Skip to main content
SpringerLink
Log in

Determination of Underivatized Glyphosate Residues in Plant-Derived Food with Low Matrix Effect by Solid Phase Extraction-Liquid Chromatography-Tandem Mass Spectrometry

  • Published:
Food Analytical Methods Aims and scope Submit manuscript

Abstract

A method was developed for the determination of glyphosate residues in plant-derived food using a two-step solid phase extraction (SPE) combined with mixed-mode liquid chromatography-tandem mass spectrometry (LC-MS/MS). The samples were extracted with water. Then, the extracting solution was pretreated by a C18 cartridge to remove protein and weak-polar interferences and further directly extracted using a strong anion exchange (SAX) cartridge to remove neutral and basic substances. The obtained glyphosate residues from the SPE were separated on a hydrophilic interaction/weak anion-exchange (HILIC/WAX) column and detected by mass spectrometry with negative electrospray ionization (ESI-) in multiple reaction monitoring (MRM) mode. This approach was evaluated by five different kinds of plant-derived food (soybean, corn, carrot, apple, and spicy cabbage) matrices in terms of matrix effect and recovery. Results showed that two-step SPE and mixed-mode chromatography separation provided the method with a very low matrix effect, and the spiked recoveries of glyphosate were satisfied in the range of 83.1 to 100.8 % at three spiked levels. The limit of quantification (LOQ) and detection (LOD) of the method in different matrices were 0.016–0.026 and 0.005–0.008 mg kg−1, respectively. The procedure was validated and showed good accuracy and precision over a large linear range of 0.02–10 mg kg−1.

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
Fig. 5

Similar content being viewed by others

References

  • Botero-Coy AM, Ibanez M, Sancho JV, Hernandez F (2013a) Improvements in the analytical methodology for the residue determination of the herbicide glyphosate in soils by liquid chromatography coupled to mass spectrometry. J Chromatogr A 1292:132–141

    Article  CAS  Google Scholar 

  • Botero-Coy AM, Ibanez M, Sancho JV, Hernandez F (2013b) Direct liquid chromatography-tandem mass spectrometry determination of underivatized glyphosate in rice, maize and soybean. J Chromatogr A 1313:157–165

    Article  CAS  Google Scholar 

  • Chen MX, Cao ZY, Jiang Y, Zhu ZW (2013) Direct determination of glyphosate and its major metabolite, aminomethylphosphonic acid, in fruits and vegetables by mixed-mode hydrophilic interaction/weak anion-exchange liquid chromatography coupled with electrospray tandem mass spectrometry. J Chromatogr A 1272:90–99

    Article  CAS  Google Scholar 

  • Chlopecka M, Mendel M, Dziekan N, Karlik W (2014) Glyphosate affects the spontaneous motoric activity of intestine at very low doses—in vitro study. Pestic Biochem Physiol 113:25–30

    Article  CAS  Google Scholar 

  • Goscinny S, Unterluggauer H, Aldrian J, Hanot V, Masselter S (2012) Determination of glyphosate and its metabolite AMPA (Aminomethylphosphonic Acid) in cereals after derivatization by isotope dilution and UPLC-MS/MS. Food Anal Methods 5:1177–1185

    Article  Google Scholar 

  • Hanke I, Singer H, Hollender J (2008) Ultratrace-level determination of glyphosate, aminomethylphosphonic acid and glufosinate in natural waters by solid-phase extraction followed by liquid chromatography-tandem mass spectrometry: performance tuning of derivatization, enrichment and detection. Anal Bioanal Chem 391:2265–2276

    Article  CAS  Google Scholar 

  • Hao C, Morse D, Morra F, Zhao X, Yang P, Nunn B (2011) 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 1218:5638–5643

    Article  CAS  Google Scholar 

  • Heller DN (2007) Ruggedness testing of quantitative atmospheric pressure ionization mass spectrometry methods: the effect of co-injected matrix on matrix effects. Rapid Commun Mass Spectrom 21:644–652

    Article  CAS  Google Scholar 

  • Hernandez F, Sancho JV, Pozo OJ (2005) Critical review of the application of liquid chromatography/mass spectrometry to the determination of pesticide residues in biological samples. Anal Bioanal Chem 382:934–946

    Article  CAS  Google Scholar 

  • Hu JY, Chen CL, Li JZ (2008) A simple method for the determination of glyphosate residues in soil by capillary gas chromatography with nitrogen phosphorus. J Anal Chem 63:371–375

    Article  CAS  Google Scholar 

  • Ibáñez M, Pozo ÓJ, Sancho JV, López FJ, Hernández F (2005) 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 1081:145–155

    Article  Google Scholar 

  • Le Bot B, Colliaux K, Pelle D, Briens C, Seux R, Clement M (2002) Optimization and performance evaluation of the analysis of glyphosate and AMPA in water by HPLC with fluorescence detection. Chromatographia 56:161–164

    Article  Google Scholar 

  • Li X, Xu J, Jiang Y, Chen L, Xu Y, Pan C (2009) Hydrophilic-Interaction Liquid Chromatography (HILIC) with DAD and mass spectroscopic detection for direct analysis of glyphosate and glufosinate residues and for product quality control. Acta Chromatogr 21:559–576

