Chemosphere 57 (2004) 10791089 www.elsevier.

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An evaluation of surfactant foam technology in remediation of contaminated soil

Suiling Wang, Catherine N. Mulligan
*
Department of Building, Civil and Environmental Engineering, Concordia University, 1455 de Maisonneuve Boulevard W., ER 303, Montreal, QC, Canada H3G 1M8 Received 3 February 2004; received in revised form 3 August 2004; accepted 11 August 2004

Abstract Soil contamination is notoriously dicult to treat because the contaminants are often tightly bound to the soil particles. Conventional remediation technologies are becoming less popular due to the high treatment costs. This paper gives a comprehensive overview and evaluation of an emerging promising alternative, surfactant foam technology. Different from other approaches, surfactant foam technology may be designed either to remove contaminants or/and simultaneously act as an augmentation for the existing technologies such as pump-and-treat systems and bioremediation processes to improve the contaminant removal eciency and cost eectiveness. Encouraging results were achieved from laboratory and eld demonstrations. However, as an innovative technology, there are many factors to be investigated with the future development. Special attention is paid to the selection of the most appropriate foaming surfactant and surfactant concentration, which are critical to the success of the implementation of the remediation process and have signicant eects on the treatment costs. Moreover, development of predictive mathematical models in for future research is helpful to optimize the remediation process. 2004 Elsevier Ltd. All rights reserved.
Keywords: Case study; Contaminated soil; Evaluation; Foam injection; Surfactant; In situ soil remediation

1. Introduction Subsurface contamination is complex and dicult to treat due to the tendency of contaminants to tightly bind or sorb onto the soil particles. Leaching from the soil thus ultimately becomes a continuous source of the groundwater contamination. The USEPA listed 129

Corresponding author. Tel.: +1 514 848 2424x7925; fax: +1 514 848 2809. E-mail address: mulligan@alcor.concordia.ca (C.N. Mulligan).

compounds and elements (114 organic compounds plus cyanide, asbestos, and 13 metals) from 65 pollutant classes as priority pollutants (Keith and Telliard, 1979; Richards and Shieh, 1986). Many common contaminants of the soil and groundwater at many government and private sites, have been found to be toxic, mutagenic, and/or carcinogenic (Harvey, 1991). Although some of these compounds may be relatively soluble in water, other inherent physicochemical properties make them particularly problematic, especially, the water immiscibility of some dense nonaqueous phases liquids (DNAPLs) and the high interfacial tension (IFT) between them and water render them

0045-6535/$ - see front matter 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.chemosphere.2004.08.019

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persistent in the subsurface as residual or trapped phases. Thus, these contaminants are particularly dicult to remediate. Matters become even more complicated since these contaminants are often mixed with metals or radionuclides (Mulligan et al., 2001a). Toxic metals have entered the subsurface from various sources resulting from their mining, extraction, and purication, as well as from other industrial, military, agricultural and municipal activities. As a result they are now widely dispersed in a range of dierent forms (Roundhill, 2001) in soils and are usually tightly bound because the cationic metals associate with the anionic components of the soils. Toxic metals are problematic in soils because of their potential reactivity, toxicity, and mobility (Selim and Michael, 1996). However, they can possibly be recovered and recycled. Considerable eorts have been expended towards developing appropriate remediation technologies for the contaminated soils. Excavation of the contaminated soil was once the rst choice. But it is becoming less popular because of the high cost of excavation and nal disposal of landlls, in addition to lack of available landll sites (Mann et al., 1993; Mulligan and Eftekhari, 2003). In situ treatments through chemical or biological transformation of the contaminant avoid the economic and technical disadvantages, as well as environmental risks caused by transport of the hazardous materials to alternate treatment facilities. They also have the advantage of dealing with all aspects of the contamination problem and of providing a permanent solution by destroying the contaminant (Lee and Ward, 1985). Solutions with the greatest potential for use in soil ushing would be water, acids/bases, complexing or chelating agents, surfactants (surface active agents), and certain reducing agents (USEPA, 1985). The feasibility of using surfactants for soil and sediment remediation has been demonstrated (Mulligan et al., 1999, 2001b). However, injection of aqueous solutions into the subsurface incurs other risks. The surfactant residuals may be toxic, and the migration of the uids containing dissolved contaminants will probably lead to the spreading of the contaminated zone and further contamination of the groundwater. The ability to control the migration of contaminantladen uids can be improved by using foam. The foam technology not only can be used as an eective technique for the treatment of soils contaminated with organic compounds such as DNAPLs but also can be used to enhance mobilization of heavy metals. It also might be used as an augmentation for the in situ pump-and-treat methods and bioremediation processes. It is more attractive because it might reduce the treatment cost greatly due to the low usage of chemicals and surfactants. The objective of this paper is to give a comprehensive overview and evaluation of the surfactant foam technology in soil remediation. The background of surfactants

