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Engineering Geology 60 (2001) 371±380

www.elsevier.nl/locate/enggeo

Surfactant-enhanced remediation of contaminated soil: a review


C.N. Mulligan a,*, R.N. Yong b, B.F. Gibbs c
a
Department of Building, Civil and Environmental Engineering, Concordia University, 1455 de Maisonneuve Blvd. W., Montreal,
Quebec, Canada H3G 1M8
b
Geoenvironmental Engineering Research Centre, Cardiff School of Engineering, Cardiff University, P.O. Box 917,
Newport Road, Cardiff, CF2 1XH, United Kingdom
c
MDS Pharma Services, 2350 Cohen Street, Montreal, Canada H4R 2N6
Accepted for publication 30 May 2000

Abstract
Extracting aqueous solutions with or without additives are employed to solubilize contaminants in soil. Since water solubility
is the controlling removing mechanism, additives are used to enhance ef®ciencies. These additives can reduce the time to treat a
site compared to the use of water alone. Additives must be of low toxicity and biodegradable. The research in this area has
focussed mainly on halogenated volatile organic compounds (VOCs) and is still quite limited for metal removal. Additives
include surfactants, organic and inorganic acids, sodium hydroxide, which can dissolve organic soil matter, water-soluble
solvents such as methanol, displacement of cations with nontoxic ones, complexing agents such as EDTA, acids in combination
with complexing agents or oxidizing/reducing agents. Cationic, anionic and nonionic surfactants are particularly used for soil
washing or ¯ushing. They contain both hydrophobic and hydrophilic portions, making them ideal for solubilization of hydro-
phobic compounds. Numerous studies have indicated that surfactants enhance recoveries of non-aqueous phase liquids
(NAPLs). There have also been indications that pretreatment of soil with surfactant washing to solubilize hydrophobic
compounds such as PAHs enhances biodegradation of these contaminants. A few in situ ®eld studies have been performed
with surfactants. Large-scale treatment has been done mostly for organic removal. Soil pH, soil type, cation exchange capacity
(CEC), particle size, permeabilities and contaminants all affect removal ef®ciencies. High clay and organic matter contents are
particularly detrimental. Understanding the chemistry of the binding of the contaminant and the hydrogeology of the site are
very important. Once the water is pumped from the soil, it must be extracted and then treated to remove the hydrocarbons and
metals. Several technologies exist such as sodium hydroxide or sodium sul®de precipitation, ion exchange, activated carbon
adsorption, ultra®ltration, reverse osmosis, electrodialysis and biological processes. Recycling of the surfactants is desired to
decrease treatment costs.
This paper will provide an overview of the laboratory research, ®eld demonstration and full-scale application of surfactants
for the remediation of contaminated soil. The majority of pilot scale in situ ¯ushing tests, particularly in the United States, have
involved the use of surfactants and co-solvents. There are only a few full-scale projects however. Recent laboratory scale efforts
by the authors concerning the use of biosurfactants, biologically produced surfactants, to enhance the removal of copper,
cadmium and zinc from contaminated soils and sediments are discussed. Three types of biosurfactants were evaluated for their
effectiveness. They included a lipopeptide called surfactin from Bacillus subtilis, a rhamnolipid from Pseudomonas aeruginosa
and a sophorolipid from Torulopsis bombicola. The results indicated the feasibility of removing the metals with the anionic
biosurfactants even though the exchangeable fractions were not signi®cant. q 2001 Elsevier Science B.V. All rights reserved.
Keywords: Soil ¯ushing; Soil remediation; Surfactant; Metals; Field studies

* Corresponding author. Fax: 11-514-848-2809.


E-mail address: mulligan@civil.concordia.ca (C.N. Mulligan).

0013-7952/01/$ - see front matter q 2001 Elsevier Science B.V. All rights reserved.
PII: S 0013-795 2(00)00117-4
372 C.N. Mulligan et al. / Engineering Geology 60 (2001) 371±380

