Development of a fast analytical method for the individual determination of pyrethrins residues in fruits and vegetables by liquid chromatography-tandem mass spectrometry.

Pyrethrins are natural insecticides derived from chrysanthemum flowers containing a mixture of six components: pyrethrin I, cinerin I, jasmolin I, pyrethrin II, cinerin II, and jasmolin II. In this work, a rapid and sensitive LC-(ESI)-MS/MS method has been developed for the individual quantification and confirmation of pyrethrin residues in fruit and vegetable samples by monitoring two specific transitions for each pyrethrin component under Selected Reaction Monitoring (SRM) mode. Samples were extracted with acetone/water or acetone, depending on the sample type, and raw extracts were directly injected in the LC-MS/MS system. Method validation was carried out evaluating linearity, accuracy, precision, specificity, limit of quantification (LOQ) and limit of detection (LOD) in eight types of fruit and vegetable samples at 0.05mg/kg and 0.5mg/kg (referred to the sum of all pyrethrins). The method based on acetone/water (70:30) extraction led to satisfactory recoveries (70-110%) and good precision (below 14%) for all pyrethrin components in lettuce, pepper, strawberry and potato. The method based on acetone extraction allowed satisfactory recoveries for lettuce, cucumber, tomato and rice samples with recoveries between 71 and 107% and RSDs below 15%. For pistachio samples, satisfactory results were obtained only for some analytes and extracts were also injected using APCI interface, but the lower sensitivity achieved allowed only the validation at 0.5mg/kg. The analytical methodology developed was applied to the analysis of fruit and vegetable samples.