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Magnetite nanoparticles as efficient materials for removal of glyphosate from water


Glyphosate is one of the most commonly used herbicides, but, due to its suspected toxicity, it is simultaneously the most disputed one. Its worldwide application in huge quantities may lead to water concentrations that locally exceed statutory contamination levels. Therefore, a simple toolkit is required to remove glyphosate and its major metabolite from water. Here we show a method for the magnetic remediation of glyphosate from artificial and real water samples to below the maximum permissible value or even below the analytical detection limit. The chemical structure of glyphosate enables fast and stable covalent binding on the surface of magnetite (Fe3O4) nanoparticles, which act as catchers and carriers for magnetic removal. The small size of the nanoparticles (~20 nm diameter) provides a large active area. The glyphosate binding was analysed by infrared spectroscopy, thermogravimetric analysis and dynamic light scattering, while the remediation was investigated by liquid chromatography–mass spectrometry. Results from molecular dynamics simulations support the proposed binding mechanism. The combination of efficient remediation with inexpensive and recyclable magnetite nanoparticles suggests a simple method for the sustainable removal of glyphosate, and the concept may lead to a general approach to eliminate this class of organophosphorus compounds from water.

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Fig. 1: A schematic outline for the proposed magnetic GLY collection.
Fig. 2: MD simulations.
Fig. 3: GLY extraction with artificial samples.
Fig. 4: GLY extraction with real water samples.
Fig. 5: Selective GLY extraction.

Data availability

The authors declare that the data supporting the findings of this study are available within the paper and its Supplementary Information. All data and scripts are available from the corresponding author upon request.


  1. Commission Implementing Regulation (EU) 2017/2324 of 12 December 2017 renewing the approval of the active substance glyphosate in accordance with Regulation (EC) No. 1107/2009 of the European Parliament and of the Council concerning placing of plant protection products on the market, and amending the Annex to Commission Implementing Regulation (EU) No 540/2011. Off. J. Eur. Union L333, 10–16 (2017).

  2. Some Organophosphate Insecticides and Herbicides / IARC Monographs on the Evaluation of Carcinogenic Risks to Humans Vol. 112 (IARC, 2017);

  3. Giesy, J. P., Dobson, S. & Solomon, K. R. in Reviews of Environmental Contamination and Toxicology: Continuation of Residue Reviews (ed. Ware, G. W.) 35–120 (Springer, 2000).

  4. Jönsson, J., Camm, R. & Hall, T. Removal and degradation of glyphosate in water treatment: a review. J. Water Supply Res. Technol. 62, 395–408 (2013).

    Article  Google Scholar 

  5. Hall, T. & Camm, R. Removal of Glyphosphate by Water Treatment WRc report UC7374 (WRC, 2007);

  6. Qu, X. & Alvarez, P. J. J. Applications of nanotechnology in water and wastewater treatment. Water Res. 47, 3931–3946 (2013).

    CAS  Article  Google Scholar 

  7. Dong, Y., Guo, D., Cui, H., Li, X. & He, Y. Magnetic solid phase extraction of glyphosate and aminomethylphosphonic acid in river water using Ti4+-immobilized Fe3O4 nanoparticles by capillary electrophoresis. Anal. Methods 7, 5862–5868 (2015).

    CAS  Article  Google Scholar 

  8. Hsu, C.-C. & Whang, C.-W. Microscale solid phase extraction of glyphosate and aminomethylphosphonic acid in water and guava fruit extract using alumina-coated iron oxide nanoparticles followed by capillary electrophoresis and electrochemiluminescence detection. J. Chromatogr. A 1216, 8575–8580 (2009).

    CAS  Article  Google Scholar 

  9. Fiorilli, S. et al. Iron oxide inside SBA-15 modified with amino groups as reusable adsorbent for highly efficient removal of glyphosate from water. Appl. Surf. Sci. 411, 457–465 (2017).

    CAS  Article  Google Scholar 

  10. Pujari, S. P., Scheres, L., Marcelis, A. T. M. & Zuilhof, H. Covalent surface modification of oxide surfaces. Angew. Chem. Int. Ed. 53, 6322–6356 (2014).

    CAS  Article  Google Scholar 

  11. Klauk, H., Zschieschang, U., Pflaum, J. & Halik, M. Ultralow-power organic complementary circuits. Nature 445, 745–748 (2007).

    CAS  Article  Google Scholar 

  12. Hotchkiss, P. J. et al. The modification of indium tin oxide with phosphonic acids: mechanism of binding, tuning of surface properties and potential for use in organic electronic applications. Acc. Chem. Res. 45, 337–346 (2012).

    CAS  Article  Google Scholar 

  13. Ma, H., Acton, O., Hutchins, D. O., Cernetic, N. & Jen, A. K.-Y. Multifunctional phosphonic acid self-assembled monolayers on metal oxides as dielectrics, interface modification layers and semiconductors for low-voltage high-performance organic field-effect transistors. Phys. Chem. Chem. Phys. 14, 14110–14126 (2012).

