Impact of varying soil structure on transport processes in different diagnostic horizons of three soil types

When soil structure varies in different soil types and the horizons of these soil types, it has a significant impact on water flow and contaminant transport in soils. This paper focuses on the effect of soil structure variations on the transport of pesticides in the soil above the water table. Transport of a pesticide (chlorotoluron) initially applied on soil columns taken from various horizons of three different soil types (Haplic Luvisol, Greyic Phaeozem and Haplic Cambisol) was studied using two scenarios of ponding infiltration. The highest infiltration rate and pesticide mobility were observed for the Bt₁ horizon of Haplic Luvisol that exhibited a well-developed prismatic structure. The lowest infiltration rate was measured for the Bw horizon of Haplic Cambisol, which had a poorly developed soil structure and a low fraction of large capillary pores and gravitational pores. Water infiltration rates were reduced during the experiments by a soil structure breakdown, swelling of clay and/or air entrapped in soil samples. The largest soil structure breakdown and infiltration decrease was observed for the Ap horizon of Haplic Luvisol due to the low aggregate stability of the initially well-aggregated soil. Single-porosity and dual-permeability (with matrix and macropore domains) flow models in HYDRUS-1D were used to estimate soil hydraulic parameters via numerical inversion using data from the first infiltration experiment. A fraction of the macropore domain in the dual-permeability model was estimated using the micro-morphological images. Final soil hydraulic parameters determined using the single-porosity and dual-permeability models were subsequently used to optimize solute transport parameters. To improve numerical inversion results, the two-site sorption model was also applied. Although structural changes observed during the experiment affected water flow and solute transport, the dual-permeability model together with the two-site sorption model proved to be able to approximate experimental data.     

Formulation of a soil-pesticide transport model based on a compartmental approach

A semianalytical soil-pesticide transport model is formulated based on a compartmental approach to determine spatial and temporal variations of pesticide residues across a soil profile. The compartmental model is implemented by drawing an analogy between a series of continuous-flow stirred tank reactors and a soil horizon that consists of multiple perfectly mixed compartments. The analogy is strengthened by exploiting a relation between the compartment series and the conventional convective-dispersive equation (CDE) for vertical transport in the soil. Consequently, the number of compartments in the model formulation is not free, but dictated as a function of transport parameters. The model formulation allows consideration of arbitrary boundary value specifications and also, for some cases, spatially varying initial concentration profiles. Sorption kinetics is represented via a two-site model that involves a linear sorption isotherm and a first-order irreversible sorption or a radial diffusive penetrating model. For these three cases, analysis of the compartmental model allows the resultant concentration profiles to be expressed in terms of the Poisson distribution. When a nonlinear kinetic sorption model is used to simulate the sorption processes, an analytical solution is not found and a numerical approach is required.     

Kinetic modeling of virus transport at the field scale

Bacteriophage removal by soil passage in two field studies was re-analyzed with the goal to investigate differences between one- and two-dimensional modeling approaches, differences between one- and two-site kinetic sorption models, and the role of heterogeneities in the soil properties. The first study involved removal of bacteriophages MS2 and PRDI by dune recharge, while the second study represented removal of MS2 by deep well injection. In both studies, removal was higher during the first meters of soil passage than thereafter. The software packages HYDRUS-ID and HYDRUS-2D, which simulate water flow and solute transport in one- and two-dimensional variably saturated porous media, respectively, were used. The two codes were modified by incorporating reversible adsorption to two types of kinetic sites. Tracer concentrations were used first to calibrate flow and transport parameters of both models before analyzing transport of bacteriophages. The one-dimensional one-site model did not fully describe the tails of the measured breakthrough curves of MS2 and PRD1 from the dune recharge study. While the one-dimensional one-site model predicted a sudden decrease in virus concentrations immediately after the peaks, measured data displayed much smoother decline and tailing. The one-dimensional two-site model simulated the overall behavior of the breakthrough curves very well. The two-dimensional one-site model predicted a more gradual decrease in virus concentrations after the peaks than the one-dimensional one-site model, but not as good as the one-dimensional two-site model. The dimensionality of the problem hence can partly explain the smooth decrease in concentration after peak breakthrough. The two-dimensional two-site model provided the best results. Values for k(att2) and k(det2) could not be determined at the last two of four monitoring wells, thus suggesting that either a second type of kinetic sites is present in the first few meters of dune passage and not beyond the second monitoring well, or that effects of soil heterogeneity and dimensionality of the problem overshadowed this process. Variations between single collector efficiencies were relatively small, whereas collision efficiencies varied greatly. This implies that the nonlinear removal of MS2 and PRD1 is mainly caused by variations in interactions between grain and virus surfaces rather than by physical heterogeneity of the porous medium. Similarly, a two-site model performed better than the one-site model in describing MS2 concentrations for the deep well injection study. However, the concentration data were too sparse in this study to have much confidence in the fitted parameters.     

