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1.
J Hazard Mater ; 465: 133303, 2024 Mar 05.
Article En | MEDLINE | ID: mdl-38141297

Recently, peracetic acid (PAA) based Fenton (-like) processes have received much attention in water treatment. However, these processes are limited by the sluggish Fe(III)/Fe(II) redox circulation efficiency. In this study, L-cysteine (L-Cys), an environmentally friendly electron donor, was applied to enhance the Fe3O4/PAA process for the sulfamethoxazole (SMX) abatement. Surprisingly, the L-Cys incorporation was found not only to enhance the SMX degradation rate constant by 3.2 times but also to switch the Fe(IV) dominated nonradical pathway into the •OH dominated radical pathway. Experiment and theoretical calculation result elucidated -NH2, -SH, and -COOH of L-Cys can increase Fe solubilization by binding to the Fe sites of Fe3O4, while -SH of L-Cys can promote the reduction of bounded/dissolved Fe(III). Similar SMX conversion pathways driven by the Fe3O4/PAA process with or without L-Cys were revealed. Excessive L-Cys or PAA, high pH and the coexisting HCO3-/H2PO4- exhibit inhibitory effects on SMX degradation, while Cl- and humic acid barely affect the SMX removal. This work advances the knowledge of the enhanced mechanism insights of L-Cys toward heterogeneous Fenton (-like) processes and provides experimental data for the efficient treatment of sulfonamide antibiotics in the water treatment.


Peracetic Acid , Water Pollutants, Chemical , Cysteine , Ferric Compounds , Water Pollutants, Chemical/analysis , Anti-Bacterial Agents , Sulfamethoxazole/analysis , Oxidation-Reduction , Hydrogen Peroxide
2.
Int J Mol Sci ; 24(4)2023 Feb 10.
Article En | MEDLINE | ID: mdl-36835021

In the present study, mulberry branch-derived biochar CuO (MBC/CuO) composite was successfully synthesized and used as a catalyst to activate persulfate (PS) for the degradation of bisphenol A (BPA). The MBC/CuO/PS system exhibited a high degradation efficiency (93%) of BPA, under the conditions of 0.1 g/L MBC/CuO, 1.0 mM PS, 10 mg/L BPA. Free radical quenching and electron spin-resonance spectroscopy (ESR) experiments confirmed that both free radicals •OH, SO4•- and O2•- and non-radicals 1O2 were involved in the MBC/CuO reaction system. Cl- and NOM displayed negligible influence on the degradation of BPA, while HCO3- promoted the removal of BPA. In addition, the toxicity tests of BPA, MBC/CuO and the degraded BPA solution were conducted by the 5th instar silkworm larvae. The toxicity of BPA was reduced after the treatment in the MBC/CuO/PS system, and no obvious toxicity of the synthesized MBC/CuO composite was found in the toxicity evaluation experiments. This work provides a new value-added utilization of mulberry branches as a cost-effective and environmentally friendly PS activator.


Bombyx , Morus , Water Pollutants, Chemical , Animals , Free Radicals/chemistry , Water Pollutants, Chemical/chemistry
3.
Chemosphere ; 307(Pt 4): 135915, 2022 Nov.
Article En | MEDLINE | ID: mdl-35977577

