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Surfactant-Enhanced Remediation of
Contaminated Soil: A Review
Article in Engineering Geology June 2001
Impact Factor: 1.74 DOI: 10.1016/S0013-7952(00)00117-4





3 authors, including:
Catherine Mulligan
Concordia University Montreal

All in-text references underlined in blue are linked to publications on ResearchGate,

letting you access and read them immediately.

Available from: Catherine Mulligan

Retrieved on: 17 May 2016

Engineering Geology 60 (2001) 371380


Surfactant-enhanced remediation of contaminated soil: a review

C.N. Mulligan a,*, R.N. Yong b, B.F. Gibbs c

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

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 efciencies. 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 hydrophobic 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 efciencies. 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 sulde precipitation, ion exchange, activated carbon
adsorption, ultraltration, 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 signicant. 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

C.N. Mulligan et al. / Engineering Geology 60 (2001) 371380

1. Introduction
The injection or inltration of solutions into soil
using surface trenches, horizontal drains or vertical
drains is called in situ ushing. Water with or without
additives are employed to solubilize contaminants.
The efciency of the extraction depends on the
hydraulic conductivity of the soil. High permeability
gives better results (greater than 1 1023 cm=s: The
solubility of pollutants and if the pollutant was originally solubilized in water or not are key factors in
determining removal efciencies. Prior mechanical
mixing of the soil can disturb the inltration of the
extractant. Understanding the chemistry of the binding of the contaminant and the hydrogeology of the
site are very important (USEPA, 1987).
Since water solubility of many organic contaminants
is the controlling removing mechanism, additives are
used to enhance efciencies. Those liquid contaminants
that remain as a separate phase are called nonaqueous
phase liquids (NAPL). NAPLs that sink below the water
table are denser than water and are called DNAPLs and
those that are lighter are called LNAPLs. The former are
thus particularly difcult to remediate (Pankow and
Cherry, 1996). Some examples include chlorinated
solvents such as trichloroethylene (TCE), polycyclic
aromatic hydrocarbons (PAHs) including phenanthrene, naphthalene, that are found in coal tar and
creosote and polychlorinated biphenyls (PCBs) such
as Arochlor 1242. Matters become even more complicated since these contaminants are often mixed with
metals or radionuclides.

2. Background on surfactants
Cationic, anionic and nonionic surfactants can be
used for soil washing or ushing. They are useful in
displacing DNAPL by reducing interfacial tension
between DNAPL and groundwater. It is these capillary forces that restrict the mobility of the DNAPL.
The mobilized contaminant can then be recovered in
extraction wells (Fig. 1). Surfactants can be used in
mixtures or with additives such as alcohol and/or salts
such as sodium chloride. Polymers or foams can also
be added to control the mobility of the contaminants.
The surfactants must be recovered and reused for the
process to be economic.

Contaminated soil



Groundwater level

Low permeability zone

Contaminant plume
Fig. 1. Typical in situ soil ushing installation.

Surfactants are amphiphilic compounds (containing

hydrophobic and hydrophilic portions) that reduce the
free energy of the system by replacing the bulk molecules of higher energy at an interface. They contain a
hydrophobic portion with little afnity for the bulk
medium and a hydrophilic group that is attracted to
the bulk medium. Surfactant monomers will form
spheroid or lamellar structures with organic pseudophase interiors. This coincides will lower surface and
interfacial tensions (Fig. 2). The minimum concentration at which this occurs is called the critical micelle
concentration (Rosen, 1978). Salinity, hydrocarbon
chain length and surfactant type (hydrophile
lipophile HLB) will inuence the concentration.
Surfactants have been used industrially as adhesives,
occulating, wetting and foaming agents, de-emulsiers

Physical property



Surface tension
Interfacial tension
Surfactant concentration

Fig. 2. Schematic diagram of the variation of surface tension, interfacial and contaminant solubility with surfactant concentration.