1. Introduction Contaminated soil

The injection or in®ltration of solutions into soil


using surface trenches, horizontal drains or vertical
drains is called in situ ¯ushing. Water with or without Surfactant Well
additives are employed to solubilize contaminants. injection
The ef®ciency of the extraction depends on the
hydraulic conductivity of the soil. High permeability Groundwater level
gives better results (greater than 1 £ 1023 cm=s†: The
solubility of pollutants and if the pollutant was origin-
ally solubilized in water or not are key factors in
determining removal ef®ciencies. Prior mechanical
mixing of the soil can disturb the in®ltration of the Low permeability zone
extractant. Understanding the chemistry of the bind-
ing of the contaminant and the hydrogeology of the Contaminant plume
site are very important (USEPA, 1987). Fig. 1. Typical in situ soil ¯ushing installation.
Since water solubility of many organic contaminants
is the controlling removing mechanism, additives are
used to enhance ef®ciencies. Those liquid contaminants Surfactants are amphiphilic compounds (containing
that remain as a separate phase are called nonaqueous hydrophobic and hydrophilic portions) that reduce the
phase liquids (NAPL). NAPLs that sink below the water free energy of the system by replacing the bulk mole-
table are denser than water and are called DNAPLs and cules of higher energy at an interface. They contain a
those that are lighter are called LNAPLs. The former are hydrophobic portion with little af®nity for the bulk
thus particularly dif®cult to remediate (Pankow and medium and a hydrophilic group that is attracted to
Cherry, 1996). Some examples include chlorinated the bulk medium. Surfactant monomers will form
solvents such as trichloroethylene (TCE), polycyclic spheroid or lamellar structures with organic pseudo-
aromatic hydrocarbons (PAHs) including phenan- phase interiors. This coincides will lower surface and
threne, naphthalene, that are found in coal tar and interfacial tensions (Fig. 2). The minimum concentra-
creosote and polychlorinated biphenyls (PCBs) such tion at which this occurs is called the critical micelle
as Arochlor 1242. Matters become even more compli- concentration (Rosen, 1978). Salinity, hydrocarbon
cated since these contaminants are often mixed with chain length and surfactant type (hydrophile±
metals or radionuclides. lipophile HLB) will in¯uence the concentration.
Surfactants have been used industrially as adhesives,
¯occulating, wetting and foaming agents, de-emulsi®ers
2. Background on surfactants
Monomer
CMC
Cationic, anionic and nonionic surfactants can be Micelle
used for soil washing or ¯ushing. They are useful in
Physical property

displacing DNAPL by reducing interfacial tension


between DNAPL and groundwater. It is these capil- Solubility
lary forces that restrict the mobility of the DNAPL.
The mobilized contaminant can then be recovered in Surface tension
extraction wells (Fig. 1). Surfactants can be used in
mixtures or with additives such as alcohol and/or salts Interfacial tension
such as sodium chloride. Polymers or foams can also Surfactant concentration
be added to control the mobility of the contaminants.
The surfactants must be recovered and reused for the Fig. 2. Schematic diagram of the variation of surface tension, inter-
process to be economic. facial and contaminant solubility with surfactant concentration.
C.N. Mulligan et al. / Engineering Geology 60 (2001) 371±380 373