Adsorption and desorption processes of MCPA in Polish mineral soils

Studies on the adsorption and desorption of MCPA (4-chloro-2-methylophenoxyacetic acid) were performed in soil horizons of three representative Polish agricultural soils. The Hyperdystric Arenosol, the Haplic Luvisol and the Hypereutric Cambisol were investigated in laboratory batch experiments. Initially, both the adsorption and desorption proceeded rapidly, and either the equilibrium was reached after approximately 30 min or the process slowed down and continued at a slow rate. In the latter case, the equilibrium was reached after 8 hours. Data on the adsorption/desorption kinetics fitted well to the two-site kinetic model. The measured sorption and desorption isotherms were of L-type. The sorption distribution coefficients (K(ads) (d)) were in the range of 0.75--0.97 for Ap soil horizons and significantly lower in deeper soil layers. The corresponding desorption coefficients (K(des) (d)) were higher and ranged from 1.02 to 2.01. Both the adsorption and desorption of MCPA in all soil horizons was strongly and negatively related to soil pH. It appears that hydrophobic sorption plays a dominant role in the MCPA retention in topsoils whereas hydrophilic sorption of MCPA anions is the dominant adsorption mechanism in subsoils.     

Continuous time random walk model better describes the tailing of atrazine transport in soil

Contaminant transport in soils is complicated and involves some physical and chemical nonequilibrium processes. In this research, the soil column displacement experiments of Cl⁻ and atrazine under different flow velocities were carried out. The data sets of Cl⁻ transport in sandy loam fitted to the convection dispersion equation (CDE) and the two-region model (TRM) indicated that the effects of physical nonequilibrium process produced by immobile water on the breakthrough curves (BTCs) of Cl⁻ and atrazine transport through the repacking soil columns were negligible. The two-site model (TSM) and the continuous time random walk (CTRW) were also used to fit atrazine transport behavior at the flow rate of 19.86 cm h⁻¹. The CTRW convincingly captured the full evolution of atrazine BTC in the soil column, especially for the part of long tailing. However, the TSM failed to characterize the tailing of atrazine BTC in the soil column. The calculated fraction of equilibrium sorption sites, F, ranging from 0.78 to 0.80 for all flow rates suggested the contribution of nonequilibrium sorption sites to the asymmetry of atrazine BTCs. Furthermore, the data sets for the flow rates of 6.68 cm h⁻¹ and 32.81 cm h⁻¹ were predicted by the TSM and the CTRW. As to the flow rate of 6.68 cm h⁻¹, the CTRW predicted the entire BTC of atrazine transport better than the TSM did. For the flow rate of 32.81 cm h⁻¹, the CTRW characterized the late part of the tail better, while the TSM failed to predict the tailings of atrazine BTC.     

A sensibility analysis of model selection in modeling the reactive transport of cesium in crushed granite

We performed a sensibility analysis of model selection in modeling the reactive transport of cesium in crushed granite through model calibration and validation. Based on some solid phase analysis data and kinetic batch experimental results, we hypothesized three two-site sorption models in the LEHGC reactive transport model to fit the breakthrough curves (BTCs) from the corresponding column experiments. The analysis of breakthrough curves shows that both the empirical two-site kinetic linear sorption model and the semi-mechanistic/semi-empirical two-site kinetic surface complexation model, regardless of their complexity, can match our experimental data fairly well under given test conditions. A numerical experiment to further compare the two models shows that they behave differently when the pore velocity is not of the same order of magnitude as our test velocities. This result indicates that further investigations to help determine a better model are needed. We suggest that a multistage column experiment, which tests over the whole range of practical flow velocities, should be conducted to help alleviate inadequate hypothesized models.     

