Stereoselective Metabolism of the Sterol Biosynthesis Inhibitor Fungicides Fenpropidin, Fenpropimorph, and Spiroxamine in Grapes, Sugar Beets, and Wheat.

Metabolism of chiral pesticides in crops is typically studied using achiral analytical methods and, consequently, the stereoisomer composition of residues is unknown. In this study, we developed an enantioselective GC-MS/MS method to quantify residues of the fungicides fenpropidin, fenpropimorph, and spiroxamine in plant matrices. In field trials, the fungicides were applied to grapevines, sugar beets, or wheat. Fenpropidin was metabolized with no or only weak enantioselectivity. For fenpropimorph, slightly enantioselective metabolism was observed in wheat but more pronounced in sugar beets. This enantioselectivity was due to different rates of metabolism and not due to interconversion of enantiomers. The four stereoisomers of spiroxamine were also metabolized at different rates, but selectivity was only found between diastereomers and not between enantiomers. trans-Spiroxamine was preferentially degraded in grapes and cis-spiroxamine in wheat. These findings may affect the consumer dietary risk assessment because toxicological end points were determined using racemic test substances.

Long-Term Monitoring for Resistance of Botryotinia fuckeliana to Anilinopyrimidine, Phenylpyrrole, and Hydroxyanilide Fungicides in Switzerland.

In Switzerland, the use of phenylpyrrole, anilinopyrimidine, and hydroxyanilide fungicides for control of Botryotinia fuckeliana, causal agent of gray mold in grapes, has been restricted to one treatment per fungicide class per year as part of an anti-resistance strategy. Resistance development in B. fuckeliana was monitored from 1995 to 2001 for the anilinopyrimidine cyprodinil and the phenylpyrrole fludioxonil and from 1997 to 2001 for the hydroxyanilide fenhexamid in experimental vineyards in Richterswil and Stäfa, Switzerland. In total, over 2,400 field isolates were tested. In 1996, the first case of field resistance to anilinopyrimidines was encountered in Richterswil. Efficacy of the anilinopyrimidine cyprodinil decreased significantly, and 54% of the isolates were resistant to anilinopyrimidines. During 7 years of monitoring, one field isolate was found that showed a slightly decreased sensitivity to the phenylpyrrole fludioxonil. Resistance to the hydroxyanilide fenhexamid was not found in 1997 and 1998. From 1999 to 2001, the level of fenhexamid-resistant isolates increased to 100% in Stäfa. The analysis of monitoring and efficacy data showed that subpopulations of B. fuckeliana resistant to cyprodinil and fenhexamid have increased significantly; however, the efficacy of a mixture of fludioxonil and cyprodinil and of fenhexamid alone was still effective. The objective of this study was to initiate long-term monitoring in order to establish an early resistance-detection system as a tool to assess the effectiveness of the anti-resistance strategy used in Switzerland.