C.N. Mulligan et al. / Engineering Geology 60 (2001) 371380

and penetrants (Mulligan and Gibbs, 1993). Petroleum users have traditionally been the major users,
as in enhanced oil removal applications. In this application, surfactants increase the solubility of petroleum
components (Falatko, 1991) or lower the interfacial
tension to enhance mobility of the petroleum. They
have also been used for mineral otation as well as the
pharmaceutical industries. Typical desirable properties include solubility enhancement, surface tension
reduction, the critical micelle concentrations, wettability and foaming capacity.
Numerous batch and column studies have indicated
that surfactants enhance recoveries of NAPL (Ellis et
al., 1985; Abdul et al., 1992; Kan et al., 1992; Soerens
et al., 1992) by solubility enhancement or desorption.
There have also been indications that pretreatment of
a soil with surfactant washing (Igepal CA-720) to
solubilize PAHs enhanced biodegradation of these
contaminants (Joshi and Lee, 1995).
Anionic and nonionic surfactants are less likely to
be absorbed to the soil. Cationic surfactants have been
used to lower aquifer permeabilities by sorption on to
the aquifer materials (Westall et al., 1992). Surfactant
soil washing was originally developed in petroleum
recovery operations. Surfactants have potential for
use in aquifer remediation of DNAPLs.
Several factors can inuence the efciency of soil
ushing with surfactants. Groundwater that is too hard
may be detrimental to the effectiveness of a surfactant
(AAEE, 1993). Surfactants can adsorb onto clay
fractions, reducing their availability. Too quick
biodegradation can inactivate the surfactant although
some degradability is required to avoid accumulation.
Removal of the surfactant from the recovered water
from ushing can be difcult and lead to high
consumption rates.
The main factors that should be considered when
selecting surfactants include effectiveness, cost,
public and regulatory perception, biodegradability
and degradation products, toxicity to humans, animals
and plants and ability to recycle. The rst consideration is that the surfactants are efcient in removing the
contaminant. This can be established by previous
experience or by laboratory studies prior to the
eld-scale demonstrations.
To reduce risk, food-grade surfactants (T-MAZ 28,
T-MAZ 20 and T-MAZ 60), which have been
approved by the Food and Drug Administration


have been examined (Shiau et al., 1995). These

surfactants were able to remove one to two orders of
magnitude more chlorinated organics such as
perchloroethylene (PCE), trichloroethylene (TCE)
and 1,2 dichloroethane (1,2-DCE) than water alone
by formation of microemulsions. Other surfactants
with indirect food additive status such as alkyl
diphenyl disulfonate (DOWFAX) indicated lower
levels of losses via sorption and precipitation while
substantially solubilizing naphthalene and other
PAHs. Recently, a plant-based surfactant from the
fruit pericarp of Sapindus mukurossi, a plant from
the tropical regions of Asia has shown potential for
the removal of hexachlorobenzene (Roy et al., 1997).
FDA approval, however, does not guarantee that the
surfactant or its biodegradation products are safe and
acceptable to the regulators and the public. Solubilization of TCE by surfactants was not permitted in a
pilot test (Fountain et al., 1996), even though the
surfactant has a toxicity similar to sucrose and that
it was used in food and food processing. Many surfactants are of low toxicity to humans but can affect
animals and plants. Ethoxylated alcohols, which are
found in laundry detergents and dish soap, are toxic to
sh. They can be, however, degraded in biological
wastewater treatment systems.
Overall, desirable surfactant characteristics include
biodegradability, low toxicity, solubility at groundwater temperatures, low adsorption to soil, effective
at concentrations lower than 3%, low soil dispersion,
low surface tensions and low CMC (Kimball, 1992).
Anionic surfactants may precipitate. However,
coinjection with a nonionic surfactant can reduce
precipitation and also CMC values (Sabatini et al.,
1995). Biosurfactants may be more biodegradable,
more tolerant to pH, salt and temperature variation,
and in some cases less expensive (West and Harwell,
2.1. Biosurfactants
Some surfactants, known as biosurfactants, are
biologically produced from yeast or bacteria from
various substrates including sugars, oils, alkanes and
wastes (Lin, 1996). For example, Pseudomonas
aeruginosa can produce rhamnolipids from substrates
including C11 and C12 alkanes, succinate, pyruvate,
citrate, fructose, glycerol, olive oil, glucose and


C.N. Mulligan et al. / Engineering Geology 60 (2001) 371380

Table 1
Classication and microbial origin of biosurfactants. (Adapted from
Mulligan and Gibbs (1993) and Banat (1995))
Surfactant class


Trehalose lipids

Arthrobacter parafneus
Corynebacterium spp.
Mycobacterium spp.
Rhodococus erythropolis


Pseudomonas aeruginosa

Sophorose lipids

Candida apicola
Candida bombicola
Candida lipolytica

Glucose-, fructose-,
saccharose lipids

Arthrobacter spp.
Corynebacterium spp.
R. erythropolis

Cellobiose lipids

Ustilago maydis

Polyol lipids

Rhodotorula glutinus
Rhodotorula graminus

Diglycosyl diglycerides

Lactobacillus fermentii


Acinetobacter calcoaceticus
Pseudomonas spp.
Candida lipolytica


Arthrobacter sp.
Bacillus pumilis
Bacillus subtilis
Bacillus licheniformis
Pseudomonas uorescens

Ornithine, lysine peptides

Thiobacillus thiooxidans
Streptomyces sioyaensis
Gluconobacter cerinus


T. thiooxidans
Corynebacterium alkanolyticum


Capnocytophaga spp.