and penetrants (Mulligan and Gibbs, 1993). Petro- have been examined (Shiau et al., 1995). These
leum users have traditionally been the major users, surfactants were able to remove one to two orders of
as in enhanced oil removal applications. In this appli- magnitude more chlorinated organics such as
cation, surfactants increase the solubility of petroleum perchloroethylene (PCE), trichloroethylene (TCE)
components (Falatko, 1991) or lower the interfacial and 1,2 dichloroethane (1,2-DCE) than water alone
tension to enhance mobility of the petroleum. They by formation of microemulsions. Other surfactants
have also been used for mineral ¯otation as well as the with indirect food additive status such as alkyl
pharmaceutical industries. Typical desirable proper- diphenyl disulfonate (DOWFAX) indicated lower
ties include solubility enhancement, surface tension levels of losses via sorption and precipitation while
reduction, the critical micelle concentrations, wett- substantially solubilizing naphthalene and other
ability and foaming capacity. PAHs. Recently, a plant-based surfactant from the
Numerous batch and column studies have indicated fruit pericarp of Sapindus mukurossi, a plant from
that surfactants enhance recoveries of NAPL (Ellis et the tropical regions of Asia has shown potential for
al., 1985; Abdul et al., 1992; Kan et al., 1992; Soerens the removal of hexachlorobenzene (Roy et al., 1997).
et al., 1992) by solubility enhancement or desorption. FDA approval, however, does not guarantee that the
There have also been indications that pretreatment of surfactant or its biodegradation products are safe and
a soil with surfactant washing (Igepal CA-720) to acceptable to the regulators and the public. Solubili-
solubilize PAHs enhanced biodegradation of these zation of TCE by surfactants was not permitted in a
contaminants (Joshi and Lee, 1995). pilot test (Fountain et al., 1996), even though the
Anionic and nonionic surfactants are less likely to surfactant has a toxicity similar to sucrose and that
be absorbed to the soil. Cationic surfactants have been it was used in food and food processing. Many surfac-
used to lower aquifer permeabilities by sorption on to tants are of low toxicity to humans but can affect
the aquifer materials (Westall et al., 1992). Surfactant animals and plants. Ethoxylated alcohols, which are
soil washing was originally developed in petroleum found in laundry detergents and dish soap, are toxic to
recovery operations. Surfactants have potential for ®sh. They can be, however, degraded in biological
use in aquifer remediation of DNAPLs. wastewater treatment systems.
Several factors can in¯uence the ef®ciency of soil Overall, desirable surfactant characteristics include
¯ushing with surfactants. Groundwater that is too hard biodegradability, low toxicity, solubility at ground-
may be detrimental to the effectiveness of a surfactant water temperatures, low adsorption to soil, effective
(AAEE, 1993). Surfactants can adsorb onto clay at concentrations lower than 3%, low soil dispersion,
fractions, reducing their availability. Too quick low surface tensions and low CMC (Kimball, 1992).
biodegradation can inactivate the surfactant although Anionic surfactants may precipitate. However,
some degradability is required to avoid accumulation. coinjection with a nonionic surfactant can reduce
Removal of the surfactant from the recovered water precipitation and also CMC values (Sabatini et al.,
from ¯ushing can be dif®cult and lead to high 1995). Biosurfactants may be more biodegradable,
consumption rates. more tolerant to pH, salt and temperature variation,
The main factors that should be considered when and in some cases less expensive (West and Harwell,
selecting surfactants include effectiveness, cost, 1992).
public and regulatory perception, biodegradability
and degradation products, toxicity to humans, animals 2.1. Biosurfactants
and plants and ability to recycle. The ®rst considera-
tion is that the surfactants are ef®cient in removing the Some surfactants, known as biosurfactants, are
contaminant. This can be established by previous biologically produced from yeast or bacteria from
experience or by laboratory studies prior to the various substrates including sugars, oils, alkanes and
®eld-scale demonstrations. wastes (Lin, 1996). For example, Pseudomonas
To reduce risk, food-grade surfactants (T-MAZ 28, aeruginosa can produce rhamnolipids from substrates
T-MAZ 20 and T-MAZ 60), which have been including C11 and C12 alkanes, succinate, pyruvate,
approved by the Food and Drug Administration citrate, fructose, glycerol, olive oil, glucose and
374 C.N. Mulligan et al. / Engineering Geology 60 (2001) 371±380

Table 1 degradability and biocompatibility (Cooper, 1986).


