenic coalbed methane. The ability to degrade the aromatic compound of coal is more important because it is perceived as the main refractory component for bioconversion. In this paper, a polycyclic aromatic hydrocarbon (PAH) degrading fungal community (PF) was enriched from produced water using phenanthrene as sole carbon source. The goal was to improve both the microbial structure of the methanogenic microflora and its coal-degrading ability. Two strategies were pursued. The first used coal pretreatment with PF (PP), followed by methane production by methanogenic microflora; the second used methane production directly from coal by mixed culture of PF and methanogenic microflora (PM). The results showed that methane productions of PP and PM increased by 29.40 and 39.52%, respectively. After 7 days of cultivation, the fungal community has been altered in PP and PM, especially for Penicillium the proportions of which were 67.37 and 89.81% higher than that in methanogenic microflora, respectively. Furthermore, volatile fatty acid accumulations increased by 64.21 and 58.15%, respectively. The 13C-NMR results showed that PF addition promoted the transformation of aromatic carbons in coal to carboxyl and carbonyl carbons, which contributed greatly to the production of methane together with oxygen-containing functional groups. These results suggest that methane production can be increased by indigenous PAH-degrading fungi by improving the fermentation of aromatics in coal and the generation of volatile fatty acids. This provided a feasible method for enhancing biomethane generation in the coal seam.

Generality and diversity on the kinetics, toxicity and DFT studies of sulfate radical-induced transformation of BPA and its analogues.

The international campaign to ban bisphenol A (BPA) has resulted in increasing application of BPA substitutes. However, investigations have mainly been confined to the removal of single contaminant from the water, resulting in an inefficient burden. Furthermore, systematic study and synthetical discussion of bisphenol analogues (BPs) kinetics and transformation pathways were largely underemphasized. Chemical oxidation of BPA and four typical alternatives (i.e., bisphenol AF, bisphenol E, bisphenol F and bisphenol S) in a UV-activated persulfate system was examined in this study. The effects of persulfate (PS) dosage, pH and water matrix constituents (i.e., bicarbonate, chloride and natural organic matter) were comprehensively examined using a combination of laboratory experiments and mathematical modeling. According to our findings, the removal characteristics of different BPs employing SO4•--induced removal technology, including degradation mechanisms and influencing trends by water matrix, revealed similarly. The second order-rate constants of SO4•- reacting with BPs served as the main variables mediating the variation in degradation kinetics. Frontier molecular orbital theory and density functional theory suggested BPs molecules possessed the same susceptible positions to free radicals. In the UV-activated PS process, transformation pathways included hydroxylation, electron-transfer, substitution, and rearrangement triggered by ortho-cleavage, with certain intermediates exhibiting higher toxicity than the parent chemicals. The findings of this study provided valuable information to estimate potential environmental risks of using BPA alternatives.

[Evaluation of Eustachian tube function in children with adenoid hypertrophy by nasopharyngeal digital photography and ETDQ-7 scores].

Objective:To evaluate the Eustachian tube function of children with simple adenoid hypertrophy and adenoid hypertrophy with secretory otitis media（OME） by using the A/N value of lateral radiograph of nasopharyngeal X-ray and EDQ-7 scale scores. Methods:Sixty cases of children with adenoid hypertrophy admitted from February 2019 to August 2021 were all underwent nasopharyngeal X-ray lateral radiographs to determine the adenoid/nasopharyngeal cavity ratio（A/N ratio） and then determine the size of adenoids. The Eustachian tube function ETDQ-7 survey was used to evaluate the patient's self-evaluation of the severity of the disease and ear symptoms, and the degree of influence were scored. Subsequently, the correlation between adenoid hypertrophy with OME and ETDQ-7 scores was statistically analyzed by using the Spearman rank correlation statistical method. Results:In adenoid hypertrophy with OME group, the ETDQ-7 scores of A/N≤0.60, A/N 0.61-0.70 and A/N≥0.71 were 4.15±1.75, 14.55±6.67 and 23.95±6.63, respectively. The higher the grade of adenoid hypertrophy, the higher the ETDQ-7 scores. In adenoid hypertrophy with OME group, the degree of adenoid hypertrophy was positively correlated with the ETDQ-7 scores（P<0.05）. Conclusion:Adenoid hypertrophy is also one of the potential factors causing OME in children.

