Environmental Science and Pollution Research

, Volume 25, Issue 21, pp 21036–21048 | Cite as

Adsorption performance and mechanism of magnetic reduced graphene oxide in glyphosate contaminated water

  • Yajuan Li
  • Chuanqi Zhao
  • Yujuan Wen
  • Yuanyuan Wang
  • Yuesuo Yang
Research Article


In this study, the magnetic reduced graphene oxide (RGO/Fe3O4), with easy separation and high adsorption performance, was prepared and used to treat glyphosate (GLY) contaminated water. GLY adsorption performance of RGO/Fe3O4 was investigated, and influences of pH, adsorption time, temperature, contaminant concentration, and competing anions were analyzed. Moreover, the adsorption mechanism was discussed in the light of several characterization methods, including scanning electron microscopy (SEM), energy dispersive spectrum (EDS), Fourier-transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). The results demonstrated that the RGO/Fe3O4 presented a significant GLY adsorption capacity and acid condition was beneficial for this adsorption. The pseudo-second-order kinetic model and the Langmuir model correlated satisfactorily to the experimental data, indicating that this process was controlled by chemical adsorption and monolayer adsorption. Thermodynamic studies revealed that the adsorption of glyphosate onto RGO/Fe3O4 was spontaneous, endothermic, and feasible process. High temperatures were beneficial to GLY adsorption. The GLY adsorption mechanism of RGO/Fe3O4 was mainly attributed to hydrogen-bond interaction, electrostatic interaction, and coordination. Therefore, the RGO/Fe3O4 investigated in this research may offer an attractive adsorbent candidate for treatment of glyphosate contaminated water and warrant further study as a mechanism for glyphosate efficient removal.


Pesticide contamination Glyphosate RGO/Fe3O4 Adsorption 


Funding information

The authors would like to acknowledge the National Natural Science Foundation (41472237, 41703120), the Liaoning Innovation Team Project (LT2015017), and the Doctoral Scientific Research Foundation of Liaoning Province (201601214).

Supplementary material

11356_2018_2282_MOESM1_ESM.docx (257 kb)
ESM 1 (DOCX 257 kb)


