Method development and determination of Neonicotinoid and carbamate pesticide residues in vegetable and fruit matrix by HPLC-MS

In this work a chemometric approach to positive electrospray ionization (ESI) optimization for the simultaneous determination of the cyromazine, carbendazim, methomyl, imidacloprid and thiophanate methyl in vegetable samples by liquid chromatography- mass spectrometry (LC-MS) has been developed. The effects of the operational parameters such as mobile phase modifier concentrations, mobile phase flow rate, column temperature, drying gas flow rate, sampling speed, percentage of formic acid/water at first stage and percentage of formic acid/water at second stage were evaluated by the 2^8-3 fractional factorial experimental design using Design Expert software 7.0. The best experimental conditions observed were 0.06% formic acid/water and 0.13% formic acid/acetonitril; 0.13 mL/min of mobile phase; 28°C column temperature; 13.6 L/min drying gas flow rate; 11 µL/sec sampling speed; and 77% v/v of 0.06% formic acid/water at first stage, 5% v/v of 0.06% formic acid/water at second stage. Throughout the last decade many official multiresidue methods were implemented for pesticide analysis. In this study, the citrate-buffered of QuEChERS was tested. Primary secondary amine and C18 were studied as the extra sorbent for cleanup step. The matrices were spinach, onion, egg plant, paprika, ginger, okras and mango. Recoveries ranged from 82.0-89.0% except for cyromazine that got 35.1% to 37.2% of recovery values. The method detection limit (MDL) ranged from 0.01-0.03 mg/kg. The values of intra-day and inter-day precision and accuracy were ≤ 9.8 and ≤ 10.3, respectively. These values were within the acceptable ranges. Therefore, it was concluded that the method could produce reproducible and accurate results. (author)