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.     

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.     

Solute transport in crystalline rocks at Äspö — II: Blind predictions, inverse modelling and lessons learnt from test STT1

Based on the results from detailed structural and petrological characterisation and on up-scaled laboratory values for sorption and diffusion, blind predictions were made for the STT1 dipole tracer test performed in the Swedish Äspö Hard Rock Laboratory. The tracers used were nonsorbing, such as uranine and tritiated water, weakly sorbing ²²Na⁺, ⁸⁵Sr²⁺, ⁴⁷Ca²⁺and more strongly sorbing ⁸⁶Rb⁺, ¹³³Ba²⁺, ¹³⁷Cs⁺.Our model consists of two parts: (1) a flow part based on a 2D-streamtube formalism accounting for the natural background flow field and with an underlying homogeneous and isotropic transmissivity field and (2) a transport part in terms of the dual porosity medium approach which is linked to the flow part by the flow porosity.The calibration of the model was done using the data from one single uranine breakthrough (PDT3). The study clearly showed that matrix diffusion into a highly porous material, fault gouge, had to be included in our model evidenced by the characteristic shape of the breakthrough curve and in line with geological observations.After the disclosure of the measurements, it turned out that, in spite of the simplicity of our model, the prediction for the nonsorbing and weakly sorbing tracers was fairly good. The blind prediction for the more strongly sorbing tracers was in general less accurate. The reason for the good predictions is deemed to be the result of the choice of a model structure strongly based on geological observation. The breakthrough curves were inversely modelled to determine in situ values for the transport parameters and to draw consequences on the model structure applied. For good fits, only one additional fracture family in contact with cataclasite had to be taken into account, but no new transport mechanisms had to be invoked. The in situ values for the effective diffusion coefficient for fault gouge are a factor of 2–15 larger than the laboratory data. For cataclasite, both data sets have values comparable to laboratory data. The extracted K_d values for the weakly sorbing tracers are larger than Swedish laboratory data by a factor of 25–60, but agree within a factor of 3–5 for the more strongly sorbing nuclides. The reason for the inconsistency concerning K_ds is the use of fresh granite in the laboratory studies, whereas tracers in the field experiments interact only with fracture fault gouge and to a lesser extent with cataclasite both being mineralogically very different (e.g. clay-bearing) from the intact wall rock.     

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.     

The Grimsel (Switzerland) migration experiment: integrating field experiments, laboratory investigations and modelling

For several years tracer migration experiments are performed at Nagra's Grimsel Test Site in the Swiss Alps as a joint undertaking of Nagra, PNC and PSI. The aim is to develop methods for field experiments at possible sites for nuclear waste repositories and to test radionuclide transport models.A hydraulic dipole field is generated in a well-defined fracture zone in granite. The tracers used are non-sorbing (uranine, ³He, ⁴He, ⁸²Br⁻, ¹²³I⁻), mildly sorbing (²²Na⁺, ²⁴Na⁺), and more strongly sorbing (⁸⁵Sr²⁺, ⁸⁶Rb⁺, ¹³⁴Cs⁺, ¹³⁷Cs⁺). These experiments have been complemented by extensive laboratory investigations on petrography, on water-rock and nuclide-rock interaction as well as by migration experiments with bore cores.The main questions addressed are: What are the relevant geometric factors and mechanisms for transport, how well can breakthrough curves be extrapolated from one dipole arrangement to another, which parameters are scale dependent, is there a difference in sorption values between laboratory and field experiments or between static and dynamic experiments. Evaluating the experimental results for the non-sorbing uranine and the mildly sorbing tracers sorption, Strontium, we show that a consistent picture of tracer transport, and specifically of tracer sorption, is obtained when exploiting all available experimental information and using not too simplistic models.     

Determination of sorption properties of intact rock samples: New methods based on electromigration

Two new methods for determining sorption coefficients in large rock samples have been developed. The methods use electromigration as a means to speed up the transport process, allowing for fast equilibration between rock sample and tracer solution. An electrical potential gradient acts as a driving force for transport in addition to the concentration gradient and forces the cations through the rock sample towards the cathode. The electrical potential gradient induces both electromigration and electroosmotic flow with a resulting solute transport that is large compared to diffusive fluxes. In one of the methods, the solute is driven through the sample and collected at the outlet side. In the other, simpler method, the rock sample is equilibrated by circulating the solute through the sample. The equilibration of rock samples, up to 5 cm in length, with an aqueous solution has been accomplished within days to months. Experiments using cesium as a sorbing tracer yield results consistent with considerably more time demanding in-diffusion experiments. These methods give lower distribution coefficients than those obtained using traditional batch experiments with crushed rock.     

