There is currently no published method for the analysis of the herbicide quizalofop-p-tefuryl or its matabolite quizalofop in biological matrices. Quizalofp-p-tefuryl is a relatively new herbicide with apparent low toxicity and is readily degraded. Its metabolite also has herbicide activity. Quizalofop-p-tefuryl is a aryloxyphenoxypropionate and is a post emergence herbicide used for pulses and vegetables. This work reports on a method for the analyses of this pesticide residue and its metabolite in soybean using HPLC on a C-18 column with UV detection at 332 nm. Several methods are tried including some involving the use of solid phase extractors like silica, Florisil and strong cationic exchange cartridges. The main method developed uses an extraction solvent hexane: acetone: acetic acid for extracting the quizalofop-p-tefuryl and quizalofop from the ground soybean. The extracts are then made alkaline with NaOH and this deprotonates the quizalofop separating it from the hexane phase which contains the quizalofop-p-tefuryl. The hexane phase is extracted with ACN and quizalofop-p-tefuryl partitions into this phase. The quizalof-p-tefuryl is repartitioned into a fresh diethyl ether: hexane phase by adding a large quantity of H2O and NaCL to the ACN layer. The organic phase is washed and evaporated to dryness before being made up to volume with ACN for direct analysis by UV detection or by derivatising it to methoxychloroquinoxaline for fluorescence detection. Using the method that directly detects the analytes, for quizalofop-p-tefuryl and quizalofop at spike levels, the method has average recoveries. The precision of recoveries for both compounds is about 9%. The method is fairly robust. Time of analysis per analyte is about 2 hrs. / Master of Science

Doctor of Philosophy / Department of Agronomy / Kassim Al-Khatib / Growth chamber, greenhouse and field experiments using conventional grain sorghum were conducted to 1) evaluate the differential response of grain sorghum hybrids to POST application of mesotrione at various rates and application timings, and 2) determine the physiology of tolerance of grain sorghum hybrids to mesotrione. Sorghum response ranged from susceptible to tolerant. Mesotrione dose-response studies on four sorghum hybrids revealed that injury symptoms were greatest in Pioneer 85G01 and least in Asgrow Seneca. Mesotrione applied EPOST (early POST) injured sorghum more than when applied at MPOST (mid POST) or LPOST (late POST) timings. Observed injury symptoms were not well correlated with grain yield and were transient, thus injury did not reduce sorghum grain yield. Foliar absorption or translocation of mesotrione in tolerant hybrids did not differ with that of susceptible hybrids but metabolism was more rapid in tolerant than in susceptible hybrids. Initial grain sorghum injury was severe and will likely be a major concern to producers. Field and growth chambers studies were conducted on herbicide-resistant grain sorghum to 1) determine the effect of quizalofop rates, application timings, and herbicide tank mixes on acetyl-coenzyme A carboxylase (ACCase)-resistant grain sorghum injury and yield, and 2) determine if herbicide metabolism is an additional mechanism that could explain the resistance of ACCase- and acetolactate synthase (ALS)-resistant grain sorghum. Depending on rate, EPOST application caused the greatest injury while the least injury occurred with LPOST application. Crop injury from quizalofop was more prominent at rates higher than the proposed use rate (62 g ha [superscript]-1) in grain sorghum. Sorghum grain yield was not affected by quizalofop regardless of rates or application timings. Weed control was greater when quizalofop was applied with other herbicides than when applied alone. Herbicide treatments except those that included 2,4-D caused slight to no sorghum injury. Results of the quizalofop metabolism study do not support the involvement of differential metabolism in the observed response of grain sorghum to quizalofop. Rimsulfuron metabolism by ALS-resistant sorghum is more rapid than the susceptible genotypes, thus explaining the observed rapid recovery of grain sorghum plants from rimsulfuron injury in the field.