The global application of neonicotinoids (NEOs) has precipitated pervasive contamination of agricultural matrices, with China’s staple crop lands representing critical exposure hotspots. The occurrence and ecological risks of ten NEOs in the field soils of three major crops (i.e., rice, wheat and corn) in China were investigated in the present study. Employing an optimized UPLC-MS/MS method (LOQ = 0.01–1.7 ng/g, RSD < 12.21%), ten NEOs across 69 representative field soils (rice: 23, corn: 18, wheat: 28) were quantified. It was found that the detection frequency (DF) of the NEOs was 100% in the soil. The DFs of NEOs in the soil followed the rule: imidacloprid (IMI, 100%) > thiamethoxam (TMX, 88.4%) > clothianidin (CLO, 87.0%) > acetamiprid (ACE, 46.4%) > dinotefuran (DIN, 7.2%) > nitenpyram (NIT, 1.4%). Mean total detected NEOs concentrations exhibited crop-dependent type: wheat (1.77–214.55 ng/g) > corn (0.79–97.53 ng/g) > rice (0.75–72.97 ng/g). The IMI, CLO and TMX triad constituted over 90% of the total contribution of detected NEOs. In addition, CLO and TMX in the rice soils, IMI, CLO and TMX in the corn soils and IMI, CLO and TMX in the wheat soils had medium ecological risks. Therefore, it is particularly important for agricultural ecological protection to strengthen monitoring and take effective measures to protect agricultural ecology.
This study addresses the absence of maximum residue limits (MRLs) for tebuconazole and trifloxystrobin in edible rose petals in China by systematically evaluating the residue behavior and dietary exposure risks of these fungicides. An analytical method based on QuEChERS sample preparation coupled with UPLC–MS/MS was developed for the simultaneous determination of tebuconazole, trifloxystrobin, and its metabolite CGA321113 in fresh and dried rose petals. Field trials under the highest application conditions (184 g a.i./hm2, applied twice) were conducted to investigate residue dissipation dynamics, storage stability, processing concentration effects, and transfer behavior during brewing. Results indicated that the target compounds remained stable in rose petals for 12 months at –20 °C ± 2 °C. The drying process significantly concentrated residues due to the hydrophobic nature of the compounds, with enrichment factors ranging from 3.0 to 3.9. Brewing tests further confirmed low transfer rates of tebuconazole, trifloxystrobin, and CGA321113 into the infusion, consistent with their low water solubility and high log Kow values. Residue dissipation followed first-order kinetics, with half-lives of 1.9–2.9 days for tebuconazole and 1.2–2.7 days for trifloxystrobin. Dietary risk assessment showed an acceptable risk for trifloxystrobin (RQ = 22.7%) but a high risk for tebuconazole (RQ = 175.1%). It is recommended to set the MRL for both tebuconazole and trifloxystrobin in edible roses at 15.0 mg/kg. This standard ensures consumer safety while accommodating agricultural needs and aligns with international regulations. For the high-risk pesticide tebuconazole, measures such as optimizing application strategies and promoting integrated management should be implemented to mitigate residue risks.
Fluopyram is a widely used nematicide with a growing number of varieties registered both domestically and overseas. However, its absorption, transportation, and metabolism behaviors in plants have not been fully elucidated, thus hindering comprehensive assessment of the risks associated with its use. This study investigated the plant uptake, distribution, and metabolic behavior of fluopyram through 168 h hydroponic experiments. Fluopyram was easily absorbed by the roots of the tested crops, and almost 90.5% and 70.9% of fluopyram was transformed in cucumber and tomato, respectively, leading to the tentative identification of 16 metabolites using Quadrupole Time-of-Flight mass spectrometry. The metabolic reactions involved were hydroxylation, hydroxylation–dechlorination, dehydrogenation, dechlorination, and glucuronidation conjugation. Most metabolites were detected in leaves, suggesting that they have considerable potential to accumulate in the upper parts, even the edible parts. Model prediction indicated that fluopyram and high-toxicity metabolites (M430A, M412C) pose significant risks to aquatic ecosystems across trophic levels, while M574A and M574B showed reduced toxicity due to glucuronidation conjugation. These findings deepen our understanding of the behavioral characteristics of fluopyram within plants, and serve as an important reference for comprehensively assessing its risks.
A sensitive and reliable analytical method based on ultra-high performance liquid chromatography–tandem mass spectrometry (UHPLC-MS/MS) was developed and validated for the simultaneous determination of bifenazate, cyflumetofen, etoxazole, and abamectin B1a in citrus leaves, whole fruit, peel, and pulp. The method exhibited good linearity (0.0001–0.1 mg/L, R2 > 0.999), a limit of quantification (LOQ) of 0.001 mg/kg, mean recoveries of 77.3–110.5%, and relative standard deviations of 3.1–19.8%. This method was applied to compare the dissipation dynamics and dietary risks of the four acaricides following knapsack spraying versus unmanned aerial vehicle (UAV) spraying. Compared to knapsack application, UAV spraying resulted in 2.2- to 4.1-fold higher initial deposits on citrus leaves and shorter dissipation half-lives. After 21 days, all terminal residues were below the maximum residue limits (MRLs) established by China, the Codex Alimentarius Commission, the United States, Australia, Korea, the European Union, and Japan. Chronic dietary risk assessment revealed risk quotients below 1% for cyflumetofen and etoxazole, and approximately 47% for bifenazate and 93% for abamectin B1a. Although all values were below the acceptable threshold of 100%, the risk for abamectin B1a approached this limit, indicating that its cumulative dietary risk should not be overlooked. This study provides scientific evidence for residue monitoring of acaricides in citrus and for the safety evaluation of UAV-based pesticide application.