Selective Transformation of β-Lactam Antibiotics by Peroxymonosulfate: Reaction Kinetics and Nonradical Mechanism

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School of Environmental Science and Engineering, Suzhou University of Science and Technology, Suzhou 215009, P. R. China
School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332, United States
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Cite this: Environ. Sci. Technol. 2018, 52, 3, 1461–1470
Publication Date (Web):January 2, 2018
Copyright © 2018 American Chemical Society
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While the β-lactam antibiotics are known to be susceptible to oxidative degradation by sulfate radical (SO4•–), here we report that peroxymonosulfate (PMS) exhibits specific high reactivity toward β-lactam antibiotics without SO4•– generation for the first time. Apparent second-order reaction constants (k2,app) were determined for the reaction of PMS with three penicillins, five cephalosporins, two carbapenems, and several structurally related chemicals. The pH-dependency of k2,app could be well modeled based on species-specific reactions. On the basis of reaction kinetics, stoichiometry, and structure–activity assessment, the thioether sulfur, on the six- or five-membered rings (penicillins and cephalosporins) and the side chain (carbapenems), was the main reaction site for PMS oxidation. Cephalosporins were more reactive toward PMS than penicillins and carbapenems, and the presence of a phenylglycine side chain significantly enhanced cephalosporins’ reactivity toward PMS. Product analysis indicated oxidation of β-lactam antibiotics to two stereoisomeric sulfoxides. A radical scavenging study and electron paramagnetic resonance (EPR) technique confirmed lack of involvement of radical species (e.g., SO4•–). Thus, the PMS-induced oxidation of β-lactam antibiotics was proposed to proceed through a nonradical mechanism involving direct two-electron transfer along with the heterolytic cleavage of the PMS peroxide bond. The new findings of this study are important for elimination of β-lactam antibiotic contamination, because PMS exhibits specific high reactivity and suffers less interference from the water matrix than the radical process.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.est.7b05543.

  • Chemicals; chromatographic and MS conditions; EPR analysis; PMS determination; pH impact on PMS-induced oxidation of AMP and PG; transformation products of CFP; exclusion of 1O2 generation; tables and figures (PDF)

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  1. Jaesang Lee, Urs von Gunten, Jae-Hong Kim. Persulfate-Based Advanced Oxidation: Critical Assessment of Opportunities and Roadblocks. Environmental Science & Technology 2020, 54 (6) , 3064-3081.
  2. Jiabin Chen, Xuefei Zhou, Peizhe Sun, Yalei Zhang, Ching-Hua Huang. Complexation Enhances Cu(II)-Activated Peroxydisulfate: A Novel Activation Mechanism and Cu(III) Contribution. Environmental Science & Technology 2019, 53 (20) , 11774-11782.
  3. Zhiqiang Sun, Lei Zhao, Caihong Liu, Yufei Zhen, Jun Ma. Catalytic Ozonation of Ketoprofen with In Situ N-Doped Carbon: A Novel Synergetic Mechanism of Hydroxyl Radical Oxidation and an Intra-Electron-Transfer Nonradical Reaction. Environmental Science & Technology 2019, 53 (17) , 10342-10351.
  4. Yuan Gao, Qing Wang, Guozhao Ji, Aimin Li. Degradation of antibiotic pollutants by persulfate activated with various carbon materials. Chemical Engineering Journal 2022, 429 , 132387.
  5. Jiabin Dan, Pinhua Rao, Qiongfang Wang, Lei Dong, Wenhai Chu, Min Zhang, Zedi He, Naiyun Gao, Jing Deng, Juxiang Chen. MgO-supported CuO with encapsulated structure for enhanced peroxymonosulfate activation to remove thiamphenicol. Separation and Purification Technology 2022, 280 , 119782.
  6. Qing Zhao, Xiao Zhang, Dezhi Huang, Long Chen, Shuxin Li, Jean-Marc Chovelon, Lei Zhou, Guangli Xiu. Cu(II) assisted peroxymonosulfate oxidation of sulfonamide antibiotics: The involvement of Cu(III). Chemosphere 2021, 284 , 131329.
