Determination of nine pyrethroid insecticides by high-performance liquid chromatography with post-column photoderivatization and detection based on acetonitrile chemiluminescence

An HPLC method was developed to determine pyrethroids, including fenpropathrin, beta-cyfluthrin, lambda-cyhalothrin, deltamethrin, fenvalerate, permethrin, acrinathrin, tau-fluvalinate, and bifenthrin, by coupling HPLC, post-column irradiation with UV light and chemiluminescence detection of the resulting photoproducts. It is based on the observation that photolyzed pyrethroids take part in a chemiluminescent reaction in presence of K3Fe(CN)6 and NaOH, whose signal increases with the percentage of acetonitrile in the reaction medium. As the yield of the photoderivatization process and the chemiluminescent signals depend on the percentage of acetonitrile, the chromatographic column (a Gemini C18, Phenomenex 150 mm x 4.6 mm, 5 microm particle size) was chosen with the aim of using high percentages of this organic solvent in the mobile phase. Previous studies showed that the rate of the chemiluminescent reaction was very fast. Therefore, a modification was carried out in the detector in order to mix the analytes and reactives as near as possible to the measure cell. The optimised method was validated with respect to linearity, precision, limits of detection and quantification accuracy. Under the optimised conditions, linear working range extends three orders of magnitude with the relative standard deviation on intra-day precision below 10% and detection limits between 0.013 and 0.049 microg mL(-1), according to the compound. The proposed method has been successfully applied to the determination of pyrethroids in tomato with good results.