Tri(2-chloroisopropyl) phosphate (TCPP), a common organophosphate flame retardant, was frequently detected in the environment and posed threats to human health. In this work, the main component of ilmenite FeTiO3 was synthesized by the sol-gel method and employed as the catalyst for the degradation of TCPP by activating persulfate (PS) under UV irradiation. The degradation processes were fitted by the pseudo-first-order kinetic. The kobs value in UV/FeTiO3/PS system was up to 0.0056 min-1 and much higher than that in UV/PS (0.0014 min-1), UV/FeTiO3 (0.0012 min-1) and FeTiO3/PS (0.0016 min-1) systems, demonstrating a distinct synergistic effect in TCPP removal. The degradation efficiency of TCPP increased with the increase of UV intensity, PS concentration and catalyst dosage, and with the decrease of pH. By quenching experiment and EPR analysis, ·OH was confirmed to be the dominant radical in the reaction of the UV/FeTiO3/PS system. The possible degradation pathways of TCPP were dechlorination, dealkylation, and further oxidation of alkyl groups based on the theoretical calculation of frontier molecular orbits. The toxicity of degradation intermediates evaluated by luminescence inhibition rate of photoluminescence was higher than TCPP. Thus, TCPP can be degraded in the UV/FeTiO3/PS system effectively at the premise of introducing controlling measures to reduce the toxicity of degradation intermediates.


Flame Retardants , Water Pollutants, Chemical , Flame Retardants/analysis , Humans , Iron , Organophosphates/chemistry , Oxidation-Reduction , Phosphates/chemistry , Titanium , Ultraviolet Rays , Water Pollutants, Chemical/analysis
4.
J Colloid Interface Sci ; 615: 849-864, 2022 Jun.
Article En | MEDLINE | ID: mdl-35182855

Employing perylene diimide supermolecule (PDI) as metal-free cocatalyst, a novel PDI/g-C3N4/Bi2WO6 (PCB) photocatalyst was constructed for the effective degradation of antibiotics. Both the photocatalytic activity and photostability of g-C3N4/Bi2WO6 (gCB) were further improved after loading PDI. Under simulated sunlight illumination, the apparent rate constant of tetracycline (TC) degradation by PCB reached 2.6 times that of gCB. The photocatalytic activity of PCB still kept over 80% after 4 cycle experiments, while gCB only remained around 21%. The superior activity of PCB was ascribed to the synergism between the extended visible light absorption range through the participation of PDI cocatalyst and facilitated gCB-to-PDI photoelectron transfer. TC would finally be transformed into non-toxic ring opening products and mineralized. This work demonstrated that PDI was an excellent metal-free cocatalyst and exhibited great potential to boost the activity of photocatalysts.


Bismuth , Perylene , Anti-Bacterial Agents , Catalysis , Graphite , Light , Nitrogen Compounds , Tetracycline , Tungsten Compounds , Water
5.
Sci Total Environ ; 780: 146483, 2021 Aug 01.
Article En | MEDLINE | ID: mdl-33773344

Environment pollution is getting serious and various poisonous contaminants with chemical durability, biotoxicity and bioaccumulation have been widespreadly discovered in municipal wastewaters and surface water. The detection and removal of pollutants show great significance for the protection of human health and other organisms. Due to its distinctive physical and chemical properties, perylene diimide (PDI) has received widespread attention from different research fields, especially in the area of environment. In this review, a comprehensive summary of the development of PDI-based materials in fluorescence detection and advanced oxidation technology for environment was introduced. Firstly, we chiefly presented the recent progress about the synthesis of PDI and PDI-based nanomaterials. Then, their application in fluorescence detection for environment was presented and categorized, principally including the detection of heavy metal ions, harmful anions and organic contaminants in the environment. In addition, the application of PDI and PDI-based materials in different advanced oxidation technologies for environment, such as photocatalysis, photoelectrocatalysis, Fenton and Fenton-like reaction and persulfate activation, was also summarized. At last, the challenges and future prospects of PDI-based materials in environmental applications were discussed. This review focuses on presenting the practical applications of PDI and PDI-based materials as fluorescent probes or catalysts (especially photocatalysts) in the detection of hazardous substances or catalytic elimination of organic contaminants. The contents are aimed at supplying the researchers with a deeper understanding of PDI and PDI-based materials and encouraging their further development in environmental applications.