Effects of temperature and water content on degradation of isoproturon in three soil profiles

The phenylurea herbicide isoproturon, 3-(4-isopropylphenyl)-1,1-dimethylurea (IPU), is widely used to control pre- and post-emergence of grass and broad-leaved weeds in cereal crops. Its degradation in soils is a key process for assessing its leaching risk to groundwater resources. The degradation properties of various samples from surface and subsurface soil (down to 1m depth) of a heterogeneous agricultural field were studied using (14)C-IPU. Laboratory incubations were carried out at 22 and 10 degrees C and at water contents 90% and 50% of the estimated water holding capacity (eWHC) corresponding to water potentials between -56 kPa and -660 MPa. Degradation was found to be more sensitive to water content variations than to temperature variations in the ranges that we used. For surface layers, at 10 and 22 degrees C, the degradation half-life increased by a factor 10 and 15, respectively, when water content decreased from 90% to 50% eWHC. Under optimal degradation conditions (i.e. 22 degrees C and 90% eWHC), 3-(4-isopropylphenyl)-1-methylurea (MDIPU) was the main metabolite in surface samples. At subsurface depths, IPU half-lives were larger than 100 d, IPU was the main compound after 92 d of incubation and the main metabolite was an unidentified polar metabolite. These results suggest a metabolic pathway involving hydroxylations for subsurface materials. IPU degradation was largely affected by water availability in both surface and subsurface horizons. Clay content seemed to play a major role in degradation processes in subsurface soil by determining through sorption IPU availability in soil solution and/or by limiting water availability for microorganisms.     

Determination of solid-liquid partition coefficients (Kd) for the herbicides isoproturon and trifluralin in five UK agricultural soils

Isoproturon and trifluralin are herbicides of contrasting chemical characters and modes of action. Standard batch sorption procedures were carried out to investigate the individual sorption behaviour of 14C-isoproturon and 14C-trifluralin in five agricultural soils (1.8-4.2% OC), and the soil solid-liquid partition coefficients (Kd values) were determined. Trifluralin exhibited strong partitioning to the soil solid phase (Kd range 106-294) and low desorption potential, thus should not pose a threat to sensitive waters via leaching, although particle erosion and preferential flow pathways may facilitate transport. For isoproturon, soil adsorption was low (Kd range 1.96-5.75) and desorption was high, suggesting a high leaching potential, consistent with isoproturon being the most frequently found pesticide in UK surface waters. Soil partitioning was directly related to soil organic carbon (OC) content. Accumulation isotherms were modelled using a dual-phase adsorption model to estimate adsorption and desorption rate coefficients. Associations between herbicides and soil humic substances were also shown using gel filtration chromatography.     

Experimental variability in characterization of cyfluthrin sorption to soil

To assess the risk of a pesticide to leach to groundwater or to run off to surface water after application, it is necessary to characterize the sorption of the pesticide to soil. For pyrethroids, their hydrophobicity, strong sorption to various materials, and low solubility make it difficult to accurately characterize sorption processes. The objective of this research was to evaluate the variability in cyfluthrin ((RS)-alpha -cyano-4-fluoro-3-phenoxybenzyl (1RS,3RS;1RS,3SR)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate) sorption to soil as affected by experiment conditions. To minimize cyfluthrin sorption on the walls of glass, silanized-glass, stainless steel, and PTFE centrifuge tubes, cyfluthrin solution was added to aqueous soil slurries or directly to soil, after which it was equilibrated with aqueous solution. Depending on the soil, variation in sorption coefficients, Koc, obtained using different experimental methodologies with one soil can be comparable to the variation in Koc values obtained for soils with different physical and chemical properties using one method. Koc values for cyfluthrin ranged from 56,000 to 300,000 L kg-1. Sorption methodology needs to be evaluated before sorption coefficients are used in predictive transport models.     