    CAS  Article  Google Scholar 

  14. Lenz, T., Schmaltz, T., Novak, M. & Halik, M. Self-assembled monolayer exchange reactions as a tool for channel interface engineering in low-voltage organic thin-film transistors. Langmuir 28, 13900–13904 (2012).

    CAS  Article  Google Scholar 

  15. Zeininger, L., Portilla, L., Halik, M. & Hirsch, A. Quantitative determination and comparison of the surface binding of phosphonic acid, carboxylic acid and catechol ligands on TiO2 nanoparticles. Chem. A Eur. J. 22, 13506–13512 (2016).

    CAS  Article  Google Scholar 

  16. Wang, B. et al. The dipole moment inversion effects in self-assembled nanodielectrics for organic transistors. Chem. Mater. 29, 9974–9980 (2017).

    CAS  Article  Google Scholar 

  17. Etschel, S. H. et al. Region-selective deposition of core-shell nanoparticles for 3D hierarchical assemblies by the huisgen 1,3-dipolar cycloaddition. Angew. Chem. Int. Ed. 54, 9235–9238 (2015).

    CAS  Article  Google Scholar 

  18. Portilla, L., Etschel, S. H., Tykwinski, R. R. & Halik, M. Green processing of metal oxide core-shell nanoparticles as low-temperature dielectrics in organic thin-film transistors. Adv. Mater. 27, 5950–5954 (2015).

    CAS  Article  Google Scholar 

  19. Demin, A. M. et al. PMIDA-modified Fe3O4 magnetic nanoparticles: synthesis and application for liver MRI. Langmuir 34, 3449–3458 (2018).

    CAS  Article  Google Scholar 

  20. Klein, S. et al. Enhanced in vitro biocompatibility and water dispersibility of magnetite and cobalt ferrite nanoparticles employed as ROS formation enhancer in radiation cancer therapy. Small 14, 1704111 (2018).

    Article  Google Scholar 

  21. Bauer, T. et al. Phosphonate- and carboxylate-based self-assembled monolayers for organic devices: a theoretical study of surface binding on aluminum oxide with experimental support. ACS Appl. Mater. Interfaces 5, 6073–6080 (2013).

    CAS  Article  Google Scholar 

  22. Laurent, S. et al. Magnetic iron oxide nanoparticles: synthesis, stabilization, vectorization, physicochemical characterizations and biological applications. Chem. Rev. 108, 2064–2110 (2008).

    CAS  Article  Google Scholar 

  23. Thomas, L. A. et al. Carboxylic acid-stabilised iron oxide nanoparticles for use in magnetic hyperthermia. J. Mater. Chem. 19, 6529–6535 (2009).

    CAS  Article  Google Scholar 

  24. Annett, R., Habibi, H. R. & Hontela, A. Impact of glyphosate and glyphosate-based herbicides on the freshwater environment. J. Appl. Toxicol. 34, 458–479 (2014).

    CAS  Article  Google Scholar 

  25. Laurent, S., Dutz, S., Häfeli, U. O. & Mahmoudi, M. Magnetic fluid hyperthermia: focus on superparamagnetic iron oxide nanoparticles. Adv. Colloid Interface Sci. 166, 8–23 (2011).

    CAS  Article  Google Scholar 

  26. Coupe, R. H., Kalkhoff, S. J., Capel, P. D. & Gregoire, C. Fate and transport of glyphosate and aminomethylphosphonic acid in surface waters of agricultural basins. Pest Manag. Sci. 68, 16–30 (2012).

    CAS  Article  Google Scholar 

  27. Aparicio, V. C. et al. Environmental fate of glyphosate and aminomethylphosphonic acid in surface waters and soil of agricultural basins. Chemosphere 93, 1866–1873 (2013).

    CAS  Article  Google Scholar 

  28. Brown, G. E. et al. Metal oxide surfaces and their interactions with aqueous solutions and microbial organisms. Chem. Rev. 99, 77–174 (1999).

    CAS  Article  Google Scholar 

  29. Weng, L., Van Riemsdijk, W. H. & Hiemstra, T. Factors controlling phosphate interaction with iron oxides. J. Environ. Qual. 41, 628–635 (2012).

    CAS  Article  Google Scholar 

  30. Guerrero, G., Mutin, P. H. & Vioux, A. Anchoring of phosphonate and phosphinate coupling molecules on titania particles. Chem. Mater. 13, 4367–4373 (2001).

    CAS  Article  Google Scholar 

  31. Brown, W. M., Kohlmeyer, A., Plimpton, S. J. & Tharrington, A. N. Implementing molecular dynamics on hybrid high performance computers—particle–particle particle–mesh. Comput. Phys. Commun. 183, 449–459 (2012).

    CAS  Article  Google Scholar 

  32. Brown, W. M., Wang, P., Plimpton, S. J. & Tharrington, A. N. Implementing molecular dynamics on hybrid high performance computers—short range forces. Comput. Phys. Commun. 182, 898–911 (2011).

    CAS  Article  Google Scholar 

  33. Brown, W. M. & Yamada, M. Implementing molecular dynamics on hybrid high performance computers—three-body potentials. Comput. Phys. Commun. 184, 2785–2793 (2013).