6.
Chemosphere ; 266: 128944, 2021 Mar.
Article En | MEDLINE | ID: mdl-33257045

Developing cost-effective metal/metal oxides for peroxymonosulfate (PMS) activation remains a key issue in the sulfate radical based advanced oxidation process. In this work, electroplating sludge (ES), a transition metal-rich byproduct, was anaerobic calcined and characterized. Then, calcined electroplating sludge (CES) was applied as PMS activator for degradation of ofloxacin (OFL) and CES/PMS system exhibited a nearly 90% of OFL removal in 60 min. In addition, effect of CES, PMS, the initial pH and water constituents (chloride, bicarbonate, natural organic matter (NOM) and water backgrounds) on OFL degradation were systematically studied. Moreover, radical quenching tests and electron spin-resonance spectroscopy studies manifested that both SO4- and HO were the ruling reactive oxygen species. X-ray photoelectron spectroscopy results of the fresh and used CES demonstrated that the PMS activation mainly occur in the transformation from Fe3+ (Cu2+) to Fe2+ (Cu+). Furthermore, liquid chromatography coupled with ion trap time-of-flight mass spectrometry was used to illustrate the possible degradation pathway of OFL. Moreover, CES showed excellent stability and reusability during reaction. This work points out a new way for value-added reuse for ES as a cost-efficient activator of PMS for organic contaminant removal.


Ofloxacin , Sewage , Electroplating , Peroxides
7.
Chemosphere ; 266: 129016, 2021 Mar.
Article En | MEDLINE | ID: mdl-33248738

In this study, phosphite (HPO32-) was used as a novel activator to activate peroxymonosulfate (PMS) for acid orange 7 (AO7) removal. Under the optimized conditions, the decolorization efficiency of AO7 was 82.1% within 60 min with rate constant values (kobs) of 0.0301 min-1. Besides, effects of the solution pH and the co-existing inorganic anions including Cl-, HCO3-, HPO42- and SO42- on AO7 removal were also investigated. Except for SO42-, other examined co-existing inorganic anions displayed favorable effects on the removal of AO7. Furthermore, the mechanism for PMS activation by the HPO32- was deeply elucidated by radical scavenger including ethanol (EtOH), tert-butanol (TBA), l-histidine and tiron, and electron spin resonance (ESR) studies. It was proposed that singlet oxygen (1O2) would be the dominant reactive oxygen species (ROS) in the HPO32-/PMS system for contamination degradation at neutral pH condition. The findings of this study provided useful information for the application of the substances in industrial wastewaters to activate PMS for organic contaminants degradation and in particular for HPO32--rich electroplating wastewater treatment.


Environmental Pollutants , Phosphites , Water Pollutants, Chemical , Kinetics , Oxidation-Reduction , Peroxides , Water Pollutants, Chemical/analysis
8.
Chemosphere ; 260: 127681, 2020 Dec.
Article En | MEDLINE | ID: mdl-32758785

In this work, magnetic separably barium ferrite nanomaterial (BaFeO) was synthesized via citrate acid assisted sol-gel combustion method. Subsequently, X-ray diffraction (XRD), scanning electron microscopy-energy dispersion spectroscopy (SEM-EDS), transmission electron microscopy (TEM) and vibrating sample magnetometer (VSM) were applied for its structural, morphological, and electromagnetic characterization. In addition, microwave (MW) absorption and thermal conversion test results indicated the BaFeO had electrothermal rather than magnetothermal conversion capacity. Meanwhile, the synthesized BaFeO showed satisfactory performance in both eliminating and mineralization of a typical triphenylmethane dye, brilliant green (BG), in MW-induced catalytic oxidation (MICO) process without extra oxidant addition. Besides, changes in element valence and content of BaFeO before and after MICO process investigated with XRD, Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) showed its relatively stable properties. Furthermore, transition oxygen species involved in MICO process was deduced as lattice oxygen species. Then, the possible degradation pathway of BG was proposed as demethylation, open-loop of triphenylmethane, releasing one ring, formation of the benzene ring and the ultimate mineralization based on the degradation intermediates tentatively identified by gas chromatography mass spectrometry (GC/MS) and liquid chromatography mass spectrometry (LC/MS), respectively. Finally, ecotoxicity analysis by ecological structure activity relationships (ECOSAR) showed that both the acute and chronic toxicity of these intermediates were lower than that of parent BG. These findings are important regarding the development of efficient catalysts in MICO process for degradation of BG analogues in wastewater.


