Skip to main content
SpringerLink
Log in

A Dilute-and-Shoot LC–MS/MS Method for Urinary Glyphosate and AMPA

  • Short Communication
  • Published:
Chromatographia Aims and scope Submit manuscript

Abstract

A method for the simultaneous determination of glyphosate and aminomethylphosphonic acid (AMPA) in urine was developed using a “dilute-and-shoot” sample preparation. A 1:1 dilution of urine sample in 15 mmol L−1 heptafluorobutyric acid (HFBA) was prepared prior to being injected into the LC–MS/MS system. The chromatographic separation was achieved by a Gemini C6-Phenyl analytical column, with the gradient elution of 15 mmol L−1 HFBA in water and acetonitrile. The limits of detection and quantitation of both compounds were 2.5 ng mL−1 and 5 ng mL−1, respectively. The sample preparation time was achieved in 2 min using only 0.1 mL of urine sample. The validated method was successfully applied to glyphosate and AMPA determination in farmer urine samples.

Graphic Abstract

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
Fig. 4

References

  1. Lindsay Murray ML, Pascu O, Hoggett KA (2015) Toxicology handbook, 3rd edn. Elsevier, Amsterdam

    Google Scholar 

  2. Williams GM, Aardema M, Acquavella J, Berry SC, Brusick D, Burns MM, de Camargo JL, Garabrant D, Greim HA, Kier LD, Kirkland DJ, Marsh G, Solomon KR, Sorahan T, Roberts A, Weed DL (2016) A review of the carcinogenic potential of glyphosate by four independent expert panels and comparison to the IARC assessment. Crit Rev Toxicol 46(sup1):3–20. https://doi.org/10.1080/10408444.2016.1214677

    Article  CAS  PubMed  Google Scholar 

  3. Valcke M, Levasseur ME, da Silva AS, Wesseling C (2017) Pesticide exposures and chronic kidney disease of unknown etiology: an epidemiologic review. Environ Health. https://doi.org/10.1186/s12940-017-0254-0

    Article  PubMed  PubMed Central  Google Scholar 

  4. Conrad A, Schroter-Kermani C, Hoppe HW, Ruther M, Pieper S, Kolossa-Gehring M (2017) Glyphosate in German adults—time trend (2001 to 2015) of human exposure to a widely used herbicide. Int J Hyg Environ Health 220(1):8–16. https://doi.org/10.1016/j.ijheh.2016.09.016

    Article  CAS  PubMed  Google Scholar 

  5. Acquavella JF, Alexander BH, Mandel JS, Gustin C, Baker B, Chapman P, Bleeke M (2004) Glyphosate biomonitoring for farmers and their families: results from the farm family exposure study. Environ Health Perspect 112(3):321–326. https://doi.org/10.1289/ehp.6667

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  6. Connolly A, Jones K, Galea KS, Basinas I, Kenny L, McGowan P, Coggins M (2017) Exposure assessment using human biomonitoring for glyphosate and fluroxypyr users in amenity horticulture. Int J Hyg Environ Health 220(6):1064–1073. https://doi.org/10.1016/j.ijheh.2017.06.008

    Article  CAS  PubMed  Google Scholar 

  7. Curwin BD, Hein MJ, Sanderson WT, Striley C, Heederik D, Kronihout H, Reynolds SJ, Alavanja MC (2007) Pesticide dose estimates for children of Iowa farmers and non-farmers. Environ Res 105(3):307–315. https://doi.org/10.1016/j.envres.2007.06.001

    Article  CAS  PubMed  Google Scholar 

  8. Arkan T, Csámpai A, Molnár-Perl I (2016) Alkylsilyl derivatization of glyphosate and aminomethylphosphonic acid followed by gas chromatography mass spectrometry. Microchem J 125:219–223. https://doi.org/10.1016/j.microc.2015.11.027

    Article  CAS  Google Scholar 

  9. Zouaoui K, Dulaurent S, Gaulier JM, Moesch C, Lachatre G (2013) Determination of glyphosate and AMPA in blood and urine from humans: about 13 cases of acute intoxication. Forensic Sci Int 226(1–3):E20–E25. https://doi.org/10.1016/j.forsciint.2012.12.010

    Article  CAS  PubMed  Google Scholar 

  10. Saito T, Miura N, Namera A, Oikawa H, Miyazaki S, Nakamoto A, Inokuchi S (2012) Mixed-mode C–C18 monolithic spin-column extraction and GC–MS for simultaneous assay of organophosphorus compounds, glyphosate, and glufosinate in human serum and urine. Forensic Toxicol 30(1):1–10. https://doi.org/10.1007/s11419-011-0120-7

    Article  CAS  Google Scholar 

  11. Jensen PK, Wujcik CE, McGuire MK, McGuire MA (2016) Validation of reliable and selective methods for direct determination of glyphosate and aminomethylphosphonic acid in milk and urine using LC–MS/MS. J Environ Sci Health B 51(4):254–259. https://doi.org/10.1080/03601234.2015.1120619

