Bisulfite enhanced degradation of diclofenac in Fe3+/persulfate system
FENG Shu1, WANG Hong-Bin1,2, LIU Yi-Qing1, FU Yong-Sheng1
1. Faculty of Geosciences and Environmental Engineering, Southwest Jiaotong University, Chengdu 611756, China; 2. School of Architecture and Civil Engineering, Chengdu University, Chengdu 610106, China
Abstract：The degradation of diclofenac (DCF) by bisulfite enhanced Fe3+/persulfate system was investigated. The influence of pH, Fe3+ dosage, HSO3- dosage, persulfate (PS) dosage and dissolved oxygen on DCF degradation in HSO3-/Fe3+/S2O82-system was explored. The main reactive radical species for DCF removal in this system was also identified by scavenging experiments. Finally, The degradation products and transformation mechanism of DCF by HSO3-/Fe3+/S2O82- were evaluated. DCF could be effectively degraded by the introduction of HSO3- in Fe3+/PS process, and the optimal pH was 4.0. The increased initial Fe3+, HSO3-or PS concentration promoted DCF degradation while excessive HSO3- could inhibit its degradation by acting as a SO4·- scavenger. The degradation rate of DCF was only reduced by 10.4% with bubbling nitrogen, and there was no obvious inhibitory effect in this system. According to the radical scavenging experiments, the contribution of SO4·-, HO· and SO5·- to DCF degradation in HSO3-/Fe3+/S2O82- system were calculated to be 83.0%, 12.8% and 4.3%, respectively. Four transformation products were detected using UPLC-Q-TOF-MS. The potential degradation mechanism of DCF was thus proposed showing four reaction pathways including hydroxylation, decarboxylation, dehydration and formylation.
Halling S B, Nielsen S N, Lanzky P, et al. Occurrence fate and effects of pharmaceutical substances in the environment-A review[J]. Chemosphere, 1998,36(2):357-393.
Ebele A J, Abdallah M A, Harrad S. Pharmaceuticals and personal care products (PPCPs) in the freshwater aquatic environment[J]. Emerging Contaminants, 2017,3:1-16.
Letzel M, Metzner G, Letzel T. Exposure assessment of the pharmaceutical diclofenac based on long-term measurements of the aquatic input[J]. Environment International, 2009,35(2):363-368.
Waldemer R H, Tratnyek P G, Johnson R L, et al. Oxidation of chlorinated ethenes by heat-activated persulfate:kinetics and products[J]. Environmental Science & Technology, 2007,41(3):1010-1015.
Huang K C, Couttenye R A, Hoag G E. Kinetics of heat-assisted persulfate oxidation of methyl tert-butyl ether (MTBE)[J]. Chemosphere, 2002,49(4):413-420.
钟敏,李孟,卢芳,等.热活化过硫酸盐联合混凝处理微乳浊液的机理[J]. 中国环境科学, 2021,41(2):704-712. Zhong M, Li M, Lu F, et al. Mechanism of thermal-activated persulfate combined with coagulation in the treatment of microemulsion[J]. China Environmental Science, 2021,41(2):704-712.
Anipsitakis G P, Dionysiou D D. Radical generation by the interaction of transition metals with common oxidants[J]. Environmental Science & Technology, 2004,38(13):3705-3712.
Liang C J, Bruell C J, Marley M C, et al. Persulfate oxidation for in situ remediation of TCE. I. Activated by ferrous ion with and without a persulfate-thiosulfate redox couple[J]. Chemosphere, 2004,55(9):1213-1223.
Zhang N, Kong X, Zhang M, et al. Study on treatment of methyl-orange in water by derivable oxidation of peroxydisulfate[J]. Journal of Advanced Oxidation Technologies, 2007,10(1):193-195.
刘美琴,宋秀兰.Fe2+激活过硫酸盐耦合活性炭深度处理焦化废水[J]. 中国环境科学, 2018,38(4):1377-1384. Liu M Q, Song X L. Advanced treatment of bio-treated coking wastewater by coupling of ferrous-activated persulfate oxidation and activated carbon adsorption[J]. China Environmental Science, 2018, 38(4):1377-1384.
Mark G, Schuchmann M N, Schuchmann H, et al. The photolysis of potassium peroxodisulphate in aqueous solution in the presence of tert-butanol:a simple actinometer for 254nm radiation[J]. Journal of Photochemistry and Photobiology A:Chemistry, 1990,55(2):157-168.
Gao Y, Gao N, Deng Y, et al. Ultraviolet (UV) light-activated persulfate oxidation of sulfamethazine in water[J]. Chemical Engineering Journal, 2012,195-196:248-253.
黄丽坤,李哲,王广智,等.紫外催化过硫酸盐深度处理垃圾焚烧厂渗滤液[J]. 中国环境科学, 2021,41(1):161-168. Huang L K, Li Z, Wang G Z, et al. Advanced treatment of landfill leachate by ultraviolet catalytic persulfate[J]. China Environmental Science, 2021,41(1):161-168.
Liang C, Su H W. Identification of sulfate and hydroxyl radicals in thermally activated persulfate[J]. Industrial & Engineering Chemistry Research, 2009,48(11):5558-5562.
Furman O S, Teel A L, Watts R J. Mechanism of base activation of persulfate[J]. Environmental Science & Technology, 2010,44(16):6423-7428.
