Atenolol adsorption onto multi-walled carbon nanotubes modified by NaOCl and ultrasonic treatment; kinetic, isotherm, thermodynamic, and artificial neural network modeling

  • Bahare Dehdashti
  • Mohammad Mehdi Amin
  • Abdolmajid GholizadehEmail author
  • Mohammad Miri
  • Lida Rafati
Research Article


The removal of pharmaceutical pollutants from the aqueous environment is a great environmental concern, mainly due to their diversity, high consumption, and sustainability. In the current study, we aimed to investigate the ability of multi-walled carbon nanotubes (MWCNTs) modified by sodium hypochlorite (NaOCl) and ultrasonic treatment in refining wastewaters contaminated with Atenolol β-blocker drug (ATN). The physical and structural characteristics of the raw MWCNTs and modified MWCNTs (M-MWCNTs) were analyzed using SEM, TEM, Raman spectroscopy, TGA, and FT-IR techniques. The effects of different parameters, including pH, initial concentration, contact time, and temperature were studied and optimized. Subsequently, the adsorption data were analyzed by several kinetic and equilibrium isotherm equations and modeled by artificial neural network (ANN). Highest ATN removal (87.89%) ((qe,exp = 46.03 mg g−1)) occurred on the adsorbent activated within 10 s of ultrasonication time and NaOCl 30%. Moreover, adsorbent modification significantly improved the ATN removal, so that the removal rate on the raw MWCNTs was about 58%, but in the same conditions, M-MWCNTs removed more than 92% of the adsorbate. The adsorption process reached equilibrium after 90 min under the optimized pH of 6. According to ANN modeling, approximately the whole values dispersed around the 45°line, indicating a good compatibility between the trial results and ANN-predicted data. The modification of MWCNTs in proper ultrasonic power via appropriate concentration of NaOCl solution removed many of the impurities and significantly improved the adsorption performance of MWCNTs.


Atenolol Wastewater Multi-walled carbon nanotube Artificial neural network 



Our deepest appreciations are expressed to the Isfahan University of Medical Sciences that supported this study financially.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

40201_2019_347_MOESM1_ESM.docx (33 kb)
ESM 1 (DOCX 32 kb)


