Determination of alkylphenols, phenylphenols, bisphenol A, parabens, organophosphorus pesticides and triclosan in different cereal-based foodstuffs by gas chromatography–mass spectrometry
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 (GC–MS). The method features low limits of detection (0.4–23 ng/kg), good precision (3.8–7.2%) 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.
KeywordsEndocrine disrupting chemicals Cereal-based foodstuffs Ultrasound-assisted extraction Automated solid-phase extraction Gas chromatography–mass spectrometry
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).
Compliance with ethical standards
Conflict of interest
The authors declare that they have no conflict of interest.
- 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.CrossRefGoogle Scholar
- 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).Google Scholar
- 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.CrossRefPubMedGoogle Scholar
- 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.CrossRefPubMedGoogle Scholar
- 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.CrossRefPubMedGoogle Scholar
- 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.CrossRefPubMedGoogle Scholar
- 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.CrossRefGoogle Scholar
- 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.CrossRefPubMedGoogle Scholar
- 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.CrossRefGoogle Scholar
- 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.CrossRefGoogle Scholar
- 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.CrossRefPubMedGoogle Scholar
- 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.CrossRefPubMedGoogle Scholar
- 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.CrossRefPubMedGoogle Scholar
- 28.Miller JN, Miller JC, Miller RD. Statistics and chemometrics for analytical chemistry. 7th ed. London: Pearson.Google Scholar
- 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.CrossRefGoogle Scholar
- 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.Google Scholar
- 32.Codex Alimentarius, 2019. http://www.fao.org/fao-who-codexalimentarius/codex-texts/dbs/pestres/pesticides/es/ Accessed 28 October 2019.