Abstract
A multi-pesticide metabolite screening method using liquid chromatography quadrupole time-of-flight mass spectrometry (UPLC-Q-Tof-MS) was developed for the detection of pesticide metabolites in fruit and vegetable samples. Based on a retrospectively created accurate mass compound database, a suspect screening approach was established for pesticides of high concern applied to a wide scope of plant-derived commodities. For each matrix, an individual scope of characteristic pesticides was selected and a scientific library of corresponding metabolites generated. The metabolite database contained a total of 648 pesticide metabolites originating from 58 active compounds. In 500 samples from daily routine analysis, 96 samples with positive detects for a total of 26 pesticides were re-analyzed for the occurrence of corresponding metabolites. Forty-seven different phase-I and phase-II metabolites were identified, respectively. The developed metabolite database can be applied for a suspect screening approach for pesticide metabolites identification in all kinds of fruits and vegetables. By the means of the results of the suspect screening workflow, a targeted screening method by UHPLC-MS/MS was established for individual pesticide metabolites. Positive detects for metabolites may give an unequivocal evidence for an illegal application of plant protection products, even if the active compound is not detectable anymore.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Bauer A, Luetjohann J, Hanschen FS, Schreiner M, Kuballa J, Jantzen E, Rohn S (2017) Identification and characterization of pesticide metabolites in Brassica species by liquid chromatography travelling wave ion mobility quadrupole time-of-flight mass spectrometry (UPLC-TWIMS-QTOF-MS). Food Chem 244:292–303. https://doi.org/10.1016/j.foodchem.2017.09.131
BVL Federal Office of Consumer Protection and Food Safety—(2017) Database of plant protection products. https://apps2.bvl.bund.de/psm/jsp/index.jsp. Accessed 25 August 2017
CEN method 15662—DIN EN 15662:2009-02 (2008) Foods of plant origin—determination of pesticide residues using GC-MS and/or LC-MS/MS following acetonitrile extraction/partitioning and clean-up by dispersive SPE—QuEChERS-method; German version EN 15662:2008
Collin College (2017). http://iws.collin.edu/biopage/faculty/mcculloch/1406/notes/cell/images/cenvac2.jpg. Accessed 16 September 2017
EFSA (2009) European food safety authority—provision of documents (07/08/2009) assessment report Azoxystrobin, UK
EFSA European Food Safety Authority (2003) metrafenon_DAR_05. Draft Report Assessment:239
EFSA European Food Safety Authority (2005) Cyprodinil existing (2nd stage). Draft Assessment Report
EU—Pesticides database (2016) Pesticides EU-MRLs regulation (EC) no 396/2005: http://ec.europa.eu/food/plant/pesticides/eu-pesticides-database/public/?event=product.selection&language=EN
European Commission (2015) Guidance document on analytical quality control and method validation procedures for pesticides residues analysis in food and feed
Gautam M, Etzerodt T, Fomsgaard IS (2017) Quantification of azoxystrobin and identification of two novel metabolites in lettuce via liquid chromatography–quadrupole-linear ion trap (QTRAP) mass spectrometry. Int J Environ Anal Chem 97(5):419–430. https://doi.org/10.1080/03067319.2017.1318867
Ismail M, Zhang J (2004) Post-harvest citrus diseases and their control. Outlooks Pest Manag 15(1):29–35. https://doi.org/10.1564/15feb12
Jabot C, Daniele G, Giroud B, Tchamitchian S, Belzunces LP, Casabianca H, Vulliet E (2016) Detection and quantification of boscalid and its metabolites in honeybees. Chemosphere 156:245–251. https://doi.org/10.1016/j.chemosphere.2016.04.135