and surfactant foam is introduced rst. Based on case studies, the applicability and limitations of this emerging technology are discussed. Factors that can aect the treatment costs are cited. At the same time, the compatibility of this technology with other existing technologies is discussed. Finally, main conclusions and recommendations for the future research are present.

2. Surfactant foam technology 2.1. Surfactants The use of surfactants to enhance the removal of soil contaminants has received increasing attentions in recent years. Surfactants are a class of natural and synthetic chemicals that promote the wetting, solubilization, and emulsication of various types of organic and inorganic contaminants. As they are amphiphilic molecules with both hydrophilic and hydrophobic portions, many surfactants, depending on concentration and surfactant type, by acting as a bridge between the air and liquid interface, can reduce the surface tension of water to approximately 25 5 mN m1 (Myers, 1999). As a result, this promotes the mobilization of contaminants from unsaturated soils, thereby making the contaminant more available for remediation. Also, surfactants have the ability to increase aqueous contaminant concentrations through partitioning the solute into the hydrophobic interior of the micelles and forming spheroid or lamellar structures with organic pseudo-phase interiors. The minimum concentration at which this occurs is termed as the critical micelle concentration (CMC). Mainly anionic and nonionic surfactants are used for soil washing or ushing (Mulligan et al., 2001a). They can be used in mixtures or with additives such as alcohol and/or salts such as sodium chloride. These agents would be most eective in promoting the mobilization of organic compounds of relative low water solubility and high lipid solubility. They can also be used as extractants for transferring metal ions from an aqueous to an organic phase (Roundhill, 2001). The possible mechanisms for the extraction of heavy metals by surfactants are ion exchange, precipitationdissolution, and counterion binding (Rosen, 1979). Prior batch and bench studies have demonstrated encouraging results of surfactant-enhanced remediation for a variety of contaminants (Edwards et al., 1994; Nivas et al., 1996). 2.2. Biosurfactants Biosurfactants are produced by bacteria or yeast. They include classes of molecular structures quite dierent from synthetic surfactants, ranging in chemical structure from simple fatty acids (soaps) to complex glycolipids, lipopeptides, lipopolysaccharides, and phos-

S. Wang, C.N. Mulligan / Chemosphere 57 (2004) 10791089 Table 1 Classications and microbial origin of biosurfactants Surfactant class Rhamnolipids Lipopeptides Microorganism Pseudomonas aeruginosa Arthrobacter sp. Bacillus pumilis Bacillus subtilis Bacillus licheniformis Pseudomonas uorescens Acinetobacter calcoaceticus Pseudomonas spp. Candida lipolytica Thiobacillus thiooxidans Corynebacterium alkanolyticum Penicillium spiculisporum Corynebacterium lepus Arthrobacter paraneus Talaramyces trachyspermus

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2.3. Surfactant foam technology Foam consists of thousands of tiny bubbles. It is an emulsion-like two-phase system where the mass of gas or air cells is dispersed in a liquid and separated by thin liquid lms called lamellae. Surfactants can be used to create or stabilize foams. Foam formation is a dynamic process and occurs far from equilibrium conditions. Aqueous surfactant foam is formed by dispersing nonwetting gas within a continuous surfactant-laden liquid phase. They may be created either by simultaneous injection of gas and liquid or by injection of alternating slugs of liquid and gas into porous media. Two important characteristics of foams are quality and stability (Mulligan and Eftekhari, 2003). Foam quality (g) is determined as the gas content of the foam based on the volume: g Gas volume V g 100% Total foam volume V f

Lipopolysaccharides

Phospholipids

Fatty acids

Mulligan and Gibbs (1993), Banat (1995), Mulligan et al. (2001a).

