Abstract
The present study explores the galvanostatic electrolysis of synthetic solutions containing the antidiabetic metformin with different support electrolytes, using a boron-doped diamond anode in an undivided electrochemical cell to test the possibility of the reuse of the treated water in the field of agriculture. It also investigated the effects of the main operating parameters, including applied current density, supporting electrolyte nature and concentration, initial chemical oxygen demand, initial pH, temperature, and NaCl concentration. This was realized considering the chemical oxygen demand removal, current efficiency, energy consumption and phytotoxicity. The experimental results showed that metformin concentration, measured by the square wave voltammetry technique and the chemical oxygen demand decay, follows a pseudo-first-order kinetics. At the beginning of the electrolysis, the electrochemical efficiency was limited by a charge-transfer process. For an initial chemical oxygen demand of 900 mg L−1 and under optimal conditions (current density of 30 mA cm−2, pH 2, Na2SO4 2 g L−1, NaCl 0.8 g L−1 and T 343.15 K), the removal of organic matter was about 90% and the complete elimination of metformin was reached after 2 h of electrolysis. Concerning the phytotoxicity tests of the treated water, they were carried out using Fenugreek and Lucerne seeds. The results indicated a positive effect on seeds germination due to the production of nitrate ions from the metformin molecules.
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References
Adel Niaei H, Rostamizadeh M (2020) Adsorption of metformin from an aqueous solution by Fe-ZSM-5 nano-adsorbent: isotherm, kinetic and thermodynamic studies. J Chem Thermodyn 142:106003. https://doi.org/10.1016/j.jct.2019.106003
Alnajjar M, Hethnawi A, Nafie G et al (2019) Silica-alumina composite as an effective adsorbent for the removal of metformin from water. J Environ Chem Eng 7:1–10. https://doi.org/10.1016/j.jece.2019.102994
Badran I, Hassan A, Manasrah AD, Nassar NN (2019a) Experimental and theoretical studies on the thermal decomposition of metformin. J Therm Anal Calorim 138:433–441. https://doi.org/10.1007/s10973-019-08213-9
Badran I, Manasrah AD, Nassar NN (2019b) A combined experimental and density functional theory study of metformin oxy-cracking for pharmaceutical wastewater treatment. RSC Adv 9:13403–13413. https://doi.org/10.1039/c9ra01641d
Balasubramani K, Sivarajasekar N, Naushad M (2020) Effective adsorption of antidiabetic pharmaceutical (metformin) from aqueous medium using graphene oxide nanoparticles: Equilibrium and statistical modelling. J Mol Liq 301:112426. https://doi.org/10.1016/j.molliq.2019.112426
Brahim BM, Ammar HB, Abdelhédi R, Samet Y (2016) Electrochemical removal of the insecticide imidacloprid from water on a boron-doped diamond and Ta/PbO2 anodes using anodic oxidation process. Korean J Chem Eng 33:2602–2609. https://doi.org/10.1007/s11814-016-0128-0
Briones RM, Sarmah AK, Padhye LP (2016) A global perspective on the use, occurrence, fate and effects of anti-diabetic drug metformin in natural and engineered ecosystems. Environ Pollut 219:1007–1020. https://doi.org/10.1016/j.envpol.2016.07.040
Carbuloni CF, Savoia JE, Santos JSP et al (2020) Degradation of metformin in water by TiO2–ZrO2 photocatalysis. J Environ Manage 262:110347. https://doi.org/10.1016/j.jenvman.2020.110347
Cavalcanti EB, Garcia-Segura S, Centellas F, Brillas E (2013) Electrochemical incineration of omeprazole in neutral aqueous medium using a platinum or boron-doped diamond anode: Degradation kinetics and oxidation products. Water Res 47:1803–1815. https://doi.org/10.1016/j.watres.2013.01.002
Chen X, Chen G, Gao F, Yue PL (2003) High-performance Ti/BDD electrodes for pollutant oxidation. Environ Sci Technol 37:5021–5026. https://doi.org/10.1021/es026443f
Chinnaiyan P, Thampi SG, Kumar M, Balachandran M (2019) Photocatalytic degradation of metformin and amoxicillin in synthetic hospital wastewater: effect of classical parameters. Int J Environ Sci Technol 16:5463–5474. https://doi.org/10.1007/s13762-018-1935-0
