Removal of 2,4-D, glyphosate, trifluralin, and butachlor herbicides from water by polysulfone membranes mixed by graphene oxide/TiO2 nanocomposite: study of filtration and batch adsorption

  • Navid Hosseini
  • Mohammad Reza ToosiEmail author
Research Article



Degradation or decomposition of the chemical herbicides by natural reagents after using can lead to produce various types of harmful intermediates. Ultrafiltration by the mixed matrix membranes blended with the graphene oxide/TiO2 can remove the residual herbicides from aqueous solution.


Graphene oxide/TiO2x% (x = 10, 30, 50%) was prepared by solvothermal method and blended by polysulfone to prepare GO/TiO2/PSf membranes for dynamic rejection of aqueous solutions of glyphosate, 2,4-D, butachlor, and trifluralin in a dead-end flow system. The blended membranes were also applied for the adsorption of herbicides in batch experiments.


Addition of GO/TiO2 nanocomposite increased water flux from 7.3 for pure membrane to 211–326 kg/m2 h for mixed matrix samples in order to increase of the membrane porosity and surface hydrophilicity. The herbicides rejections were found in the range of 50–70% related to GO/TiO2 content. It was found that the membrane blended with 0.5 wt.% of GO/TiO2(10%) demonstrated the most efficiency.


Details of dynamic filtration showed that the blended membrane acted based on the size exclusion mechanism. Adsorption experiments indicated that the strong attractions between H-bond donor sites of the herbicide and GO/TiO2 nanoparticles in membranes played a key role in the increase of adsorption of herbicides on the membrane.


Herbicide Graphene oxide Titanium oxide Membrane filtration Polysulfone 



This research was financially supported by Qaemshahr Branch of Islamic Azed University (IAU) and the authors gratefully thank Dr. Sadeqi and Dr. Tayebi for providing the herbicides samples.

Compliance with ethical standards

Competing interests

The authors declare that they have no competing interests.