邹景.羟胺对Fe2+/过硫酸盐体系的强化效能与机理研究[D]. 哈尔滨:哈尔滨工业大学, 2016. ZHOU J. Enhanced effectiveness and mechanism of Fe2+/persulfate system with hydroxylamine[D]. Harbin:Harbin Institute of Technology, 2016.
Li D W, Chen D Z, Yao Y Y, et al. Strong enhancement of dye removal through addition of sulfite to persulfate activated by a supported ferric citrate catalyst[J]. Chemical Engineering Journal, 2016,288:806-812.
Curtin M A, Taub I A, Kustin K, et al. Ascorbate-induced oxidation of formate by peroxodisulfate:product yields, kinetics and mechanism[J]. Research on Chemical Intermediates, 2004,30(6):647-661.
Wang S X, Wang G S, Fu Y S, et al. A simple Fe3+/bisulfite system for rapid degradation of sulfamethoxazole[J]. RSC Advances, 2020,10(50):30162-30168.
Liu Z Z, Guo Y Z, Shang R, et al. A triple system of Fe(III)/sulfite/persulfate:Decolorization and mineralization of reactive Brilliant Red X-3B in aqueous solution at near-neutral pH values[J]. Journal of the Taiwan Institute of Chemical Engineers, 2016,68:162-168.
Herrmann H, A Reese, R Zellner. Time-resolved UV/VIS diode array absorption spectroscopy of SOx·-(x=3, 4, 5) radical anions in aqueous solution[J]. Journal of Molecular Structure, 1995,348:183-186.
Xu J, Ding W, Wu F, et al. Rapid catalytic oxidation of arsenite to arsenate in an iron(III)/sulfite system under visible light[J]. Applied Catalysis B:Environmental, 2016,186(5):56-61.
Chen L, Peng X, Liu J, et al. Decolorization of orange II in aqueous solution by an Fe (II)/sulfite system:replacement of persulfate[J]. Industrial & Engineering Chemistry Research, 2012,51(42):13632-13638.
Buxton G V, Greenstock C L, Helman W P, 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.
Neta P, Huie R E, Ross A B. Rate constants for reactions of inorganic radicals in aqueous solution[J]. Journal of Physical and Chemical Reference Data, 1988,17(3):1027-1284.
Huber M M, Canonica S, Park G Y, et al. Oxidation of pharmaceuticals during ozonation and advanced oxidation processes[J]. Environmental Science & Technology, 2003,37(5):1016-1024.
Ahmed M M, Barbati S, Doumenq P, et al. Sulfate radical anion oxidation of diclofenac and sulfamethoxazole for water decontamination[J]. Chemical Engineering Journal, 2012,197:440-447.
Liu Y Q, He X X, Fu Y S, et al. Degradation kinetics and mechanism of oxytetracycline by hydroxyl radical-based advanced oxidation processes[J]. Chemical Engineering Journal, 2016,284:1317-1327.
Kolthoff I M, Miller I K. The chemistry of persulfate. I. The kinetics and mechanism of the decomposition of the persulfate ion in aqueous medium1[J]. Journal of the American Chemical Society, 1951,73(7):3055-3059.
Graedel T E, Weschler C J. Chemistry within aqueous atmospheric aerosols and raindrops[J]. Reviews of Geophysics, 1981,19(4):505-539.
Grgićc I, Pozničc M, Bizjak M. S(IV) autoxidation in atmospheric liquid water:The role of Fe(II) and the effect of oxalate[J]. Journal of Atmospheric Chemistry, 1999,33(1):89-102.
王鸿斌,王群,刘义青,等.亚铁活化过硫酸盐降解水中双氯芬酸钠[J]. 环境化学, 2020,39(4):869-875. Wang H B, Wang Q, Liu Y Q, et al. Degradation of diclofenac by ferrous activated persulfate[J]. Environmental Chemistry, 2020, 39(4):869-875.
Wang H B, Wang S X, Liu Y Q, et al. Degradation of diclofenac by Fe(II)-activated bisulfite:Kinetics, mechanism and transformation products[J]. Chemosphere, 2019,237:124518.
Huie R E, Neta P. Rate constants for some oxidations of S(IV) by radicals in aqueous solutions[J]. Atmospheric Environment, 1987, 21(8):1743-1747.
Huie R E, Clifton C L, Altstein N. A pulse radiolysis and flash photolysis study of the radicals SO2·-, SO3·-, SO4·-and SO5·-[J]. International Journal of Radiation Applications and Instrumentation Part C Radiation Physics and Chemistry, 1989,33(4):361-370.
Liu Y Q, He X X, Fu Y S, et al. Kinetics and mechanism investigation on the destruction of oxytetracycline by UV-254nm activation of persulfate[J]. Journal of Hazardous Materials, 2016,305:229-239.
Pérez-Estrada L A, Malato S, Gernjak W, et al. Photo-Fenton degradation of diclofenac:identification of main intermediates and degradation pathway[J]. Environmental Science & Technology, 2005,39(21):8300-8306.
Zhou T, Feng K, Xiang W, et al. Rapid decomposition of diclofenac in a magnetic field enhanced zero-valent iron/EDTA Fenton-like system[J]. Chemosphere, 2018,193:968-977.