  7. Xiaoping Liao, Jinru Cao, Ying Hu, Caixiang Zhang, Lisong Hu. Mechanism of unactivated peroxymonosulfate-induced degradation of methyl parathion: Kinetics and transformation pathway. Chemosphere 2021, 284 , 131332.
  8. Shishu Zhu, Chuanhao Li, Xiaobao Yang, Shaobin Wang, Xiaoguang Duan, Chao Jin. Oxidation of amines and their derivatives with persulfate without activation: Impact of mineral oxides and stoichiometric efficiency. Chemical Engineering Journal 2021, 426 , 131930.
  9. Wenya Peng, Yongxia Dong, Yu Fu, Lingli Wang, Qingchao Li, Yunjiao Liu, Qingya Fan, Zhaohui Wang. Non-radical reactions in persulfate-based homogeneous degradation processes: A review. Chemical Engineering Journal 2021, 421 , 127818.
  10. Haiyan Xu, Liang Meng, Xulei Zhao, Jing Chen, Junhe Lu, Jean-Marc Chovelon, Yuefei Ji. Accelerated oxidation of the emerging brominated flame retardant tetrabromobisphenol S by unactivated peroxymonosulfate: The role of bromine catalysis and formation of disinfection byproducts. Water Research 2021, 204 , 117584.
  11. Jie Dong, Weihua Xu, Shaobo Liu, Li Du, Qiang Chen, Ting Yang, Youzi Gong, Meifang Li, Xiaofei Tan, Yunguo Liu. Recent advances in applications of nonradical oxidation in water treatment: Mechanisms, catalysts and environmental effects. Journal of Cleaner Production 2021, 321 , 128781.
  12. Xiaodong Li, Jialun Shen, Zongquan Sun, Yuqin Liu, Wenwen Zhang, Bin Wu, Fujun Ma, Qingbao Gu. Degradation of 2,4-dinitrotoluene using ferrous activated persulfate: Kinetics, mechanisms, and effects of natural water matrices. Journal of Environmental Chemical Engineering 2021, 9 (5) , 106048.
  13. Xiangting Hou, Shiqi Liu, Chengze Yu, Likun Jiang, Yingjie Zhang, Guocheng Liu, Chengzhi Zhou, Tao Zhu, Yanjun Xin, Qinghua Yan. A novel magnetic CuFeAl-LDO catalyst for efficient degradation of tetrabromobisphenol a in water. Chemical Engineering Journal 2021, 148 , 133107.
  14. Samira Sheikhi, Reza Dehghanzadeh, Ammar Maryamabadi, Hassan Aslani. Chlorpyrifos removal from aqueous solution through sequential use of coagulation and advanced oxidation processes: By-products, degradation pathways, and toxicity assessment. Environmental Technology & Innovation 2021, 23 , 101564.
  15. Waseem Hayat, Yongqing Zhang, Shaobin Huang, Imtyaz Hussain, Renfeng Huang. Insight into the degradation of methomyl in water by peroxymonosulfate. Journal of Environmental Chemical Engineering 2021, 9 (4) , 105358.
  16. Ruicheng Ji, Jiabin Chen, Tongcai Liu, Xuefei Zhou, Yalei Zhang. Critical review of perovskites-based advanced oxidation processes for wastewater treatment: Operational parameters, reaction mechanisms, and prospects. Chinese Chemical Letters 2021, 310
  17. Zhiyan Huang, Pingxiao Wu, Chenhui Liu, Meiqing Chen, Shanshan Yang, Zhi Dang, Nengwu Zhu. Multiple catalytic reaction sites induced non-radical/radical pathway with graphene layers encapsulated Fe-N-C toward highly efficient peroxymonosulfate (PMS) activation. Chemical Engineering Journal 2021, 413 , 127507.
  18. Xiaomin Xu, Yongqing Zhang, Shaoqi Zhou, Renfeng Huang, Shaobin Huang, Hainan Kuang, Xianlin Zeng, Shuaifei Zhao. Activation of persulfate by MnOOH: Degradation of organic compounds by nonradical mechanism. Chemosphere 2021, 272 , 129629.
