title: Optimization and Validation of a Residue Analysis Method for Glyphosate, Glufosinate, and Their Metabolites in Plant Matrixes by Liquid Chromatography with Tandem Mass Spectrometry.
abstract: A sensitive and accurate LC with tandem MS (MS/MS)-based method was developed and validated for the analysis of the herbicide glyphosate, its metabolite aminomethylphosphonic acid (AMPA), and glufosinate after derivatization with 9-fluorenylmethyl chloroformate (FMOC-Cl) in various plant matrixes. The method also covers direct analysis of the glufosinate metabolites 3-methylphosphinicopropionic acid (3-MPPA) and N-acetyl-glufosinate (NAG). The homogenized samples were extracted with 0.1% formic acid in water-dichloromethane (50 + 50). The aqueous layer was derivatized with FMOC-Cl, cleaned through an HLB SPE cartridge, and determined by LC-MS/MS. The sample size, extraction solvent, sample-to-solvent ratio, derivatization conditions, and cleanup procedure were thoroughly optimized, the LOQs of glyphosate, glufosinate, and AMPA were 0.5 ng/g in grape, corn (leaf and seed), and cotton (leaf, seed, and oil) and 2 ng/g in soybean and tea. The LOQs of NAG and 3-MPPA were 50 ng/g in all the test matrixes, except tea and soybean, for which the LOQ was 100 ng/g. In all cases, average recoveries were >80%. The method successfully performed the estimation of glyphosate in incurred corn and cotton leaf samples collected from supervised field trials.
authors.affiliation: Indian Council of Agricultural Research, National Research Centre for Grapes, National Referral Laboratory, PO Manjri Farm, Pune 412 307, India.
authors.forename: Dasharath P
authors.initials: DP
authors.lastname: Oulkar
authors.affiliation: Indian Council of Agricultural Research, National Research Centre for Grapes, National Referral Laboratory, PO Manjri Farm, Pune 412 307, India.
authors.forename: Sandip
authors.initials: S
authors.lastname: Hingmire
authors.affiliation: Indian Council of Agricultural Research, National Research Centre for Grapes, National Referral Laboratory, PO Manjri Farm, Pune 412 307, India.
authors.forename: Arnab
authors.initials: A
authors.lastname: Goon
authors.affiliation: Indian Council of Agricultural Research, National Research Centre for Grapes, National Referral Laboratory, PO Manjri Farm, Pune 412 307, India.
authors.forename: Manjusha
authors.initials: M
authors.lastname: Jadhav
authors.affiliation: Indian Council of Agricultural Research, National Research Centre for Grapes, National Referral Laboratory, PO Manjri Farm, Pune 412 307, India.
authors.forename: Bharat
authors.initials: B
authors.lastname: Ugare
authors.affiliation: Indian Council of Agricultural Research, National Research Centre for Grapes, National Referral Laboratory, PO Manjri Farm, Pune 412 307, India.
authors.forename: Ahammed Shabeer
authors.initials: AS
authors.lastname: Thekkumpurath
authors.affiliation: Indian Council of Agricultural Research, National Research Centre for Grapes, National Referral Laboratory, PO Manjri Farm, Pune 412 307, India.
authors.forename: Kaushik
authors.initials: K
authors.lastname: Banerjee
mesh_terms: D000613:Aminobutyrates / Q000032:analysis; D002853:Chromatography, Liquid; D018556:Crops, Agricultural / Q000737:chemistry*; D005449:Fluorenes; D005998:Glycine / Q000031:analogs & derivatives / Q000032:analysis; D010573:Pesticide Residues / Q000032:analysis*; D053719:Tandem Mass Spectrometry; D000097797:Glyphosate
chemical_list: D000613:Aminobutyrates; D005449:Fluorenes; D005998:Glycine; D010573:Pesticide Residues; D000097797:Glyphosate; C003121:phosphinothricin; C054007:1-(9-fluorenyl)methyl chloroformate