Biologia, Bratislava, 61/Suppl. 19: S251—S254, 2006 Section Botany DOI: 10.2478/s11756-006-0167-9 Simulated cadmium transport in macroporous soil during heavy rainstorm using dual-permeability approach Jaromír Dušek1, Tomáš Vogel1, Ľubomír Lichner2, Andrea Čipáková3 & Michal Dohnal1 Faculty of Civil Engineering CTU, Thákurova 7, CZ–16629 Prague, Czech Republic; email: [email protected] Institute of Hydrology, Slovak Academy of Sciences, Račianska 75, SK–83102 Bratislava, Slovakia 3 Regional Public Health Authority, Ipeľská 1, SK–04220 Košice, Slovakia 1 2 Abstract: Numerical modelling is used to analyze the transport of cadmium in response to an extreme rainfall event. The cadmium transport through the soil profile was simulated by the one-dimensional dual-permeability model, which assumes the existence of two mutually communicating domains: the soil matrix domain and the preferential flow domain. The model is based on Richards’ equation for water flow and advection-dispersion equation for solute transport. A modified batch technique allowed us to consider domain specific sorption, i.e. each of the domains has its own distribution coefficient. The dual-permeability model predicts that the cadmium can be transported substantially below the root zone after the storm. On the other hand, classical single permeability approach predicted that almost all applied cadmium stays retained near the soil surface. Key words: cadmium transport, vadose zone, preferential flow, macropores, dual-permeability, sorption, particle-facilitated transport Introduction The increased vulnerability of the fresh water resources, with regard to a widespread use of agricultural fertilizers containing traces of cadmium (Lichner et al., 2006), requires a careful assessment of the potential paths of contamination from the soil surface to groundwater. Especially in lowland regions of Central and Eastern Europe, such as the Danubian Lowland, the use of such fertilizers has a long history (Lichner et al., 2006) and thus poses significant threat for both terrestrial organisms and humans (Horn et al., 2006). One of the processes that significantly affect the transport of cadmium in soils is preferential flow (water and solutes travel at considerable high velocities through preferential pathways concurrently bypassing the porous matrix). This phenomenon has a direct influence on infiltration, drainage, and specifically on solute transport. There are several types of preferential flow which may be caused e.g. by textural interfaces, soil water repellency, air entrapment, soil aggregation and spatial heterogeneity (Walter et al., 2000; Ritsema & Dekker, 2000; Wang et al., 1998; Lennartz et al., 1999). The aim of this study is to predict the cadmium penetration in the soil of interest in response to an intense rainfall by means of dual-permeability modelling. The dual-permeability model invokes local nonequilibrium in pressure head and solute concentration between c 2006 Institute of Botany, Slovak Academy of Sciences the two pore domains. This is achieved through dividing the liquid phase continuum into that of the preferential flow domain (further on abbreviated to PF-domain) and the matrix flow domain (MF-domain). Moreover, a distinct sorption coefficient for each of the two flow domains of the dual-permeability system is used to estimate the effect of particle-facilitated transport of cadmium through macropores. Material and methods Experimental site The soil at the Macov experimental station (Dunubian Lowland, Slovakia) has been classified as Calcari-Haplic Chernozem. The soil profile consists of five relatively homogeneous horizons. The field infiltration experiments accompanied by a dye tracer test have revealed significant preferential flow patterns. The soil-water retention curves for the five soil horizons were measured by standard pressure plate apparatus method on 100 cm3 undisturbed soil samples (with three replicates for each layer), and consequently the hydraulic parameters were obtained by fitting van Genuchten’s modified prediction model (VOGEL et al., 2001) to data points. The measurements of the topsoil saturated hydraulic conductivity for the matrix and the preferential domain were carried out by tension infiltrometer (LICHNER et al., 2006). The saturated conductivities of remaining soil layers were derived by a pedotransfer function model (SCHAAP et al., 2001) based on textural classes. The volumetric portion of Unauthenticated Download Date | 6/18/17 10:11 PM J. Dušek et al. S252 Table 1. Measured soil hydraulic properties (volumetric portion of the fracture domain wf as well as the retention curve parameters for the PF-domain were estimated). Domain: MF-domain PF-domain Depth (cm): 0–20 20–30 30–50 50–80 80–100 0–100 θs (–) θr (–) α (cm−1 ) n (–) hs (cm) Ks (cm d−1 ) wf 0.498 0.000 0.018 1.212 –2.48 23.2 – 0.486 0.000 