Barium Compounds/chemistry , Ferric Compounds/chemistry , Nanostructures/chemistry , Quaternary Ammonium Compounds/chemistry , Catalysis , Coloring Agents/chemistry , Magnetics , Microscopy, Electron, Scanning , Microscopy, Electron, Transmission , Microwaves , Photoelectron Spectroscopy , Wastewater , X-Ray Diffraction
9.
Chemosphere ; 253: 126751, 2020 Aug.
Article En | MEDLINE | ID: mdl-32302913

A novel n-n type inorganic/organic heterojunction of flaky-like BiOCl/PDI photocatalyst was constructed by water bath heating method. Meanwhile, a simple method - secondary self-assembly was used to prepare the BiOCl/PDI with a special band structure. The photocatalytic activities were evaluated by degrading aqueous organic pollutants under visible light (λ > 420 nm). The removal rates of 5 mg L-1 phenol (non-ionic type), methyl orange (MO, anionic type), rhodamine B (RhB, cationic type) and 10 mg L-1 RhB by secondary self-assembly BiOCl/PDI (BiOCl/PDI-2) were 8.0%, 3.4%, 27.8% and 78.9% higher than self-assembly BiOCl/PDI (BiOCl/PDI-1) under visible light (λ > 420 nm). The better photocatalytic activity for BiOCl/PDI-2 was attributed to the optimization of energy-band structures, which arose from different exposed surfaces, narrower interplanar spacing and stronger visible light absorption performance. Under acidic condition, BiOCl/PDI-2 showed a good photocatalytic activity, which was not affected by neutral ionic intensity and had good recycling properties. Moreover, the photocatalytic mechanism was explored by free radical capture test and electron paramagnetic resonance (EPR), and contribution of active species was calculated. The main active species of BiOCl/PDI-2 were ·O2-, 1O2 and h+. Our work may provide a route to design efficient inorganic/organic heterojunctions for organic pollutants degradation.


Bismuth/chemistry , Imides/chemistry , Light , Nanostructures/chemistry , Perylene/analogs & derivatives , Water Pollutants, Chemical/analysis , Azo Compounds/analysis , Azo Compounds/radiation effects , Catalysis , Perylene/chemistry , Phenols/analysis , Phenols/radiation effects , Rhodamines/analysis , Rhodamines/radiation effects , Surface Properties , Water Pollutants, Chemical/radiation effects
10.
Chemosphere ; 247: 125780, 2020 May.
Article En | MEDLINE | ID: mdl-31945719

In this study, Cu0·5Mn0·5Fe2O4 nanoparticles were synthesized through a facile coprecipitation process, evaluated as highly efficient photo-Fenton catalyst for removal of bisphenol A (BPA). Benefit for its larger surface area and unique chemical composition, the Cu0·5Mn0·5Fe2O4 catalyst exhibited superior catalytic activity toward the degradation of BPA, with a rate constant values ranging from 0.247 to 1.090 min-1 based on different operating parameters (catalyst load, initial solution pH, H2O2 concentration and reaction temperature). Importantly, an excellent BPA removal efficiency exceeding 95.2% were obtained after eight successive runs of photo-Fenton process. Electron paramagnetic resonance (EPR) spectroscopy and radical scavenger experiments demonstrated that the hydroxyl radical was the dominant radical in degradation of BPA. A possible BPA degradation pathway was proposed according to the detected intermediates by GC-MS and HPLC. In brief, this work is expected to provide a new heterogeneous photo-Fenton catalyst for the organic pollutants removal from wastewater.