Transport modes and pathways of the strongly sorbing pesticides glyphosate and pendimethalin through structured drained soils

Leaching of the strongly sorbing pesticides glyphosate and pendimethalin was evaluated in an 8-month field study focussing on preferential flow and particle-facilitated transport, both of which may enhance the leaching of such pesticides in structured soils. Glyphosate mainly sorbs to mineral sorption sites, while pendimethalin mainly sorbs to organic sorption sites. The two pesticides were applied in equal dosage to a structured, tile-drained soil, and the concentration of the pesticides was then measured in drainage water sampled flow-proportionally.The leaching pattern of glyphosate resembled that of pendimethalin, suggesting that the leaching potential of pesticides sorbed to either the inorganic or organic soil fractions is high in structured soils. Both glyphosate and pendimethalin leached from the root zone, with the average concentration in the drainage water being 3.5 and 2.7 μg L⁻¹, respectively. Particle-facilitated transport (particles >0.24 μm) accounted for only a small proportion of the observed leaching (13-16% for glyphosate and 16-31% for pendimethalin). Drain-connected macropores located above or in the vicinity of the drains facilitated very rapid transport of pesticide to the drains. That the concentration of glyphosate and pendimethalin in the drainage water remained high (>0.1 μg L⁻¹) for up to 7 d after a precipitation event indicates that macropores between the drains connected to underlying fractures were able to transport strongly sorbing pesticides in the dissolved phase. Lateral transport of dissolved pesticide via such discontinuities implies that strongly sorbing pesticides such as glyphosate and pendimethalin could potentially be present in high concentrations (>0.1 μg L⁻¹) in both water originating from the drainage system and the shallow groundwater located at the depth of the drainage system.     

Effects of water content on reactive transport of 85Sr in Chernobyl sand columns

It is known that under unsaturated conditions, the transport of solutes can deviate from ideal advective-dispersive behaviour even for macroscopically homogeneous porous materials. Causes may include physical non-equilibrium, sorption kinetics, non-linear sorption, and the irregular distribution of sorption sites. We have performed laboratory experiments designed to identify the processes responsible for the non-ideality of radioactive Sr transport observed under unsaturated flow conditions in an Aeolian sandy deposit from the Chernobyl exclusion zone. Miscible displacement experiments were carried out at various water contents and corresponding flow rates in a laboratory model system. Results of our experiments have shown that breakthrough curves of a conservative tracer exhibit a higher degree of asymmetry when the water content decreases than at saturated water content and same Darcy velocity. It is possible that velocity variations caused by heterogeneities at the macroscopic scale are responsible for this situation. Another explanation is that molecular diffusion drives the solute mass transfer between mobile and immobile water regions, but the surface of contact between these water regions is small. At very low concentrations, representative of a radioactive Sr contamination of the pore water, sorption and physical disequilibrium dominate the radioactive Sr transport under unsaturated flow conditions. A sorption reaction is described by a cation exchange mechanism calibrated under fully saturated conditions. The sorption capacity, as well as the exchange coefficients are not affected by desaturation. The number of accessible exchange sites was calculated on the basis that the solid remained in contact with water and that the fraction of solid phase in contact with mobile water is numerically equal to the proportion of mobile water to total water content. That means that for this type of sandy soil, the nature of mineral phases is the same in advective and non-advective domains. So sorption reaction parameters can be estimated from more easily conducted saturated experiments, but hydrodynamic behaviour must be characterized by conservative tracer experiments under unsaturated flow conditions.     

Solute transport in crystalline rocks at Aspö--II: blind predictions,inverse modelling and lessons learnt from test STT1

