Variation of MCPA, metribuzine, methyltriazine-amine and glyphosate degradation, sorption, mineralization and leaching in different soil horizons

Pesticide mineralization and sorption were determined in 75 soil samples from 15 individually drilled holes through the vadose zone along a 28 km long transect of the Danish outwash plain. Mineralization of the phenoxyacetic acid herbicide MCPA was high both in topsoils and in most subsoils, while metribuzine and methyltriazine-amine was always low. Organic matter and soil pH was shown to be responsible for sorption of MCPA and metribuzine in the topsoils. The sorption of methyltriazine-amine in topsoil was positively correlated with clay and negatively correlated with the pH of the soil. Sorption of glyphosate was tested also high in the subsoils. One-dimensional MACRO modeling of the concentration of MCPA, metribuzine and methyltriazine-amine at 2 m depth calculated that the average concentration of MCPA and methyltriazine-amine in the groundwater was below the administrative limit of 0.1 μg/l in all tested profiles while metribuzine always exceeded the 0.1 μg/l threshold value.     

PERFORMANCE AND PERSISTENCE OF GREEN FLUORESCENT PROTEIN （gfp） MARKED AZOTOBACTER CHROOCOCCUM IN STERILIZED AND UNSTERILIZED WHEAT RHIZOSPHERIC SOIL

ThepracticaluseofAzotobacterchroococcumasbiofertilizer hasbeenincreasinglyidentifiedinrecentyears.Oftentheefficacy ofthesebacteriaisassessedonthebasisofcropresponseswithout knowingthesurvival,persistenceandcompetitiveabilityofthein troducedstrain.Inoculat…     

Microbial degradation pathways of the herbicide dichlobenil in soils with different history of dichlobenil-exposure

This is the first detailed study of metabolite production during degradation of the herbicide 2,6-dichlorobenzonitrile (dichlobenil). Degradation of dichlobenil and three potential metabolites: 2,6-dichlorobenzamide (BAM), 2,6-dichlorobenzoic acid (2,6-DCBA) and ortho-chlorobenzamide (OBAM) was studied in soils either previously exposed or not exposed to dichlobenil using a newly developed HPLC method. Dichlobenil was degraded in all four soils; BAM and 2,6-DCBA were only degraded in soils previously exposed to dichlobenil (100% within 35-56 days and 85-100% in 56 days, respectively), and OBAM in all four soils (25-33% removal in 48 days). BAM produced from dichlobenil was either hydrolyzed to 2,6-DCBA or dechlorinated to OBAM, which was further hydrolyzed to ortho-chlorobenzoic acid. BAM was rapidly mineralized in previously exposed soils only. All potential metabolites and the finding that BAM was a dead-end metabolite of dichlobenil in soils not previously exposed to dichlobenil needs to be included in risk assessments of the use of dichlobenil.     

Fate and transport of chlormequat in subsurface environments

Background, aim and scope  

Chlormequat (Cq) is a plant growth regulator used throughout the world. Despite indications of possible effects of Cq on mammalian health and fertility, little is known about its fate and transport in subsurface environments. The aim of this study was to determine the fate of Cq in three Danish subsurface environments, in particular with respect to retardation of Cq in the A and B horizons and the risk of leaching to the aquatic environment. The study combines laboratory fate studies of Cq sorption and dissipation with field scale monitoring of the concentration of Cq in the subsurface environment, including artificial drains.     

Degradation and sorption of metribuzin and primary metabolites in a sandy soil

Leaching to the ground water of metabolites from the herbicide metribuzin [4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazin-5-one] has been measured in a Danish field experiment in concentrations exceeding the European Union threshold limit for pesticides at 0.1 microg/L. In the present work, degradation and sorption of metribuzin and the metabolites desamino-metribuzin (DA), diketo-metribuzin (DK), and desamino-diketo-metribuzin (DADK) were studied in a Danish sandy loam topsoil and subsoil from the field in question, using accelerated solvent extraction and liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis. Fast dissipation of metribuzin and the metabolites was observed in the topsoil, with 50% disappearance within 30 to 40 d. A two-compartment model described degradation of metribuzin and DA, whereas that of DADK could be described using first-order kinetics. Part of the dissipation was probably due to incorporation into soil organic matter. Degradation in subsoil occurred very slowly, with extrapolated half-lives of more than one year. Sorption in the topsoil followed the order DA > metribuzin > DK > DADK. Subsoil sorption was considerably lower, and was hardly measurable for metribuzin and DK. Abiotic degradation was considerably higher in the topsoil than the subsoil, especially concerning the de-amination step, indicating that organic matter may be related to the degradation process. The present results confirm observations of metribuzin and transformation product leaching made in the field experiment and demonstrate the need for knowledge on primary metabolites when assessing the risk for pesticide leaching.     

Analysis of acidic pesticides using in situ derivatization with alkylchloroformate and solid-phase microextraction (SPME) for GC-MS.

A solid-phase microextraction (SPME) method was developed for the analysis of acidic pesticide residues in water. The method utilizes in situ derivatization with butylchloroformate (BuCF), followed by on-line SPME extraction using a PDMS fibre, and analysis by GC-MS. Derivatives of the phenoxy acids mechlorprop (MCPP), dichlorprop (DCPP), MCPA and 2,4-D and their phenol degradation products 4-chloro-2-methylphenol and 2,4-dichlorophenol (DCP) were identified. Detection limits at 0.16-2.3 microg/l were achieved. Optimization of derivatization, ion strength, extraction time, SPME-fibre, desorption time and temperature are described. Standard curves in the range 0.5-10.0 microg/l were fitted to a second-degree polynomial. Standard deviation (n = 5) was below 10% for the phenol derivatives, but 20-50% for the phenoxy acids. For method verification groundwater samples from a field experiment were screened for content of MCPP and compared to the results from the HPLC analysis. A good agreement was obtained with respect to identification of positive samples, even though concentrations measured by the SPME were lower than with HPLC. Even if the precision and accuracy do not meet the demands for a strictly quantitative analysis, the SPME method is suitable for screening, because it is cheap, it can be automated, and uses smaller amounts of potential harmful solvents. Also, the method is less labour-intensive, as it requires a minimum of sample preparation when compared to traditional analyses. The acidic pesticides bentazon, dicamba, bromoxynil, ioxynil, dinoseb and DNOC were included in the study but could not be analysed by the current method.