mefenoxam and metalaxyl

Evaluation of chiral pesticides remains a frequently neglected matter in routine food control laboratories. This fact is due to the existence of many residue definitions but also due to the lack of robust instrumental methods for the evaluation of these isomeric compounds. However, supercritical fluid chromatography coupled to mass spectrometry (SFC-ESI-MS/MS) has been demonstrated to perform fast and highly efficient separations without the need to change the mobile phase employed in multiresidue pesticide analyses. Regarding chiral stationary phase columns, the polysaccharide-based ones clearly demonstrate the best separation technology. Two polysaccharide-based columns were tested in this study, and the robustness of their combination with SFC was verified. The enantiomers of lambda-cyhalothrin and metalaxyl were studied precisely due to their markedly distinct toxicity and enantioselectivity. Furthermore, the acute reference dose for gamma-cyhalothrin is half in comparison with its enantiomer (0.0025 and 0.005 mg/kg respectively), which is present in the lambda-cyhalothin residue definition. These enantiomers were analyzed in terms of linearity, reproducibility, and matrix effects in four representative matrices (tomato, orange, leek, and cayenne). Additionally, field tests under greenhouse conditions for these compounds were performed. The results obtained after different sample collections revealed a similar degradation in lambda-cyhalothrin enantiomers (R, S, S, and S, R, R) but not in the case of metalaxyl-M (mefenoxam) where the degradation in tomato was 2 to 6 times less in comparison with its S-enantiomer.

Topics: Alanine; Chromatography, Supercritical Fluid; Nitriles; Pesticides; Polysaccharides; Pyrethrins; Reproducibility of Results; Stereoisomerism; Tandem Mass Spectrometry

The degradation of various formulations of the racemic mixture and the enantiomers (including mefenoxam) of metalaxyl in typical soils from Germany and Cameroon in controlled incubation experiments was studied. The kinetics of the degradation or transformation was determined by means of reversed phase HPLC, while the enantiomeric ratios were measured by HPLC with a chiral Whelk O1 column. The dynamics of the quantitative changes in microbiological properties induced by the addition of these fungicides at their recommended field rates were determined in the soils during a 120-day incubation experiment. The degradation followed first-order kinetics (R > or = 0.96). Higher metalaxyl acid metabolite concentrations were found in German than in Cameroonian soils. The enantiomers of the fungicide had different degradation rates in both soils, with half-lives ranging from 17 to 38 days. All forms of metalaxyl had lower degradation rates in the Cameroonian soil than in the German soil. The degradation of the R-enantiomer was much faster than the S-enantiomer in the German soil and slower than the S-enantiomer in the Cameroonian soil, suggesting that different microbial populations, which may be using different enzymes, have different degradation preferences. The type of soil significantly influenced the effect of these fungicides on the soil parameters studied. Incorporation of these fungicides resulted in a change in the ecophysiological status of the soil microbial community as expressed by microbial activities. The activity of phosphatases and fl-glucosidase, the mineralization and availability of N and most plant nutrients in soils were stimulated, whereas the activity of dehydrogenase and the availability of NO3-, were generally adversely affected. The soil NH4+, NO3-, and enzymes activities values in general did not correlate with the degradation of metalaxyl in both soils. However, the degradation of formulated and unformulated metalaxyl was positively correlated to the activity of acid phosphatase in the German soil (R, 0.84 and 0.94 respectively) and in the Cameroonian soil (R, 0.97 and 0.96 respectively).

Topics: Acid Phosphatase; Alanine; Alkaline Phosphatase; Biodegradation, Environmental; Cameroon; Climate; Fungicides, Industrial; Germany; Glucosidases; Nitrates; Nitrogen; Oxidoreductases; Quaternary Ammonium Compounds; Soil Microbiology; Soil Pollutants

Laboratory soil sorption experiments were conducted on mefenoxam, formulated metalaxyl (F-metalaxyl), pure metalaxyl (P-metalaxyl) and metalaxyl acid metabolite to elucidate differences in their sorptive behaviour on typical Cameroonian forest soil (sand clay loam, pH 4.8 and 3.01% OC) and German soil (sandy loam, pH 7.2, 1.69% OC) using a batch equilibrium method. The data obtained on all test chemicals conformed to linear and Freundlich adsorption isotherms. The Langmuir equation failed to describe the sorption of the substances tested. All substances were adsorbed to a greater extent by the Cameroonian soil. The average percentage adsorptions for mefenoxam, F-metalaxyl, P-metalaxyl and the acid metabolite on the Cameroonian soil were 27.8%, 28.3%, 31.8% and 46.8% respectively while for the German soil they were 21.7%, 21.5%, 24.7% and 9.8% respectively. The KD and KF parameters and the Freundlich exponential term (1/n) were low, indicating that the interactions between soil particles and the fungicides were weak. The sorption parameters were lower in the German soil. P-metalaxyl exhibited a higher adsorption capacity than F-metalaxyl in both soils. Mefenoxam and F-metalaxyl exhibited similar sorption parameters in soils, whereas those of P-metalaxyl and acid metabolite differed. Differences observed in the adsorption between the two soils could be attributed to their properties. Desorption studies revealed that the adsorbed fungicides were not firmly retained by soil particles and their adsorption was reversible. Desorption of adsorbed mefenoxam, P-metalaxyl and of the acid metabolite from German soil was almost completely reversible with percentage desorption rates of more than 91.0%, whereas the rate for F-metalaxyl was 74.1%. All compounds exhibited some resistance to desorption from the Cameroonian soil, with percentage desorption rates less than 77.0%. Therefore if degradation in the soil is slow the fungicides described have a potential to leach to lower soil horizons.

Topics: Absorption; Alanine; Cameroon; Fungicides, Industrial; Germany; Kinetics; Mathematical Computing; Models, Chemical; Soil Pollutants