Abstract
The rising global cancer rate is driving up the consumption of anticancer drugs. This causing a noticeable increase in the levels of these drugs in wastewater. The drugs are not metabolized effectively by the human body, leading to their presence in human waste, as well as in the effluent from hospitals and drug manufacturing industries. Methotrexate is a commonly used drug for treating various types of cancer. Its complex organic structure makes it difficult to degrade using conventional methods. The present work proposed a non-thermal pencil plasma jet treatment for methotrexate degradation. The air plasma produced in this jet setup is electrical characterized and plasma species/radicals are identified using emission spectroscopy. The degradation of drug is monitored by studying the change in solution physiochemical properties, HPLC-UV analysis, and removal of total organic carbon, etc.
Results show that a 9-min plasma treatment completely degraded the drug solution that followed first-order degradation kinetics with rate constant 0.38 min-1 and 84.54% mineralization was observed. Additionally, an increase in electrical conductivity and dissolved solids compared to virgin water-plasma interaction indicated the formation of new, smaller compounds (2,4-Diaminopteridine-6-carboxylic acid, N-(4-Aminobenzoyl)-l-glutamic acid, etc.) after drug degradation. The plasma-treated methotrexate solution also showed lower toxicity toward freshwater chlorella algae compared to the untreated solution. Finally, it can be said that non-thermal plasma jets are economically and environmentally friendly devices that have the potential to be used for the treatment of complex and resistive anticancer drug-polluted wastewaters.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Data availability
Data is available on reasonable request from the corresponding author.
References
Aziz KHH, Miessner H, Mueller S, Kalass D, Moeller D, Khorshid I, Rashid MAM (2017) Degradation of pharmaceutical diclofenac and ibuprofen in aqueous solution, a direct comparison of ozonation, photocatalysis, and non-thermal plasma. J Chem Eng 313:1033–1041. https://doi.org/10.1016/j.cej.2016.10.137
Booker V, Halsall C, Llewellyn N, Johnson A, Williams R (2014) Prioritising anticancer drugs for environmental monitoring and risk assessment purposes. Sci Total Environ 473:159–170. https://doi.org/10.1016/j.scitotenv.2013.11.145
Cristóvão M, Torrejais J, Janssens R, Luis P, Van der Bruggen B, Dubey K, Mandal M, Bronze M, Crespo J, Pereira V (2019) Treatment of anticancer drugs in hospital and wastewater effluents using nanofiltration. Sep Purif Technol 224:273–280. https://doi.org/10.1016/j.seppur.2019.05.016
Della-Flora A, Wilde ML, Thue PS, Lima D, Lima EC, Sirtori C (2020) Combination of solar photo-Fenton and adsorption process for removal of the anticancer drug Flutamide and its transformation products from hospital wastewater. J Hazard Mater 396:122699. https://doi.org/10.1016/j.jhazmat.2020.122699
Dobrin D, Bradu C, Magureanu M, Mandache N, Parvulescu V (2013) Degradation of diclofenac in water using a pulsed corona discharge. J Chem Eng 234:389–396. https://doi.org/10.1016/j.cej.2013.08.114
Dominguez-García P, Gibert M, Lacorte S, Gómez-Canela C (2022) Long-term calculation of predicted environmental concentrations to assess the risk of anticancer drugs in environmental waters. Mol 27:3203
Espinosa A, Nélieu S, Lieben P, Skarbek C, Labruère R, Benoit P (2022) Photodegradation of methotrexate in aqueous solution: degradation kinetics and identification of transformation products. Environ Sci Pollut Res 29:6060–6071. https://doi.org/10.1007/s11356-021-15820-3
Ferrando-Climent L, Cruz-Morató C, Marco-Urrea E, Vicent T, Sarrà M, Rodriguez-Mozaz S, Barceló D (2015) Non conventional biological treatment based on Trametes versicolor for the elimination of recalcitrant anticancer drugs in hospital wastewater. Chemosphere 136:9–19. https://doi.org/10.1016/j.chemosphere.2015.03.051
