[Distribution of Typical Resistant Bacteria and Resistance Genes in Source Water of the Middle and Lower Reaches of the Yellow River].

The Yellow River water of an urban area located in the middle and lower reaches of the Yellow River was taken as the research object， in which the seasonal and along-range distribution of total culturable bacteria， typical antibiotic resistant bacteria （amoxicillin resistant bacteria and sulfamethoxazole-resistant bacteria）， and their corresponding typical resistance genes ï¼»ß-lactam resistance gene （blaCTX-M） and sulfamamide resistance genes （sulI and sulⅡ）， as well as intⅠ1 were investigated. The results showed that the total culturable bacteria， ß-lactam-resistant bacteria and sulfonamide-resistant bacteria in the Yellow River Basin were significantly affected by temperature and human activities. The composition and quantity of their genera had obvious spatiotemporal distribution characteristics， in which Bacillus and Pseudomonas were dominant in the composition and number of bacteria. The abundance of resistance genes decreased with the decrease in temperature. The proportion of ß-lactam resistance genes in the total genes was higher than that of sulfanilamide genes， and sulI was the dominant gene in sulfanilamide genes. Correlation analysis showed that class Ⅰ integron played an important role in accelerating the spread of resistance genes. This study offers insight into the status quo of water resistance pollution in the Yellow River and provides theoretical support for the risk assessment of resistance genes in the middle and lower reaches of the Yellow River Basin.

Iron-doped carbon nanotubes with magnetic enhanced Fe(VI) degradation of arsanilic acid and inorganic arsenic: Role of intermediate iron species and electron transfer.

Arsanilic acid (p-AsA), a prevalently used feed additive, is frequently detected in environment posing a great threat to humans. Potassium ferrate (Fe(VI)) was an efficient way to tackle arsenic contamination under acid and neutral conditions. However, Fe(VI) showed a noneffective removal of p-AsA under alkaline conditions due to its oxidation capacity attenuation. Herein, a magnetic iron-doped carbon nanotubes (F-CNT) was successfully prepared and further catalyzed Fe(VI) to remove p-AsA and total As species. The Fe(VI)/F-CNT system showed an excellent capability to oxidize p-AsA and adsorb total As species over an environment-related pH range of 6-9. The high-valent iron intermediates Fe(V)/Fe(IV) and the mediated electron-transfer played a significant part in the degradation of p-AsA according to the probes/scavengers experiments and galvanic oxidation process. Moreover, the situ formed iron hydroxide oxide and F-CNT significantly improved the adsorption capacity for total As species. The electron-donating groups (semiquinone and hydroquinone) and high graphitization of F-CNT were responsible for activating Fe(VI) based on the analysis of X-ray photoelectron spectroscopy (XPS). Density functional theory calculations and the detected degradation products both indicated that the amino group and the C-As bond of p-AsA were main reactive sites. Notably, Fe(VI)/F-CNT system was resistant to the interference from Cl-, SO42-, and HCO3-, and could effectively remove p-AsA and total As species even in the presence of complex water matrix. In summary, this work proposed an efficient method to use Fe(VI) for degrading pollutants under alkaline conditions and explore a new technology for livestock wastewater advanced treatment.

Degradation of tetracyclines via calcium peroxide activation by ultrasonic: Roles of reactive species, oxidation mechanism and toxicity evaluation.

Tetracyclines (TC) frequently detected in the aqueous environment pose threats to humans and ecosystems. The synergistic technology coupling ultrasound (US) and calcium peroxide (CaO2) has a great potential to abate TC in wastewater. However, the degradation efficiency and detailed mechanism of TC removal in the US/CaO2 system is unclear. This work was carried out to assess the performance and mechanism of TC removal in the US/CaO2 system. The results demonstrated that 99.2% of TC was degraded by the combination of 15 mM CaO2 with ultrasonic power of 400 W (20 kHz), but only about 30% and 4.5% of TC was removed by CaO2 (15 mM) or US (400 W) alone process, respectively. Experiments using specific quenchers and electron paramagnetic resonance (EPR) analysis indicated that the generation of hydroxyl radicals (•OH), superoxide radicals (O2-•), and single oxygen (1O2) in the process, whereas •OH and 1O2 were mainly responsible for the degradation of TC. The removal of TC in the US/CaO2 system has a close relationship with the ultrasonic power, the dosage of CaO2 and TC, and the initial pH. The degradation pathway of TC in the US/CaO2 process was proposed based on the detected oxidation products, and it mainly included N,N-dedimethylation, hydroxylation, and ring-opening reactions. The presence of 10 mM common inorganic anions including chloridion (Cl-), nitrate ion (NO3-), sulfate ion (SO42-), and bicarbonate ion (HCO3-) showed negligible influences on the removal of TC in the US/CaO2 system. The US/CaO2 process could efficiently remove TC in real wastewater. Overall, this work firstly demonstrated that •OH and 1O2 mainly contributed to the removal of pollutants in the US/CaO2 system, which was remarkable for understanding the mechanisms of CaO2-based oxidation process and its future application.