Benzhydryl Compounds/isolation & purification , Hydrogen Peroxide/chemistry , Metal Nanoparticles/chemistry , Phenols/isolation & purification , Wastewater/chemistry , Water Purification/methods , Benzhydryl Compounds/chemistry , Catalysis , Copper , Ferric Compounds , Hydrogen-Ion Concentration , Hydroxyl Radical , Manganese Compounds , Organic Chemicals/isolation & purification , Oxides , Phenols/chemistry
11.
Bioresour Technol ; 293: 122068, 2019 Dec.
Article En | MEDLINE | ID: mdl-31479856

This work aimed to examine a permanent magnetic cation-exchange resin (MCER) for synergistic co-removal of Cu(II) and tetracycline (TC) from their mixed solutions. Batch adsorption experiments and characterizations were performed to elucidate the adsorption mechanisms. The adsorption of Cu(II) followed the Langmuir isotherm model in most cases, while Freundlich isotherm model was more suitable for fitting TC adsorption, which was due to the surface coordination between adsorbed Cu(II) and TC and the formation of multilayer MCER-Cu-TC complexes. The equilibrium TC adsorption amount in binary Cu/TC system was about 5.5-13.5 times of that in sole system, whereas Cu(II) uptake was nearly unchanged. Decomplexing-bridging was ascribed as the primary mechanism, which involved the [Cu-TC] decomplexing and [resin-Cu] bridging for TC uptake. Moreover, these MCER microbeads could be reused with negligible loss in adsorption capacity during five adsorption-desorption cycles, indicative of great potential in synergistic co-removal of organics-Cu complexes from aqueous solutions.


Copper , Water Pollutants, Chemical , Adsorption , Cation Exchange Resins , Kinetics , Tetracycline
12.
J Chromatogr A ; 1602: 350-358, 2019 Sep 27.
Article En | MEDLINE | ID: mdl-31257039

This work describes development of a quick and accurate online solid-phase extraction (SPE) liquid chromatography tandem mass spectrometry method for simultaneous determination of 87 emerging organic compounds, including 22 per- and polyfluoroalkyl substances, 58 pharmaceuticals and personal care products, and 7 organophosphorus flame retardants, in diverse water matrices. Considering the wide range of physicochemical properties for the target contaminants, efficient analysis in one injection is challenging. Thus, key extraction and analytical parameters, including online SPE sorbent, mobile phase additives, sample pH, loading solvent pH and composition, injection volume, and valve-switching time, were systematically optimized. The final conditions, namely a polymeric reversed-phase column with alkaline samples and an acidic loading solvent, provided satisfactory results for all target analytes compared to conventional methods that employ acidic samples for multi-residue analysis. The method detection limits (MDLs) ranged from 0.16 to 5.13 ng L-1 with 85% of MDLs lower than 2 ng L-1 for sample volumes of just 1.8 mL. The method also demonstrated satisfactory accuracy with 82% of analytes exhibiting 70-130% recovery. Importantly, only 30 min was required per sample. The optimized method was successfully applied to investigate the removal efficiency of emerging contaminants in a drinking water treatment plant and to analyze the environmental occurrence of target analytes. The method is sensitive, reliable, labor-saving, and cost effective, and therefore has the potential to advance large-scale environmental monitoring programs.


Chromatography, Liquid/methods , Flame Retardants/analysis , Fluorocarbons/analysis , Household Products/analysis , Pharmaceutical Preparations/analysis , Solid Phase Extraction/methods , Tandem Mass Spectrometry/methods , Water Pollutants, Chemical/analysis , Automation , Environmental Monitoring , Hydrogen-Ion Concentration , Internet , Limit of Detection , Solvents/chemistry , Time Factors
13.
Chemosphere ; 218: 836-844, 2019 Mar.
Article En | MEDLINE | ID: mdl-30508802