  1. 1.
    Morteza Z, Mousavi SB, Baghestani MH, Aitio A. An assessment of agricultural pesticide use in Iran 2012-2014. J Environ Health Sci Eng. 2017;15:10–7.CrossRefGoogle Scholar
  2. 2.
    Pimentel D, Burgess M. Small amounts of pesticides reaching target insects. Environ Dev Sustain. 2012;14:1–2.CrossRefGoogle Scholar
  3. 3.
    Yang X, Li J, Wen T, Ren X, Huang Y, Wang X, et al. Adsorption of naphthalene and its derivatives on magnetic graphene composites and the mechanism investigation. Colloids Surf A: Physicochem Eng Aspects. 2013;422:118–25.CrossRefGoogle Scholar
  4. 4.
    Travlou NA, Kyzas GZ, Lazaridis NK, Deliyanni EA, Travlou N, Kyzas G, et al. Functionalization of graphite oxide with magnetic chitosan for the preparation of a nanocomposite dye adsorbent. Langmuir. 2013;29:1657–68.CrossRefGoogle Scholar
  5. 5.
    Li M, Wang J, Jiao C, Wang C, Wu Q, Wang Z. Graphene oxide framework: an adsorbent for solid phase extraction of phenylurea herbicides from water and celery samples. J Chromatography A. 2016;1469:17–24.CrossRefGoogle Scholar
  6. 6.
    Hwang T, Oh J, Yim W, Nam J, Bae C, Kim H, et al. Ultrafiltration using graphene oxide surface-embedded polysulfone membranes. Sep Purif Technol. 2016;166:41–7.CrossRefGoogle Scholar
  7. 7.
    Rezaee R, Nasseri N, Mahvi AH, Nabizadeh R, Mousavi SA, Rashidi A, et al. Fabrication and characterization of a polysulfone-graphene oxide nanocomposite membrane for arsenate rejection from water. J Environ Health Sci Eng. 2015;13:61–71.CrossRefGoogle Scholar
  8. 8.
    Hegab HM, Zou L. Graphene oxide-assisted membranes: fabrication and potential applications in desalination and water purification. J Membrane Sci. 2015;484:95–106.CrossRefGoogle Scholar
  9. 9.
    Sherlala AIA, Raman AAA, Bello MM, Asghar A. A review of the applications of organo-functionalized magnetic graphene oxide nanocomposites for heavy metal adsorption. Chemosphere. 2018;193:1004–17.CrossRefGoogle Scholar
  10. 10.
    Chung YT, Mahmoudi E, Mohammad AW, Benamor A, Johnson D, Hilal N. Development of polysulfone-nanohybrid membranes using ZnO-GO composite for enhanced antifouling and antibacterial control. Desalination. 2017;402:123–32.CrossRefGoogle Scholar
  11. 11.
    Wu H, Tang B, Wu P. Development of novel SiO2–GO nanohybrid/polysulfone membrane with enhanced performance. J Membrane Sci. 2014;451:94–102.CrossRefGoogle Scholar
  12. 12.
    Chai P, Mahmoudi E, Teow Y, Mohammad A. Preparation of novel polysulfone-Fe3O4/GO mixed-matrix membrane for humic acid rejection. J Water Process Eng. 2017;15:83–8.CrossRefGoogle Scholar
  13. 13.
    Thebo KH, Qian X, Wei Q, Zhang Q, Cheng H-M, Ren W. Reduced graphene oxide/metal oxide nanoparticles composite membranes for highly efficient molecular separation. J Mater Sci Technol. 2018;34:1481–6.CrossRefGoogle Scholar
  14. 14.
    Safarpour M, Vatanpour V, Khataee A, Esmaeili M. Development of a novel high flux and fouling-resistant thin film composite nanofiltration membrane by embedding reduced graphene oxide/TiO2. Sep Purif Technol. 2015;154:96–107.CrossRefGoogle Scholar
  15. 15.
    Safarpour M, Vatanpour V, Khataee A. Preparation and characterization of graphene oxide/TiO2 blended PES nanofiltration membrane with improved antifouling and separation performance. Desalination. 2016;393:65–78.CrossRefGoogle Scholar
  16. 16.
    Gao Y, Hu M, Mi B. Membrane surface modification with TiO2–graphene oxide for enhanced photocatalytic performance. J Membrane Sci. 2014;455:349–56.CrossRefGoogle Scholar
  17. 17.
    Emadzadeh D, Ghanbari M, Lau W, Rahbari-Sisakht M, Rana D, Matsuura T, et al. Surface modification of thin film composite membrane by nanoporous titanate nanoparticles for improving combined organic and inorganic antifouling properties. Mater Sci Eng C. 2017;75:463–70.CrossRefGoogle Scholar
  18. 18.
    Xu H, Ding M, Chen W, Li Y, Wang K. Nitrogen–doped GO/TiO2 nanocomposite ultrafiltration membranes for improved photocatalytic performance. Sep Purif Technol. 2018;195:70–82.CrossRefGoogle Scholar
  19. 19.
    Xu C, Cui A, Xu Y, Fu X. Graphene oxide–TiO2 composite filtration membranes and their potential application for water purification. Carbon. 2013;62:465–71.CrossRefGoogle Scholar
  20. 20.
    Naghdi S, Jaleh B, Shahbazi N. Reversible wettability conversion of electrodeposited graphene oxide/titania nanocomposite coating: investigation of surface structures. Appl Surf Sci. 2016;368:409–16.CrossRefGoogle Scholar
  21. 21.
    Cabir B, Yurderi M, Caner N, Agirtas MS, Zahmakiran M, Kaya M. Methylene blue photocatalytic degradation under visible light irradiation on copper phthalocyanine-sensitized TiO2 nanopowders. Mater Sci Eng B. 2017;224:9–17.CrossRefGoogle Scholar
  22. 22.
    Goei R, Lim T-T. Ag-decorated TiO2 photocatalytic membrane with hierarchical architecture: photocatalytic and anti-bacterial activities. Water Res. 2014:59207–18.Google Scholar
  23. 23.
    Toosi MR, Sarmasti Emami MR, Hajian H. Dynamic filtration and static adsorption of lead ions in aqueous solution by use of blended polysulfone membranes with nano size MCM-41 particles coated by polyaniline. Environ Sci Pollution Res. 2018;25:20217–30.CrossRefGoogle Scholar