Phosphorus removal from municipal wastewater through a novel Trichosporon asahii BZ: Performance and mechanism.

A yeast BZ was screened from a laboratory-scale anaerobic/aerobic reactor and designated as Trichosporon asahii through 26S rDNA gene sequence analysis. The screened BZ abated over 70% of phosphorus in municipal sewage with 2-10 mg/L phosphorus in the appropriate conditions. The yeast BZ had strong adaptability to pH and the dissolved oxygen, but the cultivation temperature, carbon source, the ratio of C/P and the ratio of N/P had a critical influence on the phosphorus abatement performance of yeast BZ. The analysis of phosphorus concentration in the wastewater, cells, and extracellular polymeric substances (EPS) suggested that about 55%-66% of the removed phosphorus was in the yeast cells and 34%-45% in the EPS. The proposed probable metabolic mechanism of phosphorus in yeast BZ showed that EPS acted as a dynamic phosphorous transfer station, and most of phosphorus was transferred into yeast cells through EPS transfer station. These findings have crucial implications for the development of a promising stable and easy-operation biological phosphorus abatement process for municipal wastewater treatment.

Oxidative transformation of emerging organic contaminants by aqueous permanganate: Kinetics, products, toxicity changes, and effects of manganese products.

Permanganate (Mn(VII)) has been widely studied for removal of emerging organic contaminants (EOCs) in water treatment and in situ chemical oxidation process. Studies on the reactive intermediate manganese products (e.g., Mn(III) and manganese dioxide (MnO2)) generated from Mn(VII) reduction by EOCs in recent decades shed new light on Mn(VII) oxidation process. The present work summarizes the latest research findings on Mn(VII) reactions with a wide range of EOCs (including phenols, olefins, and amines) in detailed aspects of reaction kinetics, oxidation products, and toxicity changes, along with special emphasis on the impacts of intermediate manganese products (mainly Mn(III) and MnO2) in-situ formed. Mn(VII) shows appreciable reactivities towards EOCs with apparent second-order rate constants (kapp) generally decrease in the order of olefins (kapp = 0.3 - 2.1 × 104 M-1s-1) > phenols (kapp = 0.03 - 460 M-1s-1) > amines (kapp = 3.5 × 10-3 - 305.3 M-1s-1) at neutral pH. Phenolic benzene ring (for phenols), (conjugated) double bond (for olefins), primary amine group and the N-containing heterocyclic ring (for amines) are the most reactive sites towards Mn(VII) oxidation, leading to the formation of products with different structures (e.g., hydroxylated, aldehyde, carbonyl, quinone-like, polymeric, ring-opening, nitroso/nitro and C-N cleavage products). Destruction of functional groups of EOCs (e.g., benzene ring, (conjugated) double bond, and N-containing heterocyclic) by Mn(VII) tends to decrease solution toxicity, while oxidation products with higher toxicity than parent EOCs (e.g., quinone-like products in the case of phenolic EOCs) are sometimes formed. Mn(III) stabilized by model or unknown ligands remarkably accelerates phenolic EOCs oxidation by Mn(VII) under acidic to neutral conditions, while MnO2 enhances the oxidation efficiency of phenolic and amine EOCs by Mn(VII) at acidic pH. The intermediate manganese products participate in Mn(VII) oxidation process most likely as both oxidants and catalysts with their generation/stability/reactivity affecting by the presence of NOM, ligand, cations, and anions in water matrices. This work presents the state-of-the-art findings on Mn(VII) oxidation of EOCs, especially highlights the significant roles of manganese products, which advances our understanding on Mn(VII) oxidation and its application in future water treatment processes.

