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Negative chemical ionization gas chromatography coupled to hybrid quadrupole time-of-flight mass spectrometry and automated accurate mass data processing for determination of pesticides in fruit and vegetables

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Abstract

Gas chromatography coupled to high resolution hybrid quadrupole time-of-flight mass spectrometry (GC-QTOF MS), operating in negative chemical ionization (NCI) mode and combining full scan with MSMS experiments using accurate mass analysis, has been explored for the automated determination of pesticide residues in fruit and vegetables. Seventy compounds were included in this approach where 50 % of them are not approved by the EU legislation. A global 76 % of the analytes could be identified at 1 μg kg–1. Recovery studies were developed at three concentration levels (1, 5, and 10 μg kg–1). Seventy-seven percent of the detected pesticides at the lowest level yielded recoveries within the 70 %–120 % range, whereas 94 % could be quantified at 5 μg kg–1, and the 100 % were determined at 10 μg kg–1. Good repeatability, expressed as relative standard deviation (RSD <20 %), was obtained for all compounds. The main drawback of the method was the limited dynamic range that was observed for some analytes that can be overcome either diluting the sample or lowering the injection volume. A home-made database was developed and applied to an automatic accurate mass data processing. Measured mass accuracies of the generated ions were mainly less than 5 ppm for at least one diagnostic ion. When only one ion was obtained in the single-stage NCI-MS, a representative product ion from MSMS experiments was used as identification criterion. A total of 30 real samples were analyzed and 67 % of the samples were positive for 12 different pesticides in the range 1.0–1321.3 μg kg–1.

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References

  1. Regulation (EC) No. 396/2005 of the European Parliament and of the Council of 23 February 2005 on maximum residue levels of pesticides in or on food and feed of plant and animal origin and amending Council Directive 91/414/EEC (2005)

  2. Commission Regulation (EU) No. 212/2013 of 11 March 2013 replacing Annex I to Regulation (EC) No. 396/2005 of the European Parliament and of the Council as regards additions and modifications with respect to the products covered by that Annex (2013)

  3. Regulation (EC) No. 609/2013 of the European Parliament and of the Council of 12 June 2013 on food intended for infants and young children, food for special medical purposes, and total diet replacement for weight control, and repealing Council Directive 92/52/EEC, Commission Directives 96/8/EC, 1999/21/EC, 2006/125/EC and 2006/141/EC, Directive 2009/39/EC of the European Parliament and of the Council and Commission Regulations (EC) No 41/2009 and (EC) No 953/2009 (2013)

  4. Hernández F, Sancho JV, Ibáñez M, Abad E, Portolés T, Mattioli L (2012) Current use of high-resolution mass spectrometry in the environmental sciences. Anal Bioanal Chem 403(5):1251–1264

    Article  Google Scholar 

  5. Hernández F, Portolés T, Pitarch E, López FJ (2011) Gas chromatography coupled to high-resolution time-of-flight mass spectrometry to analyze trace-level organic compounds in the environment, food safety, and toxicology. TrAC Trends Anal Chem 30(2):388–400

    Article  Google Scholar 

  6. Petucci C, Mallis L (2005) Automated accurate mass data processing using a gas chromatograph/time-of-flight mass spectrometer in drug discovery. Rapid Commun Mass Spectrom 19(11):1492–1498

    Article  CAS  Google Scholar 

  7. Zhang F, Wang H, Zhang L, Zhang J, Fan R, Yu C, Wang W, Guo Y (2014) Suspected target pesticide screening using gas chromatography-quadrupole time-of-flight mass spectrometry with high resolution deconvolution and retention index/mass spectrum library. Talanta 128:156–163

    Article  CAS  Google Scholar 

  8. Portolés T, Pitarch E, López FJ, Sancho JV, Hernández F (2007) Methodical approach for the use of GC-TOF MS for screening and confirmation of organic pollutants in environmental water. J Mass Spectrom 42(9):1175–1185

    Article  Google Scholar 

  9. Cervera MI, Portolés T, López FJ, Beltrán J, Hernández F (2014) Screening and quantification of pesticide residues in fruits and vegetables making use of gas chromatography-quadrupole time-of-flight mass spectrometry with atmospheric pressure chemical ionization. Anal Bioanal Chem 406(27):6843–55

  10. Portolés T, Mol JGJ, Sancho JV, Hernández F (2014) Use of electron ionization and atmospheric pressure chemical ionization in gas chromatography coupled to time-of-flight mass spectrometry for screening and identification of organic pollutants in waters. J Chromatogr A 1339:145–153

    Article  Google Scholar 

  11. Nácher-Mestre J, Serrano R, Portolés T, Berntssen MHG, Pérez-Sánchez J, Hernández F (2014) Screening of pesticides and polycyclic aromatic hydrocarbons in feeds and fish tissues by gas chromatography coupled to high-resolution mass spectrometry using atmospheric pressure chemical ionization. J Agric Food Chem 62(10):2165–2174

    Article  Google Scholar 

  12. Kazda R, Hajšlová J, Poustka J, Čajka T (2004) Determination of polybrominated diphenyl ethers in human milk samples in the Czech Republic: comparative study of negative chemical ionisation mass spectrometry and time-of-flight high-resolution mass spectrometry. Anal Chim Acta 520(1/2):237–243