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  12. Cuhadar S, Koseoglu M, Atay A, Dirican A (2013) The effect of storage time and freeze-thaw cycles on the stability of serum samples. Biochem Med 23(1):70–77. https://doi.org/10.11613/Bm.2013.009

    Article  CAS  Google Scholar 

  13. Wang K-C, Chen S-M, Hsu J-F, Cheng S-G, Lee C-K (2008) Simultaneous detection and quantitation of highly water-soluble herbicides in serum using ion-pair liquid chromatography–tandem mass spectrometry. J Chromatogr B 876(2):211–218. https://doi.org/10.1016/j.jchromb.2008.10.042

    Article  CAS  Google Scholar 

  14. Tsao Y-C, Lai Y-C, Liu H-C, Liu RH, Lin D-L (2016) Simultaneous determination and quantitation of paraquat, diquat, glufosinate and glyphosate in postmortem blood and urine by LC–MS–MS. J Anal Toxicol 40(6):427–436. https://doi.org/10.1093/jat/bkw042

    Article  CAS  PubMed  Google Scholar 

  15. Martins-Júnior HA, Lebre DT, Wang AY, Pires MAF, Bustillos OV (2009) An alternative and fast method for determination of glyphosate and aminomethylphosphonic acid (AMPA) residues in soybean using liquid chromatography coupled with tandem mass spectrometry. Rapid Commun Mass Spectrom 23(7):1029–1034. https://doi.org/10.1002/rcm.3960

    Article  CAS  PubMed  Google Scholar 

  16. Snyder LR, Dolan JW, Carr PW (2004) The hydrophobic-subtraction model of reversed-phase column selectivity. J Chromatogr A 1060(1–2):77–116. https://doi.org/10.1016/j.chroma.2004.08.121

    Article  CAS  Google Scholar 

  17. Connolly A, Leahy M, Jones K, Kenny L, Goggins MA (2018) Glyphosate in Irish adults—a pilot study in 2017. Environ Res 165:235–236. https://doi.org/10.1016/j.envres.2018.04.025

    Article  CAS  PubMed  Google Scholar 

  18. Panuwet P, Hunter RE, D'Souza PE, Chen XY, Radford SA, Cohen JR, Marder ME, Kartavenka K, Ryan PB, Barr DB (2016) Biological matrix effects in quantitative tandem mass spectrometry-based analytical methods: advancing biomonitoring. Crit Rev Anal Chem 46(2):93–105. https://doi.org/10.1080/10408347.2014.980775

    Article  CAS  PubMed  PubMed Central  Google Scholar 

Download references

Acknowledgements

This research was supported by the Faculty of Medicine, Chiang Mai University Research Fund [Grant no. 30-2562 and Grant no. 140-2561].

Author information

Authors and Affiliations

  1. Toxicology Unit, Department of Forensic Medicine, Faculty of Medicine, Chiang Mai University, Chiang Mai, 50200, Thailand

    Pittaya Jaikwang, Anongphan Junkuy, Supakit Khacha-ananda, Patthawee Mueangkhiao & Klintean Wunnapuk

  2. Department of Community Medicine, Faculty of Medicine, Chiang Mai University, Chiang Mai, 50200, Thailand

    Ratana Sapbamrer & Mathuramat Seesen

Authors
  1. Pittaya Jaikwang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Anongphan Junkuy
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Ratana Sapbamrer
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Mathuramat Seesen
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Supakit Khacha-ananda
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Patthawee Mueangkhiao
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Klintean Wunnapuk
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

KW, RS and AJ conceived and planned the experiments. PJ, PM, SK, MS and KW contributed to sample collection and management. PJ carried out the LC–MS/MS experiments. PJ, KW and AJ contributed to the interpretation of the results and data analysis. PJ and KW wrote the manuscript with critical feedback from all authors.

Corresponding author

Correspondence to Klintean Wunnapuk.

Ethics declarations

Conflict of interest

All authors declare that they have no conflict of interest.

Ethical approval

This study was approved by the Ethics Committee of the Faculty of Medicine, Chiang Mai University, Thailand (Study code: FOR-2560-05126, FOR-2561-05301 and FOR-2562-06349). All subjects were informed about the protocol of this study and signed the consent form according to the guidelines of the Faculty of Medicine ethical committee.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic Supplementary Material

Below is the link to the electronic supplementary material.

Supplementary file1 (PDF 624 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Jaikwang, P., Junkuy, A., Sapbamrer, R. et al. A Dilute-and-Shoot LC–MS/MS Method for Urinary Glyphosate and AMPA. Chromatographia 83, 467–475 (2020). https://doi.org/10.1007/s10337-019-03853-3

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10337-019-03853-3

Keywords

Search

Navigation