Accounting for uncertainty in pedotransfer functions in vulnerability assessments of pesticide leaching to groundwater

A simulation tool for site-specific vulnerability assessments of pesticide leaching to groundwater was developed, based on the pesticide fate and transport model MACRO, parameterized using pedotransfer functions and reasonable worst-case parameter values. The effects of uncertainty in the pedotransfer functions on simulation results were examined for 48 combinations of soils, pesticides and application timings, by sampling pedotransfer function regression errors and propagating them through the simulation model in a Monte Carlo analysis. An uncertainty factor, f(u), was derived, defined as the ratio between the concentration simulated with no errors, c(sim), and the 80th percentile concentration for the scenario. The pedotransfer function errors caused a large variation in simulation results, with f(u) ranging from 1.14 to 1440, with a median of 2.8. A non-linear relationship was found between f(u) and c(sim), which can be used to account for parameter uncertainty by correcting the simulated concentration, c(sim), to an estimated 80th percentile value. For fine-textured soils, the predictions were most sensitive to errors in the pedotransfer functions for two parameters regulating macropore flow (the saturated matrix hydraulic conductivity, K(b), and the effective diffusion pathlength, d) and two water retention function parameters (van Genuchten's N and alpha parameters). For coarse-textured soils, the model was also sensitive to errors in the exponent in the degradation water response function and the dispersivity, in addition to K(b), but showed little sensitivity to d. To reduce uncertainty in model predictions, improved pedotransfer functions for K(b), d, N and alpha would therefore be most useful.     

Testing MACRO (version 5.1) for pesticide leaching in a Dutch clay soil

Testing of pesticide leaching models against comprehensive field-scale measurements is necessary to increase confidence in their predictive ability when used as regulatory tools. Version 5.1 of the MACRO model was tested against measurements of water flow and the behaviour of bromide, bentazone [3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide] and imidacloprid [1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine] in a cracked clay soil. In keeping with EU (FOCUS) procedures, the model was first calibrated against the measured moisture profiles and bromide concentrations in soil and in drain water. Uncalibrated pesticide simulations based on laboratory measurements of sorption and degradation were then compared with field data on the leaching of bentazone and imidacloprid. Calibrated parameter values indicated that a high degree of physical non-equilibrium (i.e. strong macropore flow) was necessary to describe solute transport in this soil. Comparison of measured and simulated bentazone concentration profiles revealed that the bulk of the bentazone movement in this soil was underestimated by MACRO. Nevertheless, the model simulated the dynamics of the bentazone breakthrough in drain water rather well and, in particular, accurately simulated the timing and the concentration level of the early bentazone breakthrough in drain water. The imidacloprid concentration profiles and its persistence in soil were simulated well. Moreover, the timing of the early imidacloprid breakthrough in the drain water was simulated well, although the simulated concentrations were about 2-3 times larger than measured. Deep groundwater concentrations for all substances were underestimated by MACRO, although it simulated concentrations in the shallow groundwater reasonably well. It is concluded that, in the context of ecotoxicological risk assessments for surface water, MACRO can give reasonably good simulations of pesticide concentrations in water draining from cracking clay soils, but that prior calibration against hydrologic and tracer data is desirable to reduce uncertainty and improve accuracy.     

RunMACRO: a program to facilitate sensitivity analyses using the water flow and solute movement model MACRO

Sensitivity analyses of pesticide leaching often involve a large range of simulations based on nearly identical set-ups. Using RunMACRO it is possible to make large numbers of simulations with a minimum of exertion. Running many nearly identical model set-ups is tedious and might introduce errors in selecting the correct values from a long range of parameter files that are appropriate to the model set-up. RunMACRO makes the task easier and minimises the risk of errors in the generation of parameter files and model executions. Using RunMACRO, it is possible to create a suite of MACRO simulations based on a single parameter file where the range or a list of values for one to three parameters is specified. RunMACRO then creates a parameter file for each of the simulations and runs the simulations one by one. RunMACRO can easily be modified to be used with other simulation programs that use ASCII-based parameter files and can be started from a command prompt. RunMACRO is available free to use and modify from the Geological Survey of Denmark and Greenland's home page.     