Multifunctional capacity of CoMnFe-LDH/LDO activated peroxymonosulfate for p-arsanilic acid removal and inorganic arsenic immobilization: Performance and surface-bound radical mechanism.

Organoarsenic contaminants existing in water body threat human health and ecological environment due to insufficient bifunctional treatment technologies for organoarsenic degradation and inorganic arsenic immobilization. In order to safely and efficiently treat organoarsenic contaminants discharged into the aquatic environment, Co-Mn-Fe layered double hydroxide (CoMnFe-LDH) and Co-Mn-Fe layered double oxide (CoMnFe-LDO) were fabricated and employed as peroxymonosulfate (PMS) activator for organoarsenic degradation and inorganic arsenic immobilization, and p-arsanilic acid (p-ASA) was selected as target pollutant. Results demonstrated that the satisfactory removal of p-ASA (100.0%) in both CoMnFe-LDH/PMS and CoMnFe-LDO/PMS systems was obtained within 30 min, and substantial inorganic arsenic adsorption could be achieved (below 0.5 mg/L) in two systems with converting major inorganic arsenic species to arsenate. As XPS, ESR and quenching experiment revealed, the existence and generation of surface-bound radicals in two systems were identified. Based on density functional theory calculation and XPS analysis, the catalytic mechanism of CoMnFe-LDO/PMS system that PMS could be activated via direct electron transfer from adsorbed p-ASA was clarified, which differed from PMS activation via coupling with surface hydroxyl groups in CoMnFe-LDH/PMS system. Catalytic performance assessment under various critical operation parameters indicated that CoMnFe-LDH presented more stable ability of p-ASA removal in a wide pH range and complex aquatic environment. The recycle experiment demonstrated the excellent stability and reusability of CoMnFe-LDH(LDO). Besides, seven degradation products of p-ASA in CoMnFe-LDH/PMS system including phenolic compounds, azophenylarsonic acid, nitrobenzene and benzoquinne were identified by UV-Vis spectra and LC-TOF-MS analysis, and the corresponding degradation pathway was proposed. In summary, compared to CoMnFe-LDO/PMS, CoMnFe-LDH/PMS holds great promise for the development of an oxidation-adsorption process for efficient control of organoarsenic pollutant.

Highly efficient removal of DEET by UV-LED irradiation in the presence of iron-containing coagulant.

N,N-Diethyl-3-methyl benzoyl amide (DEET) has been detected as an emerging pollutant in various water bodies because of its widespread use as an insect repellent. In this study, the combination of UV-LED275 and iron-containing coagulant (FeCl3) was used for the elimination of DEET in water. It was found that UV-LED275/FeCl3 (98 %) system presented a favorable removal of DEET compared with UV254/FeCl3 (59 %) and UV-LED275/Fe2(SO4)3 (81 %) processes at initial pH 3.5. DEET degradation by both UV-LED275/FeCl3 and UV-LED275/Fe2(SO4)3 processes followed pseudo-first-order kinetics with the calculated pseudo-first-order rate constants (kobs) of 0.0105 and 0.0046 cm2 mJ-1, respectively. The results of ESR analysis and radicals quenching experiments indicated that hydroxyl radicals (OH) and superoxide radicals (O2-) were responsible for DEET degradation in UV-LED275/FeCl3 process, and the former played the major role. An increase in FeCl3 dosage was beneficial to the degradation. In the UV-LED275/FeCl3 process, DEET degradation increased with a decrease in pH from 3.5 to 3.0, whereas it was almost completely suppressed with an increase in pH from 4.3 to 6.3. DEET degradation was almost unchanged after the introduction of NO3-, and it impeded after the addition of humic acid (HA), HCO3-, and SO42-. The plausible degradation pathway mainly involved hydroxylation, cleavage of the C-N bond, acetylation, and dealkylation. Among the disinfection by-products (DBPs) evaluated, UV-LED275/FeCl3 pretreatment generally increased the generation of trichloromethane, chloral hydrate, dichloroacetic acid, and trichloroacetic acid, which implied that further assessment of environmental risk was needed during its practical applications.