Removal of phosphorus from wastewater by Diutina rugosa BL3: Efficiency and pathway.

A novel phosphorus removal yeast BL3 was isolated from an alternating anaerobic/aerobic biofilter and identified as Diutina rugosa by 26S rDNA gene sequence analysis. Yeast BL3 could effectively remove phosphorus from synthetic wastewater containing 2-20 mg/L phosphorus under optimal environmental conditions. The highest phosphorus removal efficiency was above 70% under the conditions of DO 6.86 mg/L, C/P ratios of 60, N/P ratios of 3.3, pH 6.0-9.0, and at 25.0-35.0 °C. The phosphorus distribution in the aqueous solution and different components of yeast BL3 analysis indicated that around 55%-70% and 20%-40% of removed phosphorus were transferred into extracellular polymeric substances (EPS) and yeast cells, respectively. The plausible phosphorus transfer pathway was proposed based on the phosphorus distribution and species analysis, suggesting the important role of EPS as a phosphorus reservoir. These results indicate that yeast BL3 can efficiently remove phosphorus under aerobic conditions without alternating anaerobic/aerobic cycling, and thus has significant potential for practical application in wastewater phosphorus removal.

Phosphate removal via biological process coupling with hydroxyapatite crystallization in alternating anaerobic/aerobic biofilter reactor.

In this work, a laboratory-scale alternating anaerobic/aerobic biofilter (A/O BF) filled with self-made steel slag media was constructed, where the integrated biological and crystalline phosphorus removal process was realized to remove phosphorus and achieve phosphorus recovery from wastewater. Phosphorus accumulating organisms (PAOs) were successfully enriched within 30 days operation, the maximum phosphate removal efficiency was close to 80% under the optimal conditions with the anaerobic time of 34 h, HRT of 4 h and influent COD of 300 mg/L. The analysis of SEM-EDS and XRD indicated that hydroxyapatite (HAP) crystals were formed inside biofilms without addition of chemical reagents. The high phosphate environment created by PAOs and the release of Ca2+ from the steel slag media might be responsible for the generation of HAP. These findings have crucial implications for the application BF technology to remove and recover phosphorus from wastewater.

Tailoring the distribution of microbial communities and gene expressions to achieve integrating nitrogen transformation in a gravity-driven submerged membrane bioreactor.

A pilot-scale upgraded gravity-driven submerged membrane (GDSM) reactor was constructed to enhance nitrogen removal. It was artificially formed multiple stratified environments (dissolved oxygen (DO) and substrate supply (TOC, TN, COD, NH4+-N, NO2--N, and NO3--N)) by embedding moving water baffles to control water-flow process in bulk liquid with slow-flowing liquid state. Significant diversity and relative abundance of microorganisms associated with nitrogen transformation paths (i.e., ammonia-oxidizing archaea, ammonia-oxidizing bacteria, nitrite oxidizing bacteria, and denitrifying bacteria) were tailored to distribute on different spatial and temporal regions, and performed their dominant functions. The process simultaneously integrated diverse and effective nitrogen transformation paths (i.e., nitrification, partial nitrification, denitrification, anammox, and dissimilatory nitrate reduction) to achieve high nitrogen removal, with NH4+-N, TN, and COD eliminated by 94.68 ± 2.55%, 55.16 ± 5.53%, and 80.17 ± 6.75%, respectively. Gene expressions involved in the nitrogen transformations were estimated by qPCR to explore the shifts of dominant nitrogen transforming bioreactions in multiple stratified environments. Pearson correlation coefficients supported that the functional genes had more stable and active ability by complementing each other. As a result, an endogenous integration of diverse nitrogen transformation paths was achieved in a single system by artificially tailoring the distributions of microbial communities and gene expressions with enhanced nitrogen removal.

Transformation of X-ray contrast media by conventional and advanced oxidation processes during water treatment: Efficiency, oxidation intermediates, and formation of iodinated byproducts.