    CAS  Article  Google Scholar 

  34. Fiorin, G., Klein, M. L. & Hénin, J. Using collective variables to drive molecular dynamics simulations. Mol. Phys. 111, 3345–3362 (2013).

    CAS  Article  Google Scholar 

  35. Dietrich, H., Schmaltz, T., Halik, M. & Zahn, D. Molecular dynamics simulations of phosphonic acid–aluminum oxide self-organization and their evolution into ordered monolayers. Phys. Chem. Chem. Phys. 19, 5137–5144 (2017).

    CAS  Article  Google Scholar 

  36. Meltzer, C. et al. Indentation and self-healing mechanisms of a self-assembled monolayer—a combined experimental and modeling study. J. Am. Chem. Soc. 136, 10718–10727 (2014).

    CAS  Article  Google Scholar 

  37. Pedone, A., Malavasi, G., Menziani, M. C., Cormack, A. N. & Segre, U. A new self-consistent empirical interatomic potential model for oxides, silicates and silica-based glasses. J. Phys. Chem. B 110, 11780–11795 (2006).

    CAS  Article  Google Scholar 

  38. Jorgensen, W. L., Chandrasekhar, J., Madura, J. D., Impey, R. W. & Klein, M. L. Comparison of simple potential functions for simulating liquid water. J. Chem. Phys. 79, 926–935 (1983).

    CAS  Article  Google Scholar 

  39. Wang, J., Wolf, R. M., Caldwell, J. W., Kollman, P. A. & Case, D. A. Development and testing of a general Amber force field. J. Comput. Chem. 25, 1157–1174 (2004).

    CAS  Article  Google Scholar 

  40. Ȧqvist, J. Ion–water interaction potentials derived from free energy perturbation simulations. J. Phys. Chem. 94, 8021–8024 (1990).

    Article  Google Scholar 

  41. Fox, T. & Kollman, P. A. Application of the RESP methodology in the parametrization of organic solvents. J. Phys. Chem. B 102, 8070–8079 (1998).

    CAS  Article  Google Scholar 

  42. Li, P., Roberts, B. P., Chakravorty, D. K. & Merz, K. M. Rational design of particle mesh Ewald compatible Lennard–Jones parameters for +2 metal cations in explicit solvent. J. Chem. Theory Comput. 9, 2733–2748 (2013).

    CAS  Article  Google Scholar 

  43. Li, P., Song, L. F. & Merz, K. M. Parameterization of highly charged metal ions using the 12-6-4 LJ-type nonbonded model in explicit water. J. Phys. Chem. B 119, 883–895 (2015).

    CAS  Article  Google Scholar 

  44. Frisch, M. J. et al. Gaussian 09, Revision C.01 (Gaussian, 2009);

  45. Anastassiades, M. et al. Quick Method for the Analysis of numerous Highly Polar Pesticides in Foods of Plant Origin via LC-MS/MS involving Simultaneous Extraction with Methanol (QuPPe-Method) (EURL-SRM, 2015);

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This work was supported by the Cluster of Excellence Engineering of Advanced Materials (EAM), funded by the Deutsche Forschungsgemeinschaft (DFG) and the ‘Graduate School Molecular Science’ (GSMS).

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Authors and Affiliations



H.P., L.P. and M.H. conceived the study. H.P. and A.M. designed and conducted the experiments. H.D. and D.Z. performed MD simulations. F.M. and L.B. carried out LC–MS analysis. T.R. conducted TEM measurements. H.P., M.S. and M.H. reviewed and interpreted the results. H.P. wrote the manuscript, with input from all authors. All authors reviewed and commented on the manuscript.

Corresponding authors

Correspondence to Dirk Zahn or Marcus Halik.

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Competing interests

The authors declare no competing interests.

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Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Extended data

Extended Data Fig. 1 Basic characterizations of Fe3O4-NPs.

(a) FTIR-ATR spectra for as purchased and GLY functionalized Fe3O4-NPs, b, TGA measurement for determining the saturated surface coverage, (c) DLS measurement of Fe3O4-NPs aqueous solution, (d) a TEM image of Fe3O4-NPs.

Extended Data Fig. 2 LCMS measurements.

Concentrations determined by LCMS for remaining GLY in DI water solution after the extraction with (a) 0.1 mg/mL, (b) 0.5 mg/mL, and (c) 1.0 mg/mL of Fe3O4-NP concentrations.

Extended Data Fig. 3 pH dependency of GLY on Fe3O4-NPs.

TGA measurements of the Fe3O4-NPs after the GLY extraction under different pH conditions.

Extended Data Fig. 4 Thermal reactivation of Fe3O4-NPs.

TGA measurements of the Fe3O4-NPs with 20 mM GLY before and after the heat treatment.

Supplementary information

Supplementary information

Supplementary Figs. 1–11, Tables 1–4 and Note 1.

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Park, H., May, A., Portilla, L. et al. Magnetite nanoparticles as efficient materials for removal of glyphosate from water. Nat Sustain 3, 129–135 (2020).

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