A refined lack‐of‐fit statistic to calibrate pesticide fate models for responsive systems

BACKGROUND: Calibration by inverse modelling was performed with the MACRO transport and fate model using long‐term (>10 years) drainflow and isoproturon (IPU) data from western France. Two lack‐of‐fit (LOF) indices were used to control the inverse modelling: sum of squares (SS) and an alternative statistic called the vertical‐horizontal distance integrator (VHDI), which is designed to account for offsets in observed and predicted arrival times of peak IPU concentration. With these data, SS was artificially inflated because it is limited to comparison of predicted and observed IPU concentrations that are concurrent in time. The LOFs were used along with the index of agreement (d) and the correlation coefficient (r) to ascertain the fit of the calibrated models. RESULTS: Predicted arrival times of peak IPU concentration differed somewhat from observed times. All four indices indicated better model fit for the second of two validation periods when inverse modelling was controlled by VHDI rather than SS (SS = 26.4, d = 0.660, r = 0.606 and VHDI = 1.25). The VHDI statistic was markedly lower compared with the uncalibrated model (38.0) and SS calibration results (24.5). The final maximum predicted IPU concentration (44.5 µg L^?1) for the calibration period was very similar to the observed value (44 µg L^?1). CONCLUSION: VHDI is seen as an effective alternative to SS for calibration and validation of pesticide fate models applied to responsive systems. VHDI provided a more realistic assessment of model performance for the transient flows and short‐lived concentrations observed here, and also effectively substituted for the objective function in inverse modelling. Copyright © 2009 Society of Chemical Industry     

Quantifying interactions between compound properties and macropore flow effects on pesticide leaching

The objective of this study was to investigate the interactions between compound properties and macropore flow effects on pesticide leaching. To this end, the dual‐porosity MACRO model was used to simulate leaching of 60 hypothetical compounds with widely differing sorption and degradation characteristics using a pre‐calibrated scenario from Lanna, south‐west Sweden, representing a structured clay soil. The model predicts that, in the worst case, macropore flow increases leaching by more than four orders of magnitude for moderately to strongly sorbed compounds with relatively short half‐lives. However, it was also notable that leaching of some very mobile compounds is actually reduced by macropore flow. For pesticides leaching between 0.0001 and 10% of the applied dose (without macropore flow), the impact of pesticide properties on leaching is markedly reduced. This suggests that reductions in applied dose become a relatively more attractive and effective means of decreasing leaching from structured soils. © 2000 Society of Chemical Industry     

Effects of soil redistribution by tillage on subsequent transport of pesticide to subsurface drains

BACKGROUND

Tillage operations will change the distribution in soil for any pesticide residues still present from earlier applications. This redistributive effect of tillage has been neglected in the study of pesticide leaching behavior. This study reviews the literature to characterize this redistributive effect for different tillage operations and uses a pesticide leaching model to investigate the impact of redistribution on pesticide transport to subsurface drains which is a significant input route to surface water bodies.

RESULTS

Inversion ploughing moves the majority of any residues of pesticide present at or near the soil surface into the bottom two-thirds of the plough layer, whereas non-inversion ploughing has only a limited redistributive effect. Incorporating this redistributive effect into model simulations resulted in large changes (typically 5–10-fold difference) in both the maximum concentration and total mass of pesticide transported to drains over the winter following cultivation. More intense cultivation decreased subsequent leaching for relatively mobile compounds (Koc ≤1000 mL g⁻¹), but increased it for strongly sorbed pesticides (Koc ≥2000 mL g⁻¹).

CONCLUSION

The redistributive effect of soil tillage on pesticide residues can have a large effect on subsequent transport to subsurface drains. This effect has been neglected in the literature. Field research is required to validate the model simulations presented here, and consideration should be given as to whether the effect needs to be included within risk assessment procedures. © 2022 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.