Based on the results from detailed structural and petrological characterisation and on up-scaled laboratory values for sorption and diffusion, blind predictions were made for the STT1 dipole tracer test performed in the Swedish Asp? Hard Rock Laboratory. The tracers used were nonsorbing, such as uranine and tritiated water, weakly sorbing 22Na(+), 85Sr(2+), 47Ca(2+)and more strongly sorbing 86Rb(+), 133Ba(2+), 137Cs(+). Our model consists of two parts: (1) a flow part based on a 2D-streamtube formalism accounting for the natural background flow field and with an underlying homogeneous and isotropic transmissivity field and (2) a transport part in terms of the dual porosity medium approach which is linked to the flow part by the flow porosity. The calibration of the model was done using the data from one single uranine breakthrough (PDT3). The study clearly showed that matrix diffusion into a highly porous material, fault gouge, had to be included in our model evidenced by the characteristic shape of the breakthrough curve and in line with geological observations. After the disclosure of the measurements, it turned out that, in spite of the simplicity of our model, the prediction for the nonsorbing and weakly sorbing tracers was fairly good. The blind prediction for the more strongly sorbing tracers was in general less accurate. The reason for the good predictions is deemed to be the result of the choice of a model structure strongly based on geological observation. The breakthrough curves were inversely modelled to determine in situ values for the transport parameters and to draw consequences on the model structure applied. For good fits, only one additional fracture family in contact with cataclasite had to be taken into account, but no new transport mechanisms had to be invoked. The in situ values for the effective diffusion coefficient for fault gouge are a factor of 2-15 larger than the laboratory data. For cataclasite, both data sets have values comparable to laboratory data. The extracted K(d) values for the weakly sorbing tracers are larger than Swedish laboratory data by a factor of 25-60, but agree within a factor of 3-5 for the more strongly sorbing nuclides. The reason for the inconsistency concerning K(d)s is the use of fresh granite in the laboratory studies, whereas tracers in the field experiments interact only with fracture fault gouge and to a lesser extent with cataclasite both being mineralogically very different (e.g. clay-bearing) from the intact wall rock.     

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.     

Prediction of some in situ tracer tests with sorbing tracers using independent data

Some recent converging tracer tests with sorbing tracers at the Asp? Hard Rock Laboratory in Sweden, the TRUE tests, have been predicted using only laboratory data and hydraulic data from borehole measurements. No model parameters were adjusted to obtain a better fit with the experiments. The independent data were fracture frequency and transmissivity data obtained in the field and laboratory data on sorption and matrix diffusion. Transmissivity measurements in five boreholes in the rock volume containing the region surrounding the injection and collection points show that there is a high frequency of water conducting fractures. Of 162 packed off sections with 0.5 m packer distances, 112 were found to have a transmissivity above the detection limit. The specific flow-wetted surface (FWS) of the rock mass could be estimated from these data. The transmissivities were found to be reasonably well described by a lognormal distribution. Laboratory data on diffusion and sorption properties together with the hydraulic data were used to "predict" the residence time distribution (RTD) of the sorbing tracers. The results were compared with the experimental breakthrough curves. In these experiments, the water residence time is very small compared to the residence time of the sorbing tracers due to their diffusion and sorption within the rock matrix. We thus could neglect the influence of the water residence time in our predictions. Therefore, no information on water residence times or on "dispersion" was needed. The dispersion of the sorbing tracers is caused by the different sorbing tracer residence times in different pathways. The sorbing tracer residence time is determined by the ratio of flowrate to the flow-wetted surface in the different pathways and not by the water residence time. Assuming a three-dimensional flow pattern and using the observed fracture frequency and flowrate distribution, breakthrough curves for three strongly sorbing tracers were predicted. Only the laboratory data, the transmissivity measurements and the pumping flowrate were used in the predictions. No information on the water residence time as obtained by the nonsorbing tracers was used. The predictions were surprisingly accurate.     

Experimental determination of sorption in fractured flow systems

Fracture "skins" are alteration zones on fracture surfaces created by a variety of biological, chemical, and physical processes. Skins increase surface area, where sorption occurs, compared to the unaltered rock matrix. This study examines the sorption of organic solutes on altered fracture surfaces in an experimental fracture-flow apparatus. Fracture skins containing abundant metal oxides, clays, and organic material from the Breathitt Formation (Kentucky, USA) were collected in a manner such that skin surface integrity was maintained. The samples were reassembled in the lab in a flow-through apparatus that simulated approximately 2.7 m of a linear fracture "conduit." A dual-tracer injection scheme was utilized with the sorbing or reactive tracer compared to a non-reactive tracer (chloride) injected simultaneously. Sorption was assessed from the ratio of the first temporal moments of the breakthrough curves and from the loss of reactive tracer mass and evaluated as a function of flow velocity and solute type. The breakthrough curves suggest dual-flow regimes in the fracture with both sorbing and non-sorbing flow fields. Significant sorption occurs for the reactive components, and sorption increased with decreasing flow rate and decreasing compound solubility. Based on moment analysis, however, there was little retardation of the center of solute mass. These data suggest that non-equilibrium sorption processes dominate and that slow desorption and boundary layer diffusion cause extensive tailing in the breakthrough curves.     

