title: Transformation kinetics and mechanism of the sulfonylurea herbicides pyrazosulfuron ethyl and halosulfuron methyl in aqueous solutions.
abstract: Pyrazosulfuron ethyl (PE) and halosulfuron methyl (HM) are two new highly active sulfonylurea herbicides that have been widely used for weed control in a variety of vegetables and other crops. These two herbicides have similar molecular structures, differing only in the substitutions on the pyrazole ring. Chemical hydrolysis is a primary process affecting the environmental fate of sulfonylurea pesticides. The hydrolytic transformation kinetics of PE and HM were investigated as a function of pH and temperature. For both herbicides, the hydrolysis rate was pH-dependent and increased with increasing temperature. The hydrolysis of both sulfonylureas was much faster in acidic or basic media than under neutral conditions. Identification of hydrolytic products by liquid chromatography-mass spectrometry (LC-MS) suggested that both PE and HM were subject to cleavage and contraction of the sulfonylurea bridge. The hydrolysis rate of HM was significantly higher than that of PE in alkaline solutions, despite their structural similarity. A chlorine substitution on HM's pyrazole ring makes HM more susceptible to bridge contraction than PE under basic conditions. The hydrolysis of HM and PE was relatively unaffected by the presence of cyclic oligosaccharides (cyclodextrins), indicating that natural OH-containing organic compounds occurring in aquatic environments may have little impact on the transformation of these sulfonylurea herbicides.
authors.affiliation: Illinois Waste Management and Research Center, 1 East Hazelwood Driver, Champaign, Illinois 61820, USA.
authors.forename: Wei
authors.initials: W
authors.lastname: Zheng
authors.forename: Scott R
authors.initials: SR
authors.lastname: Yates
authors.forename: Sharon K
authors.initials: SK
authors.lastname: Papiernik
mesh_terms: D003505:Cyclodextrins / Q000494:pharmacology; D006540:Herbicides / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D006868:Hydrolysis; D007700:Kinetics; D011720:Pyrazoles / Q000737:chemistry*; D011743:Pyrimidines / Q000737:chemistry*; D012996:Solutions; D013453:Sulfonylurea Compounds / Q000737:chemistry*; D013696:Temperature; D014867:Water / Q000737:chemistry*
chemical_list: D003505:Cyclodextrins; D006540:Herbicides; D011720:Pyrazoles; D011743:Pyrimidines; D012996:Solutions; D013453:Sulfonylurea Compounds; C532033:halosulfuron methyl; D014867:Water; C433343:ethyl 5-(4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl)-1-methylpyrazole-4-carboxylate