Simultaneous Enantiomeric Separation of Carfentrazone-Ethyl Herbicide and Its Hydrolysis Metabolite Carfentrazone by Cyclodextrin Electrokinetic Chromatography. Analysis of Agrochemical Products and a Degradation Study
Abstract
:1. Introduction
2. Results
2.1. Development of a Chiral CD-EKC Methodology for the Simultaneous Separation of Carfentrazone-Ethyl and Carfentrazone
2.2. Analytical Characteristics of the Developed Method
2.3. Determination of Carfentrazone-Ethyl in a Commercial Herbicide Formulation
2.4. Degradation of Carfentrazone-Ethyl in Sand and Soil Samples
3. Materials and Methods
3.1. Reagents and Samples
3.2. Apparatus
3.3. Preparation of Standards and Samples
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
Sample Availability
References
- Williams, A. Opportunities for Chiral Agrochemicals. Pestic. Sci. 1996, 46, 3–9. [Google Scholar] [CrossRef]
- Peter, J. Current Status of Chirality in Agrochemicals. Pest Manag. Sci. 2018, 74, 11. [Google Scholar]
- Zhang, Q.; Hua, X.; Shi, H.Y.; Liu, J.S.; Tian, M.M.; Wang, M.H. Enantioselective Bioactivity, Acute Toxicity and Dissipation in Vegetables of the Chiral Triazole Fungicide Flutriafol. J. Hazard. Mater. 2015, 284, 65–72. [Google Scholar] [CrossRef]
- Dong, M.; Ma, Y.; Liu, F.; Qian, C.; Han, L.; Jiang, S. Use of Multiwalled Carbon Nanotubes as a SPE Adsorbent for Analysis of Carfentrazone-Ethyl in Water. Chromatographia 2009, 69, 73–77. [Google Scholar] [CrossRef]
- Duan, J.; Sun, M.; Shen, Y.; Gao, B.; Zhang, Z.; Gao, T.; Wang, M. Enantioselective Acute Toxicity and Bioactivity of Carfentrazone-Ethyl Enantiomers. Bull. Environ. Contam. 2018, 101, 651–656. [Google Scholar] [CrossRef]
- Dayan, F.E.; Duke, S.O.; Weete, J.D.; Hancock, H.G. Selectivity and Mode of Action of Carfentrazone-Ethyl, a Novel Phenyl Triazolinone Herbicide. Pestic. Sci. 1997, 51, 65–73. [Google Scholar] [CrossRef]
- Koschnick, T.J.; Haller, W.T.; Chen, A.W. Carfentrazone-Ethyl Pond Dissipation and Efficacy on Floating Plants. J. Aquat. Plant Manag. 2004, 42, 103–108. [Google Scholar]
- Li, Y.; Dong, F.; Liu, X.; Xu, J.; Chen, W.; Cheng, L.; Ning, P.; Li, J.; Wang, Y.; Zheng, Y. Enantioselective Separation of the Carfentrazone-Ethyl Enantiomers in Soil, Water, and Wheat by HPLC. J. Sep. Sci. 2010, 33, 1973–1979. [Google Scholar] [CrossRef] [PubMed]
- Chai, T.; Yang, W.; Qiu, J.; Hou, S. Direct Enantioseparation of Nitrogen-Heterocyclic Pesticides on Cellulose-Based Chiral Column by High-Performance Liquid Chromatography. Chirality 2015, 27, 32–38. [Google Scholar] [CrossRef] [PubMed]
- Wang, P.; Jiang, S.; Liu, D.; Jia, G.; Wang, Q.; Wang, P.; Zhou, Z. Effect of Alcohols and Temperature on the Direct Chiral Resolutions of Fipronil, Isocarbophos and Carfentrazone-Ethyl. Biomed. Chromatogr. 2005, 19, 454–458. [Google Scholar] [CrossRef]