  1. Acosta H (2010) Glyphosate-based herbicides produce teratogenic effects on vertebrates by impairing retinoic acid signaling. Chem Res Toxicol 23:1586–1595CrossRefGoogle Scholar
  2. Bai SH, Ogbourne SM (2016) Glyphosate: environmental contamination, toxicity and potential risks to human health via food contamination. Environ Sci Pollut Res 23:18988–19001CrossRefGoogle Scholar
  3. Barja BC, Afonso MDS (1998) An ATR-FTIR study of glyphosate and its Fe(III) complex in aqueous solution. Environ Sci Technol 32:3331–3335CrossRefGoogle Scholar
  4. Barrosobogeat A, Alexandrefranco M, Fernándezgonzález C, Gómezserrano V (2014) FT-IR analysis of pyrone and chromene structures in activated carbon. Energy Fuel 28:4096–4103CrossRefGoogle Scholar
  5. Bharath G, Madhu R, Chen SM, Veeramani V, Mangalaraj D, Ponpandian N (2015) Solvent-free mechanochemical synthesis of graphene oxide and Fe3O4-reduced graphene oxide nanocomposites for sensitive detection of nitrite. J Mater Chem A 3:15529–15539CrossRefGoogle Scholar
  6. Chabot V, Higgins D, Yu A, Xiao X, Chen Z, Zhang J (2014) A review of graphene and graphene oxide sponge: material synthesis and applications to energy and the environment. Energy Environ Sci 7:1564–1596CrossRefGoogle Scholar
  7. Chen S, Liu Y (2007) Study on the photocatalytic degradation of glyphosate by TiO(2) photocatalyst. Chemosphere 67:1010–1017CrossRefGoogle Scholar
  8. Cheng D, Liao P, Yuan S (2016) Effects of ionic strength and cationic type on humic acid facilitated transport of tetracycline in porous media. Chem Eng J 284:389–394CrossRefGoogle Scholar
  9. Chimezie AB, Hajian R, Yusof NA, Pei MW, Shams N (2017) Fabrication of reduced graphene oxide-magnetic nanocomposite (rGO-Fe3O4) as an electrochemical sensor for trace determination of As(III) in water resources. J Electroanal Chem 796:33–42CrossRefGoogle Scholar
  10. Guyton KZ, Loomis D, Grosse Y, Ghissassi FE, Benbrahim-Tallaa L, Guha N, Scoccianti C, Mattock H, Straif K, Guyton KZ (2015) Carcinogenicity of tetrachlorvinphos, parathion, malathion, diazinon, and glyphosate. Lancet Oncol 16:490–491CrossRefGoogle Scholar
  11. Hu YS, Zhao YQ, Sorohan B (2011) Removal of glyphosate from aqueous environment by adsorption using water industrial residual. Desalination 271:150–156CrossRefGoogle Scholar
  12. Hu XJ, Liu YG, Wang H, Zeng GM, Hu X, Guo YM, Li TT, Chen AW, Jiang LH, Guo FY (2015) Adsorption of copper by magnetic graphene oxide-supported β-cyclodextrin: effects of pH, ionic strength, background electrolytes, and citric acid. Chem Eng Res Des 93:675–683CrossRefGoogle Scholar
  13. Huang B, Liu Y, Li B, Liu S, Zeng G, Zeng Z, Wang X, Ning Q, Zheng B, Yang C (2016) Effect of Cu(II) ions on the enhancement of tetracycline adsorption by Fe3O4@SiO2-chitosan/graphene oxide nanocomposite. Carbohydr Polym 157:576CrossRefGoogle Scholar
  14. Hüffer T, Kah M, Hofmann T, Schmidt TC (2013) How redox conditions and irradiation affect sorption of PAHs by dispersed fullerenes (nC60). Environ Sci Technol 47:6935–6942CrossRefGoogle Scholar
  15. Khan A, Wang J, Li J, Wang X, Chen Z, Alsaedi A, Hayat T, Chen Y, Wang X (2017) The role of graphene oxide and graphene oxide-based nanomaterials in the removal of pharmaceuticals from aqueous media: a review. Environ Sci Pollut Res 24:7938–7958CrossRefGoogle Scholar
  16. Kumar S, Nair RR, Pillai PB, Gupta SN, Iyengar MAR, Sood AK (2014) Graphene oxide-MnFe2O4 magnetic nanohybrids for efficient removal of lead and arsenic from water. ACS Appl Mater Interfaces 6:17426–17436CrossRefGoogle Scholar
  17. Lazaridis NK, Karapantsios TD, Georgantas D (2003) Kinetic analysis for the removal of a reactive dye from aqueous solution onto hydrotalcite by adsorption. Water Res 37:3023–3033CrossRefGoogle Scholar
  18. Lin N, Garry VF (2000) In vitro studies of cellular and molecular developmental toxicity of adjuvants, herbicides, and fungicides commonly used in Red River Valley, Minnesota. J Toxic Environ Health A 60:423–439CrossRefGoogle Scholar
  19. Liu L, Lin Y, Liu Y, Zhu H, He Q (2013) Removal of methylene blue from aqueous solutions by sewage sludge based granular activated carbon: adsorption equilibrium, kinetics, and thermodynamics. J Chem Eng Data 58:2248–2253CrossRefGoogle Scholar
  20. Mañas F, Peralta L, Raviolo J, Ovando HG, Weyers A, Ugnia L, Cid MG, Larripa I, Gorla N (2009) Genotoxicity of glyphosate assessed by the comet assay and cytogenetic tests. Environ Toxicol Pharmacol 28:37–41CrossRefGoogle Scholar
  21. Mayakaduwa SS, Kumarathilaka P, Herath I, Ahmad M, Al-Wabel M, Ok YS, Usman A, Abduljabbar A, Vithanage M (2016) Equilibrium and kinetic mechanisms of woody biochar on aqueous glyphosate removal. Chemosphere 144:2516–2521CrossRefGoogle Scholar
