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Insights into Glyphosate Adsorption in Aqueous Solutions Using Zn-Al Layered Double Oxide

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Clays and Clay Minerals

Abstract

Contamination of surface and groundwater with glyphosate, used widely on crops to control weeds, can cause severe environmental damage. Processes for glyphosate removal from water bodies have been developed, but few are effective and all are expensive. This objective of the present study was to investigate the use of a layered double oxide as a potentially effective and inexpensive material to remove glyphosate from water. Equilibrium, kinetics, and adsorption mechanisms were evaluated, in addition to the effects of competing anions and temperature on glyphosate adsorption. Up to 95% of glyphosate was removed from a synthetic solution in 50 min by Zn2Al-LDO (layered double oxide in Zn/Al ratio of 2:1) at pH 10. The adsorption isotherms were type L and the Langmuir model best fitted the experimental data, with a qmax value of 191.96 μg mg–1 at 25°C. The XRD pattern did not support the hypothesis of intercalation of glyphosate anions, whereas Fourier-transform infrared and solid-state 13C and 31P magic angle spinning nuclear magnetic resonance confirmed the adsorption of glyphosate anions on the Zn2Al-LDO surface, through carboxylate and phosphonate moiety interactions with end-on and side-on modes. The degree of removal of glyphosate increased with increasing temperature and decreased with increasing concentration of competing anions, with carbonate anions having the most prominent effect on the inhibition of glyphosate adsorption. The adsorption kinetics fitted a pseudo-first order law. Moreover, the intraparticle diffusion model suggested that the adsorption process depends on the formation and thickness of the film at the solution/solid interface.

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Acknowledgements

This study was financed in part by the Office to Coordinate Improvement of University Personnel (CAPES, finance code 001), National Council for Scientific and Technological Development (CNPq), and Rio de Janeiro State Research Foundation (FAPERJ). The XRD patterns were measured in the Laboratory of Catalysis and Sustainable Energy (LACES) of Rio de Janeiro Federal University (UFRJ). Atomic absorption analyses were performed in the Atomic Absorption Laboratory of the Institute of Agronomy at Rio de Janeiro Federal Rural University (UFRRJ).

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Authors and Affiliations

  1. Instituto de Química, Universidade Federal Rural Do Rio de Janeiro, Seropédica, RJ, Brazil

    Emanoel Hottes, Glauco Favilla Bauerfeldt, Clarissa Oliveira da Silva, Rosane Nora Castro & Marcelo Hawrylak Herbst

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  1. Emanoel Hottes
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  2. Glauco Favilla Bauerfeldt
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Contributions

All authors read and approved the final manuscript. Material preparation, experiments and data analysis were performed by Emanoel Hottes. The first draft of the manuscript was written by Emanoel Hottes and all authors commented on subsequent versions of it. Conceptualization: Emanoel Hottes, Rosane Nora Castro, Glauco Favilla Bauerfeldt, Clarissa Oliveira da Silva and Marcelo Hawrylak Herbst. Methodology: Emanoel Hottes, Glauco Favilla Bauerfeldt, Clarissa Oliveira da Silva, Rosane Nora Castro and Marcelo Hawrylak Herbst. Material characterization: Emanoel Hottes, Rosane Nora Castro and Marcelo Hawrylak Herbst. Equilibrium, kinetics and thermodynamics studies: Emanoel Hottes, Glauco Favilla Bauerfeldt and Clarissa Oliveira. Supervision: Rosane Nora Castro and Marcelo Hawrylak Herbst.

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Correspondence to Marcelo Hawrylak Herbst.

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42860_2023_257_MOESM1_ESM.docx

Supplementary file1 The FTIR/ATR and SSNMR spectra of pristine and adsorbed glyphosate, fitted by the linear Langmuir, Temkin, and Freundlich isotherms at different temperatures, are provided in the supporting information. (DOCX 295 KB)

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Hottes, E., Bauerfeldt, G.F., da Silva, C.O. et al. Insights into Glyphosate Adsorption in Aqueous Solutions Using Zn-Al Layered Double Oxide. Clays Clay Miner. 71, 497–512 (2023). https://doi.org/10.1007/s42860-023-00257-1

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