Triadimenol
Metabolite formation in all four soils was generally low, with no metabolites formed at >5% at any sampling time. The metabolite formed in the highest amount was M01, formed at a maximum of 3.88% AR at 14 DAT. Note that M01 was identified as triadimefon, a triazole fungicide closely related to triadimenol. Whilst levels were still increasing at the end of the study in some of the soils, a pragmatic view has been taken that the levels were very low, and that M01 does not need to be included in a groundwater assessment. Three other metabolites were identified, M02, M03 and M07. As with M01, the se metabolites were all observed to be increasing in concentration towards the end of the study, but the pragmatic approach taken towards M01 also applies to these metabolites with respect to groundwater assessment. It was noted in study that the ratio of triadimenol isomers A:B declined gradually in soils with the greatest ability to degrade total triadimenol most quickly; in soils with the least ability to degrade total triadimenol, the isomer ratio remained virtually unchanged over time. The A isomer is most biologically active (production batches at the time of writing this DAR have an A:B isomer ratio of 80:20), and thus it is considered that potentially faster decline of A is of no practical concern in terms of environmental exposure and risk assessment. There was no detailed route of degradation information provided on triadimenol labelled in the triazole ring position. The notifier made reference to a lysimeter study where both triazole-labelled triadimenol and triadimefon had been applied to winter wheat grown on the lysimeters. At the sample time after harvest of the crop in the first year of the study, metabolite M04 (1,2,4-triazole) was found at 8.2% AR down to 20cm depth. In the aerobic route of degradation study using phenyl-labelled triadimenol, the metabolite likely to be immediately before M04 in the metabolic pathway, M03, was formed at a maximum of 3.08% AR. The metabolite formed from M03 by elimination of 1,2,4-triazole, M07, was formed at a maximum of 2.37% AR. These maximum levels did not coincide in the same soil. The maximum observed concentration of a particular metabolite will be governed by both its rate of formation and its rate of degradation. Thus the relatively low levels of metabolites either side of M04 in the metabolic pathway cannot necessarily be taken as being indicative of correspondingly low levels of M04 in soil. With respect to formation of M04, the notifier considers it to be a ‘minor’ metabolite, citing the lysimeter study mentioned above. Whilst it is correct that the one soil sampling time in the first year found M04 at <10% AR, the level of 8.2% AR might justify consideration in a groundwater assessment as required by Sanco/221/2000 – rev.10, ‘Guidance Document on the Assessment of the Relevance of Metabolites in Groundwater of Substances Regulated under Council Directive 91/414/EEC’. Two aerobic soil studies were conducted with M04. The first route of degradation study was conducted prior to GLP requirements, and the study guidelines were not specifically stated. The study is of limited use because of the failure to sample on day 0 of any of the incubations. However, useful supporting information can be obtained from the study. Comparison of the results of incubations in non-sterile and sterile soil seem to indicate that biotic degradation of M04 may not be the most important process in dissipation of this substance. As an example, at 90 DAT, M04 had declined to 7.9% AR in the non-sterile soil and 19.2% AR in the sterile soil. However at the same time point, unextracted residues accounted for 67.2% AR in the non-sterile soil and 75.9% in the sterile soil. This would suggest that the major route of dissipation of M04 would be incorporation into unextracted residues. However, it is recognised that mineralization did occur, with 24.2% AR as CO2 at 90 DAT in non-sterile soil. In another incubation in the same study, 51.5% AR as CO2 was produced at 90 DAT with 47.4% AR unextractable at the same time point. This would suggest that the balance between mineralization and incorporation into unextracted residues is dependent on soil type. Mineralisation in sterile soil was negligible. At a very exaggerated dose of 48 mg M04/kg, equivalent to 36 kg/ha of the metabolite assuming a soil bulk density of 1.5 g/cm3, mineralization was very low (1.1% AR at 60 DAT), which may indicate that M04 is toxic to soil microbes at such high concentrations. M04 produced a major metabolite, 1,2-dihydro-triazolone, in one of the two soils studied in the route of degradation study. The peak occurrence was 30.8% AR at 12 DAT. However, in the other soil, the maximum level was 3.1% AR. It was also noted that in the aerobic rate of degradation study on M04, the maximum amount of 1,2-dihydro-triazolone was 2.61%AR. Thus it is possible that the relatively high level of 30.8%AR is an outlier, although there is no obvious explanation as to why this result should occur ; an occurrence of 30.8% AR will be used in PECsoil calculation, although given the expectation that M04 will not be observed at 100%, the assumption of 30.8% AR for PECsoil calculation is very conservative. Triazole alanine (TA, max 3.6% AR) and triazole acetic acid (TAA, max 0.2% AR) were also detected as minor metabolites. The notifier proposed a route of degradation ofM04 which included a cyclic process involving M04 transformed to TA, TA transformed to TAA and TAA transformed to M04.