Classi®cation and microbial origin of biosurfactants. (Adapted from For example, glycolipids from Rhodococcus species
Mulligan and Gibbs (1993) and Banat (1995))
413A were 50% less toxic in naphthalene solubiliza-
Surfactant class Microorganism tion tests than Tween 80 (Kanga et al., 1997).
Biosurfactants are grouped as glycolipids, lipopep-
Trehalose lipids Arthrobacter paraf®neus
tides, phospholipids, fatty acids and neutral lipids
Corynebacterium spp.
Mycobacterium spp. (Biermann et al., 1987). Most of these compounds
Rhodococus erythropolis are either anionic or neutral. Only a few are cationic
such as those containing amine groups. The hydro-
Rhamnolipids Pseudomonas aeruginosa
phobic part of the molecule is based on long-chain
Sophorose lipids Candida apicola fatty acids, hydroxy fatty acids or a-alkyl-b-hydroxy
Candida bombicola
fatty acids. The hydrophilic portion can be a carbohy-
Candida lipolytica
drate, amino acid, cyclic peptide, phosphate,
Glucose-, fructose-, Arthrobacter spp. carboxylic acid or alcohol. Their CMCs generally
saccharose lipids Corynebacterium spp.
range from 1 to 200 mg/l and their molecular weights
R. erythropolis
from 500 to 1500 amu. (Lang and Wagner, 1987). A
Cellobiose lipids Ustilago maydis wide variety of microorganisms can produce these
Polyol lipids Rhodotorula glutinus compounds (Table 1).
Rhodotorula graminus Biosurfactants have been tested in enhanced oil
Diglycosyl diglycerides Lactobacillus fermentii recovery and the transportation of crude oils (Hayes
et al., 1986). They were effective in the reduction of
Lipopolysaccharides Acinetobacter calcoaceticus
the interfacial tension of oil and water in situ and the
(RAG1)
Pseudomonas spp. viscosity of the oil, the removal of water from the
Candida lipolytica emulsions prior to processing and in the release of
bitumen from tar sands. Emulsan w has been commer-
Lipopeptides Arthrobacter sp.
Bacillus pumilis cialized for this purpose (Anonymous, 1984). It
Bacillus subtilis contains polysaccharide-attached fatty acids and
Bacillus licheniformis proteins attached. Although most biosurfactant-
Pseudomonas ¯uorescens producing organisms are aerobic, a few examples of
Ornithine, lysine peptides Thiobacillus thiooxidans anaerobic producers exist. Bacillus licheniformis JF-2
Streptomyces sioyaensis is an example, which would be well suited for in situ
Gluconobacter cerinus studies for enhanced oil recovery or soil decontami-
Phospholipids T. thiooxidans nation (Javaheri et al., 1985). A 70% bioremediation
Corynebacterium alkanolyticum and bioreclamation rate of a slop oil-contaminated
Sulfonylipids Capnocytophaga spp. soil was achieved with oil-degrading cultures (Dave
et al., 1994).
Fatty acids (corynomycolic Penicillium spiculisporum
Rhamnolipid surfactants have been tested and
acids, spiculisporic acids, etc.) Corynebacterium lepus
Arthrobacter para®neus found to release three times as much oil as water
Talaramyces trachyspermus alone from the beaches in Alaska after the Exxon
Valdez tanker spill (Harvey et al., 1990). Scheiben-
bogen et al. (1994) found that the rhamnolipids from
mannitol (Robert et al., 1989). They are synthesized P. aeruginosa UG2 were able to effectively remove a
as metabolic by-products. Composition and yields hydrocarbon mixture from a sandy loam soil and that
depend on the fermentor design, pH, nutrient compo- the degree of removal was dependent on the type of
sition, substrate and temperature used (Mulligan and hydrocarbon removed and the concentration of the
Gibbs, 1993). They can be potentially as effective surfactant used. Van Dyke et al. (1993) previously
with some distinct advantages over the highly used found that the same strain could remove at a concen-
synthetic surfactants including high speci®city, bio- tration of 5 g/l, approximately 10% more hydrocarbon
C.N. Mulligan et al. / Engineering Geology 60 (2001) 371±380 375

Table 2
Summary of surfactant soil ¯ushing ®eld tests. (PV, Pore volume; BTEX, benzene, toluene, ethylbenzene, xylene; TCE, trichloroethylene;
TCA, trichlorethane; TCET, tetrachlorethane, PCE, perchloroethylene: PCB, polychlorinated biphenyls)