Cho NH, Shaw JE, Karuranga S et al (2018) IDF Diabetes Atlas: Global estimates of diabetes prevalence for 2017 and projections for 2045. Diabetes Res Clin Pract 138:271–281. https://doi.org/10.1016/j.diabres.2018.02.023
Comninellis C, Nerini A (1995) Anodic oxidation of phenol in the presence of NaCl for wastewater treatment. J Appl Electrochem 25:23–28. https://doi.org/10.1007/BF00251260
De la Cruz N, Esquius L, Grandjean D et al (2013) Degradation of emergent contaminants by UV, UV/H2O2 and neutral photo-Fenton at pilot scale in a domestic wastewater treatment plant. Water Res 47:5836–5845. https://doi.org/10.1016/j.watres.2013.07.005
Dolatabadi M, Ahmadzadeh S (2019) A rapid and efficient removal approach for degradation of metformin in pharmaceutical wastewater using electro-Fenton process; optimization by response surface methodology. Water Sci Technol 80:685–694. https://doi.org/10.2166/wst.2019.312
Drechsel P, Qadir M, Wichelns D (2015) Wastewater: Economic asset in an urbanizing world. Wastewater: Economic Asset in an Urbanizing World 1–282. https://doi.org/10.1007/978-94-017-9545-6
Editorial G (2009) Membrane reactors—part I. Technology. https://doi.org/10.1002/apj
Eggen T, Lillo C (2012) Antidiabetic II drug metformin in plants: uptake and translocation to edible parts of cereals, oily seeds, beans, tomato, squash, carrots, and potatoes. J Agric Food Chem 60:6929–6935. https://doi.org/10.1021/jf301267c
Elizalde-Velázquez GA, Gómez-Oliván LM (2020) Occurrence, toxic effects and removal of metformin in the aquatic environments in the world: recent trends and perspectives. Sci Total Environ. https://doi.org/10.1016/j.scitotenv.2019.134924
Ellouze S, Panizza M, Barbucci A et al (2016) Ferulic acid treatment by electrochemical oxidation using a BDD anode. J Taiwan Inst Chem Eng 59:132–137. https://doi.org/10.1016/j.jtice.2015.09.008
Enache TA, Chiorcea-Paquim AM, Fatibello-Filho O, Oliveira-Brett AM (2009) Hydroxyl radicals electrochemically generated in situ on a boron-doped diamond electrode. Electrochem Commun 11:1342–1345. https://doi.org/10.1016/j.elecom.2009.04.017
Escudero A, Hunter C, Roberts J et al (2020) Pharmaceuticals removal and nutrient recovery from wastewaters by Chlamydomonas acidophila. Biochem Eng J 156:107517. https://doi.org/10.1016/j.bej.2020.107517
Gabr RQ, El-Sherbeni AA, Ben-Eltriki M, El-Kadi AO, Brocks DR (2017) Pharmacokinetics of metformin in the rat: assessment of the effect of hyperlipidemia and evidence for its metabolism to guanylurea. Can J Physiol Pharmacol 95(5):530–538. https://doi.org/10.1139/cjpp-2016-0329
García J, García-Galán MJ, Day JW et al (2020) A review of emerging organic contaminants (EOCs), antibiotic resistant bacteria (ARB), and antibiotic resistance genes (ARGs) in the environment: Increasing removal with wetlands and reducing environmental impacts. Biores Technol 307:123228. https://doi.org/10.1016/j.biortech.2020.123228
Gargouri OD, Samet Y, Abdelhedi R (2013) Electrocatalytic performance of PbO2 films in the degradation of dimethoate insecticide. Water SA 39:31–38. https://doi.org/10.4314/wsa.v39i1.5
Grasso D, Strevett K, Pesari H (2005) Impact of sodium and potassium on environmental systems. J Environ Syst 22:297–323. https://doi.org/10.2190/rrnd-6y9q-jn16-06nd
Hejzlar J, Kopáček J (1990) Determination of low chemical oxygen demand values in water by the dichromate semi-micro method. Analyst 115:1463–1467. https://doi.org/10.1039/AN9901501463
IDF Diabetes Atlas (2019) No title international diabetes federation. IDF Diabetes Atlas, 9th edn. International Diabetes Federation, Brussels. http://www.diabetesatlas.org/
Jardak K, Dirany A, Drogui P, El Khakani MA (2016) Electrochemical degradation of ethylene glycol in antifreeze liquids using boron doped diamond anode. Sep Purif Technol 168:215–222. https://doi.org/10.1016/j.seppur.2016.05.046
Kairigo P, Ngumba E, Sundberg LR et al (2020) Occurrence of antibiotics and risk of antibiotic resistance evolution in selected Kenyan wastewaters, surface waters and sediments. Sci Total Environ 720:137580. https://doi.org/10.1016/j.scitotenv.2020.137580