0.042 1.176 –2.06 29.9 – 0.502 0.000 0.057 1.184 –0.80 18.9 – 0.452 0.000 0.026 1.215 –2.61 17.6 – 0.479 0.073 0.016 1.647 –2.88 31.7 – 0.600 0.050 0.145 2.680 0.00 201.3 0.1 the PF-domain was estimated as 10% of the bulk soil. Table 1 summarizes the soil hydraulic parameters for both PFand MF-domains. Batch tests Sorption distribution coefficient for the matrix domain, Kdm , which describes the chemical partitioning between the solid and the liquid phase, was experimentally determined in the laboratory by standard batch test (SELIM et al., 1992; ČIPÁKOVÁ & MITRO, 1997). In contrast, the sorption distribution coefficient for the PF-domain, Kdf , was determined by modified batch technique (LICHNER & ČIPÁKOVÁ, 2002). In case of the latter coefficient, the liquid phase contained not only cadmium in aqueous phase, but also cadmium adsorbed on soil particles smaller than about 0.01 mm. Such soil particles may be highly mobile in the macropore network (LAEGSMAND et al., 1999), thus may travel to considerable depths as suspension. Numerical model S1D DUAL The dual-permeability approach (GERKE & VAN GENUCHTEN, 1993; VOGEL et al., 2000) assumes that the porous medium consists of two separate domains with specific hydraulic properties. One-dimensional variably-saturated water flow in the dual-permeability model is described by a pair of Richards’ equations for the PF-domain and the MF-domain pore systems. Similarly, a coupled pair of convection-dispersion equations is solved to model solute transport. The exchange of water and solute between the matrix and the fracture domains is assumed to be proportional to the local pressure difference and the concentration gradient between the two pore systems. An analogous approach to water flow modelling in macroporous soils was also applied by KODEŠOVÁ et al. (2006) in this issue. The dual sets of governing equations for flow of water and transport of cadmium are solved numerically by finite elements using the computer code S1D DUAL (VOGEL, 1999, Documentation of the S1D DUAL code – version 1.1, CTU Prague, internal report), which is extended version of the HYDRUS 5 code (VOGEL et al., 1996). Domain specific sorption When considering domain specific sorption, each pore domain (soil matrix domain and preferential flow domain) has its own sorption properties. In our study, both pore domains are assumed to contain only equilibrium sorption site characterized by the distribution coefficients Kdm (139 cm3 g−1 ) and Kdf (7 cm3 g−1 ), respectively (LICHNER & ČIPÁKOVÁ, 2002). The distribution coefficient for the PF-domain is approximately 20-times smaller than for the matrix due to the fact that the soil particles smaller than 0.01 mm (loaded with the adsorbed cadmium) are assumed to move with the soil water, so that the coefficient Kdf is exclusively related to the sorption on particles larger than 0.01 mm. Initial and boundary conditions At the beginning of the simulated period – 14 hours prior to the rainstorm event of interest – the cadmium was applied in a definite pulse of water with the concentration load 2 µg/mL (i.e. 2000 µg/L). The pulse lasted 30 minutes and comprised of 0.1 cm of water. The initial soil profile was assumed to be free of cadmium. The bottom boundary condition was set to zero concentration gradient, in order to allow the contaminant to pass freely the lower boundary at the depth of 100 cm. The soil surface was treated as the “atmospheric boundary condition”. This type of condition allows for switching between the Neumann and Dirichlet type conditions, i.e. when the top soil is not capable to transmit water during heavy rain, the flux condition is changed to pressure condition. In such a case, surplus water may either generate surface runoff or stay retained at the soil surface. The unit hydraulic gradient condition was used at the lower boundary, allowing water to leave the soil profile at the rate equal to unsaturated hydraulic conductivity. The initial condition for water flow was set close to residual water content throughout the whole soil profile. No evaporation was taken into account for the whole simulated period. The rainfall event used in our analysis was recorded at Pezinok-Myslenice weather station nearby the experimental site at Macov. The recorded storm occurred in July, 1999 and total cumulative rate amounted to 15 cm rain during 17 hours. Results and discussion Figure 1 depicts the simulated infiltration rates during the rainstorm. The simulation started about 14 hours before the beginning of the major rainfall episode and the infiltration capacity of the soil matrix became almost immediately exceeded, thus the surplus water was diverted to the PF-domain. Since the influx to the macropore domain was very high (Fig. 1) due to the small proportion of the PF-domain compared to the soil matrix domain, the preferential pathways became Unauthenticated Download Date | 6/18/17 10:11 PM Simulated cadmium transport in macroporous soil S253 Fig. 1. Simulated cumulative and infiltration rates during the natural rainfall event by dual-permeability model. The cumulative rates are multiplied by the volumetric proportion of the respective flow domain. concentration (µg/L) 1.2 0.9 PF-domain 0.6 0.3 MF-domain 0 0 3 6 9 12 15 time (hours) 18 21 24 Fig. 2. Simulated cadmium breakthrough curve in the matrix and the PF-domain at the depth of 10 cm (liquid concentrations). 