Group Process Contaminant removed Reference

SUNY-Buffalo with Dupont at Addition of 1% surfactant 73 gal carbon tetrachloride Fountain (1993)
Corpus Christi Site (approved in food successfully removed in
preparation) Witconol 2722 comparison to pump and treat
and Tergitol 15-S012
Canadian Air Forces Base at 2% mixture of surfactant 80% of PCE recovered Fountain and Hodges (1992)
Borden (SUNY) added to sandy aquifer
General Motors NAO Research 0.75% nonionic ethoxylated 10% of PCBs, oils removed in Ang and Abdul (1991)
and Development Center surfactant washing with ®rst test and 14% in second
recovery exceeding expectations
University of Michigan Injection of 4% Witconol Removal of 10% dodecane Abriola et al. (1993)
and Tween 80 and modeling required 0.7 l surfactant and
130,000 l water
Eckenfelder, Inc. Injection of 2.5% SDS and Injection of 7.7 pore volumes Underwood et al. (1993)
recycle/reuse of surfactant of 2.5% SDS removed as
much PCB as 20 to 40 pore
volumes of water (90% waste
volume reduction)
US DOE Gaseous Diffusion Site 4% sodium dihexyl DNAPLs, TCE with some Jafvert (1996)
Portmouth, OH sulfosuccinate surfactant/4% PCBs and other chlorinated
isopropyl alcohol as solvents, .90% removed by
cosolvent and 2% electrolyte solubilization
(1:1 NaCl and CaCl2)
Dover AFB, Dover DE (single Surfactant DNAPL (PCE or Internet report:
phase microemulsion) perchloroethylene) www.epa.gov/Superfund/
index.htm
Ecosites Inc., Estrie Reg. Shop, Biodegradable nontoxic Hydrocarbons, LNAPLs, Jafvert (1996)
Que., Canada surfactant ªCutting Oilº, 160,000 kg
hydrocarbon recovered in 12
months, US$ 1.2 million Cdn
for fulll scale, commercial
completed project
Fredicksburg, VA Wood treating Alkaline agent (0.5% Creosote-based wood treating Rice University (1997)
site Na2CO3), nonyl phenol oil (DNAPL), unable to inject
surfactant with 10 mol ¯uid, poor site evaluation
ethylene oxide (0.1% wt
Makon-10) and polymer
(1500 mg/l xanthan gum)
TWCC Biosolve Group Patented non-hazardous, 80% removal of NAPL, 90% USEPA (1998)
biodegradable surfactant removal of transmission ¯uids
(1±2% concentration) in Northern California,
increases biodegradation by
30%. Cost US$ 0.35±0.85 per
gallon
Hill Air Force Base, Layton, UT 6.6 PV of surfactant (2.2% LNAPL (JP-4 jet fuel, Jafvert (1996)
Cell 5, Surfactant Mobilization Aerosol OT/ 2.1%Tween) chlorinated and
and Electrolyte (CaCl2) nonchlorinated VOCs,
injected naphthalene, pesticides, PCBs,
dioxins)
Cell 6, Surfactant Solubilization 10 PV of 4.3% surfactant Mixture of VOCs, Jafvert (1996)
(Dowfax) naphthalene, pesticides, PCBs,
dioxins, JP-4 fuel
376 C.N. Mulligan et al. / Engineering Geology 60 (2001) 371±380

Table 2 (continued)

Group Process Contaminant removed Reference

Cell 8, Surfactant/cosolvent Surfactant (3.5% wt Brij 91) LNAPL (JP-4 jet fuel, AATDF (1998)
solubilization and cosolvent (2.5% wt n- chlorinated and
pentanol), , 10 PV injected nonchlorinated solvents,
PCBs), 72% average reduction
OU2-Micellar Flood 0.6 PV of surfactant (7.5% Chlorinated solvents (TCE, Jafvert (1996)
sodium dihexyl TCA, PCE, and TCET),
sulfosuccinate), cosolvent petroleum hydrocarbons,
(3.75% isopropyl alcohol) DNAPL (70% TCE), 99%
and electrolyte (7000 mg/l recovery of DNAPL
NaCl)
Picatinny Arsenal, NJ 400 mg/l of Triton X-100 TCE, rate of desorption Jafvert (1996)
increased by 30% by
surfactant addition
S.S. Papadopulos & Assoc. Non-toxic biodegradable PCBs (solubility increased by USEPA (1998)
(DeNAPL process) Delmont, PA surfactant (91% Witconol 50 times) in fractured rock.at a
SN-70, 9% Mirataine BET cost of US$ 40±100 per sq ft
C-30), maximum
concentration of 13,000 mg/l
Serrener/Varisco Consortium, Surfactants BTEX, aliphatic hydrocarbons USEPA (1998) GSI
Quebec, Canada (2500 kg/day of hydrocarbons Environmental Marketing
recovered, 85% extraction Information
ef®ciency, 1000 m 3/week)
Cost US$ 50±250/m 3
Surtek, Inc. Mobility controlled Low concentration of EPA 23,000 gallons of residual USEPA (1998)
Surfactant Flushing and FDA approved wood treating oil (DNAPL)
surfactants recovered (89%) Cost of US$
50±125 per cubic yard
Thouin Sand Quarry, Quebec, Surfactant/cosolvent Oil waste and chlorinated Jafvert (1996)
Canada, Laval University (n-butanol, hostapur (SAS), solvents in the form of
d-limonene DNAPL (density, 1.02;
viscosity, 18 cp), 86%
recovery of DNAPL
US Coast Guard, Traverse City, 2100 l of 36,000 mg/l PCE, TCE and recalcitrant jet Jafvert (1996)
MI Dowfax 8390 injected fuel, PCE and LNAPL
concentrations increased 40-
and 90-fold, respectively
US DOE Gaseous Diffusion Pint, 1% food grade sorbitan TCE (DNAPL) Rice University (1997)
Paducah, NY monooleate, (3.8 l/min over
3.8 days)
Volk Air National Guard Base, 9±14 PV of Adsee 799 and Hydrocarbons, chlorinated Nash (1988)
WI Hyonic PE-90 (50:50) blend hydrocarbons
(Dichloromethane,
chloroform, TCA, TCE)