Koagouw W, Ciocan C (2018) Impact of Metformin and Increased Temperature on Blue Mussels Mytilus edulis—evidence for Synergism. J Shellfish Res 37:467–474. https://doi.org/10.2983/035.037.0301
Lee JW, Shin YJ, Kim H et al (2019) Metformin-induced endocrine disruption and oxidative stress of Oryzias latipes on two-generational condition. J Hazard Mater 367:171–181. https://doi.org/10.1016/j.jhazmat.2018.12.084
Lissens G, Pieters J, Verhaege M et al (2003) Electrochemical degradation of surfactants by intermediates of water discharge at carbon-based electrodes. Electrochim Acta 48:1655–1663. https://doi.org/10.1016/S0013-4686(03)00084-7
Lović J, Lađarević J, Mijin D et al (2019) Electrochemical stability of metformin in NaHCO3 and Na2SO4 water solution at Au, GC and IrOx electrodes. J Serb Chem Soc 84:1319–1327. https://doi.org/10.2298/JSC190731091L
Malin SK, Kashyap SR (2014) Effects of metformin on weight loss: potential mechanisms. Curr Opin Endocrinol Diabetes Obes 21:323–329. https://doi.org/10.1097/MED.0000000000000095
Mallik R, Chowdhury TA (2018) Metformin in cancer. Diabetes Res Clin Pract 143:409–419. https://doi.org/10.1016/j.diabres.2018.05.023
Niemuth NJ, Jordan R, Crago J et al (2015) Metformin exposure at environmentally relevant concentrations causes potential endocrine disruption in adult male fish. Environ Toxicol Chem 34:291–296. https://doi.org/10.1002/etc.2793
Orata ED, De Leon PDP, Doma BT (2019) Degradation of metformin in water using electro-Fenton process. IOP Confer Ser: Earth Environ Sci. https://doi.org/10.1088/1755-1315/344/1/012007
Ottmar KJ, Colosi LM, Smith JA (2010) Development and application of a model to estimate wastewater treatment plant prescription pharmaceutical influent loadings and concentrations. Bull Environ Contam Toxicol 84:507–512. https://doi.org/10.1007/s00128-010-9990-3
Panizza M (2014) Anodic oxidation of benzoquinone using diamond anode. Environ Sci Pollut Res 21:8451–8456. https://doi.org/10.1007/s11356-014-2782-2
Panizza M, Barbucci A, Ricotti R, Cerisola G (2007) Electrochemical degradation of methylene blue. Sep Purif Technol 54:382–387. https://doi.org/10.1016/j.seppur.2006.10.010
Panizza M, Cerisola G (2009) Direct and mediated anodic oxidation of organic pollutants. Chem Rev 109:6541–6569. https://doi.org/10.1021/cr9001319
Panizza M, Dirany A, Sirés I et al (2014) Complete mineralization of the antibiotic amoxicillin by electro-Fenton with a BDD anode. J Appl Electrochem 44:1327–1335. https://doi.org/10.1007/s10800-014-0740-9
Papageorgiou M, Zioris I, Danis T et al (2019) Comprehensive investigation of a wide range of pharmaceuticals and personal care products in urban and hospital wastewaters in Greece. Sci Total Environ 694:133565. https://doi.org/10.1016/j.scitotenv.2019.07.371
Patil TR, Patil ST, Patil SPA (2018) Antimicrobial Potential of Metformin. Int J Pharmacogn Phytochem Res 10:279–283. https://doi.org/10.25258/phyto.10.7.2
Perret A, Haenni W, Skinner N et al (1999) Electrochemical behavior of synthetic diamond thin film electrodes. Diam Relat Mater 8:820–823. https://doi.org/10.1016/s0925-9635(98)00280-5
Ptáček P, Šoukal F, Opravil T (2018) Introduction to the transition state theory. Introd Effect Mass Activ Complex Discuss Wave Funct Instanton. https://doi.org/10.5772/intechopen.78705
Rabaaoui N, Moussaoui Y, Allagui MS et al (2013a) Anodic oxidation of nitrobenzene on BDD electrode: variable effects and mechanisms of degradation. Sep Purif Technol 107:318–323. https://doi.org/10.1016/j.seppur.2013.01.047
Rabaaoui N, Saad MEK, Moussaoui Y et al (2013b) Anodic oxidation of o-nitrophenol on BDD electrode: variable effects and mechanisms of degradation. J Hazard Mater 250–251:447–453. https://doi.org/10.1016/j.jhazmat.2013.02.027
Rodrigo MA, Michaud PA, Duo I et al (2001) Oxidation of 4-chlorophenol at boron-doped diamond electrode for wastewater treatment. J Electrochem Soc 148:D60. https://doi.org/10.1149/1.1362545
Rodriguez J, Rodrigo MA, Panizza M, Cerisola G (2009) Electrochemical oxidation of Acid Yellow 1 using diamond anode. J Appl Electrochem 39:2285–2289. https://doi.org/10.1007/s10800-009-9880-8
