The Effect of Surface-Active Solutes on Water Flow and Contaminant Transport in Variably Saturated Porous Media with Capillary Fringe Effects
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Journal of Contaminant Hydrology 56 (2002) 247–270 www.elsevier.com/locate/jconhyd The effect of surface-active solutes on water flow and contaminant transport in variably saturated porous media with capillary fringe effects E.J. Henry a, J.E. Smith b,* aDepartment of Hydrology and Water Resources, University of Arizona, Tucson, AZ, 85721 USA bSchool of Geography and Geology, McMaster University, 1280 Main St. West, Hamilton, ON, Canada L8S 4L8 Received 20 December 2000; received in revised form 12 October 2001; accepted 23 October 2001 Abstract Organic contaminants that decrease the surface tension of water (surfactants) can have an effect on unsaturated flow through porous media due to the dependence of capillary pressure on surface tension. We used an intermediate-scale 2D flow cell (2.44 Â 1.53 Â 0.108 m) packed with a fine silica sand to investigate surfactant-induced flow perturbations. Surfactant solution (7% 1-butanol and dye tracer) was applied at a constant rate at a point source located on the soil surface above an unconfined synthetic aquifer with ambient groundwater flow and a capillary fringe of f 55 cm. A glass plate allowed for visual flow and transport observations. Thirty instrumentation stations consist of time domain reflectometry probes and tensiometers measured in-situ moisture content and pressure head, respectively. As surfactant solution was applied at the point source, a transient flow perturbation associated with the advance of the surfactant solution was observed. Above the top of the capillary fringe the advance of the surfactant solution caused a visible drainage front that radiated from the point source. Upon reaching the capillary fringe, the drainage front caused a localized depression of the capillary fringe below the point source because the air-entry pressure decreased in proportion to the decrease in surface tension caused by the surfactant. Eventually, a new capillary fringe height was established. The height of the depressed capillary fringe was proportional to height of the initial capillary fringe multiplied by the relative surface tension of the surfactant solution. The horizontal transport of surfactant in the depressed capillary fringe, driven primarily by the ambient groundwater flow, caused the propagation of a wedge-shaped drying front in the downgradient direction. Comparison of dye transport during the surfactant experiment to dye transport in an experiment without surfactant indicated that because surfactant-induced drainage decreased the storage capacity of the vadose zone, the dye breakthrough time to the water table was * Corresponding author. Tel.: +1-905-525-9140x24534; fax: +1-905-546-0463. E-mail address: [email protected] (J.E. Smith). 0169-7722/02/$ - see front matter D 2002 Elsevier Science B.V. All rights reserved. PII: S0169-7722(01)00206-6 248 E.J. Henry, J.E. Smith / Journal of Contaminant Hydrology 56 (2002) 247–270 more than twice as fast when the contaminant solution contained surfactant. The extensive pro- pagation of the drying front and the effect of vadose zone drainage on contaminant breakthrough time suggest the importance of considering surface tension effects on unsaturated flow and trans- port in systems containing surface-active organic contaminants or systems, where surfactants are used for remediation of the vadose zone or unconfined aquifers. D 2002 Elsevier Science B.V. All rights reserved. Keywords: Unsaturated zone; Surfactants; Surface tension; Capillary pressure; Pollutants; Vadose zone 1. Introduction Although flow through porous media is commonly assumed to be independent of solute concentration, dissolved surface-active organic compounds (surfactants) can have a direct and significant effect on flow through unsaturated porous media. Most organic compounds are surface-active in aqueous solution and can reduce the surface tension of water. Because soil water pressure is a function of surface tension, surfactant-induced reductions in surface tension can result in proportional decreases in capillary pressure (i.e., increases in soil water pressure) in unsaturated porous media. The effects of surface-active solutes on the moisture characteristic relationship can be significant and have been demonstrated for a variety of organic compounds (Salehzadeh and Demond, 1994; Smith and Gillham, 1994, 1999; Lord et al., 1997, 2000; Dury et al., 1998). The effects of surfactants on unsaturated flow have been noted in experimental systems. Zartman and Bartsch (1990) surveyed the ability of 17 surfactants, including anionic, cationic, and nonionic species, to enhance drainage from dewatered soil columns over a range of surfactant concentrations. Due