X-ray contrast media (ICM), as the most widely used intravascular pharmaceuticals, have been frequently detected in various environmental compartments. ICM have attracted increasingly scientific interest owing to their role as an iodine contributor, resulting in the high risk of forming toxic iodinated byproducts (I-BPs) during water treatment. In this review, we present the state-of-the-art findings relating to the removal efficiency as well as oxidation intermediates of ICM by conventional and advanced oxidation processes. Moreover, formation of specific small-molecular I-BPs (e.g., iodoacetic acid and iodoform) during these processes is also summarized. Conventional oxidants and disinfectants including chlorine (HOCl) and chloramine (NH2Cl) have low reactivities towards ICM with HOCl being more reactive. Iodinated/deiodinated intermediates are generated from reactions of HOCl/NH2Cl with ICM, and they can be further transformed into small-molecular I-BPs. Types of disinfectants and ICM as well as solution conditions (e.g., presence of bromide (Br-) and natural organic matters (NOM)) display significant impact on formation of I-BPs during chlor(am)ination of ICM. Uncatalyzed advanced oxidation process (AOPs) involving ozone (O3) and ferrate (Fe(VI)) exhibit slow to mild reactivities towards ICM, usually leading to their incomplete removal under typical water treatment conditions. In contrast, UV photolysis and catalyzed AOPs including hydroxyl radical (HO•) and/or sulfate radical (SO4.-) based AOPs (e.g., UV/hydrogen peroxide, UV/persulfate, UV/peroxymonosulfate (PMS), and CuO/PMS) and reactive chlorine species (RCS) involved AOPs (e.g., UV/HOCl and UV/NH2Cl) can effectively eliminate ICM under various conditions. Components of water matrix (e.g., chloride (Cl-), Br-, bicarbonate (HCO3-), and NOM) have great impact on oxidation efficiency of ICM by catalyzed AOPs. Generally, similar intermediates are formed from ICM oxidation by UV photolysis and AOPs, mainly resulting from a series reactions of the side chain and/or C-I groups (e.g. cleavage, dealkylation, oxidation, and rearrange). Further oxidation or disinfection of these intermediates leads to formation of small-molecular I-BPs. Pre-oxidation of ICM-containing waters by AOPs tends to increase formation of I-BPs during post-disinfection process, while this trend also depends on the oxidation processes applied and solution conditions. This review summarizes the latest research findings relating to ICM transformation and (by)products formation during disinfection and AOPs in water treatment, which has great implications for the practical applications of these technologies.

Constructing zwitterionic polymer brush layer to enhance gravity-driven membrane performance by governing biofilm formation.

In this study, zwitterionic polymer brushes with controlled architecture were grafted on the surface of gravity-driven membrane (GDM) via surface-initiated reaction to impart antifouling property. A variety of membrane characterization techniques were conducted to demonstrate the successful functionalization of zwitterionic polymers on PVDF hollow fiber membrane. The membrane underwent 90 min of reaction time possessing strong hydrophilicity and high permeability was determined as the optimal modified membrane. Long-term GDM dynamic fouling experiments operated for 30 days using sewage wastewater as feed solution indicated zwitterionic polymer modified membrane exhibit excellent membrane fouling resistance thus enhanced stable flux. Confocal laser scanning microscopy (CLSM) imaging implied that zwitterionic polymer modification significantly inhibit the adsorption of extracellular polymeric substances (EPS) which dominates fouling propensity, resulting in the formation of a thin biofilm with high porosity under synthetic functions of foulants deposition and microbial activities. Interfacial free energy prediction affirmed the presence of zwitterionic functional layer on membrane surface could substantially decrease the interactions (e.g., electrostatic attractions and hydrophobic effects) between membrane and foulants, thereby reduced flux decline and high stable flux. Our study suggests surface hydrophilic functionalization shows promising potential for improving the performance of ultra-low pressure filtration.

Performance and bacterial community composition of volcanic scoria particles (VSP) in a biological aerated filter (BAF) for micro-polluted source water treatment.