Gillard J, Alconero L (2019) Removal of anti-cancer drugs from real wastewater effluent by photocatalytic membrane reactor (PMR). Ecole polytechnique de Louvain, Université catholique de Louvain http://hdl.handle.net/2078.1/thesis:19509. Access date 20 March 2023
Graumans MH, Hoeben WF, van Dael MF, Anzion RB, Russel FG, Scheepers PT (2021) Thermal plasma activation and UV/H2O2 oxidative degradation of pharmaceutical residues. Environ Res 195:110884. https://doi.org/10.1016/j.envres.2021.110884
Hsu M-H, Tsai C-J, Lin AY-C (2019) Mechanism and pathways underlying the self-sensitized photodegradation of methotrexate under simulated solar irradiation. J Hazard Mater 373:468–475. https://doi.org/10.1016/j.jhazmat.2019.03.095
Huo Z, Wang S, Shao H, Wang H, Xu G (2020) Radiolytic degradation of anticancer drug capecitabine in aqueous solution: kinetics, reaction mechanism, and toxicity evaluation. Environ Sci Pollut Res 27:20807–20816. https://doi.org/10.1007/s11356-020-08500-1
Janssens R, Cristovao M, Bronze M, Crespo J, Pereira V, Luis P (2019) Coupling of nanofiltration and UV, UV/TiO2 and UV/H2O2 processes for the removal of anti-cancer drugs from real secondary wastewater effluent. J Environ Chem Eng 7:103351. https://doi.org/10.1016/j.jece.2019.103351
Janssens R, Hainaut R, Gillard J, Dailly H, Luis P (2021) Performance of a slurry photocatalytic membrane reactor for the treatment of real secondary wastewater effluent polluted by anticancer drugs. Ind Eng Chem Res 60:2223–2231. https://doi.org/10.1021/acs.iecr.0c04846
Kanjal MI, Muneer M, Abdelhaleem A, Chu W (2020) Degradation of methotrexate by UV/peroxymonosulfate: kinetics, effect of operational parameters and mechanism. Chin J Chem Eng 28:2658–2667. https://doi.org/10.1016/j.cjche.2020.05.033
Kelbert M, Pereira CS, Daronch NA, Cesca K, Michels C, de Oliveira D, Soares HM (2021) Laccase as an efficacious approach to remove anticancer drugs: a study of doxorubicin degradation, kinetic parameters, and toxicity assessment. J Hazard Mater 409:124520. https://doi.org/10.1016/j.jhazmat.2020.124520
Kim K-S, Yang C-S, Mok Y (2013) Degradation of veterinary antibiotics by dielectric barrier discharge plasma. J Chem Eng 219:19–27. https://doi.org/10.1016/j.cej.2012.12.079
Koltsakidou Α, Antonopoulou M, Εvgenidou Ε, Konstantinou I, Lambropoulou D (2019) A comparative study on the photo-catalytic degradation of Cytarabine anticancer drug under Fe3+/H2O2, Fe3+/S2O82−, and [Fe (C2O4) 3] 3−/H2O2 processes. Kinetics, identification, and in silico toxicity assessment of generated transformation products. Environ Sci Pollut Res 26:7772–7784. https://doi.org/10.1007/s11356-018-4019-2
Korniłłowicz-Kowalska T, Rybczyńska-Tkaczyk K (2020) Growth conditions, physiological properties, and selection of optimal parameters of biodegradation of anticancer drug daunomycin in industrial effluents by Bjerkandera adusta CCBAS930. Int Microbiol 23:287–301. https://doi.org/10.1007/s10123-019-00102-3
Kramida A, Nave G, Reader J (2017) The Cu II Spectrum. Atoms 5:9. https://doi.org/10.3390/atoms5010009
Krause H, Schweiger B, Prinz E, Kim J, Steinfeld U (2011) Degradation of persistent pharmaceuticals in aqueous solutions by a positive dielectric barrier discharge treatment. J Electrost 69:333–338. https://doi.org/10.1016/j.elstat.2011.04.011
Lai WW-P, Hsu M-H, Lin AY-C (2017) The role of bicarbonate anions in methotrexate degradation via UV/TiO2: mechanisms, reactivity and increased toxicity. Water Res 112:157–166. https://doi.org/10.1016/j.watres.2017.01.040
Li D, Chen H, Liu H, Schlenk D, Mu J, Lacorte S, Ying G-G, Xie L (2021) Anticancer drugs in the aquatic ecosystem: environmental occurrence, ecotoxicological effect and risk assessment. Environ Int 153:106543. https://doi.org/10.1016/j.envint.2021.106543
Liu Y, Mei S, Iya-Sou D, Cavadias S, Ognier S (2012) Carbamazepine removal from water by dielectric barrier discharge: comparison of ex situ and in situ discharge on water. Chem Eng Process 56:10–18. https://doi.org/10.1016/j.cep.2012.03.003