  1. 1.
    Ghaedi A, Ghaedi M, Pouranfard A, Ansari A, Avazzadeh Z, Vafaei A, et al. Adsorption of triamterene on multi-walled and single-walled carbon nanotubes: artificial neural network modeling and genetic algorithm optimization. J Mol Liq. 2016;216:654–65.CrossRefGoogle Scholar
  2. 2.
    Samadi MT, Shokoohi R, Araghchian M, Tarlani AM. Amoxicillin removal from aquatic solutions using multi-walled carbon nanotubes. J Mazandaran Uni Med Sci. 2014;24(117):103–15.Google Scholar
  3. 3.
    Kyzas GZ, Koltsakidou A, Nanaki SG, Bikiaris DN, Lambropoulou DA. Removal of beta-blockers from aqueous media by adsorption onto graphene oxide. Sci Total Environ. 2015;537:411–20.CrossRefGoogle Scholar
  4. 4.
    Divya K, Narayana B. New visible spectrophotometric methods for the determination of atenolol in pure and dosage forms via complex formation. Indo Am j pharm res. 2014;4(1):194–203.Google Scholar
  5. 5.
    Urtiaga A, Pérez G, Ibáñez R, Ortiz I. Removal of pharmaceuticals from a WWTP secondary effluent by ultrafiltration/reverse osmosis followed by electrochemical oxidation of the RO concentrate. Desalination. 2013;331:26–34.CrossRefGoogle Scholar
  6. 6.
    Maszkowska J, Stolte S, Kumirska J, Łukaszewicz P, Mioduszewska K, Puckowski A, et al. Beta-blockers in the environment: part I. Mobility and hydrolysis study. Sci Total Environ. 2014;493:1112–21.CrossRefGoogle Scholar
  7. 7.
    Haro NK, Del Vecchio P, Marcilio NR, Féris LA. Removal of atenolol by adsorption–study of kinetics and equilibrium. J Clean Prod. 2017;154:214–9.CrossRefGoogle Scholar
  8. 8.
    Hu Y, Fitzgerald NM, Lv G, Xing X, Jiang W-T, Li Z. Adsorption of atenolol on kaolinite. Adv Mater Sci Eng. 2015;2015:1–8.Google Scholar
  9. 9.
    Papageorgiou M, Kosma C, Lambropoulou D. Seasonal occurrence, removal, mass loading and environmental risk assessment of 55 pharmaceuticals and personal care products in a municipal wastewater treatment plant in Central Greece. Sci Total Environ. 2016;543:547–69.CrossRefGoogle Scholar
  10. 10.
    Isarain-Chávez E, Rodríguez RM, Cabot PL, Centellas F, Arias C, Garrido JA, et al. Degradation of pharmaceutical beta-blockers by electrochemical advanced oxidation processes using a flow plant with a solar compound parabolic collector. Water Res. 2011;45(14):4119–30.CrossRefGoogle Scholar
  11. 11.
    Klavarioti M, Mantzavinos D, Kassinos D. Removal of residual pharmaceuticals from aqueous systems by advanced oxidation processes. Environ Int. 2009;35(2):402–17.CrossRefGoogle Scholar
  12. 12.
    Wilde ML, Montipó S, Martins AF. Degradation of β-blockers in hospital wastewater by means of ozonation and Fe 2+/ozonation. Water Res. 2014;48:280–95.CrossRefGoogle Scholar
  13. 13.
    Arola K, Hatakka H, Mänttäri M, Kallioinen M. Novel process concept alternatives for improved removal of micropollutants in wastewater treatment. Sep Purif Technol. 2017.Google Scholar
  14. 14.
    Gholizadeh A, Ebrahimi AA, Salmani MH, Ehrampoush MH. Ozone-cathode microbial desalination cell; an innovative option to bioelectricity generation and water desalination. Chemosphere. 2017;188:470–7. Scholar
  15. 15.
    Sotelo J, Rodríguez A, Álvarez S, García J. Modeling and elimination of atenolol on granular activated carbon in fixed bed column. Int J Environ Res. 2012;6(4):961–8.Google Scholar
  16. 16.
    Awual MR, Khraisheh M, Alharthi NH, Luqman M, Islam A, Karim MR, et al. Efficient detection and adsorption of cadmium (II) ions using innovative nano-composite materials. Chem Eng J. 2018;343:118–27.CrossRefGoogle Scholar
  17. 17.
    Rahmani A, Mousavi HZ, Fazli M. Effect of nanostructure alumina on adsorption of heavy metals. Desalination. 2010;253(1):94–100.CrossRefGoogle Scholar
  18. 18.
    Lu C, Su F, Hu S. Surface modification of carbon nanotubes for enhancing BTEX adsorption from aqueous solutions. Appl Surf Sci. 2008;254(21):7035–41.CrossRefGoogle Scholar
  19. 19.
