Identification and Dissipation of Chlorpyrifos and Its Main Metabolite 3,5,6-TCP during Wheat Growth with UPLC-QTOF/MS
Abstract
:1. Introduction
2. Materials and Methods
2.1. Reagents and Chemicals
2.2. Field Experiment Design
2.3. Sample Treatment
2.4. Instrumentation and Conditions
2.5. Method Validation
2.6. Statistical Analysis
3. Results and Discussion
3.1. Identification and Confirmation of Chlorpyrifos and Its Metabolites with UPLC-QTOF/MS
3.2. Method Validation for Chlorpyrifos and 3,5,6-TCP in Different Parts of Wheat
3.3. Dynamic Distribution of Chlorpyrifos in Different Parts of Wheat
3.4. Metabolic Kinetics of 3,5,6-TCP in Different Parts of Wheat
4. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
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Compound | Retention Time (min) | Formula | Observed Neutral Mass (Da) | Fragments | Adducts |
---|---|---|---|---|---|
Chlorpyrifos 3,5,6-TCP | 11.20 6.00 | C9H11Cl3NO3PS C5H2 Cl3NO | 349.9335 197.9268 | 311.2577 197.9273 96.9505 184.0724 116.0693 70.0646 | +H, +Na +H |
Compound | Formula | Exact Mass (Da) |
---|---|---|
3,5,6-TCP | C5H2Cl3NO | 198.4345 |
DEP | C4H11O4P | 154.1015 |
DETP | C4H11O3PS | 170.1671 |
CPO | C9H11Cl3NO4P | 332.9491 |
Compound | Matrix | R2 | Average Recovery and Standard Deviations (%) | LOD (µg/kg) | LOQ (µg/kg) | ||||
---|---|---|---|---|---|---|---|---|---|
Spiking Level (µg/kg) | |||||||||
20 | 50 | 100 | 200 | 500 | |||||
Chlorpyrifos | Wheatear | 0.9995 | 72.00 ± 2.18 | 71.33 ± 6.43 | 72.67 ± 7.57 | 82.83 ± 1.76 | 102.13 ± 3.35 | 0.38 | 1.30 |
Leaf | 0.9974 | 76.67 ± 5.77 | 83.33 ± 5.03 | 85.00 ± 2.00 | 85.50 ± 2.78 | 76.73 ± 4.27 | 0.85 | 2.70 | |
Stem | 0.9983 | 77.00 ± 3.29 | 78.46 ± 5.87 | 79.16 ± 7.22 | 85.45 ± 2.77 | 89.53 ± 4.88 | 0.70 | 2.20 | |
3, 5, 6-TCP | Wheatear | 0.9977 | 66.33 ± 6.24 | 70.01 ± 7.35 | 72.37 ± 8.35 | 83.57 ± 7.37 | 83.36 ± 8.99 | 2.90 | 11.00 |
Leaf | 0.9958 | 65.79 ± 5.34 | 63.38 ± 4.26 | 69.24 ± 6.38 | 72.43 ± 8.46 | 77.84 ± 6.59 | 4.50 | 14.00 | |
Stem | 0.9983 | 67.86 ± 5.76 | 71.47 ± 7.58 | 73.15 ± 5.37 | 81.38 ± 3.58 | 87.67 ± 5.68 | 4.25 | 13.50 |
Matrix | Time | Treatment | First-Order Kinetic Equation | C0 (mg/kg) | R2 | K (1/d) | t1/2 (d) |
---|---|---|---|---|---|---|---|
Wheatear | 2017 | 1× | Ct = 2.4668 e−0.2765t | 2.4668 | 0.9201 | 0.2765 | 2.51 |
2× | Ct = 4.5245 e−0.2609t | 4.5245 | 0.9638 | 0.2609 | 2.66 | ||
