An analytical method simultaneously detecting pesticide and its metabolites, especially with higher toxicity, was urgently needed for supervision and safety evaluation of agricultural products. In the present study, a modified QuEChERS method coupled with a ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) for simultaneous determination of tolfenpyrad (TFP) and its metabolites in tea matrices (fresh tea shoots, green tea, black tea, green tea infusion and black tea infusion) was established. The method validation showed good linearity (correlation coefficients ≥ 0.9945), accuracy (recoveries in 75.38–109.90%), sensitivity (limits of quantification ≤ 0.05 mg kg−1), and precision (relative standard deviations ≤ 19.09%). The established method was then applied to detect 40 market samples, resulting in 60.0% positive rate of TFP, besides, two metabolites including PT-CA, which is more toxic than the parent TFP, and PT-OH were also detected in the samples with high TFP residue (≥0.048 mg kg−1). The method established in the present work was thus of significant importance in comprehensive monitoring and of TFP in tea products.
Residue dissipation and risk assessment of difenoconazole and its metabolite difenoconazole-alcohol during tea growing, processing, and brewing was first investigated by ultra-performance liquid chromatography–tandem mass spectrometry (UPLC–MS/MS). The limits of quantification for both difenoconazole and difenoconazole-alcohol were 0.001 mg/kg in fresh tea leaves and tea, and 0.0002 mg/L in tea infusion. In field trials, the dissipation half-lives of difenoconazole in fresh tea leaves was 1.77 days. After spraying, the residues of difenoconazole-alcohol increased and then gradually dissipated like difenoconazole. After 14 days, the dissipation rates of difenoconazole and difenoconazole-alcohol reached 99%. When fresh tea leaves were harvested on different days, the total processing factors (PFs) of difenoconazole and difenoconazole-alcohol for green tea were 0.86–1.05 and 0.78–0.85, respectively, while the total PFs for black tea were 0.83–1.13 and 0.82–1.66, respectively. Metabolism of difenoconazole was accelerated during tea processing. When brewing black tea, the leaching rates (LRs) of difenoconazole and difenoconazole-alcohol were 8.4–17.9% and 31.8–38.9%, respectively, while when brewing green tea, the LRs were 15.4–23.5% and 30.4–50.6%, respectively. The LRs of difenoconazole and difenoconazole-alcohol in black tea were higher than those in green tea. The potential threat to human health for dietary intake of difenoconazole and difenoconazole-alcohol residues from tea consumption is negligible. However, the dietary risk of difenoconazole in fruits and vegetables that are essential for daily diets is concerning, with a risk probability of 158%.