A lysimeter experiment to investigate temporal changes in the availability of pesticide residues for leaching

Leaching of three pesticides (isoproturon, chlorotoluron and triasulfuron) and a tracer (bromide) were determined in four contrasting soils ranging in texture from sandy loam to clay. The compounds were applied to undisturbed columns of soil and four columns for each soil were randomly selected and leached with 24-mm equivalent of water at prescribed time intervals (3, 9, 24, 37 and 57 d after application). A rapid decline in leached loads of isoproturon and chlorotoluron as time from application to irrigation increased was observed in all soils. In contrast, triasulfuron and bromide loads only decreased rapidly in the clay soil. Bromide losses decreased with decreasing clay contents of the soil and therefore with a decrease in structural development. Magnitudes of pesticide losses varied from soil to soil, depending on structural development and the organic carbon content. Pesticide degradation experiments on disturbed and undisturbed soil samples showed that the rapid decline of leached loads with time was faster than could be explained by degradation alone. Five physico-chemical processes are put forward to explain the different patterns of pesticide leached loads observed in the soils: (1) relative extent of preferential flow, (2) sorption capacity of the compounds to the different soils, (3) extent of degradation of the compounds in the soil, (4) variation in sorption kinetics between compounds associated with pesticide diffusion into soil aggregates, and (5) protection of the compounds by a combination of intra-aggregate diffusion and the presence of preferential flow pathways.     

Effect of grass cover on water and pesticide transport through undisturbed soil columns, comparison with field study (Morcille watershed, Beaujolais)

The purpose of this work is to assess the effectiveness of two grass covers (buffer zone and grass-covered inter-row), to reduce pesticide leaching, and subsequently to preserve groundwater quality. Lower amounts of pesticides leached through grass-cover soil columns (2.7-24.3% of the initial amount) than the bare soil columns (8.0-55.1%), in correspondence with their sorption coefficients. Diuron was recovered in higher amounts in leachates (8.9-32.2%) than tebuconazole (2.7-12.9%), in agreement with their sorption coefficients. However, despite having a sorption coefficient similar to that of diuron, more procymidone was recovered in the leachates (10.2-55.1%), probably due to its facilitated transport by dissolved organic matter. Thus even in this very permeable soil, higher organic matter contents associated with grass-cover reduce the amount of pesticide leaching and limit the risk of groundwater contamination by the pesticides. The results of diuron and tebuconazole transfer through undisturbed buffer zone soil columns are in agreement with field observations on the buffer zone.     

PeLM: modeling of pesticide-losses through runoff and sediment transport

A GIS-aided pesticide loss model (PeLM) was developed to simulate pesticide losses through surface runoff and sediment transport in watershed systems. The PeLM could tackle the movement of eroded soil along with surface runoff as well as the pesticide losses in adsorbed and dissolved phases. The contributions of different soil types in the sediment were also examined. The model was applied to the Kintore Creek Watershed of southern Ontario, Canada. The simulation results were verified through observed data, indicating a correlation level of 0.89-0.98. The results also showed that clay particles usually held the largest share of contributions to pesticide losses through soil erosion. This study is significant in the efforts for modeling nonpoint source pollution in watershed systems. It provides useful information and support for the related decisions of watershed management.     

Transport of copper as affected by titania nanoparticles in soil columns

The effects of TiO₂ nanoparticles on the transport of Cu through four different soil columns were studied. For two soils (HB and DX), TiO₂ nanoparticles acted as a Cu carrier and facilitated the transport of Cu. For a third soil (BJ) TiO₂ nanoparticles also facilitated Cu transport but to a much lesser degree, but for a fourth soil (HLJ) TiO₂ nanoparticles retarded the transport of Cu. Linear correlation analysis indicated that soil properties rather than sorption capacities for Cu primary governed whether TiO₂ nanoparticles-facilitated Cu transport. The TiO₂-associated Cu of outflow in the Cu-contaminated soil columns was significantly positively correlated with soil pH and negatively correlated with CEC and DOC. During passage through the soil columns 46.6-99.9% of Cu initially adsorbed onto TiO₂ could be “stripped” from nanoparticles depending on soil, where Cu desorption from TiO₂ nanoparticles increased with decreasing flow velocity and soil pH.     

PeLM: Modeling of Pesticide-Losses Through Runoff and Sediment Transport

Abstract

A GIS-aided pesticide loss model (PeLM) was developed to simulate pesticide losses through surface runoff and sediment transport in watershed systems. The PeLM could tackle the movement of eroded soil along with surface runoff as well as the pesticide losses in adsorbed and dissolved phases. The contributions of different soil types in the sediment were also examined. The model was applied to the Kintore Creek Watershed of southern Ontario, Canada. The simulation results were verified through observed data, indicating a correlation level of 0.89–0.98. The results also showed that clay particles usually held the largest share of contributions to pesticide losses through soil erosion. This study is significant in the efforts for modeling nonpoint source pollution in watershed systems. It provides useful information and support for the related decisions of watershed management.     