With the phasing out of brominated flame retardants, organophosphate flame retardants (OPFRs) have been widely used and further detected in multiple environmental media. However, municipal landfill leachates, an important source of contamination of OPFRs to aquatic environment, have not been fully understood, especially in a developing country like China. Thus, the occurrence, aqueous removal efficiency, environmental emission, and risk assessment of 10 OPFRs were investigated in leachates from six municipal landfills across China. The results indicated that except triethyl phosphate (TEP), the remaining 9 OPFRs were detected in both raw and final leachates with different frequencies higher than 33.3%. The range of total concentrations of OPFRs (ΣOPFRs) across China was 29.0-437 and 0.652-32.4 µg L-1 in raw and final leachates, respectively. Tris(2-chloroethyl) phosphate (TCEP) was the dominant species and accounted for 78.5% and 85.8% of average ΣOPFR concentration in raw and final leachates, respectively. This may be because TCEP is the most prevalently used OPFR in China. The overall aqueous removal efficiency of ΣOPFRs across China ranged from 57.7% to 99.8%. Tris(2-butoxyethyl) phosphate was the most removed species (98.8%), whereas TCEP was the least removed species (91.5%). The annual emissions of ΣOPFRs discharged into the aquatic environment from municipal landfills across China were estimated to be between 170 and 7094 g. Further risk assessment based on risk quotient values in the final leachates showed that most OPFRs posed negligible risk except TCEP (medium and high risk) and tributyl phosphate (medium risk).


Flame Retardants/analysis , Organophosphates/analysis , Water Pollutants, Chemical/analysis , China , Environmental Pollution , Environmental Restoration and Remediation , Flame Retardants/isolation & purification , Flame Retardants/pharmacology , Organophosphates/isolation & purification , Organophosphates/pharmacology , Risk Assessment , Waste Disposal Facilities/statistics & numerical data , Water Pollutants, Chemical/isolation & purification , Water Pollutants, Chemical/pharmacology
14.
J Hazard Mater ; 344: 1220-1228, 2018 Feb 15.
Article En | MEDLINE | ID: mdl-29191611

Drinking water treatment residuals (WTRs) are safe byproducts of water treatment plants containing iron. This work studies the degradation of atrazine (ATZ) by WTR-catalyzed peroxymonosulfate (PMS) in aqueous solutions. Factors that affect the catalytic performance (the PMS concentration, catalyst dose, initial solution pH, reaction temperature and water matrix species) were investigated. The results show that the catalytic degradation efficiency of ATZ increases with the increase in PMS concentration and temperature, whereas a higher content of WTRs results in lower removal efficiency because of the quenching effect and negative effect of high pH. For an initial solution pH of 3 and 5, 94.1% and 87.4% of ATZ degradation can be achieved within 6h, whereas the value is only 26% for pH of 7. The production of sulfate radicals (SO4-) and hydroxyl radicals (OH) was confirmed by classic radical quenching and electron spin resonance (ESR) tests. Based on the GC-MS and LC-MS results, the main degradation pathways of ATZ may contain dealkylation, dechlorination-hydroxylation, and alkyl chain oxidation processes. In addition to the ATZ removal ability, the WTRs/PMS system can simultaneously remove phosphorus. This article provides a new idea for wastewater treatment and usage of WTRs as a resource.


Atrazine/chemistry , Herbicides/chemistry , Peroxides/chemistry , Water Pollutants, Chemical/chemistry , Drinking Water , Hydrogen-Ion Concentration , Temperature , Waste Disposal, Fluid/methods , Water Purification
15.
Chemosphere ; 181: 609-618, 2017 Aug.
Article En | MEDLINE | ID: mdl-28476000