    Pourzamani H, Hajizadeh Y, Fadaei S. Efficiency enhancement of multi-walled carbon nanotubes by ozone for benzene removal from aqueous solution. Int J Environ Health Eng. 2015;4(1):29.Google Scholar
  20. 20.
    Lee C-G, Lee S, Park J-A, Park C, Lee SJ, Kim S-B, et al. Removal of copper, nickel and chromium mixtures from metal plating wastewater by adsorption with modified carbon foam. Chemosphere. 2017;166:203–11.CrossRefGoogle Scholar
  21. 21.
    Gholizadeh A, Kermani M, Gholami M, Farzadkia M, Yaghmaeian K. Removal efficiency, adsorption kinetics and isotherms of phenolic compounds from aqueous solution using Rice bran ash. Asian J Chem. 2013;25(7):3871–8.CrossRefGoogle Scholar
  22. 22.
    Naghizadeh A, Momeni F, Derakhshani E. Efficiency of ultrasonic process in regeneration of graphene nanoparticles saturated with humic acid. Desalin Water Treat. 2017;70(2017):290–3.CrossRefGoogle Scholar
  23. 23.
    Nyairo WN, Eker YR, Kowenje C, Akin I, Bingol H, Tor A, et al. Efficient adsorption of lead (II) and copper (II) from aqueous phase using oxidized multiwalled carbon nanotubes/polypyrrole composite. Sep Sci Technol. 2018;53(10):1498–510.CrossRefGoogle Scholar
  24. 24.
    Baziar M, Azari A, Karimaei M, Gupta VK, Agarwal S, Sharafi K, et al. MWCNT-Fe3O4 as a superior adsorbent for microcystins LR removal: Investigation on the magnetic adsorption separation, artificial neural network modeling, and genetic algorithm optimization. J Mol Liq. 2017;241(Supplement C):102–13. Scholar
  25. 25.
    Ceylan Z, Mustafaoglu D, Malkoc E. Adsorption of phenol by MMT-CTAB and WPT-CTAB: equilibrium, kinetic and thermodynamic study. Particulate Sci Technol. 2018:36(6).Google Scholar
  26. 26.
    Behnamfard A, Salarirad MM. Equilibrium and kinetic studies on free cyanide adsorption from aqueous solution by activated carbon. J Hazard Mater. 2009;170(1):127–33.CrossRefGoogle Scholar
  27. 27.
    Gholizadeh A, Kermani M, Gholami M, Farzadkia M. Kinetic and isotherm studies of adsorption and biosorption processes in the removal of phenolic compounds from aqueous solutions: Comparative study. J Environ Health Sci Eng. 2013;11(1).
  28. 28.
    Ben-Ali S, Jaouali I, Souissi-Najar S, Ouederni A. Characterization and adsorption capacity of raw pomegranate peel biosorbent for copper removal. J Clean Prod. 2017;142(Part 4):3809–21. Scholar
  29. 29.
    Choi S, Gray ML, Jones CW. Amine-tethered solid adsorbents coupling high adsorption capacity and regenerability for CO2 capture from ambient air. ChemSusChem. 2011;4(5):628–35.CrossRefGoogle Scholar
  30. 30.
    Vairavapandian D, Vichchulada P, Lay MD. Preparation and modification of carbon nanotubes: review of recent advances and applications in catalysis and sensing. Anal Chim Acta. 2008;626(2):119–29.CrossRefGoogle Scholar
  31. 31.
    Zhang Z, Wu G, Xu Z, Wu S, Gu L. Adsorption of Methyl Blue onto uniform carbonaceous spheres prepared via an anionic polyacrylamide-assisted hydrothermal route. Mater Chem Phys. 2018.Google Scholar
  32. 32.
    Omastová M, Mičušík M, Fedorko P, Pionteck J, Kovářová J, Chehimi MM. The synergy of ultrasonic treatment and organic modifiers for tuning the surface chemistry and conductivity of multiwalled carbon nanotubes. Surf Interface Anal. 2014;46(10–11):940–4.CrossRefGoogle Scholar
  33. 33.
    Dotto GL, Santos JMN, Rodrigues IL, Rosa R, Pavan FA, Lima EC. Adsorption of methylene blue by ultrasonic surface modified chitin. J Colloid Interface Sci. 2015;446:133–40. Scholar
  34. 34.
    Su F, Lu C, Hu S. Adsorption of benzene, toluene, ethylbenzene and p-xylene by NaOCl-oxidized carbon nanotubes. Colloids Surf A Physicochem Eng Asp. 2010;353(1):83–91.CrossRefGoogle Scholar
  35. 35.
    Chen Y-C, Lu C. Kinetics, thermodynamics and regeneration of molybdenum adsorption in aqueous solutions with NaOCl-oxidized multiwalled carbon nanotubes. J Ind Eng Chem. 2014;20(4):2521–7.CrossRefGoogle Scholar
  36. 36.