  22. Milojević-Rakić M, Janošević A, Krstić J, Vasiljević BN, Dondur V, Ćirić-Marjanović G (2013) Polyaniline and its composites with zeolite ZSM-5 for efficient removal of glyphosate from aqueous solution. Microporous Mesoporous Mater 180:141–155CrossRefGoogle Scholar
  23. Mishra A, Mohanty T (2016) Structural and morphological study of magnetic Fe3O4/reduced graphene oxide nanocomposites. Mater Today Proc 3:1576–1581CrossRefGoogle Scholar
  24. Rivoira L, Appendini M, Fiorilli S, Onida B, Del Bubba M, Bruzzoniti MC (2016) Functionalized iron oxide/SBA-15 sorbent: investigation of adsorption performance towards glyphosate herbicide. Environ Sci Pollut Res 23:21682–21691CrossRefGoogle Scholar
  25. Rozenberg M, Jung C, Shoham G (2004) Low temperature FTIR spectra and hydrogen bonds in polycrystalline cytidine. Spectrochim Acta A 60:2369–2375CrossRefGoogle Scholar
  26. Saiphaneendra B, Saxena T, Singh SA, Madras G, Srivastava C (2016) Synergistic effect of co-existence of hematite (α-Fe2O3) and magnetite (Fe3O4) nanoparticles on graphene sheet for dye adsorption. J Environ Chem Eng 5:26–37CrossRefGoogle Scholar
  27. Sanchís J, Kantiani L, Llorca M, Rubio F, Ginebreda A, Fraile J, Garrido T, Farré M (2012) Determination of glyphosate in groundwater samples using an ultrasensitive immunoassay and confirmation by on-line solid-phase extraction followed by liquid chromatography coupled to tandem mass spectrometry. Anal Bioanal Chem 402:2335–2345CrossRefGoogle Scholar
  28. Sheals J, Sjöberg S, Persson P (2002) Adsorption of glyphosate on goethite: molecular characterization of surface complexes. Environ Sci Technol 36:3090–3095CrossRefGoogle Scholar
  29. Solomon K, Thompson D (2003) Ecological risk assessment for aquatic organisms from over-water uses of glyphosate. J Toxicol Environ Health B Crit Rev 6:289–324CrossRefGoogle Scholar
  30. Sviridov AV, Shushkova TV, Ermakova IT, Ivanova EV, Epiktetov DO, Leontievsky AA (2015) Microbial degradation of glyphosate herbicides (review). Appl Biochem Microbiol 51:188–195CrossRefGoogle Scholar
  31. Tejedortejedor MI, Anderson MA (1990) Protonation of phosphate on the surface of goethite as studied by CIR-FTIR and electrophoretic mobility. Langmuir 3:602–611CrossRefGoogle Scholar
  32. Waiman CV, Arroyave JM, Chen H, Tan W, Avena MJ, Zanini GP (2016) The simultaneous presence of glyphosate and phosphate at the goethite surface as seen by XPS, ATR-FTIR and competitive adsorption isotherms. Colloid Surf A 498:121–127CrossRefGoogle Scholar
  33. Xie M, Liu ZY, Xu YH (2010) Removal of glyphosate in neutralization liquor from the glycine-dimethylphosphit process by nanofiltration. J Hazard Mater 181:975–980CrossRefGoogle Scholar
  34. Yamaguchi NU, Bergamasco R, Hamoudi S (2016) Magnetic MnFe2O4–graphene hybrid composite for efficient removal of glyphosate from water. Chem Eng J 295:391–402CrossRefGoogle Scholar
  35. Yamashita T, Hayes P (2008) Analysis of XPS spectra of Fe2+ and Fe3+ ions in oxide materials. Appl Surf Sci 254:2441–2449CrossRefGoogle Scholar
  36. Yang S, Li L, Pei Z, Li C, Lv J, Xie J, Wen B, Zhang S (2014) Adsorption kinetics, isotherms and thermodynamics of Cr(III) on graphene oxide. Colloid Surf A 457:100–106CrossRefGoogle Scholar
  37. Yang X, Wang F, Bento CP, Xue S, Gai L, Van DR, Mol H, Ritsema CJ, Geissen V (2015a) Short-term transport of glyphosate with erosion in Chinese loess soil—a flume experiment. Sci Total Environ 512–513:406–414CrossRefGoogle Scholar
  38. Yang X, Zhou S, Liu L (2015b) Adsorption of Sb(III) from aqueous solution by QFGO particles in batch and fixed-bed systems. Chem Eng J 260:444–453CrossRefGoogle Scholar
  39. Yu F, Li Y, Han S, Ma J (2016) Adsorptive removal of antibiotics from aqueous solution using carbon materials. Chemosphere 153:365–385CrossRefGoogle Scholar
  40. Zhang H, Hu X (2017) Preparation of Fe3O4-rGO via a covalent chemical combination method and its catalytic performance on p-NP bioreduction. J Environ Chem Eng 5:3348–3353CrossRefGoogle Scholar
  41. Zhao C, Xu X, Chen J, Yang F (2013) Effect of graphene oxide concentration on the morphologies and antifouling properties of PVDF ultrafiltration membranes. J Environ Chem Eng 1:349–354CrossRefGoogle Scholar
  42. Zubir NA, Yacou C, Motuzas J, Zhang X, Zhao XS, Jc DDC (2015) The sacrificial role of graphene oxide in stabilising a Fenton-like catalyst GO-Fe3O4. Chem Commun 51:9291–9293CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Yajuan Li
    • 1
  • Chuanqi Zhao
    • 1
  • Yujuan Wen
    • 1
  • Yuanyuan Wang
    • 1
  • Yuesuo Yang
    • 1
  1. 1.Key Laboratory of Regional Environment and Eco-Remediation, Ministry of EducationShenyang UniversityShenyangChina

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