  19. Jiao Cao, Zhaohui Yang, Weiping Xiong, Yaoyu Zhou, You Wu, Meiying Jia, Haihao Peng, Yuxin Yuan, Yinping Xiang, Chengyun Zhou. Three-dimensional MOF-derived hierarchically porous aerogels activate peroxymonosulfate for efficient organic pollutants removal. Chemical Engineering Journal 2021, , 130830.
  20. Yao Zhang, Boji Wang, Keyu Fang, Yuyang Qin, Hongjing Li, Jiong Du. Degradation of p-aminobenzoic acid by peroxymonosulfate and evolution of effluent organic matter: The effect of chloride ion. Chemical Engineering Journal 2021, 411 , 128462.
  21. Yaobin Ding, Xueru Wang, Libin Fu, Xueqin Peng, Cong Pan, Qihang Mao, Chengjun Wang, Jingchun Yan. Nonradicals induced degradation of organic pollutants by peroxydisulfate (PDS) and peroxymonosulfate (PMS): Recent advances and perspective. Science of The Total Environment 2021, 765 , 142794.
  22. Shuo Li, Yanan Wu, Yongjie Zheng, Tao Jing, Jingzhi Tian, Heshan Zheng, Nannan Wang, Jun Nan, Jun Ma. Free-radical and surface electron transfer dominated bisphenol A degradation in system of ozone and peroxydisulfate co-activated by CoFe2O4-biochar. Applied Surface Science 2021, 541 , 147887.
  23. Yangju Li, Haoran Dong, Long Li, Lin Tang, Ran Tian, Rui Li, Jie Chen, Qianqian Xie, Zilan Jin, Junyang Xiao, Shuangjie Xiao, Guangming Zeng. Recent advances in waste water treatment through transition metal sulfides-based advanced oxidation processes. Water Research 2021, 192 , 116850.
  24. Yang Zhou, Yuan Gao, Jin Jiang, Yong-Ming Shen, Su-Yan Pang, Yang Song, Qin Guo. A comparison study of levofloxacin degradation by peroxymonosulfate and permanganate: Kinetics, products and effect of quinone group. Journal of Hazardous Materials 2021, 403 , 123834.
  25. Xuerui Yang, Xi Ding, Lei Zhou, Qing Zhao, Yuefei Ji, Xingbao Wang, Jean-Marc Chovelon, Guangli Xiu. Direct oxidation of antibiotic trimethoprim by unactivated peroxymonosulfate via a nonradical transformation mechanism. Chemosphere 2021, 263 , 128194.
  26. Yang Cao. Enhanced PMS activation property of Cu decorated MnO catalyst for antibiotic degradation. Functional Materials Letters 2021, 14 (01) , 2150003.
  27. Yang Zhang, Bo-Tao Zhang, Yanguo Teng, Juanjuan Zhao, Lulu Kuang, Xiaojie Sun. Carbon nanofibers supported Co/Ag bimetallic nanoparticles for heterogeneous activation of peroxymonosulfate and efficient oxidation of amoxicillin. Journal of Hazardous Materials 2020, 400 , 123290.
  28. Yasser Vasseghian, Alireza Khataee, Elena-Niculina Dragoi, Masoud Moradi, Samaneh Nabavifard, Gea Oliveri Conti, Amin Mousavi Khaneghah. Pollutants degradation and power generation by photocatalytic fuel cells: A comprehensive review. Arabian Journal of Chemistry 2020, 13 (11) , 8458-8480.
  29. Chaoqun Tan, Tianhui Xu, Huan He, Qinglong Xu, Chao Fang, Erdeng Du, Jing Deng, Wenhai Chu. Bimetallic oxychloride as an efficient oxone activator: Radical and non-radical oxidation of non-steroidal anti-inflammatory drugs. Chemical Engineering Journal 2020, 400 , 125921.
  30. Xuexiang He, Kevin E O’Shea. Rapid transformation of H1-antihistamines cetirizine (CET) and diphenhydramine (DPH) by direct peroxymonosulfate (PMS) oxidation. Journal of Hazardous Materials 2020, 398 , 123219.
