Magnetite nanoparticles as efficient materials for removal of glyphosate from water

Abstract

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.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

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.

References

  1. 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. 2.

    Some Organophosphate Insecticides and Herbicides / IARC Monographs on the Evaluation of Carcinogenic Risks to Humans Vol. 112 (IARC, 2017); https://go.nature.com/2YhKeo9

  3. 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. 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).

  5. 5.

    Hall, T. & Camm, R. Removal of Glyphosphate by Water Treatment WRc report UC7374 (WRC, 2007); https://go.nature.com/35UXkdw

  6. 6.

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

  7. 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).

  8. 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).

  9. 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).

  10. 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).

  11. 11.

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

  12. 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).

  13. 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).

  14. 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).

  15. 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).

  16. 16.

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

  17. 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).

  18. 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).

  19. 19.

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

  20. 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).

  21. 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).

  22. 22.

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

  23. 23.

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

  24. 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).

  25. 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).

  26. 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).

  27. 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).

  28. 28.

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

  29. 29.

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

  30. 30.

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

  31. 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).

  32. 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).

  33. 33.

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

  34. 34.

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

  35. 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).

  36. 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).

  37. 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).

  38. 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).

  39. 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).

  40. 40.

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

  41. 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).

  42. 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).

  43. 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).

  44. 44.

    Frisch, M. J. et al. Gaussian 09, Revision C.01 (Gaussian, 2009); https://gaussian.com/g09_c01/

  45. 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); http://www.crl-pesticides.eu/library/docs/srm/meth_QuPPe.pdf

Download references

Acknowledgements

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).

Author information

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.

Correspondence to Dirk Zahn or Marcus Halik.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

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.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Park, H., May, A., Portilla, L. et al. Magnetite nanoparticles as efficient materials for removal of glyphosate from water. Nat Sustain (2019). https://doi.org/10.1038/s41893-019-0452-6

Download citation