In this study, iodine-doped granular activated carbon (I-GAC) was prepared and subsequently applied to activate periodate (IO4-) to degrade organic contaminants at ambient temperature. The physicochemical properties of GAC and I-GAC were examined using scanning electron microscopy, N2 adsorption/desorption, Raman spectroscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. No significant difference was observed between the two except for the existence of triiodide (I3-) and pentaiodide (I5-) on I-GAC. The catalytic activity of I-GAC towards IO4- was evaluated by the degradation of acid orange 7 (AO7), and superior catalytic performance was achieved compared with GAC. The effects of some influential parameters (preparation conditions, initial solution pH, and coexisting anions) on the catalytic ability were also investigated. Based on radical scavenging experiments, it appeared that IO3 was the predominant reactive species in the I-GAC/IO4- system. The mechanism underlying the enhanced catalytic performance of I-GAC could be explained by the introduction of negatively charged I3- and I5- into I-GAC, which induced positive charge density on the surface of I-GAC. This accelerated the interaction between I-GAC and IO4-, and subsequently mediated the increasing generation of iodyl radicals (IO3). Furthermore, a possible degradation pathway of AO7 was proposed according to the intermediate products identified by gas chromatography-mass spectrometry.


Charcoal/chemistry , Iodine/chemistry , Periodic Acid/chemistry , Adsorption , Azo Compounds/chemistry , Benzenesulfonates/chemistry , Catalysis , Gas Chromatography-Mass Spectrometry , Iodides , Mitogens/chemistry , Photoelectron Spectroscopy , Spectrum Analysis
16.
J Hazard Mater ; 328: 98-107, 2017 Apr 15.
Article En | MEDLINE | ID: mdl-28103489

In this study, the bisulfite-peroxydisulfate system (S(IV)/PDS) widely used in polymerization was innovatively applied for organic contaminants degradation in water. The addition of S(IV) into PDS system remarkably enhanced the degradation efficiency of bisphenol A (BPA, a frequently detected endocrine disrupting chemical in the environments) from 17.0% to 84.7% within 360 min. The degradation efficiency of BPA in the S(IV)/PDS system followed pseudo-first-order kinetics, with rate constant values ranging from 0.00005min-1 to 0.02717min-1 depending on the operating parameters, such as the initial S(IV) and PDS dosage, solution pH, reaction temperature, chloride and water type. Furthermore, nitrogen purging experiment, radical scavenging experiment and electron spin resonance (ESR) analysis were used to elucidate the possible mechanism. The results revealed that sulfate radical was the dominant reactive species in the S(IV)/PDS system. Finally, based on the results of liquid chromatography-mass spectrometry (LC-MS) and gas chromatography-mass spectrometry (GC-MS), the BPA degradation pathway was proposed to involve ß-scission (CC), hydroxylation, dehydration, oxidative skeletal rearrangement, and ring opening. This study helps to characterize the combination of PDS and inorganic S(IV), a common industrial contaminant, to generate reactive species to enhance organic contaminants degradation in water.

17.
Chemosphere ; 151: 280-8, 2016 May.
Article En | MEDLINE | ID: mdl-26946115

Increasing attention has been paid to environmentally friendly activation methods of peroxymonosulfate (PMS) in advanced oxidation processes (AOPs) for organic pollutant elimination. This work demonstrates that Base can be applied as a novel activator for PMS. The Base/PMS system, at ambient temperature, was able to degrade a variety of organic pollutants, including acid orange 7 (AO7), phenol and bisphenol A. In subsequent experiments with AO7, the decolorization rates for AO7 followed pseudo-first-order kinetics, with rate constant values ranging from 0.0006 to 0.1749 min(-1) depending on the operating parameters (initial PMS, Base, AO7 concentrations and reaction temperature). Furthermore, the mechanism for PMS activation by the Base was elucidated by radical scavenger (tert-butyl alcohol, methanol, sodium azide and p-benzoquinone) and electron spin resonance trapping studies. The results revealed that superoxide anion radical and singlet oxygen other than sulfate radical were the primary reactive oxygen species in the Base/PMS system. The findings of this study present a new pathway for PMS activation and provide useful information for the treatment of wastewater.