  31. Xuexiang He, Kevin E. O'Shea. Selective oxidation of H1-antihistamines by unactivated peroxymonosulfate (PMS): Influence of inorganic anions and organic compounds. Water Research 2020, 186 , 116401.
  32. Zhuxiu Zhang, Yue Xiao, Yifan Lei, Jihai Tang, Xu Qiao. Catalytic hydrolysis of β-lactam antibiotics via MOF-derived MgO nanoparticles embedded on nanocast silica. Science of The Total Environment 2020, 738 , 139742.
  33. Yajie Qian, Jinjing Huang, Xiang Liu, Tongcai Liu, Gang Xue, Pin Gao, Xuefei Zhou, Yalei Zhang, Jiabin Chen. Rapid oxidation of histamine H2-receptor antagonists by peroxymonosulfate during water treatment: Kinetics, products, and toxicity evaluation. Water Research 2020, 185 , 116278.
  34. Mingjie Zhang, Chen Han, Wenyao Chen, Wei Luo, Yueqiang Cao, Gang Qian, Xinggui Zhou, Xiaoguang Duan, Shaobin Wang, Xuezhi Duan. Active sites and reaction mechanism for N-doped carbocatalysis of phenol removal. Green Energy & Environment 2020, 5 (4) , 444-452.
  35. Mengmeng Dou, Jin Wang, Boru Gao, Zhaokun Ma, Xue Huang. A novel in-situ chemical oxidation channel – Selective pH-dependence of refractory β-lactam antibiotics in the synergistic mechanism of persulfate and g-C3N4 under visible light. Chemical Engineering Journal 2020, 394 , 124899.
  36. Wei Wu, Dan Tian, Tongcai Liu, Jiabin Chen, Tianyin Huang, Xuefei Zhou, Yalei Zhang. Degradation of organic compounds by peracetic acid activated with Co3O4: A novel advanced oxidation process and organic radical contribution. Chemical Engineering Journal 2020, 394 , 124938.
  37. Esrafil Asgari, Mahdi Farzadkia, Ali Esrafili, Mojtaba Yegane Badi, Sevda Fallah Jokandan, Hamid Reza Sobhi. Application of a photocatalytic ozonation process using TiO2 magnetic nanoparticles for the removal of Ceftazide from aqueous solutions: Evaluation of performance, comparative study and mechanism. Optik 2020, 212 , 164667.
  38. Xuefei Zhou, Haowei Wu, Longlong Zhang, Bowen Liang, Xiaoqi Sun, Jiabin Chen. Activation of Peracetic Acid with Lanthanum Cobaltite Perovskite for Sulfamethoxazole Degradation under a Neutral pH: The Contribution of Organic Radicals. Molecules 2020, 25 (12) , 2725.
  39. Tongcai Liu, Danyu Zhang, Kai Yin, Chunping Yang, Shenglian Luo, John C. Crittenden. Degradation of thiacloprid via unactivated peroxymonosulfate: The overlooked singlet oxygen oxidation. Chemical Engineering Journal 2020, 388 , 124264.
  40. Huichao Guo, Xuefei Zhou, Yalei Zhang, Qiufang Yao, Yajie Qian, Huaqiang Chu, Jiabin Chen. Carbamazepine degradation by heterogeneous activation of peroxymonosulfate with lanthanum cobaltite perovskite: Performance, mechanism and toxicity. Journal of Environmental Sciences 2020, 91 , 10-21.
  41. Kaixuan Wang, Dahong Huang, Weilai Wang, Yangyuan Ji, Junfeng Niu. Enhanced perfluorooctanoic acid degradation by electrochemical activation of peroxymonosulfate in aqueous solution. Environment International 2020, 137 , 105562.
  42. Zhiping Chen, Sijing Bi, Guangyi Zhao, Yuancai Chen, Yongyou Hu. Enhanced degradation of triclosan by cobalt manganese spinel-type oxide activated peroxymonosulfate oxidation process via sulfate radicals and singlet oxygen: Mechanisms and intermediates identification. Science of The Total Environment 2020, 711 , 134715.