    Yu F, Ma J, Wu Y. Adsorption of toluene, ethylbenzene and xylene isomers on multi-walled carbon nanotubes oxidized by different concentration of NaOCl. Frontiers of Environmental Science & Engineering. 2012;6(3):320–9. Scholar
  37. 37.
    Alahabadi A, Rezai Z, Rahmani-Sani A, Rastegar A, Hosseini-Bandegharaei A, Gholizadeh A. Efficacy evaluation of NH4Cl-induced activated carbon in removal of aniline from aqueous solutions and comparing its performance with commercial activated carbon. Desalin Water Treat. 2016;57(50):23779–89. Scholar
  38. 38.
    Delgado LF, Charles P, Glucina K, Morlay C. Adsorption of ibuprofen and atenolol at trace concentration on activated carbon. Sep Sci Technol. 2015;50(10):1487–96.CrossRefGoogle Scholar
  39. 39.
    Kakavandi B, Jonidi AJ, Rezaei RK, Nasseri S, Ameri A, Esrafily A. Synthesis and properties of Fe3O4-activated carbon magnetic nanoparticles for removal of aniline from aqueous solution: equilibrium, kinetic and thermodynamic studies. Iranian J Environ Health Sci Eng. 2013;10(1):19. Scholar
  40. 40.
    Karaman R. From Conventional Prodrugs to Prodrugs Designed By Molecular Orbital Methods. Frontiers in Computational Chemistry. Elsevier; 2015. p. 187–249.Google Scholar
  41. 41.
    Ardakani SS, Zandipak R. Evaluation of carbon nanotubes efficiency for removal of Janus green dye from Ganjnameh River water sample. J Health Dev. 2014;3(4):282–0.Google Scholar
  42. 42.
    Moussavi G, Alahabadi A, Yaghmaeian K, Eskandari M. Preparation, characterization and adsorption potential of the NH4Cl-induced activated carbon for the removal of amoxicillin antibiotic from water. Chem Eng J. 2013;217(Supplement C):119–28. Scholar
  43. 43.
    Miraboutalebi SM, Nikouzad SK, Peydayesh M, Allahgholi N, Vafajoo L, McKay G. Methylene blue adsorption via maize silk powder: kinetic, equilibrium, thermodynamic studies and residual error analysis. Process Saf Environ Prot. 2017;106:191–202.CrossRefGoogle Scholar
  44. 44.
    Naghizadeh A, Ghafouri M, Jafari A. Investigation of equilibrium, kinetics and thermodynamics of extracted chitin from shrimp shell in reactive blue 29 (RB-29) removal from aqueous solutions. Desalin Water Treat. 2017;70:355–63.CrossRefGoogle Scholar
  45. 45.
    Ismael HA, Khdum LH, Lafta AJ. Use of Iraqi cherry seeds in the removal of paracetamol and atenolol medicines from their aqueous solutions. Int J Sci Res (IJSR). 2014;3(12):2290–5.Google Scholar
  46. 46.
    Moradi S, Sadrjavadi K, Farhadian N, Hosseinzadeh L, Shahlaei M. Easy synthesis, characterization and cell cytotoxicity of green nano carbon dots using hydrothermal carbonization of gum Tragacanth and chitosan bio-polymers for bioimaging. J Mol Liq. 2018;259:284–90. Scholar
  47. 47.
    Takdastan A, Kakavandi B, Azizi M, Golshan M. Efficient activation of peroxymonosulfate by using ferroferric oxide supported on carbon/UV/US system: A new approach into catalytic degradation of bisphenol A. Chem Eng J. 2018;331(Supplement C):729–43. Scholar
  48. 48.
    Feng Z, Odelius K, Rajarao GK, Hakkarainen M. Microwave carbonized cellulose for trace pharmaceutical adsorption. Chem Eng J. 2018;346:557–66.CrossRefGoogle Scholar

Copyright information

© Springer Nature Switzerland AG 2019

Authors and Affiliations

  1. 1.Student Research Committee, School of HealthIsfahan University of Medical SciencesIsfahanIran
  2. 2.Department of Environmental Health Engineering, School of HealthIsfahan University of Medical SciencesIsfahanIran
  3. 3.Environment Research Center, Research Institute for Primordial Prevention of Non-communicable DiseaseIsfahan University of Medical SciencesIsfahanIran
  4. 4.Esfarayen Faculty of Medical SciencesEsfarayenIran
  5. 5.Department of Environmental Health, School of Public HealthSabzevar University of Medical SciencesSabzevarIran
  6. 6.Deputy of HealthHamadan University of Medical SciencesHamadanIran

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