Azo Compounds/analysis , Benzenesulfonates/analysis , Hydroxides/chemistry , Models, Theoretical , Peroxides/chemistry , Water Pollutants, Chemical/analysis , Benzhydryl Compounds/analysis , Kinetics , Oxidation-Reduction , Phenols/analysis , Reactive Oxygen Species/chemistry , Sulfates/chemistry , Wastewater/chemistry , Water Purification/methods
18.
Chemosphere ; 150: 551-558, 2016 May.
Article En | MEDLINE | ID: mdl-26359264

In recent years, activated persulfate (PS) oxidation has been developed as a new advanced oxidation process for the degradation of organic pollutants. On the other hand, the mechanochemical method has exhibited a unique advantage in dealing with chemical wastes. The degradation of tetrabromobisphenol A (TBBPA), a widely used brominated flame retardant (BFR), in wastes has attracted considerable attention. In this study, the efficacy of a CaO-mechanochemical (CaO-MC) treatment system assisted by the addition of PS for the degradation of TBBPA was investigated. Under the optimum reaction conditions with a mole ratio of PS:CaO = 1:4 and less than 12.5% of TBBPA by mass, the degradation and debromination of TBBPA were completed within 2 h, while the mineralization was completed within 4 h. Characterization of the milled sample by XRD revealed that CaSO4 crystallization occurred. The TG results illustrate that there was little organic matter left after 4 h of milling. Raman and FT-IR spectra exhibited the TBBPA destruction process and disappearance of the organic groups. Through analysis by LC/MS/MS, seventeen intermediates were identified. The mechanism of TBBPA degradation by the PS-assisted CaO-MC treatment system was explained from two aspects, the course of crystallization and the degradation of TBBPA by activated PS, and two parallel initiation pathways were proposed.


Calcium Compounds/chemistry , Flame Retardants , Oxides/chemistry , Polybrominated Biphenyls/chemistry , Sodium Compounds/chemistry , Sulfates/chemistry , Chromatography, Liquid , Oxidation-Reduction , Spectroscopy, Fourier Transform Infrared , Spectrum Analysis, Raman , Tandem Mass Spectrometry
19.
Environ Sci Pollut Res Int ; 22(6): 4670-9, 2015 Mar.
Article En | MEDLINE | ID: mdl-25328098

The degradation performance of pentachlorophenol (PCP) by the microwave-activated persulfate (MW/PS) process was investigated in this study. The results indicated that degradation efficiency of PCP in the MW/PS process followed pseudo-first-order kinetics, and compared with conventional heating, microwave heating has a special effect of increasing the reaction rate and reducing the process time. A higher persulfate concentration and reaction temperature accelerated the PCP degradation rate. Meanwhile, increasing the pH value and ionic strength of the phosphate buffer slowed down the degradation rate. The addition of ethanol and tert-butyl alcohol as hydroxyl radical and sulfate radical scavengers proved that the sulfate radicals were the dominant active species in the MW/PS process. Gas chromatography-mass spectrometry (GC-MS) was employed to identify the intermediate products, and then a plausible degradation pathway involving dechlorination, hydrolysis, and mineralization was proposed. The acute toxicity of PCP, as tested with Photobacterium phosphoreum, Vibrio fischeri, and Vibrio qinghaiensis, was negated quickly during the MW/PS process, which was in agreement with the nearly complete mineralization of PCP. These results showed that the MW/PS process could achieve a high mineralization level in a short time, which provided an efficient way for PCP elimination from wastewater.


Microwaves , Pentachlorophenol/chemistry , Sulfates/chemistry , Water Pollutants, Chemical/chemistry , Gas Chromatography-Mass Spectrometry , Halogenation , Hydroxyl Radical , Kinetics , Osmolar Concentration , Oxidation-Reduction , Pentachlorophenol/toxicity , Photobacterium/drug effects , Vibrio/drug effects , Water Pollutants, Chemical/toxicity
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