A laboratory-scale biological aerated filter (BAF), using volcanic scoria particles (VSP), was used for treating micro-polluted source water. The system reached a steady-state stage and performed better at removing pollutants. In steady-state stage, the effluent ammonia ( NH 4 + - N ) and chemical oxygen demand (COD) were consistently maintained below 0.3 and 3 mg/L, respectively. Both the NH 4 + - N and COD removal efficiencies decreased with shorter hydraulic retention time (HRT). The effluent NH 4 + - N and COD exceeded health standards at 15 min of HRT. Although performance was relatively poor for VSP-BAF at low temperature, the NH 4 + - N removal still achieved the drinking water quality standard. The influences of influent NH 4 + - N and COD concentration changes were similar to that of temperature. A better performance was observed in NH 4 + - N removal under higher influent NH 4 + - N concentrations. In contrast, the effluent COD was more than 3 mg/L when the influent COD concentrations increased to about 9 mg/L. The phylogenetic and cluster analyses indicated that the effect of HRT on bacteria community structure was higher than that of temperature, while the ammonia-oxidizing bacteria (AOB) are sensitive to temperature. The main phyla identified in total bacteria communities were Proteobacteria, Bacteroidetes, Firmicutes, and Nitrospirae. The main AOB were Nitrosomonadales and an uncultured ammonia-oxidizing bacterium. PRACTITIONER POINTS: The BAF using VSP obtained a good performance for treating micro-polluted source water. The influence of HRT on the system was more significant than that of temperature. The system is resistant to NH 4 + - N concentration shocks while is unable to withstand the COD increasing. The effect of HRT on bacteria community structure was significantly higher than that of temperature.

Activation of ferrate by carbon nanotube for enhanced degradation of bromophenols: Kinetics, products, and involvement of Fe(V)/Fe(IV).

Very recently, several studies have found that homogeneous reducing agents (e.g., sodium thiosulfate (Na2S2O3), and sodium sulfite (Na2SO3)) can activate ferrate to enhance the degradation of selected contaminants. In this work, it was found that heterogeneous carbon nanotube (CNT) could accelerate ferrate (Fe(VI)) for the degradation of bromophenols (BrPs) of environmental concerns and alleviate the appearance of undesired by-products in effluent. Fe(VI) could react with BrPs over a wide pH range of 6-10 with apparent second-order rate constants of 1.8-1850 M-1 s-1. Electrospray ionization-triple quadrupole mass spectrometry (ESI-QqQMS) analysis showed that dibrominated dihydroxylated biphenyls and dibrominated phenoxyphenols were possibly formed via coupling reaction of BrPs radicals generated from Fe(VI) oxidation through one-electron transfer. The presence of CNT could remarkably accelerate the degradation rates of BrPs by Fe(VI) in a wide pH range from 7 to 10. Moreover, the formed undesired polybrominated products during Fe(VI)/CNT oxidation were absorbed on CNT surface and thus removed from treated water. The Fe(VI)/CNT system was capable of selectively oxidizing electron-rich pollutants (e.g., BrPs, and sulfamethoxazole (SMX)), but reluctant to iopamidol (IPM) and nitrobenzene (NB). High-valent metal-oxo intermediates Fe(V)/Fe(IV) formed in situ from the reaction of CNT with Fe(VI) were likely responsible for this activation effect of CNT, which was further confirmed via using methyl phenyl sulfoxide (PMSO) as a probe compound. Comparatively, homogeneous reducing agent Na2S2O3 could enhance Fe(VI) degradation of BrPs at pH 7 and 8, while undesired polybrominated products were detected in effluent from Fe(VI)/Na2S2O3 system. These findings have crucial implications for the development of a promising oxidation process by combination of Fe(VI) and CNT for water and wastewater treatment.

Oxidation of methylparaben (MeP) and p­hydroxybenzoic acid (p-HBA) by manganese dioxide (MnO2) and effects of iodide: Efficiency, products, and toxicity.

It is reported that methylparaben (MeP, a widely used phenolic preservative) and its major metabolite p­hydroxybenzoic acid (p-HBA) display estrogenic activity and are frequently detected in various environmental settings. Naturally occurring manganese dioxide (MnO2) plays an important role in attenuation of contaminants released into the environment, and the presence of iodide (I-) may affect these processes. In this work, it was found that both MeP and p-HBA displayed considerable reactivity towards MnO2 with their half-lives increased with decreasing MnO2 concentrations or increasing pH. The presence of I- obviously accelerated the transformation efficiency of MeP and p-HBA by MnO2 with stronger enhancement at higher I- concentrations or lower pH. Dimeric products (e.g., dimeric MeP or p-HBA) were generated from MeP/p-HBA treated by MnO2, and iodinated aromatic products (e.g., mono-/di-iodinated MeP/p-HBA) were additionally identified in the presence of I-. Higher concentrations of these iodinated aromatic products were generally formed at higher I- or lower MnO2 concentrations or lower pH. Ecotoxicity analysis showed that dimeric and iodinated aromatic products were more eco-toxic than parent MeP/p-HBA. This work shows that MnO2 may greatly affect the fate of MeP and p-HBA released into the environment, and the presence of I- can significantly affect these processes.

