Advertisement

Springer Nature is making Coronavirus research free. View research | View latest news | Sign up for updates

Determination of alkylphenols, phenylphenols, bisphenol A, parabens, organophosphorus pesticides and triclosan in different cereal-based foodstuffs by gas chromatography–mass spectrometry

Abstract

The high toxicity of endocrine disrupting chemicals (EDCs) has promoted the development of effective techniques for their separation and detection in various types of matrices. In this work, we developed a method for the rapid, reliable determination of 24 EDCs from six different families of organic compounds (viz. alkylphenols, phenylphenols, bisphenol A, parabens, organophosphorus pesticides and triclosan) in cereal-based foodstuffs. The target compounds were subjected to ultrasound-assisted extraction with methanol, cleaned up and preconcentrated by automated solid-phase extraction, and derivatized for their determination by gas chromatography–mass spectrometry (GCMS). The method features low limits of detection (0.423 ng/kg), good precision (3.87.2%) and recoveries from 82% to 105%. The proposed method was used to analyse 12 samples of products purchased in Andalusia (Spain). A total of 14 analytes were detected in most of the samples. In any case, their concentrations (3.8–620 ng/kg) were all lower than the applicable maximum residue limits.

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

Fig. 1
Fig. 2

References

  1. 1.

    De Coster S, van Larebeke N. Endocrine-disrupting chemicals: associated disorders and mechanisms of action. J Environ Public Health. 2012;713696:1–52. https://doi.org/10.1155/2012/713696.

  2. 2.

    Scognamiglio V, Antonacci A, Patrolecco L, Lambreva MD, Litescu SC, Ghuge SA, et al. Analytical tools monitoring endocrine disrupting chemicals. Trends Anal Chem. 2016;80:555–67. https://doi.org/10.1016/j.trac.2016.04.014.

  3. 3.

    Azzouz A, Kumar Kailasa S, Kumar P, Ballesteros E, Kim KH. Advances in functional nanomaterial-based electrochemical techniques for screening of endocrine disrupting chemicals in various sample matrices. Trends Anal Chem. 2019;113:256–79. https://doi.org/10.1016/j.trac.2019.02.017.

  4. 4.

    European Commission, 2007. Document SEC, 1635, COMMISSION STAFF WORKING DOCUMENT on the implementation of the “Community Strategy for Endocrine Disrupters” – a range of substances suspected of interfering with the hormone systems of humans and wildlife (COM (1999) 706), (COM (2001) 262) and (SEC (2004) 1372).

  5. 5.

    Giulivo M, López de Alda M, Capri E, Barceló D. Human exposure to endocrine disrupting compounds: their role in reproductive systems, metabolic syndrome and breast cancer. A review. Environ Res. 2016;151:251–64. https://doi.org/10.1016/j.envres.2016.07.011.

  6. 6.

    Rodríguez E, Domínguez-Álvarez GJ, García-Gómez D, García-Jiménez MG, Carabias-Martínez R. Determination of endocrine disruptors in honey by CZE-MS using restricted access materials for matrix cleanup. Electrophoresis. 2010;31:2279–88. https://doi.org/10.1002/elps.200900715.

  7. 7.

    Niu Y, Zhang J, Wu Y, Shao B. Analysis of bisphenol A and alkylphenols in cereals by automated on-line solid-phase extraction and liquid chromatography tandem mass spectrometry. J Agric Food Chem. 2012;60:6116–22. https://doi.org/10.1021/jf301401k.

  8. 8.

    Liao C, Kannan K. A survey of bisphenol A and other bisphenol analogues in foods tuffs from nine cities in China. Food Addit Contam Part A. 2014;31:319–29. https://doi.org/10.1080/19440049.2013.868611.

  9. 9.

    Liao C, Chen L, Kannan K. Occurrence of parabens in foodstuffs from China and its implications for human dietary exposure. Environ Int. 2013;57-58:68–74. https://doi.org/10.1016/j.envint.2013.04.001.

  10. 10.

    Bordin AB, Minetto L, do Nascimento Filho I, Beal LL, Moura S. Determination of pesticide residues in whole wheat flour using modified QuEChERS and LC–MS/MS. Food Anal Methods. 2017;10:1–9. https://doi.org/10.1007/s12161-016-0542-2.

