Degradation of methotrexate by UV/peroxymonosulfate: Kinetics, effect of operational parameters and mechanism

doi:10.1016/j.cjche.2020.05.033

摘要/Abstract

摘要： Methotrexate (MTX) is one of the most consumed anti-cancer drugs in the pharmaceutical market around the world. The widespread occurrence of MTX in aquatic environment through hospital effluent has attracted increasing concern due to its potential to induce water pollution. In the present study, the degradation of MTX in aqueous medium was investigated by UV-activated peroxymonosulfate (PMS). A significant improvement in degradation rate by increasing UV intensity and PMS concentration while the decrease in degradation efficiency with the increase of solution pH and initial concentration of MTX was observed. The proposed UV/PMS process could achieve more than 90% MTX degradation in 30 min with a good mineralization degree (65%). A pseudofirst order kinetic model was employed and successfully predicted the degradation of MTX. The effect of other operational parameters such as the initial concentration of the targeted compound, dosage of oxidant (PMS), solution pH and UV intensity on the degradation rate were investigated. At the last, the main transform intermediates were identified using LC-MS and possible degradation pathways were proposed. The results show that UV/ PMS can be used as an efficient technology to treat pharmaceuticals such as methotrexate containing water and wastewater.

关键词: Peroxymonosulfate, UV radiation, Advanced oxidation process, Methotrexate

Abstract: Methotrexate (MTX) is one of the most consumed anti-cancer drugs in the pharmaceutical market around the world. The widespread occurrence of MTX in aquatic environment through hospital effluent has attracted increasing concern due to its potential to induce water pollution. In the present study, the degradation of MTX in aqueous medium was investigated by UV-activated peroxymonosulfate (PMS). A significant improvement in degradation rate by increasing UV intensity and PMS concentration while the decrease in degradation efficiency with the increase of solution pH and initial concentration of MTX was observed. The proposed UV/PMS process could achieve more than 90% MTX degradation in 30 min with a good mineralization degree (65%). A pseudofirst order kinetic model was employed and successfully predicted the degradation of MTX. The effect of other operational parameters such as the initial concentration of the targeted compound, dosage of oxidant (PMS), solution pH and UV intensity on the degradation rate were investigated. At the last, the main transform intermediates were identified using LC-MS and possible degradation pathways were proposed. The results show that UV/ PMS can be used as an efficient technology to treat pharmaceuticals such as methotrexate containing water and wastewater.

Key words: Peroxymonosulfate, UV radiation, Advanced oxidation process, Methotrexate

Muhammad Imran Kanjal, Majid Muneer, Amal Abdelhaleem, Wei Chu. Degradation of methotrexate by UV/peroxymonosulfate: Kinetics, effect of operational parameters and mechanism[J]. 中国化学工程学报, 2020, 28(10): 2658-2667.