0 cadmium mass (log µg) fully saturated as well, and hence were not able to transmit all rainwater into the soil profile. The fourth rain pulse (17–18 hours) also saturated the matrix domain, but at this time, the PF-domain transmitted all rainfall excess from the matrix. In total, the composite pore system did not accept 5.8 cm of water during the whole rainfall period. This amount of water was assumed to be lost e.g. due to the surface runoff. The breakthrough curves, simulated by the dualpermeability model, are shown in Fig. 2. Cadmium residual concentration in the liquid phase from the PFdomain at the level of 10 cm beneath the soil surface was much stronger compared to cadmium outflow from the MF-domain, which showed only negligible increase of concentration. Furthermore, this minor increase can be attributed to the cadmium transfer from the preferential pathways to the matrix domain. In the model, both the higher hydraulic conductivity and the lower distribution coefficient of the PF-domain controlled the deeper and more intense cadmium penetration in the PF-domain leading to increased residual concentrations down to the depth of about 40 cm below the soil surface. When classical single-permeability model was used instead of the dual-permeability model, no increase of cadmium concentration below the depth of 8 cm was predicted (not shown in this paper). The cadmium increase in soil sub-layers down to 40 cm beneath the soil surface is evident from Fig. 3. The cadmium mass in the logarithmic scale was calculated by combining the contributions from the two flow domains. The cadmium amount in the first sub-layer (0–5 cm) mainly reflects the presence of cadmium retained in the soil matrix. The deeper cadmium contents are associated with the PF-domain. The sudden mass increase near the soil surface (horizon 0–5 cm) is related to the cadmium application. Deeper cadmium penetration in macropores was caused by the significantly smaller distribution coefficient Kdf for the PF-domain. Note that the threshold of the numerical accuracy lies in the order of magnitude 10−11 µg, hence the concentrations around this level are considered to be equal 0-5 cm 5-10 cm 10-15 cm 15-20 cm 20-25 cm 30-40 cm -4 -8 -12 0 3 6 9 12 15 time (days) 18 21 24 Fig. 3. Cadmium increase in liquid and solid phase in the individual sub-layers as predicted by the dual-permeability approach. to zero. Classical single-permeability approach would predict that nearly all applied cadmium stays retained near the soil surface in about 5 cm deep layer. Conclusions The effect of an extreme rainfall on cadmium transport through macroporous soil was examined. It is demonstrated that cadmium, according to numerical model Unauthenticated Download Date | 6/18/17 10:11 PM S254 based on dual-permeability approach, may percolate below the root zone within a short period of time. The simulation results create the most unfavourable situation: retention of cadmium in the root zone, where it can be easily accessible by plants, and, at the same time, quite deep cadmium penetration, which can pose higher contamination risk for drinking water resources. Modelling with classical single permeability approach and without considering the particle-facilitated transport, would lead to a significant underestimation of cadmium penetration by disregarding the macroporous nature of soils. Acknowledgements The research has been supported by the European Union FP6 Integrated Project AquaTerra (Project No. 505428) under the thematic priority “sustainable development, global change and ecosystems”, and by the research fund of the Ministry of Education of the Czech Republic (MSM 6840770002). Additional support was provided by the Science and Technology Assistance Agency project No. APVT-51-006502, and Slovak Scientific Grant Agency project VEGA 2/6003/26. References ČIPÁKOVÁ, A. & MITRO, A. 1997. Influence of agrochemical characteristics on 85 Sr and 137 Cs sorption in soil samples from the localities around nuclear power plants in Slovak Republic. J. Radioecol. 5: 3–8. GERKE, H.H. & van GENUCHTEN, M.Th. 1993. A dual-porosity model for simulating the preferential movement of water and solutes in structured porous media. Water Resour. Res. 29: 305–319. HORN, A.L., REIHER, W., DÜRING, R.-A. & GÄTH, S. 2006. 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