  11. 11.

    González-Curbelo MA, Herrera-Herrera AV, Ravelo-Pérez LM, Hernández-Borges J. Sample-preparation methods for pesticide-residue analysis in cereals and derivatives. Trends Anal Chem. 2012;38:32–51. https://doi.org/10.1016/j.trac.2012.04.010.

  12. 12.

    Carabias-Martínez R, Rodríguez-Gonzalo E, Revilla-Ruiz P. Determination of endocrine-disrupting compounds in cereals by pressurized liquid extraction and liquid chromatography–mass spectrometry. Study of background contamination. J Chromatogr A. 2006;1137:207–15. https://doi.org/10.1016/j.chroma.2006.10.040.

  13. 13.

    Pérez-Palacios D, Fernández-Recio MA, Moreta C, Tena MT. Determination of bisphenol-type endocrine disrupting compounds in food-contact recycled-paper materials by focused ultrasonic solid–liquid extraction and ultra-performance liquid chromatography-high resolution mass spectrometry. Talanta. 2012;99:167–74. https://doi.org/10.1016/j.talanta.2012.05.035.

  14. 14.

    González-Curbelo MA, Asensio-Ramos M, Herrera-Herrera AV, Hernández-Borges J. Pesticide residue analysis in cereal-based baby foods using multi-walled carbon nanotubes dispersive solid-phase extraction. Anal Bioanal Chem. 2012;404:183–96. https://doi.org/10.1007/s00216-012-6103-7.

  15. 15.

    González-Curbelo MA, Hernández-Borges J, Borges-Miquel TM, Rodríguez-Delgado MA. Determination of organophosphorus pesticides and metabolites in cereal-based baby foods and wheat flour by means of ultrasound-assisted extraction and hollow-fiber liquid-phase microextraction prior to gas chromatography with nitrogen phosphorus detection. J Chromatogr A. 2013;1313:166–74. https://doi.org/10.1016/j.chroma.2013.05.081.

  16. 16.

    Notardonato I, Russo MV, Vitali M, Protano C, Avino P. Analytical method validation for determining organophosphorus pesticides in baby foods by a modified liquid–liquid microextraction method and gas chromatography–ion trap/mass spectrometry analysis. Food Anal Methods. 2019;12:41–50. https://doi.org/10.1007/s12161-018-1335-6.

  17. 17.

    Rasche C, Fournes B, Dirks U, Speer K. Multi-residue pesticide analysis (gas chromatography–tandem mass spectrometry detection)—improvement of the quick, easy, cheap, effective, rugged, and safe method for dried fruits and fat-rich cereals—benefit and limit of a standardized apple purée calibration (screening). J Chromatogr A. 2015;1403:21–31. https://doi.org/10.1016/j.chroma.2015.05.030.

  18. 18.

    Grande-Martínez A, Arrebola-Liébanas FJ, Martínez-Vidal JL, Hernández-Torres ME, Garrido-Frenich A. Optimization and validation of a multiresidue pesticide method in rice and wheat flour by modified QuEChERS and GC–MS/MS. Food Anal Methods. 2016;9:548–63. https://doi.org/10.1007/s12161-015-0214-7.

  19. 19.

    He D, Ye X, Xiao Y, Zhao N, Long J, Zhang P, et al. Dietary exposure to endocrine disrupting chemicals in metropolitan population from China: a risk assessment based on probabilistic approach. Chemosphere. 2015;139:2–8. https://doi.org/10.1016/j.chemosphere.2015.05.036.

  20. 20.

    Di Ottavio FD, Pelle DF, Montesano C, Scarpone R, Escarpa A, Compagnone D, et al. Determination of pesticides in wheat flour using microextraction on packed sorbent coupled to ultra-high-performance liquid chromatography and tandem mass spectrometry. Food Anal Methods. 2017;10:1699–708. https://doi.org/10.1007/s12161-016-0720-2.

  21. 21.

    Azzouz A, Ballesteros E. Trace analysis of endocrine disrupting compounds in environmental water samples by use of solid-phase extraction and gas chromatography with mass spectrometry detection. J Chromatogr A. 2014;1360:248–57. https://doi.org/10.1016/j.chroma.2014.07.059.