Salazar C, Contreras N, Mansilla HD et al (2016) Electrochemical degradation of the antihypertensive losartan in aqueous medium by electro-oxidation with boron-doped diamond electrode. J Hazard Mater 319:84–92. https://doi.org/10.1016/j.jhazmat.2016.04.009
Samet Y, Elaoud SC, Ammar S, Abdelhedi R (2006) Electrochemical degradation of 4-chloroguaiacol for wastewater treatment using PbO2 anodes. J Hazard Mater 138:614–619. https://doi.org/10.1016/j.jhazmat.2006.05.100
Sanchez-Rangel E, Inzucchi SE (2017) Metformin: clinical use in type 2 diabetes. Diabetologia 60:1586–1593. https://doi.org/10.1007/s00125-017-4336-x
Scheurer M, Michel A, Brauch HJ et al (2012) Occurrence and fate of the antidiabetic drug metformin and its metabolite guanylurea in the environment and during drinking water treatment. Water Res 46:4790–4802. https://doi.org/10.1016/j.watres.2012.06.019
Scialdone O, Galia A, Guarisco C et al (2008) Electrochemical incineration of oxalic acid at boron doped diamond anodes: role of operative parameters. Electrochim Acta 53:2095–2108. https://doi.org/10.1016/j.electacta.2007.09.007
Tisler S, Zwiener C (2018) Formation and occurrence of transformation products of metformin in wastewater and surface water. Sci Total Environ 628–629:1121–1129. https://doi.org/10.1016/j.scitotenv.2018.02.105
Tong AZ, Ghoshdastidar AJ, Fox S (2015) The presence of the top prescribed pharmaceuticals in treated sewage effluents and receiving waters in southwest Nova Scotia, Canada. Environ Sci Pollut Res 22:689–700. https://doi.org/10.1007/s11356-014-3400-z
Trautwein C, Kümmerer K (2011) Incomplete aerobic degradation of the antidiabetic drug Metformin and identification of the bacterial dead-end transformation product Guanylurea. Chemosphere 85:765–773. https://doi.org/10.1016/j.chemosphere.2011.06.057
Vasilie S, Manea F, Baciu A, Pop A (2018) Dual use of boron-doped diamond electrode in antibiotics-containing water treatment and process control. Process Saf Environ Prot 117:446–453. https://doi.org/10.1016/j.psep.2018.05.024
Wang X, Sun C, Gao S et al (2001) Validation of germination rate and root elongation as indicator to assess phytotoxicity with Cucumis sativus. Chemosphere 44:1711–1721. https://doi.org/10.1016/S0045-6535(00)00520-8
WHO (2016) Global report on diabetes. ISBN 978:6–86
Yan JH, Xiao Y, Tan DQ et al (2019) Wastewater analysis reveals spatial pattern in consumption of anti-diabetes drug metformin in China. Chemosphere 222:688–695. https://doi.org/10.1016/j.chemosphere.2019.01.151
Yang PK, Hsu CY, Chen MJ et al (2018) The efficacy of 24-month metformin for improving menses, hormones, and metabolic profiles in polycystic ovary syndrome. J Clin Endocrinol Metab 103:890–899. https://doi.org/10.1210/jc.2017-01739
Zayneb C, Lamia K, Olfa E et al (2015) Morphological, physiological and biochemical impact of ink industry effluent on germination of Maize (Zea mays), Barley (Hordeum vulgare) and Sorghum (Sorghum bicolor). Bull Environ Contam Toxicol 95:687–693. https://doi.org/10.1007/s00128-015-1600-y
Zhang Z, Li F, Tian Y et al (2020) Metformin enhances the antitumor activity of CD8 + T lymphocytes via the AMPK–miR-107–eomes–PD-1 pathway. J Immunol 204:2575–2588. https://doi.org/10.4049/jimmunol.1901213
Zhu S, Liu Y, guo, Liu S bo, et al (2017) Adsorption of emerging contaminant metformin using graphene oxide. Chemosphere 179:20–28. https://doi.org/10.1016/j.chemosphere.2017.03.071
Acknowledgements
The authors would like to express their thanks to Professor Mohamed-Faouzi Ahmadi (Laboratoire de Toxicologie Microbiologie Environnementale et Santé (LR17ES06), Sciences Faculty of Sfax, University of Sfax, Tunisia) for reading and comments made on this paper.
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Chaabene, R., Khannous, L. & Samet, Y. Electrochemical degradation of aqueous metformin at boron-doped diamond electrode: kinetic study and phytotoxicity tests. Int. J. Environ. Sci. Technol. 20, 5169–5182 (2023). https://doi.org/10.1007/s13762-022-04325-2
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DOI: https://doi.org/10.1007/s13762-022-04325-2