  43. Fei Chen, Gui-Xiang Huang, Fu-Bing Yao, Qi Yang, Yu-Ming Zheng, Quan-Bao Zhao, Han-Qing Yu. Catalytic degradation of ciprofloxacin by a visible-light-assisted peroxymonosulfate activation system: Performance and mechanism. Water Research 2020, 173 , 115559.
  44. Weiyan Du, Qingzhu Zhang, Yanan Shang, Wei Wang, Qian Li, Qinyan Yue, Baoyu Gao, Xing Xu. Sulfate saturated biosorbent-derived [email protected] nanoarchitecture as an efficient catalyst for peroxymonosulfate activation. Applied Catalysis B: Environmental 2020, 262 , 118302.
  45. Yao Zhang, Boji Wang, Xiaonan Hu, Hongjing Li. Non-activated peroxymonosulfate oxidation of p-aminobenzoic acid in the presence of effluent organic matter. Chemical Engineering Journal 2020, 384 , 123247.
  46. Yajie Qian, Xiang Liu, Ke Li, Pin Gao, Jiabin Chen, Zhenhong Liu, Xuefei Zhou, Yalei Zhang, Hong Chen, Xiang Li, Gang Xue. Enhanced degradation of cephalosporin antibiotics by matrix components during thermally activated persulfate oxidation process. Chemical Engineering Journal 2020, 384 , 123332.
  47. Jiabin Chen, Jie Xu, Tongcai Liu, Yajie Qian, Xuefei Zhou, Shaoze Xiao, Yalei Zhang. Selective oxidation of tetracyclines by peroxymonosulfate in livestock wastewater: Kinetics and non-radical mechanism. Journal of Hazardous Materials 2020, 386 , 121656.
  48. Yiang Fan, Zhengyuan Zhou, Yong Feng, Ying Zhou, Lei Wen, Kaimin Shih. Degradation mechanisms of ofloxacin and cefazolin using peroxymonosulfate activated by reduced graphene oxide-CoFe2O4 composites. Chemical Engineering Journal 2020, 383 , 123056.
  49. Jiahui Ji, Rashed M. Aleisa, Huan Duan, Jinlong Zhang, Yadong Yin, Mingyang Xing. Metallic Active Sites on MoO2(110) Surface to Catalyze Advanced Oxidation Processes for Efficient Pollutant Removal. iScience 2020, 23 (2) , 100861.
  50. Rafael R. Solís, Ismael F. Mena, Mallikarjuna N. Nadagouda, Dionysios D. Dionysiou. Adsorptive interaction of peroxymonosulfate with graphene and catalytic assessment via non-radical pathway for the removal of aqueous pharmaceuticals. Journal of Hazardous Materials 2020, 384 , 121340.
  51. Yang Wu, Yu Wang, Tao Pan, Xin Yang. Oxidation of tetrabromobisphenol A (TBBPA) by peroxymonosulfate: The role of in-situ formed HOBr. Water Research 2020, 169 , 115202.
  52. Maolida Nihemaiti, Ratish Ramyad Permala, Jean-Philippe Croué. Reactivity of unactivated peroxymonosulfate with nitrogenous compounds. Water Research 2020, 169 , 115221.
  53. Yang Zhou, Yuan Gao, Jin Jiang, Yong-Ming Shen, Su-Yan Pang, Zhen Wang, Jiebin Duan, Qin Guo, Chaoting Guan, Jun Ma. Transformation of tetracycline antibiotics during water treatment with unactivated peroxymonosulfate. Chemical Engineering Journal 2020, 379 , 122378.
  54. Xiangjian Xu, Yu Yang, Yongfeng Jia, Xinying Lian, Yan Zhang, Fan Feng, Qiulong Liu, Beidou Xi, Yonghai Jiang. Heterogeneous catalytic degradation of 2,4-dinitrotoluene by the combined persulfate and hydrogen peroxide activated by the as-synthesized Fe-Mn binary oxides. Chemical Engineering Journal 2019, 374 , 776-786.
