An improved extraction method of rapeseed oil sample preparation for the subsequent determination in it of azole class fungicides by gas chromatography

•The distribution of 19 azole class pesticides in different systems has been studied.•Replacement of water by organic solvents results in sharp log P values falling.•The acidification of acetonitrile causes a drop of D values up to-2000 times.•Conditions of pesticides extraction from rapeseed oil have been chosen.•The improved method of pesticides determination in rapeseed oil has been developed.

The distribution of 19 azole class pesticides in hexane/aqueous–organic mixtures systems and rapeseed oil (or oil solution in hexane)/organic solvents has been studied at 20 ± 1 °C. The distribution constants (P) and coefficients (D) between hydrocarbon and polar phase are calculated. It is found that all the studied pesticides are hydrophobic, i.e., in hexane–water system log P ≫ 0. Replacement of water by organic solvents results in sharp log P falling, and their values become negative. It is revealed that solutions of strong inorganic acids in anhydrous acetonitrile extract azole class pesticides from hexane and vegetable oils most fully and selectively. In particular, the acidification of acetonitrile causes a drop of D values in 50–2000 times for the majority of the studied pesticides. This phenomenon was used for the development of the improved technique for the quantitative analysis of a widely used azole class pesticides, which can be presented at trace levels in rapeseed oil. The proposed methodology is based on dissociation extraction (DE) of azoles using perchloric acid in anhydrous acetonitrile, with following clean-up of acetonitrile extract from organic impurities by hexane and aqueous solution of dipotassium hydrogen orthophosphate, and final GC–ECD (gas chromatography with electron capture detection) determination of azole fungicides. The values of obtained recoveries were between 85% and 115% with RSD values below 10%. The obtained limits of quantitation, ranged from 3.0 to 300 μg kg−1, are below the maximum residue levels (MRLs) set by the European Union for the majority of pesticides. The developed method was successfully applied to different rapeseed oil samples.

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