    Article  CAS  Google Scholar 

  13. Moniruzzaman M, Rodríguez I, Ramil M, Cela R, Sulaiman SA, Gan SH (2014) Assessment of gas chromatography time-of-flight accurate mass spectrometry for identification of volatile and semi-volatile compounds in honey. Talanta 129:505–515

    Article  CAS  Google Scholar 

  14. Belmonte N, Uclés S, Gamón M, Ferrer C, Mezcua M, R. Fernández-Alba A (2014) Improving sensitivity and selectivity in pesticide analysis with GC-MS and GC-MS-MS. LCxGC Europe Advances in GC-MS analysis of pesticide. LCxGC Europe. http://www.chromatographyonline.com. Accessed 20 Sept 2014

  15. Martínez-Uroz MA, Mezcua M, Valles NB, Fernández-Alba AR (2012) Determination of selected pesticides by GC with simultaneous detection by MS (NCI) and μ-ECD in fruit and vegetable matrices. Anal Bioanal Chem 402(3):1365–1372

    Article  Google Scholar 

  16. Belmonte Valles N, Retamal M, Mezcua M, Fernández-Alba AR (2012) A sensitive and selective method for the determination of selected pesticides in fruit by gas chromatography/mass spectrometry with negative chemical ionization. J Chromatogr A 1264:110–116

    Article  CAS  Google Scholar 

  17. Zhu P, Miao H, Du J, Zou JH, Zhang GW, Zhao YF, Wu YN (2014) Organochlorine pesticides and pyrethroids in Chinese tea by screening and confirmatory detection using GC-NCI-MS and GC-MS/MS. J Agric Food Chem 62(29):7092–7100

    Article  CAS  Google Scholar 

  18. Gómez-Ramos MDM, Pérez-Parada A, García-Reyes JF, Fernández-Alba AR, Agüera A (2011) Use of an accurate-mass database for the systematic identification of transformation products of organic contaminants in wastewater effluents. J Chromatogr A 1218(44):8002–8012

    Article  Google Scholar 

  19. Regulation (EC) No. 400/2014 of the European Parliament and of the Council of 22 April 2014 concerning a coordinated multiannual control programme of the Union for 2015, 2016 and 2017 to ensure compliance with maximum residue levels of pesticides and to assess the consumer exposure to pesticide residues in and on food of plant and animal origin (2014)

  20. Uclés S, Belmonte N, Mezcua M, Martínez AB, Martinez-Bueno MJ, Gamón M, Fernández-Alba AR (2014) Validation of a multiclass multiresidue method and monitoring results for 210 pesticides in fruits and vegetables by gas chromatography-triple quadrupole mass spectrometry. J Environ Sci Health B 49(8):557–568

    Article  Google Scholar 

  21. Analytical Quality Control and Method Validation Procedures for Pesticide Residues Analysis in Food and Feed. Document SANCO/12571/2013 (2013)

  22. Thurman EM, Ferrer I, Fernández-Alba AR (2005) Matching unknown empirical formulas to chemical structure using LC/MS TOF accurate mass and database searching: example of unknown pesticides on tomato skins. J Chromatogr A 1067(1/2):127–134

    Article  CAS  Google Scholar 

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Acknowledgments

The authors acknowledge funding support from the European Commission, DG SANCO, Specific Agreement No. 5 of Framework Partnership Agreement No. SANCO/2005/FOOD SAFETY/0025 Pesticides in Fruit and Vegetables. N.B. acknowledges the fellowship from ANII (Agencia Nacional de Investigación e Innovación), PEDECIBA (Programa de Desarrollo de las Ciencias Básicas), AUIP (Asociación Universitaria Iberoamericana de Postgrado), and CSIC, Uruguay (Comisión Sectorial de Investigación Científica) for economic support.

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Authors and Affiliations

  1. Agrifood Campus of International excellence (ceiA3), European Union Reference Laboratory for Pesticide Residues in Fruit and Vegetables, Resticide Residue Research Group, Department of Chemistry and Physic, University of Almeria, La Cañada de San Urbano, 04120, Almería, Spain

    Natalia Besil, Samanta Uclés, Milagros Mezcúa & Amadeo R. Fernández-Alba

  2. Polo Agroalimentario y Agroindustrial, Departamento de Química Del Litoral, Universidad de la República, Km 363, Ruta 3, 60000, Paysandú, Uruguay

    Natalia Besil & Horacio Heinzen

  3. Cátedra de Farmacognosia y Productos Naturales, Facultad de Química, Universidad de la República, General Flores 2124, 11800, Montevideo, Uruguay

    Natalia Besil & Horacio Heinzen

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  1. Natalia Besil
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  2. Samanta Uclés
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  3. Milagros Mezcúa
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  4. Horacio Heinzen
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  5. Amadeo R. Fernández-Alba
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Correspondence to Amadeo R. Fernández-Alba.

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Published in the topical collection High-Resolution Mass Spectrometry in Food and Environmental Analysis with guest editor Aldo Laganà.

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Besil, N., Uclés, S., Mezcúa, M. et al. Negative chemical ionization gas chromatography coupled to hybrid quadrupole time-of-flight mass spectrometry and automated accurate mass data processing for determination of pesticides in fruit and vegetables. Anal Bioanal Chem 407, 6327–6343 (2015). https://doi.org/10.1007/s00216-015-8514-8

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  • DOI: https://doi.org/10.1007/s00216-015-8514-8

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