Do lab-derived distribution coefficient values of pesticides match distribution coefficient values determined from column and field-scale experiments? A critical analysis of relevant literature.

In this study, we analyzed sorption parameters for pesticides that were derived from batch and column or batch and field experiments. The batch experiments analyzed in this study were run with the same pesticide and soil as in the column and field experiments. We analyzed the relationship between the pore water velocity of the column and field experiments, solute residence times, and sorption parameters, such as the organic carbon normalized distribution coefficient ( ) and the mass exchange coefficient in kinetic models, as well as the predictability of sorption parameters from basic soil properties. The batch/column analysis included 38 studies with a total of 139 observations. The batch/field analysis included five studies, resulting in a dataset of 24 observations. For the batch/column data, power law relationships between pore water velocity, residence time, and sorption constants were derived. The unexplained variability in these equations was reduced, taking into account the saturation status and the packing status (disturbed-undisturbed) of the soil sample. A new regression equation was derived that allows estimating the values derived from column experiments using organic matter and bulk density with an value of 0.56. Regression analysis of the batch/column data showed that the relationship between batch- and column-derived values depends on the saturation status and packing of the soil column. Analysis of the batch/field data showed that as the batch-derived value becomes larger, field-derived values tend to be lower than the corresponding batch-derived values, and vice versa. The present dataset also showed that the variability in the ratio of batch- to column-derived value increases with increasing pore water velocity, with a maximum value approaching 3.5.

Fate of two herbicides in zero-tension lysimeters and in field soil.

In Germany, zero-tension lysimeters are used as part of the registration requirements in case pesticides pose a potential threat to contaminate the groundwater. However, the water regime and the method of pesticide sampling differ between the lysimeters and the field. We monitored the transport of the two herbicides ethidimuron [1-(5- ethylsulfonyl-1,3,4-thiadiazol-2-yl)-1,3-dimethylurea] (ETD) and methabenzthiazuron [1-benzothiazol-2-yl-1,3-dimethyl-urea] (MBT) and their main metabolite, accompanied with bromide as conservative tracer, in zero-tension lysimeters filled with undisturbed soil and in the field. The herbicides were applied as a short pulse to the bare soil surface. Herbicide concentrations were analyzed in the drainage water of the 1.2-m-deep lysimeters and from soil cores taken from the field during six campaigns. Soil coring in the field emphasized matrix flow and allowed us to estimate the field-based dissipation and sorption parameters. Based on mass recovery calculations, the field fate half-life was 870 d for ETD compared with 389 d for its main metabolite. The initially fast field-based dissipation of MBT with a half-life value of approximately 1 mo was followed by a much slower dissipation. The retardation factor was estimated from the concentration profiles by inversely solving the convection-dispersion equation and yielded 18.2 +/- 1.3 for ETD and 36.9 +/- 17.5 for MBT. For the lysimeters, a leaching period of 2 1/2 yr was too short to monitor bulk herbicide mass through the soil matrix. Only 1.7% of the applied EDT and 1.4% of the applied MBT were sampled in the drainage water at 1.2 m depth. Despite contrasting sorption and dissipation properties, both herbicides appeared fast and at the same time in the drainage water, hinting at preferential flow phenomena. Compared with field fate of herbicides measured by soil coring, zero-potential lysimeters emphasize the transport of small amounts of herbicides triggered by preferential flow events.

Transport of sulfadiazine in undisturbed soil columns: effects of flow rate, input concentration and pulse duration.

Antibiotics reach soils via spreading of manure or sewage sludge. Knowledge on the transport behavior of antibiotics in soils is needed to assess their environmental fate. The effect of flow rate and applied mass, i.e., input concentration and pulse duration, on the transport of 14C-sulfadiazine (SDZ; 4-aminoN-pyrimidin-2-yl-benzenesulfonamide) was investigated with soil column experiments and numerical studies. Sulfadiazine was applied in pulses (6.8, 68 or 306 h) under steady-state (0.051 and 0.21 cm h(-1)) and intermittent flow conditions and at two input concentrations (0.57 and 5.7 mg L(-1)). Breakthrough curves (BTCs) of 14C were measured and for one experiment concentrations of SDZ, and its transformation products 4-(2-iminopyrimidin-1(2H)-yl)aniline (An-SDZ) and N(1)-2-(4-hydroxypyrimidinyl)benzenesulfanilamide (4-OH-SDZ) were determined. After finalizing the leaching experiments, 14C was quantified in different slices of the columns. A lower flow rate led to remarkably lower eluted masses compared with the higher flow rates. All BTCs could be described well using a three-site attachment-detachment model for which a common set of parameters was determined. However, the BTC obtained with the high input concentration was slightly better described with a two-site isotherm-based model. The prediction of the concentration profiles was good with both model concepts. The fitted sorption capacities decreased in the order SDZ > 4-OH-SDZ > An-SDZ. Overall, the experiments reveal the presence of similar mechanisms characterizing SDZ transport. The dependence of model performance on concentration implies that although the three-site attachment-detachment model is appropriate to predict the transport of SDZ in soil columns, not all relevant processes are adequately captured.

Transport and transformation of sulfadiazine in soil columns packed with a silty loam and a loamy sand.

Concerning the transport of the veterinary antibiotic sulfadiazine (SDZ) little is known about its possible degradation during transport. Also its sorption behaviour is not yet completely understood. We investigated the transport of SDZ in soil columns with a special emphasis on the detection of transformation products in the outflow of the soil columns and on modelling of the concentration distribution in the soil columns afterwards. We used disturbed soil columns near saturation, packed with a loamy sand and a silty loam. SDZ was applied as a 0.57 mg L(-1) solution at a constant flow rate of 0.25 cm h(-1) for 68 h. Breakthrough curves (BTC) of SDZ and its transformation products 4-(2-iminopyrimidin-1(2H)-yl)aniline and 4-hydroxy-SDZ were measured for both soils. For the silty loam we additionally measured a BTC for an unknown transformation product which we only detected in the outflow samples of this soil. After the leaching experiments the (14)C-concentration was quantified in different layers of the soil columns. The transformation rates were low with mean SDZ mass fractions in the outflow samples of 95% for the loamy sand compared to 97% for the silty loam. The formation of 4-(2-iminopyrimidin-1(2H)-yl)aniline appears to be light dependent and did probably not occur in the soils, but afterwards. In the soil columns most of the (14)C was found near the soil surface. The BTCs in both soils were described well by a model with one reversible (kinetic) and one irreversible sorption site. Sorption kinetics played a more prominent role than sorption capacity. The prediction of the (14)C -concentration profiles was improved by applying two empirical models other than first order to predict irreversible sorption, but also these models were not able to describe the (14)C concentration profiles correctly. Irreversible sorption of sulfadiazine still is not well understood.