from a sandy loam soil than from a silt loam soil and that times more effective than SDS. The bene®t of the
sodium dodecyl sulfate (SDS) was less effective than addition of the biological and synthetic surfactants in
the biosurfactants in removing hydrocarbons. Recently, assisting the biodegradation process was less evident.
DescheÃnes et al. (1994) showed that the rhamnolipids Research with another strain, Pseudomonas marginalis,
from the same strain in a bioslurry could enhance the also indicated that the produced biosurfactants
solubilization of four-ring PAHs more signi®cantly than solubilized PAHs such as phenanthrene and enhance
three-ring PAHs and that the biosurfactants were ®ve biodegradation (Burd and Ward, 1996).
C.N. Mulligan et al. / Engineering Geology 60 (2001) 371±380 377

3. Field studies EPA R.S. Kerr Laboratory conducted a surfactant


¯ood by pumping 6.5 pore volumes of a 4.3% surfac-
Several ®eld studies have also been performed with tant through a 3 £ 5 m sheet piling cell at Hill, AFB,
surfactant in situ ¯ushing. In 1988, a wood-treating Utah. In this case, the contamination was mainly a
site was used to test surfactant washing (Sale et al., 8.5% saturation of LNAPL consisting of weathered
1989). Two blends were tested, one as a prewash and jet fuel and other components. The surfactant was
the other to further lower oil levels. Blend 1 consisted able to remove 90% of the LNAPL by mobilization.
of 1% Polystep A, 0.7% NaHCO3, 0.1% Na2CO3 and In the same year at the same site, the University of
1000 mg/l xanthan gum and second blend comprised Florida conducted a test by injecting 9 pore volumes
of 1.4% Makon-10 surfactant, 0.7% NaHCO3, 0.8% of 3% surfactant and 2.5% pentanol followed by a
Na2CO3 and 1000 mg/l xanthan gum. Ninety-®ve pore volume of 3% surfactant and then 6.5 pore
percent of the oil was reduced and 99% of the surfac- volumes of water. Core data indicated that 90% of
tants were recovered. The combination of surfactants the NAPL was removed while partitioning tracer
and sodium hydroxide has been used in enhanced oil data indicated that 72% removal was achieved (Jawitz
recovery to reduce interfacial tensions. Alkaline et al., 1998). In this case, solubilization was the main
agents can also react with hydrocarbons to form mechanism of removal.
surfactants. The combination of these surfactants In general, high permeability soil is favored for
and the added surfactants can effectively reduce inter- surfactant ¯ushing since numerous pore volumes can
facial tension and enhance oil recovery (Sale and be passed through the contaminated area. Layered
Pitts, 1988). This same mechanism then can be systems are dif®cult to remediate due to limited
responsible for removal of hydrocarbons from a contact in less permeable areas. Also, fractured rock
contaminated soil. The addition of polymer enhances is extremely challenging due to the ¯ow complexity in
the mobility ratio (i.e. enables the contaminant to be the fractured media. However, these challenges are
pushed instead of ¯ow passing around it). relevant for all remediation technologies. Compari-
At a Canadian Forces Base Borden in Ontario, a test sons under the same conditions in these dif®cult
was performed in 1990±91. The hydraulic conductiv- media should be performed to determine if surfactant
ity at the site was 1 £ 1024 cm=s with a low cation ¯ushing is able to remove contaminants faster than
exchange capacity (CEC) and organic matter content. other technologies.
Based on the data at this site, approximately 21 pore
volumes of 1% surfactant solution would be needed to
remove TCE over a four-year period, whereas pump- 4. Metal removal by surfactants
ing and treating groundwater would require 2000 pore
volumes over a period 100 times longer to deconta- The research in the area for metal removal is still
minate the site (AAEE, 1993). Other examples are quite limited, particularly where metal removal is
shown in Table 2. concerned (USEPA, 1987). They include organic
Abdul et al. (1992) examined treatment of PCB- and inorganic acids, sodium hydroxide, which can
contaminated soils. The hydraulic conductivity was dissolve organic soil matter, water-soluble solvents
1 £ 1023 cm=s: A 0.75% solution of Witconol was such as methanol, displacement of toxic cations with
applied to the surface. During the test, 1.6 kg of nontoxic cations, complexing agents such as EDTA,
PCBs and 16.9 kg of carrier oil were recovered. acids in combination with complexation agents or
In 1996, Intera, Radian and the University of Texas oxidizing/reducing agents. Soil pH, soil type, CEC,
conducted a study where 2.5 pore volumes of an 8% particle size, permeabilities and contaminants affect
surfactant solution, 4% isopropanol and sodium removal ef®ciencies. High clay and organic matter
chloride were used to remove mainly TCE. No contents are particularly detrimental.
con®ning walls were used. Approximately 99% of At Superfund sites, with signed Records of
the DNAPL was removed to reach as ®nal ground- Decision (ROD), the combination of hydrocarbons
water concentration of 10 mg/l (Brown et al., 1999). and metals is found at 49% of the sites (USEPA,
In 1996, the University of Oklahoma and the US 1997). Even though organic and metal contamination
378 C.N. Mulligan et al. / Engineering Geology 60 (2001) 371±380

