1. Research Center for Eco-Environmental Engineering, Dongguan University of Technology, Dongguan 523808, China; 2. College of Environmental Science and Engineering, North China Electric Power University, Beijing 102206, China; 3. Global Centre for Environmental Remediation, University of Newcastle, Callaghan NSW 2308, Australia
Abstract：Low-frequency ultrasound (20kHz, 78W) assisted electrochemical oxidation (Ti/SnO2-Sb/La-PbO2 as the anode) was used to eliminate aqueous fluconazole, and the degradation mechanism was further investigated. Fluconazole cannot be directly degraded by low-frequency ultrasound. The acceleration electrochemical degradation of fluconazole might be ascribed to the increased ·OH electrochemical production (81.95 times) under low-frequency ultrasound. Moreover, the mass transfer rate and the electron transfer ability at the electrode interface were also enhanced, which were conducive to the electrochemical degradation of fluconazole. The reaction rate constants of fluconazole degradation increased by 42.68% when the ultrasound power increased from 26W to 130W, and increased by 24.00 times when the current density increased from 2mA/cm2 to 20mA/cm2. The main degradation mechanism of fluconazole was the indirect oxidation of ·OH (relative contribution of 82.45%~85.71%). Fluconazole was degraded by defluorination, bond cleavage, cyclization and oxidation, followed by the formation of formic acid, oxalic acid, NO3- and F-.
王樱凝,崔 迪,庞长泷,等.水中PPCPs的污染现状及其控制技术研究进展[J]. 中国给水排水, 2015,31(24):25-29. Wang Y N, Cui D, Pang C L, et al. Pollution status and control technologies of pharmaceuticals and personal care products:Review[J]. China Water & Wastewater, 2015,31(24):25-29.
[2]
Gabriela C, Jorge C, Isaac R, et al. Time-of-flight mass spectrometry assessment of fluconazole and climbazole UV and UV/H2O2 degradability:Kinetics study and transformation products elucidation[J]. Water Research, 2016,88:681-690.
[3]
衷从强,梁林玥,韩卫清,等.电催化氧化处理三唑类杀菌剂模拟废水[J]. 环境工程学报, 2016,10(2):755-760. Zhong C Q, Liang L Y, Han W Q, et al. Electrochemical degradation of triazole fungicides in aqueous solution[J]. Chinese Journal of Environmental Engineering, 2016,10(2):755-760.
[4]
Lindberg R H, Stman M, Olofsson U, et al. Occurrence and behaviour of 105 active pharmaceutical ingredients in sewage waters of a municipal sewer collection system[J]. Water Research, 2014,58(3):221-229.
[5]
Casado J, Rodríguez I, Ramil M, et al. Selective determination of antimycotic drugs in environmental water samples by mixed-mode solid-phase extraction and liquid chromatography quadrupole time-of-flight mass spectrometry[J]. Journal of Chromatography A, 2014,1339:42-49.
[6]
Liu W R, Yang Y Y, Liu Y S, et al. Biocides in wastewater treatment plants:Mass balance analysis and pollution load estimation[J]. Journal of Hazardous Materials, 2017,329:310-320.
[7]
Kjærstad M B, Rstad C, Taxvig C, et al. Endocrine disrupting effects in vitro of conazole antifungals used as pesticides and pharmaceuticals[J]. Reproductive Toxicology, 2010,30(4):573-582.
[8]
Altamirano S, Fang D, Simmons S, et al. Fluconazole-induced ploidy change in cryptococcus neoformans results from the uncoupling of cell growth and nuclear division[J]. Msphere, 2017,2(3):e00205-17.
[9]
Tiboni G M, Marotta F, Carletti E. Fluconazole alters CYP26 gene expression in mouse embryos[J]. Reproductive Toxicology, 2009,27 (2):199-202.