Fatty acids (corynomycolic

acids, spiculisporic acids, etc.)

Penicillium spiculisporum
Corynebacterium lepus
Arthrobacter paraneus
Talaramyces trachyspermus

mannitol (Robert et al., 1989). They are synthesized

as metabolic by-products. Composition and yields
depend on the fermentor design, pH, nutrient composition, substrate and temperature used (Mulligan and
Gibbs, 1993). They can be potentially as effective
with some distinct advantages over the highly used
synthetic surfactants including high specicity, bio-

degradability and biocompatibility (Cooper, 1986).

For example, glycolipids from Rhodococcus species
413A were 50% less toxic in naphthalene solubilization tests than Tween 80 (Kanga et al., 1997).
Biosurfactants are grouped as glycolipids, lipopeptides, phospholipids, fatty acids and neutral lipids
(Biermann et al., 1987). Most of these compounds
are either anionic or neutral. Only a few are cationic
such as those containing amine groups. The hydrophobic part of the molecule is based on long-chain
fatty acids, hydroxy fatty acids or a-alkyl-b-hydroxy
fatty acids. The hydrophilic portion can be a carbohydrate, amino acid, cyclic peptide, phosphate,
carboxylic acid or alcohol. Their CMCs generally
range from 1 to 200 mg/l and their molecular weights
from 500 to 1500 amu. (Lang and Wagner, 1987). A
wide variety of microorganisms can produce these
compounds (Table 1).
Biosurfactants have been tested in enhanced oil
recovery and the transportation of crude oils (Hayes
et al., 1986). They were effective in the reduction of
the interfacial tension of oil and water in situ and the
viscosity of the oil, the removal of water from the
emulsions prior to processing and in the release of
bitumen from tar sands. Emulsan w has been commercialized for this purpose (Anonymous, 1984). It
contains polysaccharide-attached fatty acids and
proteins attached. Although most biosurfactantproducing organisms are aerobic, a few examples of
anaerobic producers exist. Bacillus licheniformis JF-2
is an example, which would be well suited for in situ
studies for enhanced oil recovery or soil decontamination (Javaheri et al., 1985). A 70% bioremediation
and bioreclamation rate of a slop oil-contaminated
soil was achieved with oil-degrading cultures (Dave
et al., 1994).
Rhamnolipid surfactants have been tested and
found to release three times as much oil as water
alone from the beaches in Alaska after the Exxon
Valdez tanker spill (Harvey et al., 1990). Scheibenbogen et al. (1994) found that the rhamnolipids from
P. aeruginosa UG2 were able to effectively remove a
hydrocarbon mixture from a sandy loam soil and that
the degree of removal was dependent on the type of
hydrocarbon removed and the concentration of the
surfactant used. Van Dyke et al. (1993) previously
found that the same strain could remove at a concentration of 5 g/l, approximately 10% more hydrocarbon

C.N. Mulligan et al. / Engineering Geology 60 (2001) 371380


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)


Contaminant removed


SUNY-Buffalo with Dupont at

Corpus Christi Site

Addition of 1% surfactant
(approved in food
preparation) Witconol 2722
and Tergitol 15-S012
2% mixture of surfactant
added to sandy aquifer
0.75% nonionic ethoxylated
surfactant washing with
Injection of 4% Witconol
and Tween 80 and modeling

73 gal carbon tetrachloride

successfully removed in
comparison to pump and treat

Fountain (1993)

80% of PCE recovered

Fountain and Hodges (1992)

10% of PCBs, oils removed in

rst test and 14% in second
exceeding expectations
Removal of 10% dodecane
required 0.7 l surfactant and
130,000 l water
Injection of 7.7 pore volumes
of 2.5% SDS removed as
much PCB as 20 to 40 pore
volumes of water (90% waste
volume reduction)
DNAPLs, TCE with some
PCBs and other chlorinated
solvents, .90% removed by

Ang and Abdul (1991)

Canadian Air Forces Base at

Borden (SUNY)
General Motors NAO Research
and Development Center
University of Michigan
Eckenfelder, Inc.

