Multi-Platform Chromatographic Analysis of Pesticide Residues in Table Grapes

Researchers at the University of Messina (Italy), working with Merck Chemicals (Wien, Austria) and Sigma Aldrich Chemicals Pvt Ltd (Bengaluru, India), developed a simplified workflow for detecting 236 pesticides in white table grapes within the European Union (EU) multi-annual control program, along with chronic, acute and cumulative risk assessments. Their method involved two complementary analytical platforms: low-pressure gas chromatography (GC) for volatile/semi-volatile pesticides and ultra-high-performance liquid chromatography (UHPLC) for polar/thermally labile pesticides, both coupled to triple quadrupole mass spectrometry (QqQMS). A paper based on their research was published in Journal of Chromatography A.¹

There is a great deal of interest in studying pesticide residues in grapes due to the fruit’s global economic importance and health benefits.^2,3 Among the most widely cultivated fruit in the world, with an estimated 75 million tons harvested in 2022, grapes are considered a functional food because of their high content of nutrients and healthy molecules, especially polyphenols, which have been shown to possess nutritional and therapeutic properties such as antioxidants, anti-inflammatory and anti-aging.^4,5

The wide use of pesticides in modern agricultural practices has led to frequent detection of their residues in food products.⁶ Monitoring pesticide residues is crucial to safeguard food safety due to their potentially toxic effects on human health.⁷ For this reason, the EU created a coordinated Community monitoring program in 1999 that has been extended over the years by several subsequent Commission Regulations.⁸ The coordinated Community monitoring program, currently defined as coordinated multi-annual control program (MACP), was developed to assess consumer exposure to pesticides and evaluate the effectiveness of EU legislation, with 40 key foods selected for assessment, including table grapes, for which the MACP plans to monitor 176 pesticides.⁹ Although the study aimed to cover all pesticides listed in the MACP, practical constraints led to the exclusion of 22 compounds. Despite this, the analytes included comprise over 90 % of the high priority residues for table grapes.¹

The researchers validated their methods in terms of linearity (correlation coefficients ≥0.998 for all analytes), extraction recovery (mean recoveries of 70-120 % for >90 % of pesticides), precision (intra- and inter-day relative standard deviations ≤20 % for all validated concentrations), trueness (in the range 63-135 %), and limit of quantification (ranging from 0.002 to 0.01 mg Kg^-1 for low-pressure GC-QqQMS and from 0.002 to 0.05 mg Kg^-1 for UHPLC-QqQMS).¹

“This approach,” write the authors of the study,¹ “utilizes a simple extraction with magnesium sulfate and ethyl acetate, thereby minimizing chemical usage and streamlining the extraction process by reducing the number of steps involved.’

Analysis of 20 samples revealed the presence of 23 pesticides, five of which exceeded MRLs. Risk assessment showed that parathion-methyl poses unacceptable chronic and acute risks (exceedance up to 234 % and 193 % respectively), especially for children under <10 years old and toddlers due to their high consumption and low body weight.¹

In the minds of the authors of the study,¹ their findings highlight “the need for stricter monitoring and regulatory measures to minimize pesticide exposure to widely consumed fruits.”

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References

1. Rinaldi, G.; Donnarumma, D.; Ferracane, A. et al. Multiresidual Analysis of Pesticides in White Table Grapes Using Hyphenated Chromatographic Techniques: Compliance and Risk Assessment. J Chromatogr A 2026, 11, 466799. DOI: 10.1016/j.chroma.2026.466799
2. Naushad, K.; Shah, F.; Mahnoor, N. et al. Grape Production: Critical Review in the World. SSRN Electron. J. 2020. DOI: 10.2139/ssrn.3595842
3. Yang, J.; Xiao. Y. Y. Grape Phytochemicals and Associated Health Benefits. Crit. Rev. Food Sci. Nutr. 2013, 53, 1202-1225. DOI: 10.1080/10408398.2012.692408
4. Crops and Livestock Products. Food and Agriculture Organization of the United Nations website. https://www.fao.org/faostat/en/#data/QCL, 2022 (accessed 2024-11-01).
5. Seccia, A.; Viscecchia, R.; Nardone, G. Table Grapes as Functional Food: Consumer Preferences for Health and Environmental Attributes. BioConf2019, 15, 03011. DOI: 10.1051/bioconf/20191503011
6. Sinha, N.; Rao, M. V. V.; Vasudev, K. et al. A Liquid Chromatography Mass Spectrometry-Based Method to Measure Organophosphorous Insecticide, Herbicide, and Non-Organophosphorous Pesticide in Grape and Apple Samples. Food Control2012, 25, 636-646. DOI: 10.1016/j.foodcont.2011.11.031
7. Venkateswarlu, P.; Kurakalva, R. M.; Kumar, C. H. R. et al. Monitoring of Multi-Class Pesticide Residues in Fresh Grape Samples using Liquid Chromatography with Electrospray Tandem Mass Spectrometry. Food Chem.2007, 105, 1760-1766. DOI: 10.1016/j.foodchem.2007.04.074
8. European Commission, Commission Recommendation of 3 March 1999 Concerning a Coordinated Community Monitoring Programme for 1999 to Ensure Compliance with Maximum Levels of Pesticide Residues in and on Cereals and Certain Products of Plant Origin, Including Fruit and Vegetables; 1999.
9. European Commission, Commission Implementing Regulation (EU) 2021/601 of 13 April 2021 Concerning a Coordinated Multiannual Control Programme of the Union for 2022, 2023 and 2024 to Ensure Compliance with Maximum Residue Levels of Pesticides and to Assess the Consumer Exposure to Pesticide Residues in and on Food of Plant and Animal Origin; 2021.