[10]
Frankowski R, Płatkiewicz J, Stanisz E, et al. Biodegradation and photo-Fenton degradation of bisphenol A, bisphenol S and fluconazole in water[J]. Environmental Pollution, 2021,289(11):117947.1-117947.12.
[11]
Zhang N Q, Xue C J, Wang K, et al. Efficient oxidative degradation of fluconazole by a heterogeneous Fenton process with Cu-V bimetallic catalysts[J]. Chemical Engineering Journal, 2020,380:122516.
[12]
Yang J F, Yang L M, Zhang S B, et al. Degradation of azole fungicide fluconazole in aqueous solution by thermally activated persulfate[J]. Chemical Engineering Journal, 2017,321:113-122.
[13]
Wu D, Lu G, Yao J, et al. Adsorption and catalytic electro-peroxone degradation of fluconazole by magnetic copper ferrite/carbon nanotubes[J]. Chemical Engineering Journal, 2019,370:409-419.
[14]
Wan D, Zhang G F, Chen Y, et al. Photogeneration of hydroxyl radical in Fe(III)-citrate-oxalate system for the degradation of fluconazole:mechanism and products[J]. Environmental Science and Pollution Research International, 2019,26(9):8640-8649.
[15]
Li J, Li Y J, Xiong Z K, et al. The electrochemical advanced oxidation processes coupling of oxidants for organic pollutants degradation:A mini-review[J]. Chinese Chemical Letters, 2019,30(12):2139-2146.
[16]
王爱民,杨立红,张素娟,等.电化学方法治理含染料废水的现状与进展[J]. 工业水处理, 2001,21(8):4-7. Wang A M, Yang L H, Zhang S J, et al. Status quo and progress on treating wastewater containing dyestuff by electrochemical method[J]. Industrial Water Treatment. 2001,21(8):4-7.
[17]
Lan Y D, Clémence C, Christel C, et al. An experimental and modelling study of the electrochemical oxidation of pharmaceuticals using a boron-doped diamond anode[J]. Chemical Engineering Journal, 2018,333:486-494.
[18]
Caemen M D, Nihal O, Arturo R, et al. Removal of organochlorine pesticides from lindane production wastes by electrochemical oxidation[J]. Environmental Science and Pollution Research, 2018,25 (35):34985-34994.
[19]
Qian X B, Peng K F, Xu L, et al. Electrochemical decomposition of PPCPs on hydrophobic Ti/SnO2-Sb/La-PbO2 anodes:Relationship between surface hydrophobicity and decomposition performance[J]. Chemical Engineering Journal, 2022,429:132309.
[20]
张睿琦,吴红辉,徐海音,等.基于RuO2-IrO2/Ti和Fe0电极的电氧化-电絮凝处理含TI废水[J]. 中国环境科学, 2022,42(6):2656~2661. Zhang R Q, Wu H H, Xu H Y, et al. Electrooxidation-electrocoagulation treatment of thallium containing wastewater based on RuO2-IrO2/Ti and Fe0electrodes[J]. China Environmental Science, 2022,40(8):3441-3448.
[21]
徐 聪,张璐瑶,徐 劼,等.铟掺杂PbO2电极制备及电催化降解强力霉素[J]. 中国环境科学, 2020,42(6):2656-2661. Xu C, Zhang L Y, Xu J, et al. Preparation of Indium doped PbO2electrode and its electrocatalytic degradation of doxycycline[J]. China Environmental Science, 2020,40(8):3441-3448.
[22]
Ritesh P, Srivastava V C. Understanding of ultrasound enhanced electrochemical oxidation of persistent organic pollutants[J]. Journal of Water Process Engineering, 2020,37(20):101378.
[23]
何志桥,宋 爽,周华敏,等.臭氧/超声联合降解水中对氨基苯酚的动力学[J]. 化工学报, 2006,57(12):2964-2969. He Z Q, Song S, Zhou H M, et al. Kinetics of degradation of 4-aminophenol in aqueous solution by ozonation combined with sonolysis[J]. Journal of Chemical Industry and Engineering (China), 2006,57(12):2964-2969.
