Pesticide residues quantification in frozen fruit and vegetables in Chilean domestic market using QuEChERS extraction with ultra-high-performance liquid chromatography electrospray ionization Orbitrap mass spectrometry
Introduction
In recent years the use of pesticides commercial in agriculture has led to a better efficiency and raise of production not only for export, but also for internal market. Abundance of agricultural commodities at a reasonably low cost and local consumer demand for a wide variety of products and availability of them along the whole year have promoted the development of frozen products that can be found nationwide in retail. However, current consumer awareness for food safety (Kaushik, Satya, & Naik, 2009) and agricultural commodities disadvantage of pesticide residual presence (Krol, Arsenault, Pylypiw, & Incorvia Mattina, 2000) contributed to establish strict maximum residue levels (MRL) to comply with the limitation of consumer’s total dietary intake of pesticides. Furthermore, in literature there is enough documentation that evidences that many of these compounds are known carcinogens and/or toxins, and therefore can cause significant health damage to humans (Alavanja et al., 2013, Koutros et al., 2010). Although, in Chile the government agency that has enforcement control of manufacturing, marketing, and application of pesticides and fertilizers is the Agriculture and Livestock Service (SAG), the institutions that set the national standards of MRL of pesticides that may occur in food are the Ministry of Health and the Secretariat of Public Health under the Exempt Resolution Norm 33 (Ministerio de Salud, 2010). According to the Exempt Resolution Norm 33 the MRLs range depending on the commodity and pesticide from 0.01 to 7 mg/kg.
Therefore, food safety inspection authorities require quick, sensitive and precise analytical methods to detect a wide diversity of pesticide residues and their levels on products such as frozen fruit and vegetables. Multiresidue methods incorporate a single extraction technique with analytical equipment that is able to determine diverse compounds (Krol et al., 2000). Determination of pesticide residues in food frequently involves quantification using gas chromatography (GC) combined with mass spectrometry (GC–MS) (Fillion et al., 2000, Gamon et al., 2001) since is very useful with volatile and semi-volatile compounds as well as with non-polar compounds because of an outstanding separation capacity and resolution (Wang, Wang, & Cai, 2013). However, other techniques have become broadly common recently such as liquid chromatography (LC) – tandem mass spectrometry (MS–MS) with triple quadrupole in selected reaction monitoring (SRM) mode for the quantitation of polar pesticides in food (Agüera et al., 2004, Cairns et al., 1993, Jansson et al., 2004, Klein and Alder, 2003, Štajnbaher and Zupančič-Kralj, 2003). Moreover, Ferrer et al. developed a multi-residue methodology using liquid chromatography–time-of-flight mass spectrometry (LC–TOF-MS) for routine pesticide residues determination in fruit and vegetables. LC-MS is widely applied for the simultaneous separation and analysis of complex food samples, including food contaminants and food components (Ferrer, Garcia-Reyes, Mezcua, Thurman, & Fernández-Alba, 2005). LC is used to separate not only the analytes but also some polar or non-polar interfering compounds in food samples (Wang et al., 2013). Moreover, LC together with full scan high-resolution mass spectrometry (LC–full scan HRMS) has demonstrated to be a successful method to detect the presence of a wide variety of analytes in food samples (García-Reyes et al., 2007, Kaufmann, 2012). Mol et al. evaluated the analytical capabilities of LC combined with single-stage HRMS using Orbitrap ion trap analyzer for selective detection during screening and to identify pesticides in 21 different vegetable and fruit commodities (Mol, Zomer, & de Koning, 2012). Authors achieved a screening detection limit of 0.01 or 0.05 mg/kg for 66% and 23% of the pesticides, respectively, therefore this method showed potential for testing maximum residue levels compliance of pesticides in commodities. Furthermore, ultra-high performance liquid chromatography (UHPLC) instrumentation has been developed and coupled to MS for food analysis, thus providing greater sensitivity, better peak capacity, higher speed, and increased resolution since the particle size of the stationary phase is significantly smaller (Bakırcı et al., 2014, Wang et al., 2009).
With all these considerations there is an assumption that there is potential of UHPLC coupled with Orbitrap MS technique for applicability in frozen fruit and vegetables pesticide routine analysis. Thus, the aim of this study has been to determine pesticide profile of frozen fruit and vegetables from Chilean retail stores using UHPLC- Orbitrap MS technique to evaluate compliance with MRL established in Chilean and international regulations.
