Simultaneous Determination of Glyphosate and 13 Multiclass Pesticides in Agricultural Soil by Direct-Immersion SPME Followed by Solid–Liquid Extraction
A new method is presented for the simultaneous determination of 13 multiclass pesticides along with glyphosate. The multiclass pesticides were extracted by creating a soil slurry with 2% ethanol in water (<i>v</i>/<i>v</i>), and then, applying direct-immersion solid-phase mic...
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2024-09-01
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| author | João Brinco Paula Guedes Marco Gomes da Silva Eduardo P. Mateus Alexandra B. Ribeiro |
| author_facet | João Brinco Paula Guedes Marco Gomes da Silva Eduardo P. Mateus Alexandra B. Ribeiro |
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| description | A new method is presented for the simultaneous determination of 13 multiclass pesticides along with glyphosate. The multiclass pesticides were extracted by creating a soil slurry with 2% ethanol in water (<i>v</i>/<i>v</i>), and then, applying direct-immersion solid-phase microextraction (DI-SPME) with a new type of semi-disposable SPME fiber configuration called LC-Tips. The fibers were then retroextracted to ethanol, and aqueous ammonia was added to the slurry to extract glyphosate. Derivatization of the glyphosate extract was accomplished with a mixture of trifluoroacetic anhydride and trifluoroethanol, after which the reaction mixture was dried and resuspended with the SPME ethanol extract. To this, a mixture of analyte protectants was added, and it was analyzed by GC-MS/MS in multiple-reaction-monitoring mode. All analytes showed a coefficient of determination greater than 0.95 in the 0.1–100 µg/kg calibrated range, and the limits of detection were between 0.1 and 1 µg/kg, except for glyphosate, which was 0.01 µg/kg. The method shows relatively high replicate relative standard deviation (as much as 37% for five extractions at 20 µg/kg), but the isotopically labeled internal standard was effective at mitigating this effect for some analytes. |
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| publishDate | 2024-09-01 |
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| spelling | doaj-art-d03e98b212cc4c139afe2ffffea8fa592025-08-20T01:47:44ZengMDPI AGApplied Sciences2076-34172024-09-011419858410.3390/app14198584Simultaneous Determination of Glyphosate and 13 Multiclass Pesticides in Agricultural Soil by Direct-Immersion SPME Followed by Solid–Liquid ExtractionJoão Brinco0Paula Guedes1Marco Gomes da Silva2Eduardo P. Mateus3Alexandra B. Ribeiro4CENSE—Center for Environmental and Sustainability Research, CHANGE—Global Change and Sustainability Institute, NOVA School of Science and Technology, NOVA University Lisbon, Campus de Caparica, 2829-516 Caparica, PortugalCENSE—Center for Environmental and Sustainability Research, CHANGE—Global Change and Sustainability Institute, NOVA School of Science and Technology, NOVA University Lisbon, Campus de Caparica, 2829-516 Caparica, PortugalLAQV/REQUIMTE, Department of Chemistry, NOVA School of Science and Technology, NOVA University Lisbon, 2829-516 Caparica, PortugalCENSE—Center for Environmental and Sustainability Research, CHANGE—Global Change and Sustainability Institute, NOVA School of Science and Technology, NOVA University Lisbon, Campus de Caparica, 2829-516 Caparica, PortugalCENSE—Center for Environmental and Sustainability Research, CHANGE—Global Change and Sustainability Institute, NOVA School of Science and Technology, NOVA University Lisbon, Campus de Caparica, 2829-516 Caparica, PortugalA new method is presented for the simultaneous determination of 13 multiclass pesticides along with glyphosate. The multiclass pesticides were extracted by creating a soil slurry with 2% ethanol in water (<i>v</i>/<i>v</i>), and then, applying direct-immersion solid-phase microextraction (DI-SPME) with a new type of semi-disposable SPME fiber configuration called LC-Tips. The fibers were then retroextracted to ethanol, and aqueous ammonia was added to the slurry to extract glyphosate. Derivatization of the glyphosate extract was accomplished with a mixture of trifluoroacetic anhydride and trifluoroethanol, after which the reaction mixture was dried and resuspended with the SPME ethanol extract. To this, a mixture of analyte protectants was added, and it was analyzed by GC-MS/MS in multiple-reaction-monitoring mode. All analytes showed a coefficient of determination greater than 0.95 in the 0.1–100 µg/kg calibrated range, and the limits of detection were between 0.1 and 1 µg/kg, except for glyphosate, which was 0.01 µg/kg. The method shows relatively high replicate relative standard deviation (as much as 37% for five extractions at 20 µg/kg), but the isotopically labeled internal standard was effective at mitigating this effect for some analytes.https://www.mdpi.com/2076-3417/14/19/8584multiclass pesticide analysisglyphosate extractiondirect-immersion solid-phase microextraction |
| spellingShingle | João Brinco Paula Guedes Marco Gomes da Silva Eduardo P. Mateus Alexandra B. Ribeiro Simultaneous Determination of Glyphosate and 13 Multiclass Pesticides in Agricultural Soil by Direct-Immersion SPME Followed by Solid–Liquid Extraction Applied Sciences multiclass pesticide analysis glyphosate extraction direct-immersion solid-phase microextraction |
| title | Simultaneous Determination of Glyphosate and 13 Multiclass Pesticides in Agricultural Soil by Direct-Immersion SPME Followed by Solid–Liquid Extraction |
| title_full | Simultaneous Determination of Glyphosate and 13 Multiclass Pesticides in Agricultural Soil by Direct-Immersion SPME Followed by Solid–Liquid Extraction |
| title_fullStr | Simultaneous Determination of Glyphosate and 13 Multiclass Pesticides in Agricultural Soil by Direct-Immersion SPME Followed by Solid–Liquid Extraction |
| title_full_unstemmed | Simultaneous Determination of Glyphosate and 13 Multiclass Pesticides in Agricultural Soil by Direct-Immersion SPME Followed by Solid–Liquid Extraction |
| title_short | Simultaneous Determination of Glyphosate and 13 Multiclass Pesticides in Agricultural Soil by Direct-Immersion SPME Followed by Solid–Liquid Extraction |
| title_sort | simultaneous determination of glyphosate and 13 multiclass pesticides in agricultural soil by direct immersion spme followed by solid liquid extraction |
| topic | multiclass pesticide analysis glyphosate extraction direct-immersion solid-phase microextraction |
| url | https://www.mdpi.com/2076-3417/14/19/8584 |
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