- Yang, W.; Qiu, J.; Chen, T.; Yang, S.; Hou, S. Direct Enantioseparation of Nitrogen-heterocyclic Pesticides on Amylose-tris-(5-chloro-2-methylphenylcarbamate) by Reversed-Phase High-Performance Liquid Chromatography. Chirality 2012, 24, 1031–1036. [Google Scholar] [CrossRef] [PubMed]
- Merino, M.E.D.; Lancioni, C.; Padró, J.M.; Castells, C.B. Chiral Separation of Several Pesticides on an Immobilized Amylose Tris(3-chloro-5-methylphenylcarbamate) Column Under Polar-Organic Conditions. Influence of Mobile Phase and Temperature on Enantioselectivity. J. Chromatogr. A 2020, 1624, 461240. [Google Scholar] [CrossRef] [PubMed]
- Merino, M.E.D.; Echevarría, R.N.; Lubomirsky, E.; Padró, J.M.; Castells, C.B. Enantioseparation of the Racemates of a Number of Pesticides on a Silica-Based Column with Immobilized Amylose Tris(3-chloro-5-methylphenylcarbamate). Microchem. J. 2019, 149, 103970. [Google Scholar] [CrossRef]
- Li, Y.; Dong, F.; Liu, X.; Xu, J.; Chen, X.; Han, Y.; Liang, X.; Zheng, Y. Development of a Multi-Residue Enantiomeric Analysis Method for 9 Pesticides in Soil and Water by Chiral Liquid Chromatography/Tandem Mass Spectrometr. J. Hazard. Mater. 2013, 250, 9–18. [Google Scholar] [CrossRef] [PubMed]
- Hellinghausen, G.; Readel, E.R.; Wahab, M.F.; Lee, J.T.; Lopez, D.A.; Weatherly, C.A.; Armstrong, D.W. Mass Spectrometry-Compatible Enantiomeric Separations of 100 Pesticides Using Core–Shell Chiral Stationary Phases and Evaluation of Iterative Curve Fitting Models for Overlapping Peaks. Chromatographia 2019, 82, 221. [Google Scholar] [CrossRef]
- Duan, J.; Dong, X.; Shen, Y.; Gao, B.; Zhang, Z.; Gao, T.; Wang, M. Simultaneous Determination of Enantiomers of Carfentrazone-Ethyl and its Metabolite in Eight Matrices Using High-Performance Liquid Chromatography with Tandem Mass Spectrometry. J. Sep. Sci. 2018, 41, 3697. [Google Scholar] [CrossRef]
- Duan, J.; Gao, B.; Dong, X.; Sun, M.; Shen, Y.; Zhang, Z.; Gao, T.; Wang, M. Stereoselective Degradation Behaviour of Carfentrazone-Ethyl and its Metabolite Carfentrazone in Soils. RSC Adv. 2018, 8, 35897–35902. [Google Scholar] [CrossRef] [Green Version]
- Ali, I.; Kumerer, K.; Aboul-Enein, H.Y. Mechanistic Principles in Chiral Separations using Liquid Chromatography and Capillary Electrophoresis. Chromatographia 2006, 63, 295–307. [Google Scholar] [CrossRef]
- Bermejo, S.B.; López, E.S.; Puyana, M.C.; Marina, M.L. Chiral Capillary Electrophoresis. Trends Anal. Chem. 2020, 124, 115807. [Google Scholar] [CrossRef]
- Fanali, S. Enantioselective Determination by Capillary Electrophoresis with Cyclodextrins as Chiral Selectors. J. Chromatogr. A 2000, 875, 89–122. [Google Scholar] [CrossRef]
- National Center for Biotechnology Information. PubChem Compound Summary for CID 86222, Carfentrazone-Ethyl. 2021. Available online: https://pubchem.ncbi.nlm.nih.gov/compound/Carfentrazone-ethyl (accessed on 26 July 2021).
