| Literature DB >> 36080310 |
Yiyue Yang1, Ming Yang1, Tong Zhao2, Lingyi Pan1, Li Jia1, Lufei Zheng1.
Abstract
This study describes the variation in residue behavior of fluopyram in soil, carrot root, and carrot leaf samples after the application of fluopyram (41.7% suspension, Bayer) by foliar spray or root irrigation at the standard of 250.00 g active ingredient per hectare (a.i./ha) and double-dose treatment (500.00 g a.i./ha). Fluopyram and its metabolite fluopyram-benzamide were extracted and cleaned up using the QuEChERS method and subsequently quantified with LC-QQQ-MS/MS. The LOD and LOQ of the developed method were in the range of 0.05-2.65 ug/kg and 0.16-8.82 ug/kg, respectively. After root irrigation, the final residues detected in edible parts were 0.60 and 1.80 mg/kg, respectively, when 250.00 and 500.00 g a.i./ha were applied, which is much higher than the maximum residue limit in China (0.40 mg/kg). In contrast, after spray application, most of the fluopyram dissipated from the surface of carrot leaves, and the final residues in carrot roots were both only 0.05 mg/kg. Dietary risk assessments revealed a 23-40% risk quotient for the root irrigation method, which was higher than that for the foliar spray method (8-14%). This is the first report comparing the residue behavior of fluopyram applied by root irrigation and foliar spray. This study demonstrates the difference in risk associated with the two application methods and can serve as a reference for the safe application of fluopyram.Entities:
Keywords: LC-QQQ-MS/MS; carrot; fluopyram; pesticide residue analysis; pesticide risk assessment
Mesh:
Substances:
Year: 2022 PMID: 36080310 PMCID: PMC9457905 DOI: 10.3390/molecules27175544
Source DB: PubMed Journal: Molecules ISSN: 1420-3049 Impact factor: 4.927
Figure 1(a) The chemical structure of fluopyram; (b) The chemical structure of fluopyram-benzamide.
Recovery and precision of fluopyram and fluopyram benzamide from carrots and soils measured by LC-QQQ-MS/MS.
| Sample | Spiking Concentration (mg/kg) | Percent Recovery ± SD (%) | RSD (%) |
|---|---|---|---|
| Fluopyram | |||
| carrot root | 0.01 | 106 ± 5 | 5 |
| 0.5 | 83 ± 9 | 10 | |
| 1 | 102 ± 3 | 3 | |
| carrot leaf | 0.01 | 105 ± 16 | 15 |
| 0.5 | 84 ± 2 | 3 | |
| 1 | 83 ± 4 | 5 | |
| soil | 0.01 | 96 ± 2 | 3 |
| 0.5 | 98 ± 10 | 10 | |
| 1 | 102 ± 4 | 4 | |
| Fluopyram-benzamide | |||
| carrot root | 0.01 | 116 ± 3 | 3 |
| 0.5 | 95.9 ± 0.4 | 0.4 | |
| 1 | 100 ± 4 | 4 | |
| carrot leaf | 0.01 | 115 ± 4 | 4 |
| 0.5 | 89 ± 4 | 4 | |
| 1 | 89 ± 4 | 5 | |
| soil | 0.01 | 80 ± 1 | 1 |
| 0.5 | 93 ± 8 | 9 | |
| 1 | 98 ± 4 | 4 | |
Figure 2Fluopyram residue concentration in carrot roots expressed as the average of three biological replicates ± standard deviation.
Residues of fluopyram in the edible part (carrot root).
| Days after Treatment | Residues ± SD (mg/kg) | |||||
|---|---|---|---|---|---|---|
| Untreated | Root Irrigation | Foliar Spray | ||||
| Treatment at | Treatment at | Treatment at | Treatment at | |||
| 0 | (10 min) | ND | 0.26 ± 0.01 | 0.56 ± 0.03 | 0.13 ± 0.01 | 0.213 ± 0.003 |
| (2 h) | ND | 0.33 ± 0.05 | 0.75 ± 0.08 | 0.14 ± 0.01 | 0.24 ± 0.01 | |
| (6 h) | ND | 0.170 ± 0.004 | 0.30 ± 0.05 | 0.07 ± 0.03 | 0.38 ± 0.01 | |
| 1 | ND | 0.41 ± 0.02 | 0.39 ± 0.01 | 0.23 ± 0.01 | 0.47 ± 0.04 | |
| 2 | ND | 0.40 ± 0.02 | 0.67 ± 0.05 | 0.16 ± 0.02 | 0.36 ± 0.03 | |
| 3 | ND | 0.37 ± 0.04 | 0.88 ± 0.03 | 0.19 ± 0.01 | 0.54 ± 0.03 | |
| 5 | ND | 0.43 ± 0.01 | 0.62 ± 0.09 | 0.16 ± 0.02 | 0.27 ± 0.03 | |
| 7 | ND | 0.16 ± 0.02 | 1.01 ± 0.10 | 0.17 ± 0.03 | 0.12 ± 0.02 | |
| 9 | ND | 0.64 ± 0.06 | 0.84 ± 0.05 | 0.12 ± 0.01 | 0.11 ± 0.02 | |
| 11 | ND | 0.32 ± 0.03 | 0.99 ± 0.01 | 0.10 ± 0.03 | 0.06 ± 0.01 | |
| 15 | ND | 0.47 ± 0.04 | 0.67 ± 0.06 | 0.118 ± 0.002 | 0.09 ± 0.01 | |
| 21 | ND | 0.30 ± 0.02 | 1.20 ± 0.04 | 0.06 ± 0.02 | 0.22 ± 0.02 | |
| 28 | ND | 0.60 ± 0.05 | 1.80 ± 0.04 | 0.05 ± 0.01 | 0.05 ± 0.01 | |
ND = not detected.
