Influence of the Soil Composition on the Determination of 2,4-D and Fipronil in Environmental Samples by SLE-LC-MS/MS

The main objective of this work was to develop and validate an analytical method using solid-liquid extraction and liquid chromatography coupled with mass spectrometry in tandem (LC-MS/MS) for the simultaneous determination of the herbicide 2-(2,4-dichlorophenoxy)acetic acid (2,4-D) and the insecticide fipronil and its degradation products, fipronil sulfone and fipronil sulfide in different types of soil from Brazil (Oxisol and Entisol). Solid-liquid extraction was performed in two cycles using 20 mL of dichloromethane per cycle and sonication. The extraction efficiency of 2,4-D was more influenced by soil composition than the other compounds. The limits of quantification of the method were between 0.015 and 0.75 mg kg^-1 and recovery values from 61 to 118%, with a maximum relative standard deviation (RSD) value of 4%. The method was further applied to over 500 real soil and sediment samples. 2,4-D and fipronil concentrations varied from 0.03 to 1145 µg kg^-1 and 1.1 to 282 µg kg^-1, respectively.

Keywords:
pesticides; soil; solid-liquid extraction; method validation