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.

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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.

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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).

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Contributions

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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The authors declare no competing interests.

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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). https://doi.org/10.1038/s41893-019-0452-6

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