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Ultrasound-assisted extraction followed by liquid chromatography coupled to tandem mass spectrometry for the simultaneous determination of multiclass herbicides in soil

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Abstract

An analytical methodology based on ultrasound-assisted extraction (UAE) followed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) has been developed for the identification and quantification of 9 authorized herbicides in soil (dimethenamid-P, imazamox, S-metolachlor, nicosulfuron, pendimethalin, prosulfuron, bentazone, terbuthylazine, and mesotrione). Preliminary experiments dealing with solvent extraction, the extraction technique, and herbicide response comparison in soil, with and without organic amendments, were carried out with the purpose of obtaining high sample throughput and sensitivity. UAE and the solvent mixture water:methanol demonstrated higher efficiency and they were selected as sample treatment and extraction solvent, respectively. Critical parameters affecting UAE were optimized by experimental design. In the present research, the extraction technique used in the official EPA microwave-assisted extraction (MAE) methodology (United States Environmental Protection Agency) and UAE optimized methodology were compared. The results indicated that the developed method showed better efficacy since microwave extraction gave very poor responses for nicosulfuron and prosulfuron. The temperature extraction was also optimized; room temperature was the most suitable to work with. Under the optimized conditions, the proposed UAE-LC-MS/MS method was assessed in terms of linearity (R2 ≥ 0.9912), accuracy (recoveries around 100%), and precision (relative standard deviation, RSD < 13%). The absence of significant matrix effects allowed quantification in real samples by external calibration with standards prepared in water:methanol. Method sustainability was also evaluated using the metric tool AGREEPrep. Finally, the analysis of real contaminated samples revealed the presence of 7 out of the 9 studied herbicides with S-metolachlor at high concentrations in all samples.

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Acknowledgements

This research is based on the Sample Preparation Study Group and Network which is backed by the DAC of the EuChemS.

Funding

The present investigation received financial support from the projects ED431 2020/06 and IN607B 2022/15 (Consolidated Research Groups Program, Xunta de Galicia). Authors are affiliated with the National Network for Sustainability in Sample Preparation, RED2022-134079-T (Ministry of Science, Innovation and Universities, Spain), H.G.L. acknowledges the collaboration grant (Ministry of Education and Vocational Training, Spain). A.C.L. acknowledges the grant for the initiation of USC Master’s research (Santander Research Grants) and the predoctoral contract ED481A/IN606A, Xunta de Galicia.

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Authors and Affiliations

  1. CRETUS, Department of Analytical Chemistry, Nutrition and Food Science, Universidade de Santiago de Compostela, E-15782, Santiago de Compostela, Spain

    Ana Castiñeira-Landeira, Lua Vazquez, Helena Gonzalez-Leirado & María Llompart

  2. Galician Agency for Food Quality - Agronomic Research Centre (AGACAL-CIAM) – Unit of Organic Contaminants, Mail Box 10, E-15080, A Coruña, Spain

    Thierry Dagnac

Authors
  1. Ana Castiñeira-Landeira
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  2. Lua Vazquez
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  3. Helena Gonzalez-Leirado
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  4. María Llompart
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Contributions

Ana Castiñeira-Landeira: investigation, statistical analysis, writing. Lua Vazquez: investigation, statistical analysis. Helena Gonzalez-Leirado: investigation, statistical analysis. Thierry Dagnac: resources, investigation, review, funding. Maria Llompart: project manager, conceptualization, investigation, methodology, statistical analysis, review, funding.

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Correspondence to María Llompart.

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Castiñeira-Landeira, A., Vazquez, L., Gonzalez-Leirado, H. et al. Ultrasound-assisted extraction followed by liquid chromatography coupled to tandem mass spectrometry for the simultaneous determination of multiclass herbicides in soil. Anal Bioanal Chem 415, 7197–7209 (2023). https://doi.org/10.1007/s00216-023-04987-y

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