[24]
樊 杰,曾 萍,张盼月,等.Fenton-超声联合处理金刚烷胺制药废水[J]. 环境工程学报, 2014,8(5):1744-1748. Fan jie, Zeng P, Zhang P Y, et al. Treatment of wastewater from amantadine production by Fenton-ultrasound process[J]. Chinese Journal of Environmental Engineering, 2014,8(5):1744-1748.
[25]
Xu L, Qian X B, Wang K, et al. Electrochemical mineralization mechanisms of perfluorooctanoic acid in water assisted by low frequency ultrasound[J]. Journal of Cleaner Production, 2020,263:121546.
[26]
Masoud M, Yasser V, Hossein A, et al. Electrocoagulation and ultrasonic removal of humic acid from wastewater[J]. Environmental Progress & Sustainable Energy, 2017,36(3):822-829.
[27]
Mena I F, Cotillas S, Díaz E, et al. Sono and photoelectrocatalytic processes for the removal of ionic liquids based on the 1-butyl-3-methylimidazolium cation[J]. Journal of Hazardous Materials, 2019, 372:77-84.
[28]
Cotillas S, Clematis D, Canizares P, et al. Degradation of dye Procion Red MX-5B by electrolytic and electro-irradiated technologies using diamond electrodes[J]. Chemosphere, 2018,199:445-452.
[29]
Cotillas S, Clematis D, Canizares P, et al. Electrolytic and electro-irradiated technologies for the removal of chloramphenicol in synthetic urine with diamond anodes[J]. Water Research, 2018,128:383-392.
[30]
Steter J R, Barros W R P, Lanza M R V, et al. Electrochemical and sonoelectrochemical processes applied to amaranth dye degradation[J]. Chemosphere, 2014,117:200-207.
[31]
Xu, L, Tang S Y, Li D, et al. Electrochemical degradation of tris(2-chloroethyl) phosphate by metal-oxide-coated Ti anodes:Kinetics, toxicity and mechanism[J]. Separation and Purification Technology, 2021,265:118489.
[32]
Xu L, Ma X, Niu J F, et al. Removal of trace naproxen from aqueous solution using a laboratory-scale reactive flow-through membrane electrode[J]. Journal of Hazardous Materials, 2019,379:120692.
[33]
Chen Z F, Ying G G, Jiang Y X, et al. Photodegradation of the azole fungicide fluconazole in aqueous solution under UV-254:Kinetics, mechanistic investigations and toxicity evaluation[J]. Water Research, 2014,52:83-91.
[34]
David S W, Knox C, Guo A C, et al. DrugBank:a knowledgebase for drugs, drug actions and drug targets[J]. Nucleic Acids Research, 2008,36(suppl_1):D901-D906.
[35]
Ana I, Garcia-Valcarcel and Tadeo J L. Influence of moisture on the availability and persistence of clotrimazole and fluconazole in sludge-amended soil[J]. Environmental Toxicology and Chemistry, 2012, 31(3):501-507.
[36]
Thokchom B, Pandit A B, Qiu P P, et al. A review on sonoelectrochemical technology as an upcoming alternative for pollutant degradation[J]. Ultrasonics Sonochemistry, 2015,27:210-234.
[37]
Klima J. Application of ultrasound in electrochemistry. An overview of mechanisms and design of experimental arrangement[J]. Ultrasonics, 2011,51(2):202-209.
[38]
Sivakumar M, Pandit A B. Ultrasound enhanced degradation of Rhodamine B:optimization with power density[J]. Ultrasonics Sonochemistry, 2001,8(3):233-240.
[39]
陈 霞.声辅助电催化处理水相氯酚的研究[D]. 杭州:浙江工业大学, 2007. Chen X. Ultrasound assisted electrocatalytic decomposition of chlorophenol in aqueous solution[D]. Hangzhou:Zhejiang University of technology, 2007.
