A review of model applications for structured soils: b) Pesticide transport.

The past decade has seen considerable progress in the development of models simulating pesticide transport in structured soils subject to preferential flow (PF). Most PF pesticide transport models are based on the two-region concept and usually assume one (vertical) dimensional flow and transport. Stochastic parameter sets are sometimes used to account for the effects of spatial variability at the field scale. In the past decade, PF pesticide models were also coupled with Geographical Information Systems (GIS) and groundwater flow models for application at the catchment and larger regional scales. A review of PF pesticide model applications reveals that the principal difficulty of their application is still the appropriate parameterization of PF and pesticide processes. Experimental solution strategies involve improving measurement techniques and experimental designs. Model strategies aim at enhancing process descriptions, studying parameter sensitivity, uncertainty, inverse parameter identification, model calibration, and effects of spatial variability, as well as generating model emulators and databases. Model comparison studies demonstrated that, after calibration, PF pesticide models clearly outperform chromatographic models for structured soils. Considering nonlinear and kinetic sorption reactions further enhanced the pesticide transport description. However, inverse techniques combined with typically available experimental data are often limited in their ability to simultaneously identify parameters for describing PF, sorption, degradation and other processes. On the other hand, the predictive capacity of uncalibrated PF pesticide models currently allows at best an approximate (order-of-magnitude) estimation of concentrations. Moreover, models should target the entire soil-plant-atmosphere system, including often neglected above-ground processes such as pesticide volatilization, interception, sorption to plant residues, root uptake, and losses by runoff. The conclusions compile progress, problems, and future research choices for modelling pesticide displacement in structured soils.

A review of model applications for structured soils: a) Water flow and tracer transport.

Although it has many positive effects, soil structure may adversely affect the filtering function of the vadose zone that protects natural water resources from various sources of pollution. Physically based models have been developed to analyze the impacts of preferential water flow (PF) and physical non-equilibrium (PNE) solute transport on soil and water resources. This review compiles results published over the past decade on the application of such models for simulating PF and PNE non-reactive tracer transport for scales ranging from the soil column to the catchment area. Recent progress has been made in characterizing the hydraulically relevant soil structures, dynamic flow conditions, inverse parameter and uncertainty estimations, independent model parameterizations, stochastic descriptions of soil heterogeneity, and 2D or 3D extensions of PNE models. Two-region models are most widely used across all scales; as a stand-alone approach to be used up to the field scale, or as a component of distributed, larger scale models. Studies at all scales suggest that inverse identification of parameters related to PF is generally not possible based on a hydrograph alone. Information on flux-averaged and spatially distributed local resident concentrations is jointly required for quantifying PNE transport. At the column and soil profile scale, model predictions of PF are becoming increasingly realistic through the implementation of the 3D soil structure as derived from hydrogeophysical and tracer techniques. At the field scale, integrating effects of the soil structure and its spatial variability has been attempted by combining 1D PNE approaches with stochastic parameter sampling. At the catchment area scale, the scarcity of data makes validation of PF related model components a task yet to be accomplished. The quest for easily measurable proxy variables, as 'the missing link' between soil structure and model parameters, continues in order to improve the practical predictive capability of PF-PNE models. A follow-up paper complementing this manuscript reviews model applications involving non-equilibrium transport of pesticides, as representatives of reactive solutes.

Multi-process herbicide transport in structured soil columns: experiments and model analysis.

Model predictions of pesticide transport in structured soils are complicated by multiple processes acting concurrently. In this study, the hydraulic, physical, and chemical nonequilibrium (HNE, PNE, and CNE, respectively) processes governing herbicide transport under variably saturated flow conditions were studied. Bromide (Br-), isoproturon (IPU, 3-(4-isoprpylphenyl)-1,1-dimethylurea) and terbuthylazine (TER, N2-tert-butyl-6-chloro-N4-ethyl-1,3,5-triazine-2,4-diamine) were applied to two soil columns. An aggregated Ap soil column and a macroporous, aggregated Ah soil column were irrigated at a rate of 1 cm h(-1) for 3 h. Two more irrigations at the same rate and duration followed in weekly intervals. Nonlinear (Freundlich) equilibrium and two-site kinetic sorption parameters were determined for IPU and TER using batch experiments. The observed water flow and Br- transport were inversely simulated using mobile-immobile (MIM), dual-permeability (DPM), and combined triple-porosity (DP-MIM) numerical models implemented in HYDRUS-1D, with improving correspondence between empirical data and model results. Using the estimated HNE and PNE parameters together with batch-test derived equilibrium sorption parameters, the preferential breakthrough of the weakly adsorbed IPU in the Ah soil could be reasonably well predicted with the DPM approach, whereas leaching of the strongly adsorbed TER was predicted less well. The transport of IPU and TER through the aggregated Ap soil could be described consistently only when HNE, PNE, and CNE were simultaneously accounted for using the DPM. Inverse parameter estimation suggested that two-site kinetic sorption in inter-aggregate flow paths was reduced as compared to within aggregates, and that large values for the first-order degradation rate were an artifact caused by irreversible sorption. Overall, our results should be helpful to enhance the understanding and modeling of multi-process pesticide transport through structured soils during variably saturated water flow.