are major concerns, very few technologies are capable A


100
of dealing with both types of contaminants. As
previously mentioned, surfactants can be used to
80
assist in the remediation of numerous types of hydro-

Cu removal (%)
carbon contaminants. Only recently, has it been 60
shown that surfactants can be used to enhance metal
removal (Mulligan et al., 1999a,b). Biologically 40
produced surfactants, surfactin, rhamnolipids and
sophorolipids (Mulligan et al., 1999a) were able to 20
remove copper and zinc from a hydrocarbon-contami-
nated soil. This is due to the anionic character of these 0
surfactants. A series of washings was performed with 0 1 2 3 4 5
surfactin and compared to a control. Initial concentra- Time (days)

tions of oil and grease were 12.6% and the initial B 30


copper content of the soil was 550 mg/kg. Five conse-
cutive washings were performed each lasting 24 h
(Fig. 3). For copper, the control showed a ®nal cumu-
Zn removal (%)
20
lative removal of 20% while approximately 70% was
removed by the surfactin. At the same time, approxi-
mately 50% of the hydrocarbons were removed by
surfactin compared to 30% by the control. Therefore, 10
these results seem very promising. Other advantages
of these biosurfactants are that they are biodegradable
and low in toxicity. In addition, they potentially can
0
be produced in situ using the organic contaminants as
0 1 2 3 4 5
substrates for their production. Larger scale studies, Time (days)
however, are required to determine their potential.
C 20

5. Conclusions
Cd removal (%)

It has been demonstrated that high contaminant 10


removal rates are possible by using surfactants in in
situ ®eld tests. Large quantities of soil do not need to
be excavated and handled. The addition of the surfac-
tants can accelerate remediation work and potentially 0
a wide variety of contaminants in the vadose and 0 1 2 3 4 5
saturated zones can be remediated. Time (days)

However, limited studies have been performed over Fig. 3. Series of washings for (A) copper, (B) zinc and (C) cadmium
a long period of time to determine the levels of by 0.25% surfactin with 1% NaOH (B) and the control (1% NaOH)
residual contamination that are achievable at full (A) according to Mulligan et al. (1999b).
scale. Some of the limitations may include low soil
permeability, heterogeneity and extremely insoluble treatment zone to receive more solution than others
contaminants. For example, low permeability clays and thus increase solution requirements. Control of
with hydraulic conductivities in the order of mobility by the addition of polymers or foam can
10 24 cm/s may signi®cantly increase the time for the reduce this problem. Another potential factor in
surfactant to permeate through the contaminated zone. surfactant ¯ushing that must be taken into considera-
Heterogeneities could cause some sections of the tion is that since the NAPLs are mobilized by the
C.N. Mulligan et al. / Engineering Geology 60 (2001) 371±380 379

surfactant, there is the potential for downward or The impact of a biological and chemical anionic surfactants on
horizontal movement of the contaminant and subse- the biodegradation and solubilization of PAHs in a creosote
contaminated soil. Presented at the Fourth Annual Symposium
quent groundwater contamination. Research is under-
on Groundwater and Soil Remediation, September 21±23,
way to minimize this possibility (Fountain, 1998). Calgary, Alta.
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