pholipids. Some of the major types and their microbial origin are listed in Table 1. Most of these compounds are either anionic or neutral. Only a few are cationic such as those containing amine groups (Mulligan et al., 2001a). Biosurfactants as a class contribute signicantly to the repertoire of available surfactants. Eective physicochemical properties (for low interfacial tensions IFTs and CMCs) and temperature stability are characteristics of these compounds. The CMCs of biosurfactants range from 1 to 2000 mg l1. Surface and IFTs of good biosurfactants are less than 30 and 1 mN m1, respectively (Mulligan and Gibbs, 1993). Other distinct advantages of biosurfactants over synthetic surfactants include higher specicity, lower toxicity, higher biodegradability, better environmental compatibility (Mulligan et al., 2001a), and the ability to be synthesized from renewable feedstocks. Biosurfactants exhibit high specicity and are consequently suited to new applications. They are frequently used in detergents and food products to alter the properties of solution interfaces. They also can be added to washing water to assist in the solubilization, dispersion and desorption of contaminants from excavated soils in a washing unit for subsequent return of the cleaned soils to their original site (Mulligan et al., 2001c). Numerous studies have demonstrated the feasibility of biosurfactants enhanced recoveries of hydrophobic organic contaminants (Harvey et al., 1990; Mulligan and Eftekhari, 2003). Biosurfactant enhanced remediation of heavy metal contaminated soil has also been demonstrated (Mulligan et al., 1999, 2001b; Wang and Mulligan, 2004).

Foams can be prepared that have a lifetime (persistence) of minutes, days, or even months, even though they are inherently unstable systems and have an ultimate tendency to collapse. Foam stability reects the ability of the foam to resist bubble collapse. It can be quantied by the time required for collapsing half of the foam. The overall question of foam stability requires the consideration of both the static and dynamic aspects of bubble interactions. Rothmel et al. (1998) concluded that foam stability does not appear to be dependent upon inherent properties such as hydrophileliphophile balance and CMC. Dierent surfactants display dierent foamabilities. Foam parameters can be measured in laboratory. Foam can be generated by a column equipped with circular porous stone plates by injecting surfactant solution and air simultaneously. The surfactant solution can be fed by a pump. The ows of the solution and the air can be controlled by two ow meters. The ow rates of the surfactant solution and air can be varied independently in order to control the foam quality and generation rate. After reaching a uniform and steady state in terms of bubble size and appearance, the foam exiting the column can be sampled for quality and stability analyses. Mulligan and Eftekhari (2003) evaluated the foamability of ten dierent commercial surfactants (Table 2), of which, Triton X-100 and JBR425 showed better abilities to foam when compared with others. A series of experiments were performed by Wang and Mulligan (2004) to evaluate the foamability of rhamnolipid solutions with dierent concentrations (0.5%, 1.0% and 1.5%). Samples (50 ml each) were collected at room temperature (25.0 0.2 C) and were left to collapse under atmospheric pressure. High foam quality up to 99% was generated and foam stability varied from 17 min and 41 min. Results showed that foams could be

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40

Table 2 Foamability comparison of dierent surfactants Surfactants CHAPS Polytergen 305 LP Surfynol 104 A Triyon Taurodeoxycholic acid Triton X-100 Cetylpyridinium chloride JBR425 Igepal CA-630 Pluronic F68 Stability (min) Negligible Negligible Negligible Negligible Negligible 6.2 6.0 6.1 4.6 6.1 Quality (%) Negligible Negligible Negligible Negligible Negligible 99 95 99 98 95

35 30 25 20

15 10 5 0 50 60 70 80 (%) 90 100

Mulligan and Eftekhari (2003).

generated from a low concentration of rhamnolipid solution (0.5% or perhaps less) with enough stability for injection. It was observed that foam quality and surfactant concentration had signicant inuences on the foam stability. Generally, foam stability increased with the increase of surfactant concentration (up to 1.5%), and highest foam stability was produced with the quality between 90% and 99%. A primary characteristic of foam is that it has very low density with a large surface area for a given weight. Aqueous foam with bubble diameters of about 1 cm and lamellar thickness of 103 cm has a density of approximately 0.003 g cm3 (Myers, 1999). Under the assumptions that the eects of temperature and pressure are negligible and the foam bubbles are of aspheric shapes, the interfacial area increased coecient (n) from liquid solution to foam can be simply determined as:

Fig. 1. Relationship between the interfacial area increased coecient (n) and foam quality (g).

n 1 g3 The relationship curve between n and g is illustrated in Fig. 1. From it, it can be observed obviously that, when the foam quality is greater than 80%, the interfacial area increases sharply with the increase of the foam quality. The direct result of the lowered density and increased interfacial areas is that it oers a more ecient contact between the surfactant and contaminants which leads to a higher contaminant removal eciency. Experiments by Wang and Mulligan (2004) showed that, when transferred from liquid solution to foam, rhamnolipid removed 11% more of the Cd and 17% more of the Ni, while Triton X-100 removed 12% more of the Cd and 12% more of the Ni.