Transformation of bisphenol AF and bisphenol S by permanganate in the absence/presence of iodide: Kinetics and products.

Recent studies have reported that permanganate (Mn(VII)) shows a good performance in treatment of phenolic compounds, and the presence of iodide (I-) may display a great impact on Mn(VII) oxidation with the formation of toxic iodinated aromatic products. In this work, transformation of bisphenol AF (BPAF) and bisphenol S (BPS) by Mn(VII) in the absence or presence of I- was studied. Mn(VII) showed considerable reactivity towards BPAF with apparent second-order rate constants (0.09-1.65 M-1s-1) higher than those of Mn(VII) with BPS (0.02-0.12 M-1s-1) reported in literature over the pH range of 5-9. The presence of I- apparently accelerated the transformation rates of BPAF and BPS by Mn(VII), and these results could be explained by the contribution of hypoiodous acid (HOI) in situ formed from Mn(VII) oxidation of I-. A kinetic model involving the competitive reactions (i.e., Mn(VII) with I- and bisphenols, HOI with Mn(VII) and bisphenols) well simulated BPAF/BPS transformation by Mn(VII) in the presence of I- under various conditions. Hydroxylated, bond-cleavage, and polymeric products were identified from BPAF/BPS oxidation by Mn(VII), and iodinated aromatic products (e.g., mono- and multi-iodinated BPAF/BPS) were additionally detected in the presence of I-. Reaction pathways involving Mn(VII) one-electron oxidation as well as HOI substitution of BPAF/BPS were proposed. Eco-toxicity analysis by ECOSAR showed that the toxicity of these products generally followed the order of polymeric and iodinated aromatic products > parent BPAF/BPS > hydroxylated products > bond-cleavage products.

Transformation of bisphenol AF and bisphenol S by manganese dioxide and effect of iodide.

In this work, transformation of bisphenol A (BPA) alternatives bisphenol AF (BPAF) and bisphenol S (BPS) by manganese dioxide (MnO2) and the effect of iodide (I-) during these processes were investigated in comparison with BPA for the first time. These three bisphenols showed appreciable reactivity towards MnO2 with the half-lives of their loss following the order of BPA < BPAF < BPS under similar conditions, and a higher transformation efficiency was generally obtained at a lower pH. The presence of I- apparently accelerated the transformation of BPAF and BPS by MnO2 at pH ≤ 7 but negligibly affected BPA transformation over the pH range of 5-9. This discrepancy could be well explained by the relative contribution of hypoiodous acid (HOI) in situ formed from I- oxidation by MnO2. Polymers, hydroxylated derivatives, and bond-cleavage products were detected from BPAF and BPS treated by MnO2, where a series of reactions of BPAF/BPS radicals formed from one-electron oxidation of BPAF/BPS were likely involved, similar to the case of BPA reported in literature. A group of iodinated aromatic products were additionally identified from BPAF/BPS treated by MnO2 in the presence of I- (e.g., iodinated BPAF/BPS and iodinated BPAF/BPS dimers), and they could be further transformed. This study suggests that naturally occurring manganese oxides play a significant role in the attenuation of bisphenols released into the environment and the presence of I- can display a great effect on their transformation.

Organic contaminants degradation from the S(IV) autoxidation process catalyzed by ferrous-manganous ions: A noticeable Mn(III) oxidation process.