参考文献

[1] K. Kümmerer, Drugs in the environment:emission of drugs, diagnostic aids and disinfectants into wastewater by hospitals in relation to other sources-A review, Chemosphere 45(2001) 957-969.
[2] I.J. Buerge, H.R. Buser, T. Poiger, M.D. Muller, Occurrence and fate of the cytostatic drugs cyclophosphamide and ifosfamide in wastewater and surface waters, Environ. Sci. Technol. 40(2006) 7242-7250.
[3] S. Mompelat, B. Le Bot, O. Thomas, Occurrence and fate of pharmaceutical products and by-products, from resource to drinking water, Environ. Int. 35(2009) 803-814.
[4] B.I. Escher, R. Baumgartner, M. Koller, K. Treyer, J. Lienert, C.S. McArdell, Environmental toxicology and risk assessment of pharmaceuticals from hospital wastewater, Water Res. 45(2011) 75-92.
[5] T. Hoppe-Tichy, Current challenges in European oncology pharmacy practice, J. Oncol. Pharm. Pract. 16(2010) 9-18.
[6] J.F. Zhang, V.W.C. Chang, A. Giannis, J.Y. Wang, Removal of cytostatic drugs from aquatic environment:a review, Sci. Total Environ. 445(2013) 281-298.
[7] D.R. Baker, B. Kasprzyk-Hordern, Spatial and temporal occurrence of pharmaceuticals and illicit drugs in the aqueous environment and during wastewater treatment:new developments, Sci. Total Environ. 454(2013) 442-456.
[8] A. Jelic, M. Gros, A. Ginebreda, R. Cespedes-Sanchez, F. Ventura, M. Petrovic, D. Barcelo, Occurrence, partition and removal of pharmaceuticals in sewage water and sludge during wastewater treatment, Water Res. 45(2011) 1165-1176.
[9] A.Y.C. Lin, T.H. Yu, S.K. Lateef, Removal of pharmaceuticals in secondary wastewater treatment processes in Taiwan, J. Hazard. Mater. 167(2009) 1163-1169.
[10] J. Yin, B. Shao, J. Zhang, K. Li, A preliminary study on the occurrence of cytostatic drugs in hospital effluents in Beijing, China, Bull. Environ. Contam. Toxicol. 84(2010) 39-45.
[11] S. Castiglioni, R. Bagnati, D. Calamari, R. Fanelli, E. Zuccato, A multiresidue analytical method using solid-phase extraction and high-pressure liquid chromatography-tandem mass spectrometry to measure pharmaceuticals of different therapeutic classes in urban wastewaters, J. Chromatogr. A 1092(2005) 206-215.
[12] N. Negreira, M. López de Alda, D. Barceló, On-line solid phase extraction-liquid chromatography-tandem mass spectrometry for the determination of 17 cytostatics and metabolites in waste, surface and groundwater samples, J. Chromatogr. A 1280(2013) 64-74.
[13] G.W. Aherne, J. English, V. Marks, The role of immunoassay in the analysis of microcontaminants in water samples, Ecotox. Environ. Safe. 9(1985) 79-83.
[14] A.Y.C. Lin, Y.C. Lin, W.N. Lee, Prevalence and sunlight photolysis of controlled and chemotherapeutic drugs in aqueous environments, Environ. Pollut. 187(2014) 170-181.
[15] N. Negreira, M.L. De Aida, D. Barcelo, Cytostatic drugs and metabolites in municipal and hospital wastewaters in Spain:filtration, occurrence, and environmental risk, Sci. Total Environ. 497(2014) 68-77.
[16] S. Basha, D. Keane, K. Nolan, M. Oelgemöller, J. Lawler, J.M. Tobin, A. Morrissey, UVinduced photocatalytic degradation of aqueous acetaminophen:The role of adsorption and reaction kinetics, Environ. Sci. Pollut. Res. 22(2015) 2219-2230.
[17] T. Okuda, Y. Kobayashi, R. Nagao, N. Yamashita, H. Tanaka, S. Tanaka, S. Fuji, C. Konishi, I. Houwa, Removal efficiency of 66 pharmaceuticals during wastewater treatment process in Japan, Water Sci. Technol. 57(2008) 65-71.
[18] J.A. Khan, C. Han, N.S. Shah, H.M. Khan, M.N. Nadagouda, V. Likodimos, P. Falaras, K. O'Shea, D.D. Dionysiou, Ultraviolet-visible light-sensitive high surface area phosphorous fluorine-co-doped TiO₂ nanoparticles for the degradation of atrazine in water, Environ. Eng. Sci. 31(2014) 435-446.
[19] N.H. Ince, I.G. Apikayan, Synthetic endocrine disruptors in the environment and water remediation by advanced oxidation processes, J. Env. Manag. 85(2007) 816-832.
