Annette E. Rosenbom

Numerical analysis of water and solute transport in variably-saturated fractured clayey till

This study numerically investigates the influence of initial water content and rain intensities on the preferential migration of two fluorescent tracers, Acid Yellow 7 (AY7) and Sulforhodamine B (SB), through variably-saturated fractured clayey till. The simulations are based on the numerical model HydroGeoSphere, which solves 3D variably-saturated flow and solute transport in discretely-fractured porous media. Using detailed knowledge of the matrix, fracture, and biopore properties, the numerical model is calibrated and validated against experimental high-resolution tracer images/data collected under dry and wet soil conditions and for three different rain events. The model could reproduce reasonably well the observed preferential migration of AY7 and SB through the fractured till, although it did not capture the exact depth of migration and the negligible impact of the dead-end biopores in a near-saturated matrix. A sensitivity analysis suggests fast flow mechanisms and dynamic surface coating in the biopores, and the presence of a plough pan in the till.

Leaching of azoxystrobin and its degradation product R234886 from Danish agricultural field sites.

The objective was to estimate leaching of the fungicide azoxystrobin (methyl (αE)-2-[[6-(2-cyanophenoxy)-4-pyrimidinyl]oxy]-α-(methoxymethylene)benzene-acetate) and one of its primary degradation products R234886 ([(E)-2-(2-[6-cyanophenoxy)-pyrimidin-4-yloxyl]-phenyl-3-methoxyacrylic acid], major fraction) at four agricultural research fields (one sandy and three loamy) in Denmark. Water was sampled from tile drains, suction cups and groundwater wells for a minimum period of two years after application of azoxystrobin. Neither azoxystrobin nor R234886 were detected at the sandy site, but did leach through loamy soils. While azoxystrobin was generally only detected during the first couple of months following application, R234886 leached for a longer period of time and at higher concentrations (up to 2.1μgL(-1)). Azoxystrobin is classified as very toxic to aquatic organisms and R234886 as very harmful. Our study shows that azoxystrobin and R234886 can leach through loamy soils for a long period of time following application of the pesticide and thereby pose a potential threat to vulnerable aquatic environments and drinking water resources. We thus recommend the inclusion of azoxystrobin and R234886 in pesticide monitoring programmes and further investigation of their long-term ecotoxicological effects.

Long-term leaching of rimsulfuron degradation products through sandy agricultural soils

The objective was to quantify leaching of the widely used low-dosage sulfonylurea herbicides rimsulfuron and its primary degradation products IN70941 ([N-(4,6-dimethoxypyrimidin-2-yl)-N-((3-ethylsulfonyl)-2-pyridinyl)urea]) and IN70942 ([N-((3-ethylsulfonyl)-2-pyridinyl)-4,6-dimethoxy-2-pyrimidineamine]) at two sandy research fields in Denmark. Water was sampled monthly from the vadose and groundwater zones at the two sites (Tylstrup and Jyndevad) over a 4-6-year period following application of rimsulfuron. No rimsulfuron was detected in the water samples. At the Jyndevad site, IN70941 was detected in the vadose zone at a depth of 1m for as long as three years in annual average concentrations exceeding the EU limit value for drinking water of 0.1microgL(-1). At the Tylstrup site, IN70941 was detected at a depth of 2m in concentrations just below 0.1microgL(-1). The groundwater concentration of IN70941 occasionally exceeded 0.1microgL(-1) at the Jyndevad site, but is only detected on one occasion (and at a low concentration) at the Tylstrup site. At both sites IN70941 was relatively stable and persisted in the soil water for several years, with relatively little degrading further to IN70942. Thus, the concentration of IN7092 was much lower and apart from four samples from the Jyndevad site, never exceeded 0.1microgL(-1). Nevertheless, our findings show that degradation products of rimsulfuron can leach through sandy soils in relatively high concentrations and could potentially contaminate vulnerable aquatic environments. In view of this risk, IN70941 and IN70942 should be included in pesticide monitoring programmes, and their long-term ecotoxicological effects should be investigated further.

Fluorescence imaging applied to tracer distributions in variably saturated fractured clayey till.

The study of mechanisms controlling preferential flow and transport in variably saturated fractured clayey till is often hindered by insufficient spatial resolution or unknown measuring volume. With the objective to study these mechanisms while circumventing the obstacles, tracer experiments with two fluorescent tracers Acid Yellow 7 (AY7) and Sulforhodamine B (SB) were performed at three different rain events for a fall and a summer season. Irrigated areas were excavated down to depths of 2.8 m and the movement of both tracers in the exposed profiles was delineated simultaneously by high spatial resolution apparent concentration maps (pixel approximately 1 mm(2)) obtained with an imaging device. The device consists of a light source and a CCD camera, both equipped with tracer-specific-filters for fluorescent light. The fluorescence images were corrected for nonuniform lighting, changing surface roughness, and varying optical properties of the soil profile. The resulting two-dimensional apparent concentration distribution profiles of the tracers showed that: (i) relative low water content in the upper 10 cm of the irrigated till in summer had a pronounced retardation effect on the AY7-migration and no effect on the SB-migration; (ii) the dead-end biopores were not activated in the fall season; (iii) only 3D fracture-plans connected to hydraulically active 1D-biopores contributed to the leaching; (iv) the tracer migration primary followed macropores during both seasons, though AY7 also followed a topsoil piston transport in summer; (v) the highest tracer pixel apparent concentrations were often found in macropores and most pronounced in the summer season; and (vi) 3D-dilution in fractures seems to play a dominating role in AY7-migration in the fall season.