Remarkable atrazine degradation in the S(IV) autoxidation process catalyzed by Fe2+-Mn2+ (Fe2+/Mn2+/sulfite) was demonstrated in this study. Competitive kinetic experiments, alcohol inhibiting methods and electron spin resonance (ESR) experiments proved that sulfur radicals were not the major oxidation species. Mn(III) was demonstrated to be the primary active species in the Fe2+/Mn2+/sulfite process based on the comparison of oxidation selectivity. Moreover, the inhibiting effect of the Mn(III) hydrolysis and the S(IV) autoxidation in the presence of organic contaminants indicated the existence of three Mn(III) consumption routes in the Fe2+/Mn2+/sulfite process. The absence of hydroxyl radical and sulfate radical was interpreted by the competitive dynamics method. The oxidation capacity of the Fe2+/Mn2+/sulfite was independent of the initial pH (4.0-6.0) because the fast decay of S(IV) decreased initial pH below 4.0 rapidly. The rate of ATZ degradation was independent of the dissolved oxygen (DO) because that the major DO consumption process was not the rate determining step during the production of SO5•-. Phosphate and bicarbonate were confirmed to have greater inhibitory effects than other environmental factors because of their strong pH buffering capacity and complexing capacity for Fe3+. The proposed acetylation degradation pathway of ATZ showed the application of the Fe2+/Mn2+/sulfite process in the research of contaminants degradation pathways. This work investigated the characteristics of the Fe2+/Mn2+/sulfite process in the presence of organic contaminants, which might promote the development of Mn(III) oxidation technology.

Transformation of Methylparaben by aqueous permanganate in the presence of iodide: Kinetics, modeling, and formation of iodinated aromatic products.

This work investigated impacts of iodide (I-) on the transformation of the widely used phenolic preservative methylparaben (MeP) as well as 11 other phenolic compounds by potassium permanganate (KMnO4). It was found that KMnO4 showed a low reactivity towards MeP in the absence of I- with apparent second-order rate constants (kapp) ranging from 0.065 ±â€¯0.0071 to 1.0 ±â€¯0.1 M-1s-1 over the pH range of 5-9. The presence of I- remarkably enhanced the transformation rates of MeP by KMnO4 via the contribution of hypoiodous acid (HOI) in situ formed, which displayed several orders of magnitude higher reactivity towards MeP than KMnO4. This enhancing effect of I- was greatly influenced by solution conditions (e.g., I- or KMnO4 concentration or pH), which could be well simulated by a kinetic model involving competition reactions (i.e., KMnO4 with I-, KMnO4 with MeP, HOI with KMnO4, and HOI with MeP). Similar enhancing effect of I- on the transformation kinetics of 5 other selected phenols (i.e., p-hydroxybenzoic acid, phenol, and bromophenols) at pH 7 was also observed, but not in the cases of bisphenol A, triclosan, 4-n-nonylphenol, and cresols. This discrepancy could be well explained by the relative reactivity of KMnO4 towards phenols vs I-. Liquid chromatography-tandem mass spectrometry analysis showed that iodinated aromatic products and/or iodinated quinone-like product were generated in the cases where I- enhancing effect was observed. Evolution of iodinated aromatic products generated from MeP (10 µM) treated by KMnO4 (50-150 µM) in the presence of I- (5-15 µM) suggested that higher I- or moderate KMnO4 concentration or neutral pH promoted their formation. A similar enhancing effect of I- (1 µM) on the transformation of MeP (1 µM) by KMnO4 (12.6 µM) and formation of iodinated aromatic products were also observed in natural water. This work demonstrates an important role of I- in the transformation kinetics and product formation of phenolic compounds by KMnO4, which has great implications for future applications of KMnO4 in treatment of I--containing water.

Microwave-assisted in situ synthesis of reduced graphene oxide-BiVO4 composite photocatalysts and their enhanced photocatalytic performance for the degradation of ciprofloxacin.

To improve the photodegradation efficiency for ciprofloxacin (CIP), a new-type microwave-assisted in situ growth method is developed for the preparation of reduced graphene oxide (RGO) -BiVO4 composite photocatalysts. The as-produced RGO-BiVO4 composite photocatalysts show extremely high enhancement of CIP degradation ratio over the pure BiVO4 photocatalyst under visible light. Specially, the 2 wt% RGO-BiVO4 composite photocatalyst exhibits the highest CIP degradation ratio (68.2%) in 60 min, which is over 3 times than that (22.7%) of the pure BiVO4 particles. The enhancement of photocatalytic activities of RGO-BiVO4 photocatalysts can be attributed to the effective separation of electron-hole pairs rather than the improvement of light absorption.