Department of Chemistry, University of Cyprus, P.O. Box 20537, 1678 Nicosia, Cyprus; State General Laboratory, Pesticide Residues Laboratory, Nicosia, Cyprus.
State General Laboratory, Pesticide Residues Laboratory, Nicosia, Cyprus.
Food Chem. 2021 Oct 30;360:129964. doi: 10.1016/j.foodchem.2021.129964. Epub 2021 Apr 27.
A multi-residue method for the simultaneous analysis of a wide range of pesticides in raisins using liquid and gas chromatography-tandem mass spectrometry (LC-MS/MS and GC-MS/MS) has been validated. Pesticides are extracted from raisins with ethyl acetate, followed by centrifugation. The validation study was in accordance with DG SANTE guidelines. Validation experiments have been performed in both analytical instruments. A total number of 314 pesticides were spiked in raisins of organic farming at two spiking levels for GC-MS/MS (0.025 and 0.1 mg/kg), and at three spiking levels for LC-MS/MS (0.005, 0.05, and 0.1 mg/kg) with 6 replicates at each concentration. The scope of validation included linearity, limits of quantification (LOQ), accuracy, precision, and matrix effects (%) for each pesticide. The validated method was then applied for the analysis of 37 commercial raisin samples purchased from the market. For the evaluation of the results, processing factors (PFs) have been applied to derive the amount of residue in raisins, from the maximum residue levels (MRLs) of grapes, and which in this paper will be referred as to the MRL expressed in raisins. In all conventional samples, pesticides were detected at concentrations above the LOQ. In total, 55 different pesticides were detected. All conventional samples contained multiple pesticides ranging from 2 to 24. On the other hand, samples from organic farming were found to be free of the analysed pesticides. The 13.5% of the examined samples were considered as violations. The exposure assessment for the acute risk of the violating samples indicated that no potential risk derives from the detected and approved in the EU pesticides, while the detection of not approved pesticides in the EU, and the lack of toxicological reference values for certain pesticides raise concerns for the human health, especially for children. The results of the survey study indicate the need to include processed samples, and in particular dry fruits with a high consumption rate such as raisins, in the official controls of pesticide residues in food.
已验证了一种使用液质联用（LC-MS/MS）和气质联用（GC-MS/MS）同时分析葡萄干中多种农药残留的多残留方法。用乙酸乙酯从葡萄干中提取农药，然后离心。验证研究符合 DG SANTE 指南。在两种分析仪器中都进行了验证实验。在有机种植的葡萄干中，共添加了 314 种农药，在 GC-MS/MS 中添加了 2 个添加水平（0.025 和 0.1 mg/kg），在 LC-MS/MS 中添加了 3 个添加水平（0.005、0.05 和 0.1 mg/kg），每个浓度有 6 个重复。验证范围包括每个农药的线性、定量限（LOQ）、准确度、精密度和基质效应（%）。然后，该方法用于分析从市场购买的 37 个商业葡萄干样品。为了评估结果，已应用加工因子（PF）从葡萄的最大残留限量（MRL）中推导出葡萄干中的残留量，并在本文中称为以葡萄干表示的 MRL。在所有常规样品中，农药的浓度均高于 LOQ。共检测到 55 种不同的农药。所有常规样品均含有 2 至 24 种不同的农药。另一方面，有机种植的样品未检测到分析的农药。13.5%的检查样品被认为是违规的。对违规样品的急性风险进行的暴露评估表明，从检测到的和在欧盟批准的农药中没有潜在风险，而在欧盟检测到未经批准的农药，以及某些农药缺乏毒理学参考值，这对人类健康，特别是儿童健康构成了担忧。调查研究的结果表明，需要将加工样品，特别是高消费率的干水果，如葡萄干，纳入食品中农药残留的官方控制。