Flow Meter Air Compressor Ground Surface

Foam Generator

Flow Meter Pump Surfactant Recycle Surfactant Solution Separation

Contaminant Treatment Vacuum Pump Extraction Well

Fig. 2. Conceptual in situ surfactant foam ushing installation.

Injection Well Contaminated Soil Low Permeability Aquitard

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Surfactant foam technology has been suggested to achieve better mobility control in porous media and to improve removal eciencies of several remediation processes. It has been investigated to remove hydrophobic organic compounds (Kilbane et al., 1997; Rothmel et al., 1998; Jeong et al., 2000; Huang and Chang, 2000; Mulligan and Eftekhari, 2003) and heavy metals (Wang and Mulligan, 2004) from contaminated soils. A conceptual surfactant foam ushing installation is illustrated in Fig. 2. Surfactant foam is ushed through the contaminated zone where it essentially wash and sweep the soil, thereby signicantly expediting contaminant extraction, and bringing the contaminants to the surface for further treatment. The sweep eciency of surfactant foam in a porous medium is determined by the value of capillary number (Ca), a dimensionless number dened as the ratio of viscous forces to capillary forces. Depending on the Darcy velocity (u), uid viscosity (l) and interfacial tension (r), it is commonly formulated as: C a l u=r It represents the interplay between the viscous force (retention force) and capillary force (mobilization force) and determines the distribution and mobilization of contaminants. It was reported that the Ca after water ooding ranges from 1 107 to 1 105 (Lake, 1989). Most studies have shown that a Ca around 103 is required for complete recovery of residual organics (Jeong and Corapcioglu, 2003). The main potential of increasing the Ca is to decrease the IFT because the increase of the viscosity force is limited by certain conditions. This increase can be accomplished by using surfactant foam. Relying on the properties of the surfactant, it can produce high Ca values, even at low injection velocities, by reducing the IFT between the contaminant and the ushing uid. Jeong and Corapcioglu (2003) found that the sweep eciency and removal eciency of surfactant foam ood increased greatly with increasing Ca values. It is suggested that a suitable Ca of surfactant foam ooding should be determined prior to a eld application, considering ow path heterogeneity and surfactant type and concentration.

3. Case studies and discussion 3.1. Case studies A number of laboratory and eld studies that involve surfactant foams to enhance the remediation of contaminated soils have been performed. They are summarized in Table 3. Mulligan and Eftekhari (2003) investigated the capability of foam generated by two surfactants, Triton X-100 and a commercial rhamnolipid, JBR425, to remove pentachlorophenol (PCP) from the contami-

nated soil. PCP removal mechanisms are volatilization and mobilization. In terms of nal removal eciency, better results were obtained by using Triton X-100. Under the conditions of a ow rate of 15 ml min1 with a foam quality greater than 96%, Triton X-100 (1%) removed 85% and 84% of PCP from ne sand soil and sandy-silt, respectively, contaminated with 1000 mg kg1 PCP. Of this, 66% and 57% of the PCP was removed by volatilization. PCP removal was approximately the same for a higher contaminant level (3000 mg kg1) but more pore volumes of foam were required for the ne sand (23 pore volumes compared to 12). For the sandy-silt soil, PCP removal was higher for the higher contaminant level, 84% compared to 76%. However, more pore volumes were required (35 compared to 21). Results showed that the 1% Triton X-l00 foam removed more than twice as much PCP in all cases than the liquid surfactant solution. In their conclusions, the authors pointed out that the foam could be used as a uid to enhance soil remediation under low pressures. Jeong et al. (2000) used a micromodel study to evaluate the residue TCE removal by foam generated from an anionic surfactant, sodium C1416 olen sulfonate (Bio-terge AS-40). Inuence of Ca on TCE saturation was demonstrated. Surfactant foam ooding is more eciently in displacing the TCE than water ooding and surfactant ooding. It removed 99% of the TCE at a Ca of 1.7 105. Further study by Jeong and Corapcioglu (2003) examined the eects of foam quality (gas fraction), surfactant concentration, pore structure and NAPL types on NAPL removal during foam ooding. It was observed that foam was stable in contacting with TCE but collapsed with dodecane. Low quality foam (50% and 66%) was more ecient for TCE removal and sweep eciencies than a high quality foam (85%). TCE removal increased with surfactant concentration at a xed foam quality. It was concluded that Ca is an important parameter in determining sweep eciency, gas saturation of surfactant foam in a nonhomogeneous porous medium. Increases in Ca increased TCE removal signicantly. Results also showed that TCE removal was more dependent on Ca than foam quality and surfactant concentration. Column experiments were conducted to evaluate the feasibility of using a rhamnolipid foam to remove heavy metals (Cd and Ni) from a sandy soil contaminated with Cd (1706 mg kg1) and Ni (2010 mg kg1) (Wang and Mulligan, 2004). Foamability of JBR425 (mixed rhamnolipid) solution was examined rst. High quality foam with restricted ow rate (<5 ml min1) was used. Best results were obtained from the foam generated by a 0.5% rhamnolipid solution with an initial pH value of 10 after 20-pore-volume ushing. These conditions removed 73% of the Cd and 68% of the Ni. Removal eciencies by foam generated by a synthetic surfactant, Triton X-100, were investigated as a comparison. It removed

