Rapid determination of residues of pesticides in honey by µGC-ECD and GC-MS/MS: Method validation and estimation of measurement uncertainty according to document No. SANCO/12571/2013

Abstract

A simple and straightforward method for simultaneous determination of residues of 13 pesticides in honey samples (acrinathrin, bifenthrin, bromopropylate, cyhalothrin-lambda, cypermethrin, chlorfenvinphos, chlorpyrifos, coumaphos, deltamethrin, fluvalinate-tau, malathion, permethrin and tetradifon) from different pesticide classes has been developed and validated. The analytical method provides dissolution of honey in water and an extraction of pesticide residues by n-Hexane followed by clean-up on a Florisil SPE column. The extract was evaporated and taken up by a solution of an injection internal standard (I-IS), ethion, and finally analyzed by capillary gas chromatography with electron capture detection (GC-µECD). Identification for qualitative purpose was conducted by gas chromatography with triple quadrupole mass spectrometer (GC-MS/MS). A matrix-matched calibration curve was performed for quantitative purposes by plotting the area ratio (analyte/I-IS) against concentration using a GC-µECD instrument. According to document No. SANCO/12571/2013, the method was validated by testing the following parameters: linearity, matrix effect, specificity, precision, trueness (bias) and measurement uncertainty. The analytical process was validated analyzing blank honey samples spiked at levels equal to and greater than 0.010 mg/kg (limit of quantification). All parameters were satisfactorily compared with the values established by document No. SANCO/12571/2013. The analytical performance was verified by participating in eight multi-residue proficiency tests organized by BIPEA, obtaining satisfactory z-scores in all 70 determinations. Measurement uncertainty was estimated according to the top-down approaches described in Appendix C of the SANCO document using the within-laboratory reproducibility relative standard deviation combined with laboratory bias using the proficiency test data.

Optimization of Method for Pesticide Detection in Honey by Using Liquid and Gas Chromatography Coupled with Mass Spectrometric Detection

“…The LOD and LOQ values for all the tested pesticides were 0.005 and 0.01 mg/kg, respectively [ 1 ]. Paoloni et al [ 40 ] used Florisil for sample cleanup after extraction with n-Hexane for determining 13 pesticides in honey using GC-MS/MS. The LOQ for all tested pesticides was 0.01 mg/kg, and the LOD was not provided [ 40 ].…”

“…Paoloni et al [40] used Florisil for sample cleanup after extraction with n-Hexane for determining 13 pesticides in honey using GC-MS/MS. The LOQ for all tested pesticides was 0.01 mg/kg, and the LOD was not provided [40].Česnik et al [31] used a GC-MS method for detecting 75 pesticides and an LC-MS/MS method for detecting 60 pesticides in honey after extraction with a mixture of petroleum ether and dichloromethane. The LOQ ranged from 0.01 to 0.05 mg/kg with the GC-MS method and from 0.003 to 0.01 mg/kg with the LC-MS/MS method [31].…”

Exploring the Potential of Microextraction in the Survey of Food Fruits and Vegetable Safety

“…The EC regulation 396/2005 provides a coherent system of setting MRLs for all food treated with pesticides [55]. Moreover, in the EU document SANCO12571/2013, the EC states the methods of sampling for pesticide residues [52,56,57]. The EFSA is also responsible for legislating and regulating food additives in the EU by working with regulatory bodies worldwide to refine methodologies and provide risk assessors to determine possible combined effects derived from multiple pesticide exposure through food [58].…”

Identification of cattle poisoning by Bifenthrin via earwax analysis by HS/GC–MS

“…One of the most used pyrethroids is bifenthrin, a nonalpha cyan type‐I pyrethroid insecticide applied worldwide against pests in the production of cereals, maize, fruits, vegetables and cotton (Wilkins, 2015). Bifenthrin is widely used owing to its insecticidal properties, low costs, low toxicity towards mammals and high biodegradability (Rehman et al, 2014; Saillenfait, Ndiaye, & Sabaté, 2015); nevertheless, this vast scale of utilization leads to residues being found in human feed, as already detected in eggs (Parente et al, 2017), milk (Oliveira et al, 2014), honey (Paoloni, Alunni, Pelliccia, & Pecorelli, 2016) and tea (le Zhao et al, 2014). In Brazil, bifenthrin use for agricultural purposes is allowed by the Ministry of Agriculture, Livestock, and Supply with the protocol number 01578899 (Ministério da Agricultura, Pecuária e Abasteciment, 2009).…”