  55. Xiaowan Li, Xitao Liu, Chunye Lin, Huijuan Zhang, Zhou Zhou, Guoxuan Fan, Jun Ma. Cobalt ferrite nanoparticles supported on drinking water treatment residuals: An efficient magnetic heterogeneous catalyst to activate peroxymonosulfate for the degradation of atrazine. Chemical Engineering Journal 2019, 367 , 208-218.
  56. Hongchao Li, Chao Shan, Bingcai Pan. Development of Fe-doped g-C3N4/graphite mediated peroxymonosulfate activation for degradation of aromatic pollutants via nonradical pathway. Science of The Total Environment 2019, 675 , 62-72.
  57. Chen-Xuan Li, Chang-Bin Chen, Yun-Jie Wang, Xian-Zhong Fu, Shuo Cui, Jia-Yuan Lu, Jie Li, Hou-Qi Liu, Wen-Wei Li, Tai-Chu Lau. Insights on the pH-dependent roles of peroxymonosulfate and chlorine ions in phenol oxidative transformation. Chemical Engineering Journal 2019, 362 , 570-575.
  58. Salvador Cotillas, Engracia Lacasa, Miguel Herraiz, Cristina Sáez, Pablo Cañizares, Manuel A. Rodrigo. The Role of the Anode Material in Selective Penicillin G Oxidation in Urine. ChemElectroChem 2019, 6 (5) , 1376-1384.
  59. Guilong Peng, Tong Li, Boxuan Ai, Shengge Yang, Jiawen Fu, Qiang He, Gang Yu, Shubo Deng. Highly efficient removal of enrofloxacin by magnetic montmorillonite via adsorption and persulfate oxidation. Chemical Engineering Journal 2019, 360 , 1119-1127.
  60. Jianfei Yan, Jun Li, Jiali Peng, Heng Zhang, Yunhong Zhang, Bo Lai. Efficient degradation of sulfamethoxazole by the [email protected] (EPC) coupled PMS system: Optimization, degradation pathways and toxicity evaluation. Chemical Engineering Journal 2019, 359 , 1097-1110.
  61. Na Li, Shoufeng Tang, Yandi Rao, Jinbang Qi, Qingrui Zhang, Deling Yuan. Peroxymonosulfate enhanced antibiotic removal and synchronous electricity generation in a photocatalytic fuel cell. Electrochimica Acta 2019, 298 , 59-69.
  62. Jian Peng, Enhui Wu, Nannan Wang, Xingxing Quan, Mingze Sun, Qi Hu. Removal of sulfonamide antibiotics from water by adsorption and persulfate oxidation process. Journal of Molecular Liquids 2019, 274 , 632-638.
  63. Yuefei Ji, Junhe Lu, Lu Wang, Mengdi Jiang, Yan Yang, Peizeng Yang, Lei Zhou, Corinne Ferronato, Jean-Marc Chovelon. Non-activated peroxymonosulfate oxidation of sulfonamide antibiotics in water: Kinetics, mechanisms, and implications for water treatment. Water Research 2018, 147 , 82-90.
  64. Yang Zhou, Yuan Gao, Su-Yan Pang, Jin Jiang, Yi Yang, Jun Ma, Yue Yang, Jiebin Duan, Qin Guo. Oxidation of fluoroquinolone antibiotics by peroxymonosulfate without activation: Kinetics, products, and antibacterial deactivation. Water Research 2018, 145 , 210-219.
  65. Yajie Qian, Pin Gao, Gang Xue, Zhenhong Liu, Jiabin Chen. Oxidation of Cefalexin by Permanganate: Reaction Kinetics, Mechanism, and Residual Antibacterial Activity. Molecules 2018, 23 (8) , 2015.
  66. Yajie Qian, Gang Xue, Jiabin Chen, Jinming Luo, Xuefei Zhou, Pin Gao, Qi Wang. Oxidation of cefalexin by thermally activated persulfate: Kinetics, products, and antibacterial activity change. Journal of Hazardous Materials 2018, 354 , 153-160.
  67. Lays B. Vieira, Michael W. Casimiro, Ronaldo G. Santos. Surface Tension of Aqueous Amoxicillin + Peg Systems. Colloid and Interface Science Communications 2018, 24 , 93-97.