  22. 22.

    Wu L, Song Y, Xu X, Li N, Shao M, Zhang H, et al. Medium-assisted non-polar solvent dynamic microwave extraction for determination of organophosphorus pesticides in cereals using gas chromatography-mass spectrometry. Food Chem. 2014;162:253–60. https://doi.org/10.1016/j.foodchem.2014.04.057.

  23. 23.

    He Z, Wang L, Peng Y, Luo M, Wang W, Liu X. Multiresidue analysis of over 200 pesticides in cereals using a QuEChERS and gas chromatography–tandem mass spectrometry-based method. Food Chem. 2015;169:372–80. https://doi.org/10.1016/j.foodchem.2014.07.102.

  24. 24.

    Zhu X, Jia C, Zheng Z, Feng X, He Y, Zhao E. Solid-phase extraction combined with dispersive liquid–liquid microextraction for the determination of pyrethroid pesticides in wheat and maize samples. J Sep Sci. 2016;39:4621–8. https://doi.org/10.1002/jssc.201600840.

  25. 25.

    Pastor-Belda M, Viñas P, Campillo N, Hernández-Córdoba M. Magnetic solid phase extraction with CoFe2O4/oleic acid nanoparticles coupled to gas chromatography-mass spectrometry for the determination of alkylphenols in baby foods. Food Chem. 2017;221:76–81. https://doi.org/10.1016/j.foodchem.2016.10.035.

  26. 26.

    Mezcua M, Martínez-Uroz MA, Gómez-Ramos MM, Gómez MJ, Navas JM, Fernández-Alba AR. Analysis of synthetic endocrine-disrupting chemicals in food: a review. Talanta. 2012;100:90–106. https://doi.org/10.1016/j.talanta.2012.07.078.

  27. 27.

    Pico Y. Ultrasound-assisted extraction for food and environmental samples. Trends Anal Chem. 2013;43:84–99. https://doi.org/10.1016/j.trac.2012.12.005.

  28. 28.

    Miller JN, Miller JC, Miller RD. Statistics and chemometrics for analytical chemistry. 7th ed. London: Pearson.

  29. 29.

    Liao C, Liu F, Kannan K. Occurrence of a dietary exposure to parabens in foodstuffs from the United States. Environ Sci Technol. 2013;47:3918–25. https://doi.org/10.1021/es400724s.

  30. 30.

    Maher HM, Alzoman NZ, Almeshal MA, Alotaibi HA, Alotaibi NN, Al-Showiman H. Quantitative screening of parabens in ready-to-eat foodstuffs available in the Saudi market using high performance liquid chromatography with photodiode array detection. Arab J Chem. 2018. https://doi.org/10.1016/j.arabjc.2018.07.019.

  31. 31.

    European Commission. Commission regulation (EU) 2017/1135 of 23 June 2017 amending annexes II and III to regulation (EC) no 396/2005 of the European Parliament and of the council as regards maximum residue levels for dimethoate and omethoate in or on certain products. Off J Eur Comm. 2017;L164:28–51.

  32. 32.

    Codex Alimentarius, 2019. http://www.fao.org/fao-who-codexalimentarius/codex-texts/dbs/pestres/pesticides/es/ Accessed 28 October 2019.

Download references

Acknowledgements

This work was funded by Spain’s Ministry of Economy and Competitiveness (MINECO, Grant CTQ-2015-71321) and partly co-funded by Fondo Europeo de Desarrollo Regional (FEDER).

Author information

Correspondence to Evaristo Ballesteros.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Additional information

Publisher’s note

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

Electronic supplementary material

ESM 1

(PDF 272 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Azzouz, A., Colón, L.P., Hejji, L. et al. Determination of alkylphenols, phenylphenols, bisphenol A, parabens, organophosphorus pesticides and triclosan in different cereal-based foodstuffs by gas chromatography–mass spectrometry. Anal Bioanal Chem (2020). https://doi.org/10.1007/s00216-020-02491-1

Download citation

Keywords

  • Endocrine disrupting chemicals
  • Cereal-based foodstuffs
  • Ultrasound-assisted extraction
  • Automated solid-phase extraction
  • Gas chromatography–mass spectrometry