Abstract
The aim of this article is to provide a unified analytical methodology that allows the determination of 181 pesticides in flowers, leaves and tree trunks, in compliance with the current legislation in Europe. Most of these commodities are not included in the regulation and do not have established a maximum residue limit as many of them are not edible. Moreover, the analysis of pesticides of these commodities is very important to evaluate the exposure of phytosanitary products on plants throughout their life. The present study was performed over 7 years, allowing the creation of a database of Catalan agricultural production capable of providing a global perspective on the use of phytosanitary products in crops before harvest and to evaluate their sustainable use. During this study, 590 samples were analysed, of which 77% reported positive results, with an average of two positive pesticides per sample. To determine these different pesticides, a multi-residue analysis method was developed, where the different matrix group products were divided into different subgroups, according to their composition, in order to be able to quantify them more efficiently. The pesticides were extracted using a modified QuEChERS protocol. On the one hand, for trunks, a generic clean-up process was introduced, which allows the elimination of the principal interferences; additionally, for leaves, this clean-up process also contains active carbon that allows the elimination of chlorophylls, which reduces the matrix effect. On the other hand, a freezing step was introduced in addition to a clean-up process for fats, which allows the elimination of waxes present in flowers. Finally, the resultant extracts were analysed by liquid and gas chromatography coupled to a triple quadrupole mass spectrometer. This methodology was validated in accordance with the standards described in the SANTE/11312/2021 guidelines, achieving a good level of sensitivity and selectivity at the limits of quantification. In addition, excellent accuracy was also achieved with recoveries between 70 and 120% and good precision with relative standard deviation below 20%, as well as excellent linearity.
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References
AENOR (2017) Requisitos generales para la competencia de los laboratorios de ensayo y calibración. UNE-EN ISO/IEC 17025:2017
Agencia Española de Seguridad Alimentaria y Nutrición, Gobierno de España, Ministerio de Agricultura, Pesca y Alimentación, et al. (2021) Plan Nacional de la Cadena Alimentaria 2021–2025. Spain
Anastassiades M, Scherbaum E, Taşdelen B, štajnbaher, D. (2007) Recent developments in QuEChERS methodology for pesticide multiresidue analysis. Pesticide Chemistry: Crop Protection. Public Health, Environmental Safety, pp 439–458
De Lima Franzen F, Rodrigues de Oliveira MS, Lidório HF et al (2019) Chemical composition of rose sunflower and calendula flower petals for human food use. Cienc Tecnol Agropecu 20:159–168. https://doi.org/10.21930/rcta.vol20_num1_art1252
European Commission (2005) 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
European Commission (2018) Commission Regulation (EU) 2018/62 of 17 January 2018 replacing Annex I to Regulation (EC) No 396/2005 of the European Parliament and of the Council
European Parliament (2009) Directive 2009/128/EC of the European Parliament and the Council of 21 October 2009 establishing a framework for Community action to achieve the sustainable use of pesticides
González-Curbelo M, Socas-Rodríguez B, Herrera-Herrera AV et al (2015) Evolution and applications of the QuEChERS method. TrAC Trends Anal Chem 71:169–185. https://doi.org/10.1016/J.TRAC.2015.04.012
Hepperle J, Dörk D, Barth A et al (2015) Studies to improve the extraction yields of incurred pesticide residues from crops using the QuEChERS method. J AOAC Int 98:450–463. https://doi.org/10.5740/jaoacint.13-068