Residues of fluopyram in the carrot leaf.
| Days after | Residues ± SD (mg/kg) | |||||
|---|---|---|---|---|---|---|
| Untreated | Root Irrigation | Foliar Spray | ||||
| Treatment at | Treatment at | Treatment at | Treatment at | |||
| 0 | (10 min) | ND | 1.64 ± 0.05 | 3.37 ± 0.42 | 12.62 ± 0.78 | 23.55 ± 0.08 |
| (2 h) | ND | 1.31 ± 0.11 | 2.80 ± 0.06 | 13.52 ± 0.22 | 25.29 ± 0.18 | |
| (6 h) | ND | 0.58 ± 0.03 | 1.25 ± 0.06 | 14.15 ± 0.18 | 27.48 ± 0.28 | |
| 1 | ND | 0.51 ± 0.01 | 1.26 ± 0.14 | 11.45 ± 0.35 | 17.77 ± 0.14 | |
| 2 | ND | 0.64 ± 0.22 | 1.28 ± 0.07 | 8.63 ± 0.27 | 17.53 ± 0.51 | |
| 3 | ND | 1.45 ± 0.12 | 2.37 ± 0.18 | 9.32 ± 0.55 | 15.91 ± 0.55 | |
| 5 | ND | 0.41 ± 0.01 | 1.03 ± 0.03 | 5.82 ± 0.26 | 11.72 ± 0.27 | |
| 7 | ND | 0.31 ± 0.02 | 0.77 ± 0.08 | 1.37 ± 0.04 | 1.70 ± 0.03 | |
| 9 | ND | 0.37 ± 0.02 | 0.91 ± 0.06 | 1.42 ± 0.08 | 1.76 ± 0.02 | |
| 11 | ND | 0.49 ± 0.01 | 0.68 ± 0.03 | 1.55 ± 0.04 | 1.44 ± 0.11 | |
| 15 | ND | 0.27 ± 0.01 | 0.73 ± 0.01 | 0.97 ± 0.21 | 1.26 ± 0.01 | |
| 21 | ND | 0.16 ± 0.01 | 0.50 ± 0.01 | 0.12 ± 0.04 | 1.47 ± 0.06 | |
| 28 | ND | 0.13 ± 0.01 | 0.53 ± 0.01 | 1.10 ± 0.03 | 1.44 ± 0.03 | |
ND = not detected.
Dynamic models of fluopyram in carrot samples from the two application methods.
| Application Method | Treatment Concentration | Matrix | Dynamic Equation | Half-Life (d) |
|---|---|---|---|---|
| Root irrigation | 250.00 g a.i./ha | carrot root | - | - |
| carrot leaf | Ct = 0.8736 e−0.076t | 9.1 | ||
| 500.00 g a.i./ha | carrot root | - | - | |
| carrot leaf | Ct = 1.6557 e−0.048t | 14.4 | ||
| Foliar spray | 250.00 g a.i./ha | carrot root | Ct = 0.1963 e−0.049t | 14.1 |
| carrot leaf | Ct = 9.108 e−0.108t | 6.4 | ||
| 500.00 g a.i./ha | carrot root | Ct = 0.3059 e−0.063t | 11 | |
| carrot leaf | Ct = 15.868 e−0.125t | 5.5 |
The dietary risk assessment of fluopyram in carrot samples.
| Age (Years) | Sex | Body Weight (kg) | Fi(g/d) | NEDI (mg/kg bw) | RQ (%) | ||
|---|---|---|---|---|---|---|---|
| Root Irrigation | Foliar Spray | Root Irrigation | Foliar Spray | ||||
| 2–7 | 17.9 | 194.8 | 0.07 | 0.025 | 40 | 14 | |
| 8–12 | 33.1 | 272.4 | 0.10 | 0.034 | 30 | 10 | |
| 13–19 | M | 56.4 | 396.7 | 0.15 | 0.050 | 26 | 9 |
| F | 50 | 317.9 | 0.12 | 0.040 | 23 | 8 | |
| 20–50 | M | 63 | 436.4 | 0.16 | 0.055 | 25 | 9 |
| F | 56 | 412.1 | 0.15 | 0.052 | 27 | 9 | |
| 51–65 | M | 65 | 477.9 | 0.18 | 0.060 | 27 | 9 |
| F | 58 | 447 | 0.16 | 0.056 | 28 | 10 | |
| >65 | M | 59.5 | 413.3 | 0.15 | 0.052 | 25 | 9 |
| F | 52 | 364.1 | 0.13 | 0.046 | 26 | 9 | |
M = male; F = female; Fi = the food consumption data of a certain agricultural product or food in China; NEDI = national estimated daily intake; RQ = risk quotient.
Multiple reaction monitoring (MRM) conditions.
| Name | Molecular Formula | Retention Time (min) | Precursor Ion | Product Ion | Collision Energy |
|---|---|---|---|---|---|
| Fluopyram | C16H11ClF6N2O | 3.3 | 397 | 207 | 25 |
| 173 | 25 | ||||
| Fluopyram- benzamide | C8H6ClF3NO | 1.3 | 190 | 170 | 10 |
| 130 | 25 |