5× | Ct = 12.3650 e−0.2510t | 12.3650 | 0.9653 | 0.2510 | 2.76 | ||
10× | Ct = 24.3582 e−0.2080t | 24.3582 | 0.9265 | 0.2080 | 3.33 | ||
2018 | 1× | Ct = 2.4479 e−0.1921t | 2.4479 | 0.9693 | 0.1921 | 3.61 | |
2× | Ct = 2.9560 e−0.1653t | 2.9560 | 0.8646 | 0.1653 | 4.19 | ||
5× | Ct = 9.3164 e−0.1775t | 9.3164 | 0.8839 | 0.1775 | 3.90 | ||
10× | Ct = 34.7860 e−0.1562t | 34.7860 | 0.9595 | 0.1562 | 4.44 | ||
Leaf | 2017 | 1× | Ct = 7.6341 e−0.2199t | 7.6341 | 0.9771 | 0.2199 | 3.15 |
2× | Ct = 10.8377 e−0.1580t | 10.8377 | 0.9726 | 0.1580 | 4.39 | ||
5× | Ct = 32.4195 e−0.1954t | 32.4195 | 0.9381 | 0.1954 | 3.55 | ||
10× | Ct = 56.8813 e−0.1494t | 56.8813 | 0.9898 | 0.1494 | 4.64 | ||
2018 | 1× | Ct = 8.6738 e−0.2117t | 8.6738 | 0.9863 | 0.2117 | 3.27 | |
2× | Ct = 10.5375 e−0.1516t | 10.5375 | 0.9778 | 0.1516 | 4.57 | ||
5× | Ct = 25.7491 e−0.1512t | 25.7491 | 0.9909 | 0.1512 | 4.58 | ||
10× | Ct = 62.3189 e−0.1372t | 62.3189 | 0.9919 | 0.1372 | 5.05 | ||
Stem | 2017 | 1× | Ct = 1.0919 e−0.2687t | 1.0919 | 0.8979 | 0.2687 | 2.58 |
2× | Ct = 1.8643 e−0.2954t | 1.8643 | 0.9253 | 0.2954 | 2.35 | ||
5× | Ct = 6.8317 e−0.3142t | 6.8317 | 0.9685 | 0.3142 | 2.21 | ||
10× | Ct = 27.7730 e−0.2979t | 27.7730 | 0.9742 | 0.2979 | 2.33 | ||
2018 | 1× | Ct = 1.8867 e−0.2950t | 1.8867 | 0.9893 | 0.2950 | 2.35 | |
2× | Ct = 2.3523 e−0.2311t | 2.3523 | 0.9799 | 0.2311 | 3.00 | ||
5× | Ct = 8.0059 e−0.2213t | 8.0059 | 0.9843 | 0.2213 | 3.13 | ||
10× | Ct = 20.6520 e−0.2002t | 20.6520 | 0.9923 | 0.2002 | 3.46 |
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Yu, L.; Li, J.; Feng, M.; Tang, Q.; Jiang, Z.; Chen, H.; Shan, T.; Li, J. Identification and Dissipation of Chlorpyrifos and Its Main Metabolite 3,5,6-TCP during Wheat Growth with UPLC-QTOF/MS. Metabolites 2022, 12, 1162. https://doi.org/10.3390/metabo12121162
Yu L, Li J, Feng M, Tang Q, Jiang Z, Chen H, Shan T, Li J. Identification and Dissipation of Chlorpyrifos and Its Main Metabolite 3,5,6-TCP during Wheat Growth with UPLC-QTOF/MS. Metabolites. 2022; 12(12):1162. https://doi.org/10.3390/metabo12121162
Chicago/Turabian StyleYu, Lili, Jia Li, Meiqin Feng, Qian Tang, Zejun Jiang, Hui Chen, Tingting Shan, and Junhui Li. 2022. "Identification and Dissipation of Chlorpyrifos and Its Main Metabolite 3,5,6-TCP during Wheat Growth with UPLC-QTOF/MS" Metabolites 12, no. 12: 1162. https://doi.org/10.3390/metabo12121162