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Table 3 Summary of surfactant foam enhanced soil remediations Description Filed demonstration of surfactant/ foam process for aquifer NAPL (mixture of TCE, TCA and PCE) remediation at Hill Air Force Base in Utah. Foam-enhanced surfactant solution ooding in removing n-pentadecane from contaminated column Micromodel study of surfactant foam remediation of residual TCE Remediation of PAH-contaminated soils using foams Soil ushing using colloid gas aphron (CGA) suspensions generated from a plant-based surfactant to remove HCB from soil Remediation with surfactant foam of PCP-contaminated soil Bench-scale study of surfactant foam/ bioaugmentation technology for in situ treatment of TCE-DNAPLs Column tests to evaluate rhamnolipid foam enhanced remediation of Cd and Ni contaminated soil Surfactants Sodium dihexylsulfosuccinate Main results The average DNAPL saturation of the swept volume was reduced to 0.03% References Hirasaki et al. (1997)

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Triton SP-series

Slightly over 74% of the n-pentadecane was removed at a gasliquid ratio of 10/1 99% of the residual TCE was removed Foams readily desorbed PAHs from contaminated soils and moved well at pressure of 33.9 kPa/m (1.5 psi/ft) or less CGA suspension recovered 670 lg in 12 pore volumes compared to 8 lg by waterood

Huang and Chang (2000)

Bioterge As-40 Biosurfactants +50% ethanol

Jeong et al. (2000) Kilbane et al. (1997)

Natural surfactant from Sapindus mukorossi (Soapnut)

Kommalapati et al. (1998)

Triton X-100, JBR 425 Steol CS-330

Triton X-100 (1%) foam removed 85% and 84% of PCP from ne sand and sandy-silt, respectively Injecting the foam in a pulsed operation removed 75% of the contaminant, and adding the microbes resulted in 9599% degradation of the residual Foam removed 73% of the Cd and 68% of the Ni from the contaminated soil

Mulligan and Eftekhari (2003) Rothmel et al. (1998)

JBR 425, Triton X-100

Wang and Mulligan (2004)