Section snippets
Plant material
Frozen fruit and vegetables from the same brand were sampled from 4 food markets in the city of Talca, Maule region, Chile, at 3 time-points during 2014 (April 29th, July 29th and Sept 29th). These were: blueberries (Vaccinium corymbosum), Raspberry (Rubus idaeus), Strawberry (Fragaria ananassa) Berries mix (blueberries, raspberries, strawberries); Vegetables: Pea (Pisum sativum), Fava Bean (Vicia faba), Corn (Zea mays), and Green Bean (Phaseolus vulgaris).
At each time-point, three bags of each
UHPLC-MS method optimization
Most published LC–MS-based methods involve extensive, costly, and labour-demanding clean-up procedures for processing crude extracts, which unavoidably results in a loss of some target analytes. The pesticide mix (Abamectin, Chlorpyrifos, Imidacloprid, Iprodione, λ-cyhalothrin, and Spinosad) was detected and quantified with high resolution (Table 2). Negative ion mode resulted in higher recovery of all pesticide molecules (data not shown). Retention times of most of these compounds were in the
Declaration of Competing Interest
None.
Acknowledgements
Funding provided by Conicyt Regional/Gore Maule/CEAP (R0912001) and Conicyt Fondequip (EQM120191), and Interdisciplinary Excellence Research Program on Healthy Aging (PIEI-ES) group, Universidad de Talca.
References (40)
- et al.
One-year routine application of a new method based on liquid chromatography–tandem mass spectrometry to the analysis of 16 multiclass pesticides in vegetable samples
Journal of Chromatography A
(2004) - et al.
Pesticide residues in fruits and vegetables from the Aegean region, Turkey
Food Chemistry
(2014) - et al.
Cumulative risk assessment of pesticide residues in food
Toxicology Letters
(2008) - et al.
Multi-residue pesticide analysis in fruits and vegetables by liquid chromatography–time-of-flight mass spectrometry
Journal of Chromatography A
(2005) - et al.
Determination of pesticide residues in olive oil and olives
TrAC Trends in Analytical Chemistry
(2007) - et al.
Pesticide residues in fruits and vegetables from South America – A Nordic project
Food Control
(2011) - et al.
A new multi-residue method for analysis of pesticide residues in fruit and vegetables using liquid chromatography with tandem mass spectrometric detection
Journal of Chromatography A
(2004) - et al.
Food processing a tool to pesticide residue dissipation – A review
Food Research International
(2009) - et al.
Validation and uncertainty study of a comprehensive list of 160 pesticide residues in multi-class vegetables by liquid chromatography-tandem mass spectrometry
Journal of Chromatography A
(2008) - et al.
Screening of fresh fruit and vegetables for pesticide residues on Croatian market
Food Control
(2009)
Pesticide residues in fruits and vegetables of the Argentine domestic market: Occurrence and quality
Food Control
Food contamination by metals and pesticides in the European Union. Should we worry?
Toxicology Letters
Multiresidue method for determination of 90 pesticides in fresh fruits and vegetables using solid-phase extraction and gas chromatography-mass spectrometry
Journal of Chromatography A
The latest developments and applications of mass spectrometry in food-safety and quality analysis
TrAC Trends in Analytical Chemistry
Increased cancer burden among pesticide applicators and others due to pesticide exposure
CA: A Cancer Journal for Clinicians
Biological properties of spinosad
Down to Earth
Multiresidue pesticide analysis by ion-trap mass spectrometry
Rapid Communications in Mass Spectrometry
Cited by (39)
The concentration of pesticide residues in vegetables: A systematic review and meta-analyses
2024, Journal of Agriculture and Food ResearchAssessment of pesticide residues in vegetables commonly consumed in Chile and Mexico: Potential impacts for public health
2022, Journal of Food Composition and AnalysisPesticide residues analysis in passion fruit and its processed products by LC–MS/MS and GC–MS/MS: Method validation, processing factors and dietary risk assessment
2022, Food ChemistryCitation Excerpt :The LOQ values established in this work for passion fruit matrices (0.005 or 0.010 mg kg−1) are similar to other multiresidue methods that used GC–MS/MS or LC–MS/MS for fruit matrices (Ferreira et al., 2016; Machado, Gérez, Pistón, Heinzen, & Cesio, 2017). Kemmerich et al. (2019) obtained LOQ values of 0.0025 mg kg−1 for 90% of the 170 analytes monitored in the multi-residue method validated in the pear matrix using UHPLC–MS/MS, while values greater than 0.010 mg kg−1 had been reported, including in passion fruit (Hjorth et al., 2011; Botero-Coy et al., 2012; Paz et al., 2015; Volpatto et al., 2016; Concha-Meyer et al., 2019). The LOQs of the analytical method are below the MRLs established by the Brazilian legislation for passion fruit (ANVISA, 2021a).