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Evaluation of MS2 workflows in LC-Q-Orbitrap for pesticide multi-residue methods in fruits and vegetables

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Abstract

LC-Q-Orbitrap efficiency was evaluated for pesticide multi-residue analysis by using three workflows involving simultaneous MS and MS2 analysis. They were as follows: data-dependent MS2 (dd-MS2), all-ion fragmentation (AIF) and variable data-independent analysis (vDIA). These MS2 workflows were tested for the main method validation parameters such as detection and identification capabilities, repeatability, linear range and quantitation. QuEChER acetonitrile extracts (blanks and spiked with 166 pesticides) of 11 different fruits and vegetables were used for this evaluation. Blank extracts were analysed to evaluate isobaric compounds and potential false identification. Spiked extracts (at 0.01 and 0.1 mg kg−1) were analysed to evaluate the false negatives potentially produced (considering a retention mass window of 0.2 min). At 0.01 mg kg−1, dd-MS2 had the highest identification rate (96–100%, depending on the matrix). In vDIA, it was 86–100% and in AIF 81–100%. But these two last workflows offered more possibilities for applying screening analysis. It was observed that application of the ion ratio criterion established in the SANTE Guidelines for identification can generate some artificial false negative results. It could be overcome by considering a mass error threshold (i.e. 5 ppm) as a selected criterion. Detection and quantitation were carried out in full-scan MS. MS2 data were used for identification. Dd-MS2 provided the highest number of points per chromatographic peak, and by that peak area, repeatability was the best (typically <10%). AIF and vDIA were characterised by longer cycle times; thus, the obtained peak area repeatability was slightly worse, but acceptable (<20%). All workflows showed very good linearity in the range 0.01–0.5 mg kg−1. The three MS2 workflows were applied to real samples with good results.

LC-Q-Orbitrap was used for pesticide residues analysis in fruit and vegetables. Three approaches to MS2 identificaton were evaluated

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Acknowledgements

The authors would like to thank Thermo Fisher Scientific for facilitating QExactive Focus and for technical support. The authors acknowledge funding support from the European Commission, DG SANTE (Specific Agreement No. 7 to Framework Partnership Agreement No. SANTE/2005/FOOD SAFETY/0025-Pesticides in Fruit and Vegetables).

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Authors and Affiliations

  1. European Union Reference Laboratory for Pesticide Residues in Fruit & Vegetables, University of Almeria, Agrifood Campus of International Excellence (ceiA3), Ctra. Sacramento s/n, La Cañada de San Urbano, Almeria, 04120, Spain

    Łukasz Rajski, María del Mar Gómez Ramos & Amadeo R. Fernández-Alba

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  1. Łukasz Rajski
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  2. María del Mar Gómez Ramos
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  3. Amadeo R. Fernández-Alba
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Correspondence to Amadeo R. Fernández-Alba.

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Published in the topical collection Advances in LC-MS/MS Analysis with guest editors Damià Barceló and Mira Petrovic.

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Rajski, Ł., del Mar Gómez Ramos, M. & Fernández-Alba, A.R. Evaluation of MS2 workflows in LC-Q-Orbitrap for pesticide multi-residue methods in fruits and vegetables. Anal Bioanal Chem 409, 5389–5400 (2017). https://doi.org/10.1007/s00216-017-0220-2

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  • DOI: https://doi.org/10.1007/s00216-017-0220-2

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