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65% of the Cd and 57% of the Ni under the same conditions. Compared with the metal removal eciencies by liquid solution, using foam increased the metal removal eciencies signicantly, because it provides a more uniform and ecient contact between surfactant and metal ions, and improves the soil wettability and desorption. This study showed that rhamnolipid foam technology could be an eective means for the remediation of cadmium and nickel contaminated soil. Bench-scale studies were performed to investigate the surfactant foam technology for mobilizing and dispersing TCE-DNAPLs combined with a bioaugmentation technology to remediate TCE in situ (Rothmel et al., 1998). Three surfactants, Tergitol 15-S-12, Biosoft D40 and Steol CS-330, were evaluated. Results indicated that the Steol CS-330 surfactant foam was the most ecient for the TCE mobilization. Further studies showed that a pulsed injection of foam (foam/articial groundwater/foam) was more eective in mobilizing and dispersing the TCE. 75% of the initial TCE was removed, and the dispersed residual TCE was fairly evenly distributed and reduced to levels compatible with biodegradation (<500 lg g1). Results indicated that the use of the surfactant foam resulted in improving both the dispersion and survival of the injected TCE-degrading bacteria as compared to the injection of the Steol CS-330 surfactant solution. Adding the TCE-degrading bacterial strain ENV 435 simultaneously with the second pulse of foam resulted in 9599% degradation of the residual TCE. This technology is proposed as an improvement of great signicance over current pump-and-treat methods. Combination of this technology with bioaugmentation to degrade the residual organics was thought able to lead to a comprehensive in situ remediation treatment for contaminated sites. The rst eld demonstration of a surfactant/foam process for removal of DNAPL from a heterogeneous alluvial aquifer was conducted during the Spring of 1997 at Hill Air Force Base, UT (Hirasaki et al., 1997). Contaminants consisted of 70% TCE and smaller amounts of other solvents and dissolved grease. Approximately 79 l of contaminant was present initially. Site hydraulic conductivity ranged from 104 m s1 to more than 103 m s1. A solution containing 3.5% (by weight) of the anionic surfactant sodium dihexylsulfosuccinate was injected over a period of 3.2 days, for a total amount of 3.2 times the swept pore volume of the aquifer. During most of this time, air was injected for two-hour intervals at the three injection wells on a rotating basis to form in situ foam. Analysis of the euent showed that 140 l of DNAPL was produced. The authors postulated that the additional DNAPL likely entered the region beyond the injection well. Moreover, injection of the nonpartitioning tracer with the surfactant indicated that foam reduced the swept volume by approximately 50%. The amount of DNAPL remaining at the end of

the test was very low and the average nal DNAPL saturation in the swept volume based on the higher of these estimates was only 0.03% (77 mg kg1 soil). These studies showed that surfactant foam could be used potentially in remediating contaminated soils. They illustrate some general considerations that are important for the use of foams for eld applications. Foam can be injected either continuously or in a pulsed way. Contaminant removal eciencies can be improved greatly by using foam compared with the liquid solution ushing. Also, it was shown that foam could be used as a pretreatment for the bioremediation processes to reduce the contaminant concentration to a bacterial amenable level. 3.2. Technology compatibility 3.2.1. Enhancement for pump-and-treat system The pump-and-treat process using surfactants as extractants was initially used for cleanup soils that were contaminated by both organic and inorganic contaminants. However, it is relatively ineective for the economical remediation of contaminated soils. Previous research has demonstrated that it might require ushing hundreds to thousands of pore volumes for remediating these contaminants (Hunt et al., 1988; Powers et al., 1992, 1994). It is dicult to contain treatment uids at the remediation zone. Moreover, adsorption and precipitation of surfactants is detrimental for these applications and residual surfactants in the subsurface can be toxic. Furthermore, in most cases, heavy metals are often present in soil as a component of mixed contamination with organics such as PAHs. This can cause serious limitations for in situ treatment technologies. Mulligan et al. (1999) have demonstrated the feasibility of using biosurfactants (e.g., surfactin, rhamnolipid and sophorolipid) to remove heavy metals and oil together from a contaminated soil. It was postulated that surfactants could enhance oil remediation by lowering the IFT between the oil and the soil, and could also enable metal removal due to their negative charge and the IFT lowering. Also, metals that are associated with the oil may be removed with oil simultaneously. It gives the light that surfactant foam could also be used possibly for the removal of the organics and metal mixed contamination. Surfactant foam instead of surfactant solution can be used to improve the performance of the pump-and-treat process (Fig. 2). Foam can be injected or produced in situ by injecting surfactant and air simultaneously or alternately. Experiments demonstrated that the eective permeability of the porous medium to each phase is signicantly decreased when foam is present. For example, due to an increase in the air eective permeability and an increase in air viscosity, air mobility could be reduced 200600 fold (Bernard and Holm, 1964; Bernard et al.,

