Analytical and Bioanalytical Chemistry

, Volume 407, Issue 21, pp 6327–6343 | Cite as

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

  • Natalia Besil
  • Samanta Uclés
  • Milagros Mezcúa
  • Horacio Heinzen
  • Amadeo R. Fernández-AlbaEmail author
Research Paper
Part of the following topical collections:
  1. High-Resolution Mass Spectrometry in Food and Environmental Analysis


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.


Gas chromatography Quadrupole time-of-flight mass spectrometry Negative chemical ionization High resolution Pesticides 



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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Copyright information

© Springer-Verlag Berlin Heidelberg 2015

Authors and Affiliations

  • Natalia Besil
    • 1
    • 2
    • 3
  • Samanta Uclés
    • 1
  • Milagros Mezcúa
    • 1
  • Horacio Heinzen
    • 2
    • 3
  • Amadeo R. Fernández-Alba
    • 1
    Email author
  1. 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 PhysicUniversity of AlmeriaAlmeríaSpain
  2. 2.Polo Agroalimentario y Agroindustrial, Departamento de Química Del LitoralUniversidad de la RepúblicaPaysandúUruguay
  3. 3.Cátedra de Farmacognosia y Productos Naturales, Facultad de QuímicaUniversidad de la RepúblicaMontevideoUruguay

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