[40]
Sankar C, Vijayanand S M. Investigations in synergism of hybrid advanced oxidation processes with combinations of Sonolysis + Fenton Process + UV for degradation of Bisphenol A[J]. Industrial & Engineering Chemistry Research, 2014,53(16):6855-6865.
[41]
Patidar R, Srivastava V C. Ultrasound-assisted electrochemical treatment of cosmetic industry wastewater:Mechanistic and detoxification analysis[J]. Journal of Hazardous Materials, 2022,422:126842.
[42]
Bringas E, Saiz J, Ortiz I. Kinetics of ultrasound-enhanced electrochemical oxidation of diuron on boron-doped diamond electrodes[J]. Chemical Engineering Journal, 2011,172(2):1016-1022.
[43]
Xu L, Tang S Y, Wang K, et al. Insights into the degradation and detoxication mechanisms of aqueous capecitabine in electrochemical oxidation process[J]. Chemosphere, 2019,241:125058.
[44]
Xu L, Cui X Y, Liao J B, et al. Synchronous mineralization of three aqueous non-steroidal anti-inflammatory drugs in electrochemical advanced oxidation process[J]. Chinese Chemical Letters, 2022,33(8):3701-3704.
[45]
伏明浩,卢 钧,陈泉源,等.磁性氧化石墨电催化活性及净化印染废水效能[J]. 中国环境科学, 2022,42(4):1672-1680. Fu M H, Lu J, Chen Q Y, et al. Magnetic graphite oxide as efficient catalyst for electrochemical treatment of printing and dyeing wastewater[J]. China Environmental Science, 2022,42(4):1672-1680.
[46]
Chen S, He P, Zhou P, et al. Development of a novel graphitic carbon nitride and multiwall carbon nanotube co-doped Ti/PbO2 anode for electrocatalytic degradation of acetaminophen[J]. Chemosphere, 2021,271:129830.
[47]
李晓良,徐 浩,延 卫.高效Ti/PbO2电极制备及对酸性红G的降解研究[J]. 中国环境科学, 2017,37(7):2591-2598. Li X L, Xu H, Yan W. Studies on the preparation of high efficient Ti/PbO2 electrode and degradation of acid red G[J]. China Environmental Science, 2017,37(7):2591-2598.
[48]
Qu X, Min T, Liao B, et al. Enhanced electrochemical treatment of phenolic pollutants by an effective adsorption and release process[J]. Electrochimica Acta, 2010,55(19):5367-5374.
[49]
George V B, Clive L G, Phillips H, et al. Critical review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (OH/O) in Aqueous Solution[J]. Journal of Physical and Chemical Reference Data, 1988,17(2):513-886.
[50]
谢欣卓,钟金魁,李 静,等.Fe3O4-nZVI类Fenton法降解水中磺胺甲恶唑[J]. 中国环境科学, 2022,42(7):3103-3111. Xie X Z, Zhong J K, Li J, et al. Degradation of sulfamethoxazole in water by Fenton-like method using Fe3O4-nZVI[J]. China Environmental Science, 2022,42(7):3103-3111.
[51]
Chen C, Xu L, Huo J B, et al. Simultaneous removal of butylparaben and arsenite by MOF-derived porous carbon coated lanthanum oxide:Combination of persulfate activation and adsorption[J]. Chemical Engineering Journal, 2019,391:123552.
[52]
Lin J C, Lo S L, Hu C Y, et al. Enhanced sonochemical degradation of perfluorooctanoic acid by sulfate ions[J]. Ultrasonics Sonochemistry, 2015,22:542-547.
[53]
Cai W W, Peng T, Yang B, et al. Kinetics and mechanism of reactive radical mediated fluconazole degradation by the UV/Chlorine process:Experimental and theoretical studies[J]. Chemical Engineering Journal, 2020,402:126224.