Pesticide leaching through sandy and loamy fields - long-term lessons learnt from the Danish Pesticide Leaching Assessment Programme.

The European Union authorization procedure for pesticides includes an assessment of the leaching risk posed by pesticides and their degradation products (DP) with the aim of avoiding any unacceptable influence on groundwater. Twelve-years results of the Danish Pesticide Leaching Assessment Programme reveal shortcomings to the procedure by having assessed leaching into groundwater of 43 pesticides applied in accordance with current regulations on agricultural fields, and 47 of their DP. Three types of leaching scenario were not fully captured by the procedure: long-term leaching of DP of pesticides applied on potato crops cultivated in sand, leaching of strongly sorbing pesticides after autumn application on loam, and leaching of various pesticides and their DP following early summer application on loam. Rapid preferential transport that bypasses the retardation of the plow layer primarily in autumn, but also during early summer, seems to dominate leaching in a number of those scenarios.

Does microbial centimeter-scale heterogeneity impact MCPA degradation in and leaching from a loamy agricultural soil?

The potential for pesticide degradation varies greatly at the centimeter-scale in agricultural soil. Three dimensional numerical simulations were conducted to evaluate how such small-scale spatial heterogeneity may affect the leaching of the biodegradable pesticide 2-methyl-4-chlorophenoxyacetic acid (MCPA) in the upper meter of a variably-saturated, loamy soil profile. To incorporate realistic spatial variation in degradation potential, we used data from a site where 420 mineralization curves over 5 depths have been measured. Monod kinetics was fitted to the individual curves to derive initial degrader biomass values, which were incorporated in a reactive transport model to simulate heterogeneous biodegradation. Six scenarios were set up using COMSOL Multiphysics to evaluate the difference between models having different degrader biomass distributions (homogeneous, heterogeneous, or no biomass) and either matrix flow or preferential flow through a soil matrix with a wormhole. MCPA leached, within 250 days, below 1m only when degrader biomass was absent and preferential flow occurred. Both biodegradation in the plow layer and the microbially active lining of the wormhole contributed to reducing MCPA-leaching below 1m. The spatial distribution of initial degrader biomass within each soil matrix layer, however, had little effect on the overall MCPA-leaching.

The gompertz function can coherently describe microbial mineralization of growth-sustaining pesticides.

Mineralization of (14)C-labeled tracers is a common way of studying the environmental fate of xenobiotics, but it can be difficult to extract relevant kinetic parameters from such experiments since complex kinetic functions or several kinetic functions may be needed to adequately describe large data sets. In this study, we suggest using a two-parameter, sigmoid Gompertz function for parametrizing mineralization curves. The function was applied to a data set of 252 normalized mineralization curves that represented the potential for degradation of the herbicide MCPA in three horizons of an agricultural soil. The Gompertz function fitted most of the normalized curves, and trends in the data set could be visualized by a scatter plot of the two Gompertz parameters (rate constant and time delay). For agricultural topsoil, we also tested the effect of the MCPA concentration on the mineralization kinetics. Reduced initial concentrations lead to shortened lag-phases, probably due to reduced need for bacterial growth. The effect of substrate concentration could be predicted by simply changing the time delay of the Gompertz curves. This delay could to some extent also simulate concentration effects for 2,4-D mineralization in agricultural soil and aquifer sediment and 2,6-dichlorobenzamide mineralization in single-species, mineral medium.

Environmental Fate of the Herbicide Fluazifop-P-butyl and Its Degradation Products in Two Loamy Agricultural Soils: A Combined Laboratory and Field Study

The herbicide fluazifop-P-butyl (FPB) is used against grasses in agricultural crops such as potato, oilseed rape, and sugar beet. Limited information is available in scientific literature on its environmental fate, therefore extensive monitoring at two agricultural test fields was combined with laboratory studies to determine leaching and the underlying degradation and sorption processes. Water samples from drains, suction cups, and groundwater wells showed leaching of the degradation products fluazifop-P (FP) and 2-hydroxy-5-trifluoromethyl-pyridin (TFMP) following FPB treatment. Laboratory experiments with soil from each field revealed a rapid degradation of FPB to FP. The degradation was almost exclusively microbial, and further biodegradation to TFMP occurred at a slower rate. Both degradation products were sorbed to the two soils to a small extent and were fairly persistent to degradation during the two-month incubation period. Together, the field and laboratory results from this study showed that the biodegradation of FPB in loamy soils gave rise to the production of two major degradation products that sorbed to a small extent. In this study, both degradation products leached to drainage and groundwater during precipitation. It is therefore recommended that these degradation products be included in programs monitoring water quality in areas with FPB use.

Degradation and sorption of the fungicide tebuconazole in soils from golf greens

The fungicide tebuconazole (TBZ) is used to repress fungal growth in golf greens and ensure their playability. This study determined the degradation and sorption of TBZ applied as an analytical grade compound, a commercial fungicide formulation or in combination with a surfactant product in thatch and soils below two types of greens (USGA and push-up greens) in 12-cm vertical profiles covered by three different types of turf grass. Only minor TBZ degradation was observed and it was most pronounced in treatments with the commercial fungicide product or in combination with the surfactant compared to the analytical grade compound alone. A tendency for higher TBZ sorption when applied as the formulated product and lowest sorption when applied as a formulated product in combination with the surfactant was observed, with this effect being most distinct on USGA greens. No correlation between occurrence of degradation and soil depth, green type or grass type was observed. Sorption seemed to be the main process governing the leaching risk of TBZ from the greens and a positive correlation to the organic matter content was shown. In light of these findings, organic matter content should be taken into consideration during the construction of golf courses, especially when following USGA guidelines.