  24. 24.
    Tabar Y, Toosi MR. Adsorptive filtration of azo dyes by polysulfone membranes blended with polyaniline based MCM-48 mesopore prepared from rice husk. Desalin Water Treat. 2018.
  25. 25.
    Babu VS, Padakia M, D'Souza LP, Déon S, Balakrishna RG, Ismail AF. Effect of hydraulic coefficient on membrane performance for rejection of emerging contaminants. Chem Eng J. 2018;334:2392–400.CrossRefGoogle Scholar
  26. 26.
    Ghaemi N, Nasirmanesh F. Synthesis of a hybrid organic-inorganic polyethersulfone membrane incorporated with phosphotungstic acid: controversial performance in removal of dinitroaniline herbicides from water. J Cleaner Production. 2018.
  27. 27.
    Plakas KV, Karabelas AJ, Wintgens T, Melin T. A study of selected herbicides retention by nanofiltration membranes-the role of organic fouling. J Membrane Sci. 2006;284:291–300.CrossRefGoogle Scholar
  28. 28.
    Acero JL, Benitez FJ, Real FJ. Carolina García, removal of phenyl-urea herbicides in natural waters by UF membranes: permeate flux, analysis of resistances and rejection coefficients. Sep Purif Technol. 2009;65:322–30.CrossRefGoogle Scholar
  29. 29.
    Yuan J, Duan J, Saint CP, Mulcahy D. Removal of glyphosate and aminomethylphosphonic acid from synthetic water by nanofiltration. Environmental Technol. 2017.
  30. 30.
    Song J, Li X-M, Figoli A, Huang H, Pan C, He T, et al. Composite hollow fiber nanofiltration membranes for recovery of glyphosate from saline wastewater. Water Res. 2013;47:2065–74.CrossRefGoogle Scholar
  31. 31.
    Piccolo A, Celano G, Pietramellara G. Adsorption of the herbicide glyphosate on a metal-humic acid complex. Sci Total Environ. 1992;123:77–82.CrossRefGoogle Scholar
  32. 32.
    Carneiro RT, Taketa TB, Neto RJ, Oliveira JL, Campos EV, Moraes MA, et al. Removal of glyphosate herbicide from water using biopolymer membranes. J Environ Manag. 2015;151:353–60.CrossRefGoogle Scholar
  33. 33.
    Milojević-Rakić M, Janošević A, Krstić J, Vasiljević BN, Dondur V, Ćirić-Marjanović G. Polyaniline and its composites with zeolite ZSM-5 for efficient removal of glyphosate from aqueous solution. Micropor Mesopor Mater. 2013;180:141–55.CrossRefGoogle Scholar
  34. 34.
    Hu Y, Zhao Y, Sorohan B. Removal of glyphosate from aqueous environment by adsorption using water industrial residual. Desalination. 2011;271:150–6.CrossRefGoogle Scholar
  35. 35.
    Chen F, Zhou C, Li G, Peng F. Thermodynamics and kinetics of glyphosate adsorption on resin D301. Arab J Chem. 2016;9:s1665–9.CrossRefGoogle Scholar
  36. 36.
    Dehghani M, Nasseri S, Karamimanesh M. Removal of 2,4-Dichlorophenolyxacetic acid (2,4-D) herbicide in the aqueous phase using modified granular activated carbon. J Environ Health Sci Eng. 2014;12:28–37.CrossRefGoogle Scholar
  37. 37.
    Zhang X, Lu X, Li S, Zhong M, Shi X, Luo G, et al. Investigation of 2,4-dichlorophenoxyacetic acid adsorption onto MIEX resin: optimization using response surface methodology. J Taiwan Institute Chem Eng. 2014;45:1835–41.CrossRefGoogle Scholar
  38. 38.
    Manna S, Saha P, Roy D, Sen R, Adhikari B. Removal of 2,4-dichlorophenoxyacetic acid from aqueous medium using modified jute. J Taiwan Institute Chem Eng. 2016;67:292–9.CrossRefGoogle Scholar
  39. 39.
    Zhao R, Li X, Sun B, Ji H, Wang C. Diethylenetriamine-assisted synthesis of amino-rich hydrothermal carbon-coated electrospun polyacrylonitrile fiber adsorbents for the removal of Cr(VI) and 2,4-dichlorophenoxyacetic acid. J Colloid Interface Sci. 2017;487:297–309.CrossRefGoogle Scholar
  40. 40.
    Zhang F, Song Y, Song S, Zhang R, Hou W. Synthesis of magnetite–graphene oxide-layered double hydroxide composites and applications for the removal of Pb(II) and 2,4-Dichlorophenoxyacetic acid from aqueous solutions. ACS Appl Mater Interface. 2015;7:7251–63.CrossRefGoogle Scholar
  41. 41.
    Pal O, Vanjara A. Removal of malathion and butachlor from aqueous solution by clays and organoclays. Sep Purif Technol. 2001;24:167–72.CrossRefGoogle Scholar
  42. 42.
    Leovac A, Vasyukova E, Ivančev-Tumbas I, Uhl W, Kragulj M, Tričković J. Dalmacija B sorption of atrazine, alachlor and trifluralin from water onto different geosorbents. RSC Adv. 2015;5:8122–33.CrossRefGoogle Scholar
  43. 43.
    Lule GM, Atalay MU. Comparison of Fenitrothion and Trifluralin adsorption on Organo-zeolites and activated carbon. Part I: pesticides adsorption isotherms on adsorbents. Particulate Sci Tech. 2014;32:418–25.CrossRefGoogle Scholar
  44. 44.
    Kyriakopoulos G, Doulia D, Anagnostopoulos E. Adsorption of pesticides on porous polymeric adsorbents. Chem Eng Sci. 2005;60:1177–86.CrossRefGoogle Scholar
  45. 45.
    Melo AM, Valentim IB, Goulart MO, Abreu FC. Adsorption studies of trifluralin on chitosan and its voltammetric determination on a modified chitosan glassy carbon electrode. J Brazilian Chem Soc. 2008;19:704–10.CrossRefGoogle Scholar

Copyright information

© Springer Nature Switzerland AG 2019

Authors and Affiliations

  1. 1.Department of Chemistry, Qaemshahr BranchIslamic Azad UniversityQaemshahrIran

Personalised recommendations