Lutterbeck CA, Baginska E, Machado ÊL, Kümmerer K (2015) Removal of the anti-cancer drug methotrexate from water by advanced oxidation processes: aerobic biodegradation and toxicity studies after treatment. Chemosphere 141:290–296
Magureanu M, Piroi D, Mandache N, David V, Medvedovici A, Bradu C, Parvulescu V (2011) Degradation of antibiotics in water by non-thermal plasma treatment. Water Res 45:3407–3416. https://doi.org/10.1016/j.watres.2011.03.057
Marković M, Jović M, Stanković D, Kovačević V, Roglić G, Gojgić-Cvijović G, Manojlović D (2015) Application of non-thermal plasma reactor and Fenton reaction for degradation of ibuprofen. Sci Total Environ 505:1148–1155. https://doi.org/10.1016/j.scitotenv.2014.11.017
Mello Souza D, Reichert JF, Ramos do Nascimento V, Figueiredo Martins A (2022) Ozonation and UV photolysis for removing anticancer drug residues from hospital wastewater. J Environ Sci Health A 57:635–644. https://doi.org/10.1080/10934529.2022.2099195
Nassour C, Barton SJ, Nabhani-Gebara S, Saab Y, Barker J (2020) Occurrence of anticancer drugs in the aquatic environment: a systematic review. Environ Sci Pollut Res 27:1339–1347. https://doi.org/10.1007/s11356-019-07045-2
Pan X-y, Qiao X-c (2019) Influences of nitrite on paracetamol degradation in dielectric barrier discharge reactor. Ecotoxicol Environ Saf 180:610–615. https://doi.org/10.1016/j.ecoenv.2019.04.037
Panorel I, Preis S, Kornev I, Hatakka H, Louhi-Kultanen M (2013) Oxidation of aqueous paracetamol by pulsed corona discharge. Ozone Sci Eng 35:116–124. https://doi.org/10.1080/01919512.2013.760415
Parkansky N, Alterkop BA, Boxman RL, Mamane H, Avisar D (2008) Submerged arc breakdown of sulfadimethoxine (SDM) in aqueous solutions. Plasma Chem Plasma Process 28:583–592. https://doi.org/10.1007/s11090-008-9145-z
Pereira CS, Kelbert M, Daronch NA, Michels C, de Oliveira D, Soares HM (2020) Potential of enzymatic process as an innovative technology to remove anticancer drugs in wastewater. Appl Microbiol Biotechnol 104:23–31. https://doi.org/10.1007/s00253-019-10229-y
Preisz Z, Kunsági-Máté S (2021) Effect of methotrexate and its photodegradation products on the temperature induced denaturation of human serum albumin. Spectrochim Acta A Mol Biomol 245:118905. https://doi.org/10.1016/j.saa.2020.118905
Rathore V, Nema SK (2021) Optimization of process parameters to generate plasma activated water and study of physicochemical properties of plasma activated solutions at optimum condition. J Appl Phys 129:084901. https://doi.org/10.1063/5.0033848
Rathore V, Nema SK (2022a) The role of different plasma forming gases on chemical species formed in plasma activated water (PAW) and their effect on its properties. Phys Scr 97:065003. https://doi.org/10.1088/1402-4896/ac6d1b
Rathore V, Nema SK (2022b) A comparative study of dielectric barrier discharge plasma device and plasma jet to generate plasma activated water and post-discharge trapping of reactive species. Phys Plasmas 29:033510. https://doi.org/10.1063/5.0078823
Rathore V, Patel D, Shah N, Butani S, Pansuriya H, Nema SK (2021) Inactivation of Candida albicans and lemon (Citrus limon) spoilage fungi using plasma activated water. Plasma Chem Plasma Process 41:1397–1414. https://doi.org/10.1007/s11090-021-10186-3
Rathore V, Desai V, Jamnapara NI, Nema SK (2022a) Activation of water in the downstream of low-pressure ammonia plasma discharge. Plasma Res Express 4:025008. https://doi.org/10.1088/2516-1067/ac777e
Rathore V, Patil C, Sanghariyat A, Nema SK (2022b) Design and development of dielectric barrier discharge setup to form plasma-activated water and optimization of process parameters. Eur Phys J D 76:77. https://doi.org/10.1140/epjd/s10053-022-00397-4
Rathore V, Tiwari BS, Nema SK (2022c) Treatment of pea seeds with plasma activated water to enhance germination, plant growth, and plant composition. Plasma Chem Plasma Process 42:109–129. https://doi.org/10.1007/s11090-019-10028-3
Rong S-P, Sun Y-B, Zhao Z-H (2014) Degradation of sulfadiazine antibiotics by water falling film dielectric barrier discharge. Chin Chem Lett 25:187–192. https://doi.org/10.1016/j.cclet.2013.11.003
