title: Degradation and Isotope Source Tracking of Glyphosate and Aminomethylphosphonic Acid.
abstract: Glyphosate [N-(phosphonomethyl) glycine], an active ingredient of the herbicide Roundup, and its main metabolite, aminomethylphosphonic acid (AMPA), have been frequently reported to be present in soils and other environments and thus have heightened public concerns on their potential adverse effects. Understanding the fate of these compounds and differentiating them from other naturally occurring compounds require a toolbox of methods that can go beyond conventional methods. Here, we applied individual isotope labeling technique whereby each compound or mineral involved in the glyphosate and AMPA degradation reaction was either synthesized or chosen to have distinct (18)O/(16)O ratios so that the source of incorporated oxygen in the orthophosphate generated and corresponding isotope effect during C-P bond cleavage could be identified. Furthermore, we measured original isotope signatures of a few commercial glyphosate sources to identify their source-specific isotope signatures. Our degradation kinetics results showed that the rate of glyphosate degradation was higher than that of AMPA in all experimental conditions, and both the rate and extent of degradation were lowest under anoxic conditions. Oxygen isotope ratios (δ(18)OP) of orthophosphate generated from glyphosate and AMPA degradation suggested that one external oxygen atom from ambient water, not from dissolved oxygen or mineral, was incorporated into orthophosphate with the other three oxygen atoms inherited from the parent molecule. Interestingly, δ(18)OP values of all commercial glyphosate products studied were found to be the lightest among all orthophosphates known so far. Furthermore, isotope composition was found to be unaffected due to variable degradation kinetics, light/dark, and oxic/anoxic conditions. These results highlight the importance of phosphate oxygen isotope ratios as a nonconventional tool to potentially distinguish glyphosate sources and products from other organophosphorus compounds and orthophosphate in the environment.
authors.affiliation: Department of Plant and Soil Sciences, University of Delaware , Newark, Delaware 19716, United States.
authors.forename: Hui
authors.initials: H
authors.lastname: Li
authors.affiliation: Department of Plant and Soil Sciences, University of Delaware , Newark, Delaware 19716, United States.
authors.forename: Sunendra R
authors.initials: SR
authors.lastname: Joshi
authors.affiliation: Department of Plant and Soil Sciences, University of Delaware , Newark, Delaware 19716, United States.
authors.forename: Deb P
authors.initials: DP
authors.lastname: Jaisi
mesh_terms: D004784:Environmental Monitoring; D005998:Glycine / Q000031:analogs & derivatives* / Q000737:chemistry; D006540:Herbicides / Q000737:chemistry*; D007555:Isoxazoles; D007700:Kinetics; D063065:Organophosphonates / Q000737:chemistry*; D010103:Oxygen Isotopes / Q000737:chemistry*; D013777:Tetrazoles; D000097797:Glyphosate
chemical_list: D005998:Glycine; D006540:Herbicides; D007555:Isoxazoles; D063065:Organophosphonates; D010103:Oxygen Isotopes; D013777:Tetrazoles; D000097797:Glyphosate; C418233:2-amino-3-(3-hydrox-5(2-methyl-2H-tetrazol-5-yl)isoxazol-4-yl)propionic acid
keywords: aminomethylphosphonic acid (AMPA); glyphosate; isotope source tracking; orthophosphate