Development and Validation of an Analytical Method for the Determination of Fipronil and its Degradation Products in 28 Organic and Regular Honey Samples by GC-ECD

Recently, there has been a worldwide problem of increased bee mortality (Colony Collapse Disorder) and the intensive use of pesticides is suspected as one of the causes. Honey samples are one of many indicators to assess bee exposure to pesticides. In this work, a method for the simultaneous analysis of the pesticide Fipronil and its degradation products in honey samples by gas chromatography with electron capture detector (GC-ECD) is presented and validated. The extraction procedure was investigated using C18-SPE with different solvents and methanol showed the best performance. The analytical quantification was performed by internal standard matrix-matched calibration, which resulted in analytical curves presenting correlation coefficients higher than 0.99. The proposed method was validated with good results, such as recoveries around 70 - 99%, limits of detection and quantification bellow 0.014 and 0.072 μg mL-1, respectively, and relative standard deviations below 7%. The method is simple, effective and was successfully applied to 28 commercial honey samples, regular and organic, from different floral sources. The results showed the presence of fipronil desulfinyl, the main degradation product of fipronil, in some samples, even among the organic ones.