- Buerge, I.J.; Poiger, T.; Müller, M.D.; Buser, H.R. Enantioselective Degradation of Metalaxyl in Soils: Chiral Preference Changes with Soil pH. Environ. Sci. Technol. 2003, 37, 2668–2674. [Google Scholar] [CrossRef] [PubMed]
Carfentrazone-Ethyl | Carfentrazone | |||||||
---|---|---|---|---|---|---|---|---|
A1 | A2 | B1 | B2 | |||||
External standard calibration method a | ||||||||
Range | 0.3–50 mg L−1 | 0.3–50 mg L−1 | 0.3–50 mg L−1 | 0.3–50 mg L−1 | ||||
Slope ± t × Sslope | 0.064 ± 0.001 | 0.063 ± 0.002 | 0.091 ± 0.002 | 0.091 ± 0.002 | ||||
Intercept ± t × Sintercept | −0.040 ± 0.050 | −0.050 ± 0.050 | −0.030 ± 0.050 | −0.050 ± 0.050 | ||||
R2 | 99.8% | 99.8% | 99.8% | 99.8% | ||||
Standard additions calibrations method | ||||||||
Commercial formulationb | ||||||||
Range | 0–35 mg L−1 | 0–35 mg L−1 | -- | -- | ||||
Slope ± t × Sslope | 0.067 ± 0.006 | 0.066 ± 0.006 | -- | -- | ||||
R2 | 99.0% | 99.1% | -- | -- | ||||
p-value c | 0.6402 | 0.8569 | -- | -- | ||||
Accuracy d | ||||||||
Recovery 1 (%) | 102 ± 5 | 99 ± 5 | -- | -- | ||||
Recovery 2 (%) | 101 ± 3 | 98 ± 3 | -- | -- | ||||
Sand samplee | ||||||||
Range | 0.3–40 mg L−1 | 0.3–40 mg L−1 | 0.3–50 mg L−1 | 0.3–50 mg L−1 | ||||
Slope ± t × Sslope | 0.065 ± 0.002 | 0.063 ± 0.002 | 0.091 ± 0.003 | 0.091 ± 0.006 | ||||
R2 | 99.9% | 99.9% | 99.9% | 99.4% | ||||
p-value c | 0.5370 | 0.5114 | 0.9500 | 0.7009 | ||||
Accuracy f | ||||||||
Recovery (%) | 98 ± 7 | 95 ± 7 | 94 ± 6 | 95 ± 5 | ||||
Soil sampleg | ||||||||
Range | 0.3–40 mg L−1 | 0.3–40 mg L−1 | 0.3–40 mg L−1 | 0.3–40 mg L−1 | ||||
Slope ± t × Sslope | 0.062 ± 0.003 | 0.062 ± 0.003 | 0.089 ± 0.002 | 0.089 ± 0.002 | ||||
R2 | 99.8% | 99.8% | 99.9% | 99.9% | ||||
p-value c | 0.1169 | 0.2470 | 0.1784 | 0.1362 | ||||
Accuracy h | ||||||||
Recovery (%) | 104 ± 5 | 105 ± 5 | 97 ± 4 | 98 ± 4 | ||||
Precision | ||||||||
mg L−1 | 5 | 30 | 5 | 30 | 5 | 30 | 5 | 30 |
Instrumental repeatabilityi | ||||||||
t, RSD (%) | 0.7 | 0.9 | 0.6 | 0.9 | 0.7 | 0.9 | 0.7 | 1.0 |
Ac, RSD (%) | 1.0 | 1.1 | 1.0 | 1.0 | 0.9 | 1.1 | 0.9 | 1.0 |
Method repeatabilityj | ||||||||
t, RSD (%) | 1.0 | 1.2 | 1.0 | 1.1 | 1.2 | 1.1 | 1.3 | 1.1 |
Ac, RSD (%) | 1.3 | 1.4 | 1.2 | 1.3 | 1.9 | 1.8 | 1.9 | 2.0 |
Intermediate precisionk | ||||||||
t, RSD (%) | 1.2 | 1.1 | 1.2 | 1.1 | 1.1 | 1.4 | 1.3 | 1.5 |
Ac, RSD (%) | 1.9 | 2.0 | 1.6 | 1.7 | 2.1 | 2.5 | 1.5 | 2.2 |
LOD l | 0.4 mg L−1 | 0.4 mg L−1 | 0.3 mg L−1 | 0.3 mg L−1 | ||||
LOQ m | 1.4 mg L−1 | 1.4 mg L−1 | 0.8 mg L−1 | 0.9 mg L−1 |
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García-Cansino, L.; García, M.Á.; Marina, M.L. Simultaneous Enantiomeric Separation of Carfentrazone-Ethyl Herbicide and Its Hydrolysis Metabolite Carfentrazone by Cyclodextrin Electrokinetic Chromatography. Analysis of Agrochemical Products and a Degradation Study. Molecules 2021, 26, 5350. https://doi.org/10.3390/molecules26175350
García-Cansino L, García MÁ, Marina ML. Simultaneous Enantiomeric Separation of Carfentrazone-Ethyl Herbicide and Its Hydrolysis Metabolite Carfentrazone by Cyclodextrin Electrokinetic Chromatography. Analysis of Agrochemical Products and a Degradation Study. Molecules. 2021; 26(17):5350. https://doi.org/10.3390/molecules26175350
Chicago/Turabian StyleGarcía-Cansino, Laura, María Ángeles García, and María Luisa Marina. 2021. "Simultaneous Enantiomeric Separation of Carfentrazone-Ethyl Herbicide and Its Hydrolysis Metabolite Carfentrazone by Cyclodextrin Electrokinetic Chromatography. Analysis of Agrochemical Products and a Degradation Study" Molecules 26, no. 17: 5350. https://doi.org/10.3390/molecules26175350