[20] M. Klavarioti, D. Mantzavinos, D. Kassinos, Removal of residual pharmaceuticals from aqueous systems by advanced oxidation processes, Environ. Int. 35(2009) 402-417.
[21] B.A. Wols, C.H.M. Hofman-Caris, Review of photochemical reaction constants of organic micropollutants required for UV advanced oxidation processes in water, Water Res. 46(2012) 2815-2827.
[22] Y. Deng, C.M. Ezyske, Sulfate radical-advanced oxidation process (SR-AOP) for simultaneous removal of refractory organic contaminants and ammonia in landfill leachate, Water Res. 45(2011) 6189-6194.
[23] J.A. Khan, X. He, H.M. Khan, N.S. Shah, D.D. Dionysiou, Oxidative degradation of atrazine in aqueous solution by UV/H₂O₂/Fe²⁺, UV/S₂O₈^2-/Fe²⁺ and UV/HSO₅^-/Fe²⁺ processes:a comparative study, Chem. Eng. J. 218(2013) 376-383.
[24] L. Wang, Q. Yang, D. Wang, X. Li, G. Zeng, Z. Li, Y. Deng, J. Liu, K. Yi, Advanced landfill leachate treatment using iron-carbon microelectrolysis-Fenton process:process optimization and column experiments, J. Hazard. Mater. 318(2016) 460-467.
[25] G. Del Moro, A. Mancini, G. Mascolo, C. Di Iaconi, Comparison of UV/H₂O₂ based AOP as an end treatment or integrated with biological degradation for treating landfill leachates, Chem. Eng. J. 218(2006) 133-137.
[26] M. Hassan, Y. Zhao, B. Xie, Employing TiO₂ photocatalysis to deal with landfill leachate:current status and development, Chem. Eng. J. 285(2016) 264-275.
[27] M. Chys, V.A. Oloibiri, W.T.M. Audenaert, K. Demeestere, S.W.H. Van Hulle, Ozonation of biologically treated landfill leachate:efficiency and insights in organic conversions, Chem. Eng. J. 277(2015) 104-111.
[28] B. Tsitonaki, M. Petri, H. Crimi, R.L. MosbÆK, P.L. Siegrist, In situ chemical oxidation of contaminated soil and groundwater using persulfate:A review, Crit. Rev. Environ. Sci. Technol. 40(2010) 55-91.
[29] A. Long, Y. Lei, H. Zhang, In situ chemical oxidation of organic contaminated soil and groundwater using activated persulfate process, Prog. Chem. 26(2014) 898-908.
[30] G.P. Anipsitakis, D.D. Dionysiou, Degradation of organic contaminants in water sulfate radicals generated by the conjunction of peroxymonosulfate with cobalt, Environ. Sci. Technol. 37(2003) 4790-4797.
[31] A. Rastogi, S.R. Al-Abed, D.D. Dionysiou, Sulfate radical-based ferrous peroxymonosulfate oxidative system for PCBs degradation in aqueous and sediment systems, Appl. Catal. B Environ. 85(2009) 171-179.
[32] C. Qi, X. Liu, J. Ma, C. Lin, X. Li, H. Zhang, Activation of peroxymonosulfate by base:Implications for the degradation of organic pollutants, Chemosphere 151(2016) 280-288.
[33] C.A. Delcomyn, K.E. Bushway, M.V. Henley, Inactivation of biological agents using neutral oxone-chloride solutions, Environ. Sci. Technol. 40(2006) 2759-2764.
[34] G.P. Anipsitakis, D.D. Dionysiou, Radical generation by the interaction of transition metal with common oxidants, Environ. Sci. Technol. 38(2004) 3705-3712.
[35] H. Wu, C. Lai, G. Zeng, J. Liang, J. Chen, J. Xu, J. Dai, X. Li, J. Liu, M. Chen, L. Lu, L. Hu, J. Wan, The interactions of composting and biochar and their implications for soil amendment and pollution remediation:a review, Crit. Rev. Biotechnol. 37(2017) 754-764.
[36] J. Fang, C. Shang, Bromate formation from bromide oxidation by the UV/persulfate process, Environ. Sci. Technol. 46(2012) 8976-8983.
[37] W.W.P. Lai, M.H. Hsu, A.Y.C. Lin, The role of bicarbonate anions in methotrexate degradation via UV/TiO₂:mechanisms, reactivity and increased toxicity, Water Res. 112(2017) 157-166.
[38] C.A. Lutterbeck, E. Baginska, E.L. Machado, K. Kummerer, Removal of the anti-cancer drug methotrexate from water by advanced oxidation processes:Aerobic biodegradation and toxicity studies after treatment, Chemosphere 141(2015) 290-296.
[39] P. Calza, C. Medana, M. Sarro, V. Rosato, R. Aigotti, C. Baiocchi, C. Minero, Photocatalytic degradation of selected anticancer drugs and identification of their transformation products in water by liquid chromatography-high resolution mass spectrometry, J. Chromato:A. 1362(2014) 135-147.
