LC/MS analysis of cyclohexanedione oxime herbicides in water.

A multiresidue method for the determination of alloxydim (methyl 2, 2-dimethyl-4, 6-dioxo-5-[1-[2-propenyloxy)amino]butylidene]cyclohexanec arb oxylate), clethodim (E, E)-(+/-)-2-[1-[[3-chloro-2-propenyl)oxy]imino]propyl]-5-[2-(ethylthio )propyl]-3-hydroxy-2-cyclohexen-1-one), sethoxydim ((+/-)-2-[1-(ethoxyimino)butyl]-5-[2-ethylthio)propyl]-3-hydroxy-2 -cy clohexen-1-one), and two metabolites, clethodim sulfoxide ((E, E)-(+/-)-2-[1-[[3-chloro-2-propenyl)oxy]imino]propyl]-5-[2-(ethylsulf inyl)propyl]-3-hydroxy-2-cyclohexen-1-one) and sethoxydim sulfoxide ((+/-)-2-[1-(ethoxyimino)butyl]-5-[2-ethylsulfinyl)propyl]-3 -hydroxy- 2-cyclohexen-1-one), in water by high-performance liquid chromatography/electrospray/mass spectrometry (LC/ES/MS) is reported. River water and distilled water were spiked at 0.08 and 0.8 microgram L(-1) with all three herbicides, which were then extracted from the water by C(18)-SPE (SPE = solid-phase extraction). The herbicides and metabolites were quantified and confirmed using selected ion monitoring. The percent recoveries of the herbicides from water spiked at 0.8 microgram L(-1) were as follows: alloxydim, 117 +/- 11%; clethodim, 96 +/- 14%; sethoxydim, 89 +/- 13%. There was no evidence of oxidation of clethodim and sethoxydim during the extraction to their respective sulfoxides. The limit of quantitation was <0.1 microgram L(-1). We have shown that we can analyze and confirm three cyclohexanedione oxime herbicides and two metabolites in water by LC/ES/MS. This multiresidue method should also be appropriate for other cyclohexanedione oximes.

Influence of soil pH-sorption interactions on imazethapyr carry-over.

Soil pH affects imazethapyr sorption-desorption, which in turn can affect persistence and bioavailability. Long-term imazethapyr carry-over has been observed in soil that is below pH 6.5, resulting in significant sugarbeet damage. Imazethapyr concentration decreased rapidly in field soil, regardless of pH. Despite similar amounts of imazethapyr remaining in aged soils at different pH levels, there were differences in bioavailability, which can be explained by sorption-desorption. At low pH more imazethapyr was sorbed than at high pH, but it readily desorbed. At high pH less imazethapyr was sorbed initially, but it did not readily desorb. Thus, after 3 months, the remaining imazethapyr in low-pH soil was desorbable and bioavailable, resulting in injury to canola and sugarbeet. Liming aged, low-pH soil released bound imazethapyr residues, which would then be degraded and result in less carry-over.