    Article  Google Scholar 

  • Marek LJ, Koskinen WC (2014) Simplified analysis of glyphosate and aminomethylphosphonic acid in water, vegetation and soil by liquid chromatography-tandem mass spectrometry. Pest Manag Sci 70:1158–1164

    Article  CAS  Google Scholar 

  • Matuszewski BK, Constanzer ML, Chavez-Eng CM (2003) Strategies for the assessment of matrix effect in quantitative bioanalytical methods based on HPLC-MS/MS. Anal Chem 75:3019–3030

    Article  CAS  Google Scholar 

  • Nagatomi Y, Yoshioka T, Yanagisawa M, Uyama A, Mochizuki N (2013) Simultaneous LC-MS/MS analysis of glyphosate, glufosinate, and their metabolic products in beer, barley tea, and their ingredients. Biosci Biotechnol Biochem 77:2218–2221

    Article  CAS  Google Scholar 

  • Nedelkoska TV, Low GKC (2004) High-performance liquid chromatographic determination of glyphosate in water and plant material after pre-column derivatisation with 9-fluorenylmethyl chloroformate. Anal Chim Acta 511:145–153

    Article  CAS  Google Scholar 

  • Richard S, Moslemi S, Sipahutar H, Benachour N, Seralini GE (2005) Differential effects of glyphosate and roundup on human placental cells and aromatase. Environ Health Perspect 113:716–720

    Article  CAS  Google Scholar 

  • Sanchis J, Kantiani L, Llorca M, Rubio F, Ginebreda A, Fraile J, Garrido T, Farre M (2012) Determination of glyphosate in groundwater samples using an ultrasensitive immunoassay and confirmation by on-line solid-phase extraction followed by liquid chromatography coupled to tandem mass spectrometry. Anal Bioanal Chem 402:2335–2345

    Article  CAS  Google Scholar 

  • Shen A, Guo Z, Cai X, Xue X, Liang X (2012) Preparation and chromatographic evaluation of a cysteine-bonded zwitterionic hydrophilic interaction liquid chromatography stationary phase. J Chromatogr A 1228:175–182

    Article  CAS  Google Scholar 

  • Standardization Administration of China and Ministry of Health of the People’s Republic of China, National food safety standard maximum residue limits for pesticides in food, GB 2763–2014

  • Szternfeld P, Malysheva SV, Hanot V, Joly L (2015) A robust transferable method for the determination of glyphosate residue in liver after derivatization by ultra-high pressure liquid chromatography–tandem mass spectrometry. Food Anal Methods. doi:10.1007/s12161-015-0293-5

    Google Scholar 

  • Van Eeckhaut A, Lanckmans K, Sarre S, Smolders I, Michotte Y (2009) Validation of bioanalytical LC-MS/MS assays: evaluation of matrix effects. J Chromatogr B 877:2198–2207

    Article  Google Scholar 

  • Yoshioka N, Asano M, Kuse A, Mitsuhashi T, Nagasaki Y, Ueno Y (2011) Rapid determination of glyphosate, glufosinate, bialaphos, and their major metabolites in serum by liquid chromatography-tandem mass spectrometry using hydrophilic interaction chromatography. J Chromatogr A 1218:3675–3680

    Article  CAS  Google Scholar 

  • 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:e20–e25

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was supported by the National Natural Science Foundation of China (21207130) and the STS program of the Chinese Academy of Sciences (KFT-EW-STS-099).

Author information

Authors and Affiliations

  1. Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Key Laboratory of Separation Science for Analytical Chemistry, Dalian, 116023, China

    Junjie Ding, Gaowa Jin, Aijin Shen, Zhimou Guo, Jingyu Yan & Xinmiao Liang

  2. Dandong Entry-Exit Inspection and Quarantine Bureau of People’s Republic of China, Dandong, People’s Republic of China

    Gehui Jin, Bing Yu & Yang Jiao

Authors
  1. Junjie Ding
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Gehui Jin
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Gaowa Jin
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Aijin Shen
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Zhimou Guo
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Bing Yu
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Yang Jiao
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Jingyu Yan
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Xinmiao Liang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Jingyu Yan or Xinmiao Liang.

Ethics declarations

Conflict of Interest

Junjie Ding declares that she has no conflict of interest. Gehui Jin declares that he has no conflict of interest. Gaowa Jin declares that she has no conflict of interest. Aijin Shen declare that she has no conflict of interest. Zhimou Guo declares that he has no conflict of interest. Bing Yu declares that he has no conflict of interest. Yang Jiao declares that he has no conflict of interest. Jingyu Yan declares that she has no conflict of interest. Xinmiao Liang declares that he has no conflict of interest.

Ethical Approval

This article does not contain any studies with human participants performed by any of the authors.

Informed Consent

Informed consent was obtained from all individual participants included in the study.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Ding, J., Jin, G., Jin, G. et al. Determination of Underivatized Glyphosate Residues in Plant-Derived Food with Low Matrix Effect by Solid Phase Extraction-Liquid Chromatography-Tandem Mass Spectrometry. Food Anal. Methods 9, 2856–2863 (2016). https://doi.org/10.1007/s12161-016-0468-8

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12161-016-0468-8

Keywords

Search

Navigation