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1965). Thus, foam can easily overcome gravitation effects, restrain possible channeling eectively and reach most of the regions in a heterogeneous reservoir, then provide a longer, more uniform and ecient contact between the surfactant and the contaminants (Wang and Mulligan, 2004). The treatment eciency is thus improved potentially and the use of surfactants is lowered, which makes this technology more cost feasible. An important consideration in these processes is the selection of the most appropriate surfactant for each application. Besides the site characteristics and contaminant speciation, selection of a surfactant for a specic application requires the evaluation of many inherent properties including solubility, toxicity, foamability, biodegradability, chemical stability, reactivity, wetting ability, and corrosivity (Admas et al., 1996). The use of biosurfactant foam was suggested as an eective, lowtoxic means, because biosurfactants are natural products and they may be more benign to biodegrading bacteria and be more biodegradable themselves, and therefore may be better candidates for the remediation of contaminated sites (Mulligan et al., 2001a; Wang and Mulligan, 2004). It is also imperative that surfactants must be recoverable and reusable for economic and thus successful implementation of this technology. It has been demonstrated that surfactants can be recovered by precipitation using mono- or multivalent counterions (i.e. the ions of opposite charge to those of the surfactant) from the micellar-enhanced ultraltration (MEUF) (Lipe et al., 1996; Vane et al., 2001; Juang et al., 2003). The surfactant concentration is another important factor to be considered. It was found that metal removal eciencies would increase linearly with the increasing surfactant concentration below the CMC, and remain relatively constant above the CMC (Doong et al., 1998). However, for organic contaminants such as PAHs, the solubility increased when a higher surfactant concentration above the CMC was used (Liu et al., 1991). Things become more complex when high concentrations of surfactant solutions (110%) are required to overcome dilution and binding eects (Oolman et al., 1995; Fountain et al., 1996), result in plugging by the dispersion of ne materials or by the formation of viscous emulsions (Nash, 1987; Rothmel et al., 1998). These phenomena would probably cause high pressure gradients in the soil and result in a series of problems such as channeling or soil heaving. Thus, a preliminary test based on site characteristics and contaminant speciation is a must to determine the proper surfactant concentration. 3.2.2. Enhancement of bioremediation processes In situ bioremediation is utilized frequently due to its low cost for the remediation of contaminated sites. It is well known that microorganisms are capable of degrad-

ing a wide range of organic compounds and this behavior is optimized to achieve ecient remediation processes. But most bacteria in the subsurface are rmly attached to soil particles (Wilson et al., 1986) and most organic contaminants do not contain all the necessary elements for bacterial growth. Thus, adequate amounts of nitrogen, sulfur, phosphorus, and certain trace minerals must be applied to enhance the biodegradation rate. Foam is being developed as a promising new medium to carry out augmentations for such processes. It has been found that the oxygen mass transfer was enhanced greatly by using foam to deliver oxygen in a gaseous form, and it was much more ecient than the use of oxygenated solutions (Wallis et al., 1986). Dierent from other approaches, foams can be designed to remove pollutants and enhance bioremediation simultaneously. The foam can be either produced in situ or injected into the contaminated zone. As depicted in Fig. 2, injection wells (vertical and/or horizontal) can be used to assist in delivering, transporting, and monitoring foams through the subsurface. Nutrients and pH buers can be added together to optimize the site conditions to stimulate growth of the organisms that will metabolize the particular contaminants of concern eciently. Rothmel et al. (1998) demonstrated the feasibility of using foam ushing followed by aerobic biodegradation to remove TCE from the contaminated soil. But some other chlorinated aliphatics, such as tetrachloroethylene and carbon tetrachloride are known to degrade readily under methanogenic conditions through reductive dechlorination. From a theoretical standpoint, such conditions can be created by using foam, depending on the selected carrier gas for foam generation. Naturally occurring biodegradation at the contaminated site may be aected by the addition of surfactants. Several studies have shown that biodegradation was enhanced in the presence of surfactants (Guerin and Jones, 1988; Grimberg et al., 1996), while in other cases inhibitions were induced (Laha and Luthy, 1992; Deschenes et al., 1996) or no eects were observed (Liu et al., 1995). Such phenomena were found to be related to the nature of surfactants. Nonionic surfactants generally donate greater enhancement whereas ionic surfactants are more inhibitory (Rouse et al., 1994). Cort and Bielefeldt (2000) run batch tests to evaluate the eect of surfactants on PCP degradation rates by Sphingomonas chlorophenolicum strain RA2 as function of surfactant type, surfactant concentration, and temperature. The four tested surfactants were cetyl triammonium bromide (CTAB-cationic), sodium dodecyl sulfate (SDS-anionic), Triton X-100 (TX 100-nonionic) and Tergitol NP-10 (TNP 10-nonionic). PCP degradation by the bacterium was observed in the presence of SDS, TX 100 and TNP 10. It was shown that the anionic surfactant, SDS, caused inhibition at lower concentrations than the two nonionic surfactants, and SDS caused partial