to the dependence of surface tension on surfactant concentration, they observed an increase in gravity-induced outflow with increasing surfactant concentration. The volume of column outflow observed was greater than the volume of surfactant solution applied; thus, surfactant enhanced drainage had occurred as a result of reduced surface tension. Here, we apply the general definition of the term ‘surfactant’ to include all organic compounds that reduce the surface tension of water: commercial surfactants, alcohols, humic substances, aliphatics, aromatics, amines, etc. It should be noted that there are definitions of ‘surfactant’ that do not include alcohols (West and Harwell, 1992). However, the terms ‘surfactant’ or ‘co-surfactant’ have been used to refer to alcohols in the chemical engineering (Karkare et al., 1993) and environmental (Jain and Demond, 1999) literature. Tschapek and Boggio (1981) found that the presence of the surface-active compound, myristyl alcohol, in one half of a homogeneous, uniformly wetted, closed, unsaturated sand column resulted in flow from the surfactant containing side of the horizontal column to the side that contained no surfactant. Karkare and Fort (1993) and Henry et al. (1999) conducted experiments similar to those of Tschapek and Boggio (1981) and concluded that the observed water movement was due to surfactant-induced capillary pressure gradients. Karkare et al. (1993) applied the same experimental technique to study the water moving ability of 33 surfactants (long chain alcohols, acids, esters, and amines) and E.J. Henry, J.E. Smith / Journal of Contaminant Hydrology 56 (2002) 247–270 249 found that in order for surfactants to be effective at moving water, they must be water- insoluble and must form a condensed solid film at their equilibrium spreading pressure. However, Henry et al. (1999) showed that a soluble alcohol, butanol, was effective at moving water in such systems and that the resultant moisture content distribution in the column was much different than when the low-solubility alcohol, myristyl alcohol, was used. Other experimental observations of surfactant-induced flow perturbations have been seen in one-dimensional (1D) miscible displacement experiments, though the observed effects were sometimes secondary to the objectives of the experiment. Bruell et al. (1997, 1998) examined the removal of the nonaqueous phase liquid (NAPL), m-xylene, from unsaturated porous media using surfactant flushing. They found that as surfactant solution (1% Witconol SN90) was applied, column dewatering occurred and the effluent flow rate subsequently decreased due to ‘‘reductions in interconnected water filled pores through which flow occurred, leading to a reduction in the effective permeability’’ (Bruell et al., 1998). Allred and Brown (1996) studied surfactant transport in unsaturated columns by applying two types of anionic surfactants to a dry soil column. They noted a ‘notch’ in the resultant moisture content profiles within the column that was not seen in experiments run with pure water. The notch coincided with the surfactant solute front and they concluded that it was caused by variation in the water retention relationship in the transition zone between high and low surfactant concentrations. Smith and Gillham (1999) presented laboratory column experiments designed speci- fically to examine solute concentration-dependent surface tension effects on flow and transport in a vertical unsaturated sand column. They used 1-butanol as a representative surface-active solute. During experiments conducted under constant flux upper boundary conditions, they observed a transient flow perturbation associated with the advance of the solute front. As the solute front reached the bottom of a column with a water table lower boundary, depression of the capillary fringe was measured. The steady-state height of the depressed capillary fringe relative to the original height was proportional to the ratio of the surface tension of the butanol solution relative to that of pure water, as predicted by the dependence of capillary pressure (and thus air-entry pressure) on surface tension. The effects of surface-active solutes on unsaturated flow and transport have also been seen in two-dimensional (2D) laboratory experiments related to NAPL transport and remediation. Chevalier et al. (1998) studied NAPL lens configurations by applying unleaded gasoline through an injection well located in the unsaturated zone of a 2D flow cell with a fixed and level water table (i.e., no horizontal groundwater flow). As the gasoline reached the top of the capillary fringe, the height of the capillary fringe was depressed from 14.1 to 10.7 cm across the entire width of the box, despite the fact that the NAPL lens remained confined to the middle of the box. The capillary fringe depression was attributed to ‘capillary