Skip to main content
SpringerLink
Log in

Direct determination of glyphosate, glufosinate, and AMPA in soybean and corn by liquid chromatography/tandem mass spectrometry

  • Research Paper
  • Published:
Analytical and Bioanalytical Chemistry Aims and scope Submit manuscript

Abstract

Glyphosate, glufosinate, and aminomethylphosphonic acid (AMPA) are amphoteric, low mass, high water soluble, and do not have chromophore. They are very difficult to be retained on a reversed phase HPLC and detected by UV or fluorescence detectors. A liquid chromatography/tandem mass spectrometry (LC-MS/MS) method was developed to determine these analytes in soybean and corn using a reversed phase with weak anion-exchange and cation-exchange mixed-mode Acclaim™ Trinity™ Q1 column. The sample was shaken with water containing ethylenediaminetetraacetic acid disodium salt (Na2EDTA) and acetic acid for 10 min to precipitate protein and extract the analytes into the solution. The supernatant was passed thru an Oasis HLB SPE to retain suspended particulates and non-polar interferences. The sample was directly injected and analyzed in 6 min by LC-MS/MS with no sample concentration or derivatization steps. Three isotopically labeled internal standards corresponding to each analyte were used to counter matrix suppression effect. Linearity of the detector response with a minimum coefficient of determination (R 2) of more than 0.995 was demonstrated in the range of 10 to 1000 ng/mL for each analyte. Accuracy (recovery %) and precision (relative standard deviation or RSD %) were evaluated at the fortification levels of 0.1, 0.5, and 2 μg/g in seven replicates in both soybean and corn samples.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3

Similar content being viewed by others

References

  1. European Commission Health & Consumer Protection Directorategeneral. Review report for the active substance glyphosate. http://ec.europa.eu/food/plant/protection/evaluation/existactive/list1_glyphosate_en.pdf (accessed September 1, 2015).

  2. United States EPA 2007 Pesticide Market Estimates http://www.epa.gov/opp00001/pestsales/07pestsales/table_of_contents2007.htm (accessed September 1, 2015).

  3. Electronic code of federal regulations http://www.ecfr.gov/cgi-bin/text-idx?c=ecfr&sid=f41eea8cfec706a8f961b47685450107&tpl=/ecfrbrowse/Title40/40cfr180_main_02.tpl (accessed September 1, 2015).

  4. Alferness PL, Iwata Y. Determination of glyphosate and (aminomethyl) phosphonic acid in soil, plant and animal matrixes, and water by capillary gas chromatography with mass-selective detection. J Agric Food Chem. 1994;42:2751–9.

    Article  CAS  Google Scholar 

  5. Qian K, Tang T, Shi T, Li P, Li J, Cao Y. Solid-phase extraction and residue determination of glyphosate in apple by ion‐pairing reverse-phase liquid chromatography with pre-column derivatization. J Sep Sci. 2009;32:2394–400.

    Article  CAS  Google Scholar 

  6. Ibáñez M, Pozo ÓJ, Sancho JV, López FJ, Hernández F. Residue determination of glyphosate, glufosinate and aminomethylphosphonic acid in water and soil samples by liquid chromatography coupled to electrospray tandem mass spectrometry. J Chromatogr A. 2005;1081:145–55.

    Article  Google Scholar 

  7. Vreeken RJ, Speksnijder P, Bobeldijk-Pastorova I, Noij THM. Selective analysis of the herbicides glyphosate and aminomethylphosphonic acid in water by on-line solid-phase extraction–high-performance liquid chromatography–electrospray ionization mass spectrometry. J Chromatogr A. 1998;794:187–99.

    Article  CAS  Google Scholar 

  8. Schreiber A, Cabrices OG. Automated derivatization, SPE cleanup and LC-MS/MS determination of glyphosate and other polar pesticides: application note 8013813–01 http://www.newfoodmagazine.com/wp-content/uploads/Glyphosate_QTRAP-4500_Gerstel_AB-SCIEX_8013813-01.pdf.

  9. Hao C, Morse D, Morra F, Zhao X, Yang P, Nunn B. Direct aqueous determination of glyphosate and related compounds by liquid chromatography/tandem mass spectrometry using reversed-phase and weak anion-exchange mixed-mode column. J Chromatogr A. 2011;1218:5638–43.

    Article  CAS  Google Scholar 

  10. Anastassiades M, Kolberg DI, Mack D, Wildgrube C, Sigalov I, Dörk D. Quick method for the analysis of residues of numerous highly polar pesticides in foods and plant origin involving simultaneous extraction with methanol and LC-MS/MS determination (QuPPe-Method) http://www.crl-pesticides.eu/library/docs/srm/meth_QuPPe.pdf (accessed Jan 27, 2015).

  11. Botero-Coy AM, Ibáñez M, Sancho J, Hernández F. Direct liquid chromatography–tandem mass spectrometry determination of underivatized glyphosate in rice, maize and soybean. J Chromatogr A. 2013;1313:157–65.

    Article  CAS  Google Scholar 

  12. Martins-Júnior HA, Lebre DT, Wang AY, Pires MAF, Bustillos OV. An alternative and fast method for determination of glyphosate and aminomethylphosphonic acid (AMPA) residues in soybean using liquid chromatographycoupled with tandem mass spectrometry. Rapid Commun Mass Spectrom. 2009;23:1029–34.

    Article  Google Scholar 

  13. Neuvonen P. Interactions with the absorption of tetracyclines. Drugs. 1976;11:45–54.

    Article  CAS  Google Scholar 

  14. Bruno F, Curini R, Corcia AD, Nazzari M, Pallagrosi M. An original approach to determining traces of tetracycline antibiotics in milk and eggs by solid‐phase extraction and liquid chromatography/mass spectrometry. Rapid Commun Mass Spectrom. 2002;16:1365–76.

    Article  CAS  Google Scholar 

  15. Pena A, Lino C, Silveira I. Determination of oxytetracycline, tetracycline, and chlortetracycline in milk by liquid chromatography with postcolumn derivatization and fluorescence detection. J AOAC Int. 1998;82:55–60.

    Google Scholar 

  16. Chamkasem N, Morris C, Harmon T. Direct determination of glyphosate, glufosinate, and AMPA in milk by liquid chromatography/tandem mass spectrometry. J Reg Sci. 2015;3:20–6.

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Southeast Regional Laboratory, U.S. Food and Drug Administration, 60 Eighth Street, N.E., Atlanta, GA, 30309, USA

    Narong Chamkasem & Tiffany Harmon

Authors
  1. Narong Chamkasem
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Tiffany Harmon
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Narong Chamkasem.

Ethics declarations

Conflict of interest

The authors declare that there is no conflict of interest. Research was funded by U.S. Food and Drug Administration.

Disclaimer

The views expressed are those of the authors and should not be construed to represent the views or policies of the U.S. Food and Drug Administration. Any reference to a specific commercial product, manufacturer, or otherwise, is for the information and convenience of the public and does not constitute an endorsement, recommendation or favoring by the U.S. Food and Drug Administration.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Chamkasem, N., Harmon, T. Direct determination of glyphosate, glufosinate, and AMPA in soybean and corn by liquid chromatography/tandem mass spectrometry. Anal Bioanal Chem 408, 4995–5004 (2016). https://doi.org/10.1007/s00216-016-9597-6

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-016-9597-6

Keywords

Search

Navigation