Sorption of Isoxaflutole Diketonitrile Degradate (DKN) and Dicamba in Unsaturated Soil

When analyzing the sorption characteristics of weakly sorbing or labile pesticides, batch methods tend to yield a high margin of error attributable to errors in concentration measurement and to degradation, respectively. This study employs a recently developed unsaturated transient flow method to determine the sorption of isoxaflutole's herbicidally active diketonitrile degradate (DKN) and dicamba. A 20-cm acrylic column was packed with soils with varied texture that had been uniformly treated with ¹⁴C-labeled chemical.

The antecedent solution herbicide in equilibrium with sorbed phase herbicide was displaced by herbicide-free water, which was infiltrated into the column. Sorption coefficients, K_d, were obtained from a plot of total herbicide concentration in the soil versus water content in the region where the antecedent solution accumulated. DKN K_d values were ～2–3 times (average K_d = 0.71 L kg^?1) greater using the unsaturated transient flow method as compared to the batch equilibration method in clay loam (K_d = 0.33 L kg^?1), but similar for the two methods in sand (0.12 vs 0.09 L kg^?1) soils. Dicamba K_d values were 3 times greater using the unsaturated transient flow method as compared to the batch equilibration method in the clay loam soil (0.38 vs 0.13 L kg^?1), however, the K_d values were the same for the two methods in the sand (～0.06 L kg^?1). This demonstrates that to determine sorption coefficients for labile hydrophilic pesticides, an unsaturated transient flow method may be a suitable alternative to the batch method. In fact, it may be better in cases where transport models have overpredicted herbicide leaching when batch sorption coefficients have been used.     

Simultaneous transport of parent and daughter compounds in aquifers with linear first-order sorption kinetics

In soils, daughter compounds may be generated from a parent compound by microbial metabolism, chemical reactions, radioactive decay, or other mechanisms. These daughter compounds are also acted upon by soil physical, chemical and biological processes. A system often referred to as a cascade or chain of compounds system results. While a great deal of attention has been given to this problem with the linear equilibrium assumption applied uniformly to all transport and reacting compounds, little attention has been given to the simultaneous transport and fate of a parent-daughter chain with a first-order rate assumed for the adsorption-desorption kinetics of each compound and with the soil partitioned into three sorption classes.A general one-dimensional cascade or chain model for the simultaneous transport of parent and daughter compounds in sorbing, homogeneous, water table aquifers is presented. The model is based on an advective-dispersive mass accounting formulation for both compounds and includes: (a) first-order rate of conversion of parent to daughter; (2) first-order rates of loss of either parent or daughter or both due to metabolism, chemical reaction and/or irreversible processes; (3) partitioning of the aquifer material into three sorption classes, namely mildly sorbing, strongly sorbing and organic matter; (4) linear first-order kinetic rules for adsorption and desorption operating on each of the sorbing soil fractions for each compound; (5) constantly emitting sources of rectangular shape of parent compound; and (6) mass accounting boundary conditions; and a tailorable initial distribution on [0, ∞). Mathematical analysis yields a coupled, linear system of equations including two transport and fate equations, initial and boundary data, and six kinetic rules, namely three each for parent and daughter compound. A numerical scheme for solving the system of equations was developed using readily available procedures since analytical solutions could not be found. Solutions for scenarios based on leaking underground sources are presented.     

Environmental behavior of benalaxyl and furalaxyl enantiomers in agricultural soils

The enantioselective environmental behavior of the chiral fungicides benalaxy and furalaxyl in agricultural soils in China was studied. Although sorption onto soils was non-enantioselective, the leaching of benalaxy and furalaxyl was enantioselective in soil columns. The concentrations of the S-enantiomers of both fungicides in the leachates were higher than the R-enantiomers. This can be attributed to enantioselective degradation of the two fungicides in the soil column. Enantioselective degradation of the two fungicides was verified by soil dissipation experiments, and the R-enantiomers degraded faster than the S-enantiomers in partial soils. The half-life was 27.7–57.8 days for S-benalaxyl, 20.4–53.3 days for R-benalaxyl, 19.3–49.5 days for S-furalaxyl and 11.4–34.7 days for R-furalaxyl. The degradation process of the two fungicide enantiomers followed the first-order kinetics (R² > 0.96). Compared to furalaxyl, benalaxyl degraded more slowly and degradation was less enantioselective. These results are attributed to the influence of soil physicochemical properties, soil microorganisms, and environmental factors.