Roy N, Talukder M (2018) Effect of pressure on the properties and species production in gliding arc Ar, O 2, and air discharge plasmas. Phys Plasmas 25:093502. https://doi.org/10.1063/1.5043182
Sajib SA, Billah M, Mahmud S, Miah M, Hossain F, Omar FB, Roy NC, Hoque KMF, Talukder MR, Kabir AH (2020) Plasma activated water: the next generation eco-friendly stimulant for enhancing plant seed germination, vigor and increased enzyme activity, a study on black gram (Vigna mungo L.). Plasma Chem Plasma Process 40:119–143. https://doi.org/10.1007/s11090-019-10028-3
Shenstone AG (1948) The first spectrum of copper (Cu I). Philos Trans Royal Soc A 241:297–322. https://doi.org/10.1098/rsta.1948.0021
Singh RK, Philip L, Ramanujam S (2017) Rapid degradation, mineralization and detoxification of pharmaceutically active compounds in aqueous solution during pulsed corona discharge treatment. Water Res 121:20–36. https://doi.org/10.1016/j.watres.2017.05.006
Slamani S, Abdelmalek F, Ghezzar MR, Addou A (2018) Initiation of Fenton process by plasma gliding arc discharge for the degradation of paracetamol in water. J Photochem Photobiol A 359:1–10. https://doi.org/10.1016/j.jphotochem.2018.03.032
Tang S, Yuan D, Rao Y, Zhang J, Qu Y, Gu J (2018) Evaluation of antibiotic oxytetracycline removal in water using a gas phase dielectric barrier discharge plasma. J Environ Manage 226:22–29. https://doi.org/10.1016/j.jenvman.2018.08.022
Turkay O, Barışçı S, Ulusoy E, Şeker MG, Dimoglo A (2018) Anodic oxidation of anti-cancer drug Imatinib on different electrodes: kinetics, transformation by-products and toxicity assessment. Electrochimica Acta 263:400–408. https://doi.org/10.1016/j.electacta.2018.01.079
Xue L, Zhao C, Mo Q, Zhou Y, Huang K (2021) An electrodeless atmospheric microwave plasma jet for efficient degradation of antibiotic norfloxacin. J Environ Manage 291:112729. https://doi.org/10.1016/j.jenvman.2021.112729
Zeng J, Yang B, Wang X, Li Z, Zhang X, Lei L (2015) Degradation of pharmaceutical contaminant ibuprofen in aqueous solution by cylindrical wetted-wall corona discharge. J Chem Eng 267:282–288. https://doi.org/10.1016/j.cej.2015.01.030
Zhang Y, Yu T, Han W, Sun X, Li J, Shen J, Wang L (2016) Electrochemical treatment of anticancer drugs wastewater containing 5-Fluoro-2-Methoxypyrimidine using a tubular porous electrode electrocatalytic reactor. Electrochimica Acta 220:211–221. https://doi.org/10.1016/j.electacta.2016.10.104
Acknowledgements
Authors are thankful to Mr. Nimish kalavadia and Mr. Munish Kumar Buch for providing the HPLC-UV facility for the present work. Total organic carbon analyzer (maker - O-I-Analytical Aurora, model - 1030 TOC analyzer, autosampler - Aurora model 1088) used in the present work is procured using RUSA grant components 3 provided to National Forensic Sciences University. This work is supported by the department of atomic energy (Government of India) doctorate fellowship scheme (DDFS). Authors sincerely thank Mr. Chirayu Patil and Mr. Adam Sanghariyat for providing constant support and useful suggestions during this work.
Author information
Authors and Affiliations
Contributions
All authors contributed to the concept and design of manuscripts. Vikas Rathore, Shruti Patel, and Akanksha Pandey were involved in data collection and data analysis. The first draft of manuscript was prepared by Vikas Rathore. Jignasa Savjani, Shital Butani, Heman Dave, and Sudhir Kumar Nema supervised the research and reviewed the manuscript.
Corresponding author
Ethics declarations
Ethics approval and consent to participate
Not applicable.
Consent for publication
Not applicable.
Competing interests
The authors declare no competing interests.
Additional information
Responsible Editor: Weiming Zhang
Publisher’s note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Rathore, ., Patel, S., Pandey, A. et al. Methotrexate degradation in artificial wastewater using non-thermal pencil plasma jet. Environ Sci Pollut Res (2023). https://doi.org/10.1007/s11356-023-28502-z
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s11356-023-28502-z