Determination and Dissipation of Fipronil and Its Metabolites in Peanut and Soil

Abstract

In this study, a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method was established for the extraction and cleanup of fipronil and its three metabolites (fipronil solfone, sulfide, and desulfinyl) in peanut kernel, shell, straw, seedling, and soil samples, and liquid chromatography-tandem mass spectrometry (LC-MS/MS) was used for analysis. The average recoveries were 66-116% at the level of 0.001-0.1 mg/kg with the RSD <19%, and the limit of detection was 0.3 ng/g for all matrices. The dissipation experiment results demonstrated that fipronil dissipated more rapidly in peanut seedling than in soil, with half-lives of <1 day in peanut seedling and 32-57 days in soil depending on the soil pH. The final residues at harvest of peanut kernels were all below 0.02 mg/kg, whereas in peanut shell and straw, the total highest residues were 0.99 and 0.30 mg/kg, respectively. Fipronil-desulfinyl and fipronil-sulfone were the highest residue metabolites in peanut plant (seedling and straw) and soil samples, respectively.

Residue analysis and persistence evaluation of fipronil and its metabolites in cotton using high-performance liquid chromatography-tandem mass spectrometry

“…GC combined with ECD, MS detectors [13, 18, 19] and LC-MS/MS [6, 20] presented a good response for fipronil and its metabolites in various matrices. However, UPLC-MS/MS provided higher sensitivity and selectivity of detection and shorter chromatography run-times than conventional GC or HPLC-MS techniques.…”

“…Dutta et al [24] observed that fipronil was degraded to sulfone and desulfinyl in cabbage, and the amount of fipronil sulfone residue was greater than desulfinyl. However, Bhardwaj et al [3] and Li et al [6] studied the dissipation of fipronil on cabbage and peanut seedlings, respectively, and found that desulfinyl was the main metabolite, followed by sulfone.…”

“…Moreover, fipronil is degraded by reduction, oxidation and photolysis to produce a variety of metabolites. The degradation products (metabolites) of fipronil are more toxic than the parent compound [6]. Desulfinyl (MB46513) was found to be a product of photolysis [7] and has a higher acute toxicity to mammals than fipronil itself by a factor of 10 (Pesticide Action Network-UK (PAN), 2000).…”

“…Samples were extracted with acetonitrile, followed by cleanup with dispersive SPE and analysis by mass spectrometry (MS). QuEChERS extraction followed by mass spectrometry analysis (LC-MS/MS or GC-MS) has been successfully used for the determination of fipronil and its metabolites in vegetables and fruit, corn, sugarcane juice, jiggery, peanut, and okra [6, 13–16]. …”

Rapid and sensitive detection of fipronil and its metabolites in edible oils by solid‐phase extraction based on humic acid bonded silica combined with gas chromatography with electron capture detection

“…Earlier, various methods, like GC with electron capture detection (ECD) and MS, HPLC-MS have been reported for the analysis of fipronil and its metabolites in different matrices, such as maize [5,7], peanut [2], soil [8,9], vegetables and fruits [1,4,[10][11][12], rice [13], honey [14][15][16], pollen [17,18], sugar [6], and plasma [19,20]. However, earlier studies did not focus on development of a specific method for the analysis of fipronil and its metabolites in edible oils.…”