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and complete inhibitory eects at concentration well below the CMC. Degradation was ceased when SDS concentration was near the CMC, whereas degradation activity was demonstrated in cultures containing nonionic surfactants with concentrations above the CMC. It was found that for the anionic and nonionic surfactants, increased surfactant concentrations generally led to increased toxicity. Moreover, the inhibitory eect induced by surfactant addition was more announced at lower temperatures. In every case, the concentration of surfactant required to completely inhibit PCP degradation decreased with a decrease in temperature. These results note that the future application of surfactant foam enhanced bioremediation counts on, to a large extent, the ability to accurately predict the eects of surfactant type and concentration as well as temperature on a given bacterial culture with a known set of organic contaminants. 3.3. Factors aecting treatment costs The cost of surfactant foam enhanced soil remediation is highly variable and is a function of many factors. The main inuencing factors include the site characteristics, contamination speciation, surfactant type and concentration, other additives, scale of application, required treatment level, and regulatory factors. The initial cost of the surfactant plays an important role in the overall cost of in situ foam ushing. Depending on the site characteristics and the number of pore volumes required, the initial cost can be relatively low or extremely high. Generally, surfactant foam technology should be more economical compared with conventional ushing processes due to the reduced use of surfactant and chemicals and improved treatment eciencies. 3.4. Limitations As for other remediation technologies, the treatment and cost eciencies of the surfactant foam technology depend greatly on the specic site geologic conditions and the speciation of contaminants. Although promising results were obtained, it cannot be treated as a panacea for all-purpose applications (Wang and Mulligan, 2004). For example, it might not be applicable for the soils with low permeability and high content of clay. Although, another innovative technology, electrokinetics, is being developed as an alternative for such kind of soils (Bruell et al., 1992; Vane and Zang, 1997), it is not without its problems such as high capital and operation costs. It was reported that surfactants could also be used in this process as an enhancement (Reddy and Saichek, 2003). Secondly, the foam behavior in porous media is far from being understood. Previous studies provided some insights that foam can be used potentially for achieving mobility control (Bernard and Holm, 1964; Bernard

et al., 1965; Bertin et al., 1999), and diverting uid to low permeability strata within the heterogeneous porous media (Llave et al., 1990; Zehrboub et al., 1994). However, many important aspects inuencing the mobility control and diversion such as foam texture, foam viscosity, aqueous phase saturation, pressure gradient, etc., have not been explored denitively. Another factor that cannot be neglected is that regulatory approval could be dicult to obtain due to the current lack of information on performance, and uncertainties involving scaling up from bench- to pilot to full-scale. Also, another concern is the possible surfactant residuals remaining in the subsurface, even though it can be reduced greatly by using foam. Several investigators suggested the use of food grade surfactants because they are more likely to gain acceptance by the general public and regulatory ocials for subsurface remediation projects (Shiau et al., 1995, 2000). It is attractive, but it was observed that, compared with the use of nonfood grade surfactants, the use of food grade surfactants experienced a higher mass loss due to the surfactant sorption and precipitation (Shiau et al., 1995). It probably makes the remediation not feasible from technical and/or economical aspects. Plant-based surfactants may also be an alternative (Kommalapati et al., 1998).

4. Summary and recommendations In conclusion, the surfactant foam technology provides a better candidate for the remediation of contaminated soils. A number of interesting applications of surfactant foam technology have been investigated. It is applicable to remove various soil contaminants and has perfect compatibility with the existing remediation technologies such as pump-and-treat systems and bioremediation. Performance and cost eciencies of these remediation processes can be greatly improved. However, as an innovative technology, there are many factors to be investigated for the future development. Soil matrix characteristics, contaminant speciation, eectiveness of pulsed operation and surfactant partitioning must be thoroughly analyzed to determine the applicability and eectiveness of in situ foam ushing to the subsurface conditions. Site geologic conditions should be specied rst during in eld applications. Proper selection of a foaming surfactant and surfactant concentration is critical to the success of the remediation once applicability has been veried. The role of surfactant on the remediation of contaminated soils still remains unclear. Continuous kinetic studies are preferred to involve the interactions among surfactant foam, soil, and contaminant. Development of predictive mathematical models is helpful to make meaningful predictions regarding optimal surfactant selection for subsurface

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