Kiljanek T, Niewiadowska A, Semeniuk S, Gawel M, Borzecka M, Posyniak A (2016) Multi-residue method for the determination of pesticides and pesticide metabolites in honeybees by liquid and gas chromatography coupled with tandem mass spectrometry—honeybee poisoning incidents. J Chromatogr A 1435:100–114. https://doi.org/10.1016/j.chroma.2016.01.045
Levsen K, Schiebel H-M, Behnke B, Dötzer R, Dreher W, Elend M, Thiele H (2005) Structure elucidation of phase-II metabolites by tandem mass spectrometry: an overview. J Chromatogr A 1067(1-2):55–72. https://doi.org/10.1016/j.chroma.2004.08.165
López MG, Fussell RJ, Stead SL, Roberts D, McCullagh M, Rao R (2014) Evaluation and validation of an accurate mass screening method for the analysis of pesticides in fruits and vegetables using liquid chromatography-quadrupole-time of flight-mass spectrometry with automated detection. J Chromatogr A 1373:40–50. https://doi.org/10.1016/j.chroma.2014.10.099
López A, Yusa V, Millet M, Coscolla C (2016) Retrospective screening of pesticide metabolites in ambient air using liquid chromatography coupled to high-resolution mass spectrometry. Talanta 150:27–36. https://doi.org/10.1016/j.talanta.2015.11.068
Moschet C, Piazzoli A, Singer H, Hollender J (2013) Alleviating the reference standard dilemma using a systematic exact mass suspect screening approach with liquid chromatography-high resolution mass spectrometry. Anal Chem 85(21):10312–10320. https://doi.org/10.1021/ac4021598
Pramanik BN, Chen G, Lee MS (2011) Characterization of impurities and degradants using mass spectrometry. doi: https://doi.org/10.1002/9780470921371
Reglinski T, Elmer PAG, Taylor JT, Parry FJ, Marsden R, Wood PN (2005) Suppression of Botrytis bunch rot in Chardonnay grapevines by induction of host resistance and fungal antagonism. Austral Plant Pathol 34(4):481. https://doi.org/10.1071/AP05057
Sandermann H (1994) Higher plant metabolism of xenobiotics: the ‘green liver’ concept. Pharmacogenetics 4(5):225–241. https://doi.org/10.1097/00008571-199410000-00001
Sandermann H, Musick TJ, Aschbacher PW (1992) Animal bioavailability of a 3,4-dichloroaniline-lignin metabolite fraction from wheat. J Agric Food Chem 40(10):2001–2007. https://doi.org/10.1021/jf00022a053
Storck V, Lucini L, Mamy L, Ferrari F, Papadopoulou ES, Nikolaki S, Karas PA, Servien R, Karpouzas DG, Trevisan M, Benoit P, Martin-Laurent F (2016) Identification and characterization of tebuconazole transformation products in soil by combining suspect screening and molecular typology. Environ Pollut 208(Pt B):537–545. https://doi.org/10.1016/j.envpol.2015.10.027
Thurman EM, Ferrer I, Zavitsanos P, Zweigenbaum JA (2013) Identification of imidacloprid metabolites in onion (Allium cepa L.) using high-resolution mass spectrometry and accurate mass tools. Rapid Commun Mass Spectrom 27(17):1891–1903. https://doi.org/10.1002/rcm.6637
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of Interest
Anna Bauer declares that she has no conflict of interest. Jens Luetjohann declares that she has no conflict of interest. Sascha Rohn declares that she has no conflict of interest. Eckard Jantzen declares that he has no conflict of interest. Jürgen Kuballa declares that he has no conflict of interest.
Ethical Approval
This article does not contain any studies with human participants or animals performed by any of the authors.
Informed Consent
Not applicable.
Electronic Supplementary Material
ESM 1
(DOCX 20 kb)
Rights and permissions
About this article
Cite this article
Bauer, A., Luetjohann, J., Rohn, S. et al. Development of a Suspect Screening Strategy for Pesticide Metabolites in Fruit and Vegetables by UPLC-Q-Tof-MS. Food Anal. Methods 11, 1591–1607 (2018). https://doi.org/10.1007/s12161-017-1143-4
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s12161-017-1143-4