Limitations on the role of incorporated organic matter in reducing pesticide leaching.

The use of organic amendments has been suggested as a method of controlling pesticide leaching through soils. The enarenados soils of the intensive horticulture of the Almeria province of southern Spain contain buried organic matter horizons above a soil layer amended with clay. This region is ideal for understanding the potential for and limitations of organic amendments in preventing pesticide pollution. This study measured the sorption and degradation potential of carbofuran in this soil system and the hydrological behaviour of the soil horizons. The sorption of carbofuran was controlled by the organic carbon content, the degradation was strongly pH-dependent and the acidic organic layer protected the sorbed carbofuran against degradation. Hydrologically, the soil system is dominated by ponding above an amended clay layer and by the presence of macropores that can transport water through this clay. A simple model is proposed on this basis and shows that although high levels of dissolved organic carbon can be released by buried organic horizons, the major control on re-release of sorbed pesticide is the potential for sorption hysteresis in this organic layer. A comparison of sorption and degradation data for carbamate insecticides used in the region with groundwater observations for these compounds shows that no amount of incorporated organic would protect against pollution from highly water-soluble compounds.     

Determination of bromacil transport as a function of water and carbon content in soils

This study was conducted to determine the significance of bromacil transport as a function of water and carbon content in soils and to explore the implications of neglecting sorption when making assessments of travel time of bromacil through the vadose zone. Equilibrium batch sorption tests were performed for loamy sand and sandy soil added with four different levels of powdered activated carbon (PAC) content (0, 0.01, 0.05, and 0.1%). Column experiments were also conducted at various water and carbon contents under steady-state flow conditions. The first set of column experiments was conducted in loamy sand containing 1.5% organic carbon under three different water contents (0.23, 0.32, and 0.41) to measure breakthrough curves (BTCs) of bromide and bromacil injected as a square pulse. In the second set of column experiments, BTCs of bromide and bromacil injected as a front were measured in saturated sandy columns at the four different PAC levels given above. Column breakthrough data were analyzed with both equilibrium and nonequilibrium (two-site) convection-dispersion equation (CDE) models to determine transport and sorption parameters under various water and carbon contents. Analysis with batch data indicated that neglect of the partition-related term in the calculation of solute velocity may lead to erroneous estimation of travel time of bromacil, i.e. an overestimation of the solute velocity by a factor of R. The column experiments showed that arrival time of the bromacil peak was larger than that of the bromide peak in soils, indicating that transport of bromacil was retarded relative to bromide in the observed conditions. Extent of bromacil retardation (R) increased with decreasing water content and increasing PAC content, supporting the importance of retardation in the estimation of travel time of bromacil even at small amounts of organic carbon for soils with lower water content.     

Mapping field spatial distribution patterns of isoproturon-mineralizing activity over a three-year winter wheat/rape seed/barley rotation

The temporal and spatial variability of the activity of soil microorganisms able to mineralize the herbicide isoproturon (IPU) pesticide was investigated over a three-year long crop rotation between 2008 and 2010. Isoproturon mineralization was higher in 2008, when winter wheat was treated with this herbicide, than in 2009 and 2010, when rape seed and barley were treated with different herbicides. Under laboratory conditions, we showed that isoproturon mineralization was not promoted by sulfonylurea herbicide applied on barley crop in 2010. IPU mineralization was shown to be highly variable at the field scale in years 2009 and 2010. Principal component analyses and analyses of similarities revealed that soil pH and equivalent humidity, and to a lesser extent soil organic matter content and cation exchange capacity (CEC) were the main drivers of isoproturon-mineralizing activity variance. Using a rather simple model that yields the rate of isoproturon mineralization as a function of soil pH and equivalent humidity, we explained up to 85% of the variance observed. Mapping field-scale distribution of isoproturon mineralization over the three-year survey indicated higher variability in 2009 and in 2010 as compared to 2008, suggesting that isoproturon treatment applied to winter wheat promoted isoproturon mineralization activity and reduced its spatial variability. Field-scale distribution of isoproturon mineralization showed important similarity to the distribution of soil pH, equivalent humidity and to a lesser extent to soil organic matter and cation exchange capacity (CEC) thereby confirming our model.