[40] X. Liu, T. Zhang, Y. Zhou, L. Fang, Y. Shao, Degradation of atenolol by UV/peroxymonosulfate:Kinetics, the effect of operational parameters and mechanism, Chemosphere. 93(2013) 2717-2724.
[41] Y. Guan, J. Ma, X. Li, J. Fang, L. Chen, Influence of pH on the formation of sulfate and hydroxyl radicals in the UV/peroxymonosulfate system, Environ. Sci. Technol. 45(2011) 9308-9314.
[42] P. Neta, R.H. Huie, A.B. Ross, Rate constants for reactions of inorganic radicals in aqueous solution, J Phy. Chem. Ref. Data. 17(1988) 1027-1284.
[43] P. Maruthamuthu, P. Neta, Radiolytic chain decomposition of peroxomonophosphoric and peroxomonosulfuric acids, J. Phys. Chem. 81(1977) 937-940.
[44] J. Sharma, I.M. Mishra, D.D. Dionysiou, V. Kumar, Oxidative removal of Bisphenol a by UV-C/peroxymonosulfate (PMS):kinetics, influence of co-existing chemicals and degradation pathway, Chem. Eng. J. 276(2015) 193-204.
[45] S. Khan, X. He, J.A. Khan, H.M. Khan, D.L. Boccelli, D.D. Dionysiou, Kinetics and mechanism of sulfate radical-and hydroxyl radical-induced degradation of highly chlorinated pesticide lindane in UV/peroxymonosulfate system, Chem. Eng. J. 318(2017) 135-142.
[46] M. Mahdi-Ahmed, S. Chiron, Ciprofloxacin oxidation by UV-C activate peroxymonosulfate in wastewater, J. Hazard. Mater. 265(2014) 41-46.
[47] Y.R. Wang, W. Chu, Photo-assisted degradation of 2,4,5-trichlorophenoxyacetic acid by Fe (II)-catalyzed activation of Oxone process:the role of UV irradiation, reaction mechanism and mineralization, Appl. Catal. B Environ. 123-124(2012) 151-161.
[48] N.S. Shah, X. He, H.M. Khan, J.A. Khan, K.E. O'shea, D.L. Boccelli, D.D. Dionysiou, Efficient removal of endosulfan from aqueous solution by UV-C/peroxides:a comparative study, J. Hazard. Mater. 263(2013) 584-592.
[49] R.E. Huie, C.L. Clifton, Kinetics of the self-reaction of hydroxymethylperoxyl radicals, Chem. Phy. Lett. 205(1993) 163-167.
[50] U.K. Klaning, K. Sehested, E.H. Appelman, Laser flash photolysis and pulse radiolysis of aqueous solutions of the fluoroxysulfate ion, Inor. Chem. 30(1991) 3582-3584.
[51] A. Mehrdad, B. Massoumi, R. Hashemzadeh, Kinetic study of the degradation of Rhodamine B in the presence of hydrogen peroxide and some metal oxide, Chem. Eng. J. 168(2011) 1073-1078.
[52] G.V. Buxton, C.L. Greenstock, W.P. Helman, A.B. Ross, Critical review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (·OH/·O-) in aqueous solution, J. Phy. Chem. Ref. Data. 17(1988) 513-886.
[53] S. Yang, P. Wang, X. Yang, L. Shan, W. Zhang, X. Shao, R. Niu, Degradation efficiencies of azo dye Acid Orange 7 by the interaction of heat, UV and anions with common oxidants:persulfate, peroxymonosulfate and hydrogen peroxide, J. Hazard. Mater. 179(2010) 552-558.
[54] M.M. Ahmed, M. Brienza, V. Goetz, S. Chiron, Solar photo-Fenton using peroxymonosulfate for organic micropollutants removal from domestic wastewater:Comparison with heterogeneous TiO₂ photocatalysis, Chemosphere. 117(2014) 256-261.
[55] Y. Gao, N. Gao, Y. Deng, Y. Yang, Y. Ma, Ultraviolet (UV) light-activated persulfate oxidation of sulfamethazine in water, Chem. Eng. J. 195-196(2012) 248-253.
[56] C. Jiang, Y. Ji, Y. Shi, J. Chen, T. Cai, Sulfate radical-based oxidation of fluoroquinolone antibiotics:kinetics, mechanisms and effects of natural water matrices, Water Res. 106(2016) 507-517.
[57] B.C. Widemann, E. Sung, L. Anderson, W.L. Salzer, F.M. Balis, K.S. Montijo, C. McCully, M. Hawkins, P.C. Adamson, Pharmacokinetics and metabolism of the methotrexate metabolite 2, 4-diamino-n10-methylpteroic acid, J. Pharmacol. Exp. Ther. 294(2000) 894-902.
[58] L.B.M. Ellis, L.P. Wackett, Use of the University of Minnesota biocatalysis/biodegradation database for study of microbial degradation, Microb. Infor. Experiment. 2(2012) 1-11.