Lehotay SJ, Son KA, Kwon H et al (2010) Comparison of QuEChERS sample preparation methods for the analysis of pesticide residues in fruits and vegetables. J Chromatogr A 1217:2548–2560. https://doi.org/10.1016/j.chroma.2010.01.044
Manzano Santana P, Miranda Martínez M, de Oca M, Porto R et al (2013) Estudio químico de los compuestos lipídicos de las hojas, tallos y flores de Vernonanthura patens (Kunth) H. Rob. (Asteraceae). Rev Cuba Plantas Med 18:575–585
Mastovska K, Dorweiler KJ, Lehotay SJ et al (2010) Pesticide multiresidue analysis in cereal grains using modified QuEChERS method combined with automated direct sample introduction GC-TOFMS and UPLC-MS/MS techniques. J Agric Food Chem 58:5959–5972. https://doi.org/10.1021/jf9029892
Ministerio de la Presidencia/Gobierno de España (2016) Real Decreto 1311 / 2012 , de 14 de septiembre , por el que se establece el marco de actuación para conseguir un uso sostenible de los productos fitosanitarios . TEXTO CONSOLIDADO
Mol HGJ, Van Dam RCJ, Steijger OM (2003) Determination of polar organophosphorus pesticides in vegetables and fruits using liquid chromatography with tandem mass spectrometry: selection of extraction solvent. J Chromatogr A 1015:119–127. https://doi.org/10.1016/S0021-9673(03)01209-3
Pareja L, Cesio V, Heinzen H, Fernández-Alba AR (2011) Evaluation of various QuEChERS based methods for the analysis of herbicides and other commonly used pesticides in polished rice by LC–MS/MS. Talanta 83:1613–1622. https://doi.org/10.1016/J.TALANTA.2010.11.052
Pereira PCG, Parente CET, Carvalho GO et al (2021) A review on pesticides in flower production: a push to reduce human exposure and environmental contamination. Environ Pollut 289:117817. https://doi.org/10.1016/J.ENVPOL.2021.117817
Sanchez Costa L, Rodríguez Martínez P, Medina Sala M (2018) Determination of 23 organochlorine pesticides in animal feeds by GC-MS/MS after QuEChERS with EMR-lipid clean-up. Anal Methods 10:5171–5180. https://doi.org/10.1039/c8ay01436a
SANTE/EU (2021) Analytical quality control and method validation procedures for pesticide residues analysis in food and feed SANTE 11312/2021
Tienstra M, Portolés T, Hernández F, Mol JGJ (2015) Fast gas chromatographic residue analysis in animal feed using split injection and atmospheric pressure chemical ionisation tandem mass spectrometry. J Chromatogr A 1422:289–298. https://doi.org/10.1016/j.chroma.2015.10.032
Uclés S, Lozano A, Sosa A et al (2017) Matrix interference evaluation employing GC and LC coupled to triple quadrupole tandem mass spectrometry. Talanta 174:72–81. https://doi.org/10.1016/j.talanta.2017.05.068
Walorczyk S, Drozdzyński D (2012) Improvement and extension to new analytes of a multi-residue method for the determination of pesticides in cereals and dry animal feed using gas chromatography-tandem quadrupole mass spectrometry revisited. J Chromatogr A 1251:219–231. https://doi.org/10.1016/j.chroma.2012.06.055
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All authors contributed to the study conception and design. Material preparation, data collection and analysis were performed by Laia Sanchez Costa, Judit Pujol Boira, Miriam Aragó Iglesias, Pilar Rodríguez Martínez and Mireia Medina Sala. The first draft of the manuscript was written by Laia Sanchez Costa and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.
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This research was performed in the Laboratori Agroalimentari (Agrifood Laboratory) of the Generalitat de Catalunya with the support of its Departament d’Acció Climàtica, Alimentació i Agenda Rural (Department of Climate Action, Food and Rural Agenda).
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Costa, L.S., Boira, J.P., Iglesias, M.A. et al. Analysis of 181 Pesticides with Multi-residue Method by LC–MS/MS and GC–MS/MS in Flowers, Leaves and Tree Trunks and the Results of Catalan Production from 2014 to 2021. Food Anal. Methods 16, 239–251 (2023). https://doi.org/10.1007/s12161-022-02407-y
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DOI: https://doi.org/10.1007/s12161-022-02407-y