Injection of 2.5% SDS and

recycle/reuse of surfactant

US DOE Gaseous Diffusion Site

Portmouth, OH

4% sodium dihexyl
sulfosuccinate surfactant/4%
isopropyl alcohol as
cosolvent and 2% electrolyte
(1:1 NaCl and CaCl2)

Dover AFB, Dover DE (single

phase microemulsion)
Ecosites Inc., Estrie Reg. Shop,
Que., Canada

Biodegradable nontoxic

Fredicksburg, VA Wood treating


Alkaline agent (0.5%

Na2CO3), nonyl phenol
surfactant with 10 mol
ethylene oxide (0.1% wt
Makon-10) and polymer
(1500 mg/l xanthan gum)
Patented non-hazardous,
biodegradable surfactant
(12% concentration)

TWCC Biosolve Group

Hill Air Force Base, Layton, UT

Cell 5, Surfactant Mobilization

6.6 PV of surfactant (2.2%

Aerosol OT/ 2.1%Tween)
and Electrolyte (CaCl2)

Cell 6, Surfactant Solubilization

10 PV of 4.3% surfactant

Hydrocarbons, LNAPLs,
Cutting Oil, 160,000 kg
hydrocarbon recovered in 12
months, US$ 1.2 million Cdn
for fulll scale, commercial
completed project
Creosote-based wood treating
oil (DNAPL), unable to inject
uid, poor site evaluation

80% removal of NAPL, 90%

removal of transmission uids
in Northern California,
increases biodegradation by
30%. Cost US$ 0.350.85 per
LNAPL (JP-4 jet fuel,
chlorinated and
nonchlorinated VOCs,
naphthalene, pesticides, PCBs,
Mixture of VOCs,
naphthalene, pesticides, PCBs,
dioxins, JP-4 fuel

Abriola et al. (1993)

Underwood et al. (1993)

Jafvert (1996)

Internet report:
Jafvert (1996)

Rice University (1997)

USEPA (1998)

Jafvert (1996)

Jafvert (1996)


C.N. Mulligan et al. / Engineering Geology 60 (2001) 371380

Table 2 (continued)


Contaminant removed


Cell 8, Surfactant/cosolvent

Surfactant (3.5% wt Brij 91)

and cosolvent (2.5% wt npentanol), , 10 PV injected

AATDF (1998)

OU2-Micellar Flood

0.6 PV of surfactant (7.5%

sodium dihexyl
sulfosuccinate), cosolvent
(3.75% isopropyl alcohol)
and electrolyte (7000 mg/l
400 mg/l of Triton X-100

LNAPL (JP-4 jet fuel,

chlorinated and
nonchlorinated solvents,
PCBs), 72% average reduction
Chlorinated solvents (TCE,
TCA, PCE, and TCET),
petroleum hydrocarbons,
DNAPL (70% TCE), 99%
recovery of DNAPL
TCE, rate of desorption
increased by 30% by
surfactant addition
PCBs (solubility increased by
50 times) in fractured rock.at a
cost of US$ 40100 per sq ft

Jafvert (1996)

BTEX, aliphatic hydrocarbons

(2500 kg/day of hydrocarbons
recovered, 85% extraction
efciency, 1000 m 3/week)
Cost US$ 50250/m 3
23,000 gallons of residual
wood treating oil (DNAPL)
recovered (89%) Cost of US$
50125 per cubic yard
Oil waste and chlorinated
solvents in the form of
DNAPL (density, 1.02;
viscosity, 18 cp), 86%
recovery of DNAPL
PCE, TCE and recalcitrant jet
fuel, PCE and LNAPL
concentrations increased 40and 90-fold, respectively

USEPA (1998) GSI

Environmental Marketing

Hydrocarbons, chlorinated
chloroform, TCA, TCE)

Nash (1988)

Picatinny Arsenal, NJ
S.S. Papadopulos & Assoc.
(DeNAPL process) Delmont, PA

Serrener/Varisco Consortium,
Quebec, Canada

Non-toxic biodegradable
surfactant (91% Witconol
SN-70, 9% Mirataine BET
C-30), maximum
concentration of 13,000 mg/l

Surtek, Inc. Mobility controlled

Surfactant Flushing

Low concentration of EPA

and FDA approved

Thouin Sand Quarry, Quebec,

Canada, Laval University

(n-butanol, hostapur (SAS),

US Coast Guard, Traverse City,


2100 l of 36,000 mg/l

Dowfax 8390 injected

US DOE Gaseous Diffusion Pint,

Paducah, NY

1% food grade sorbitan

monooleate, (3.8 l/min over
3.8 days)
914 PV of Adsee 799 and
Hyonic PE-90 (50:50) blend

Volk Air National Guard Base,


from a sandy loam soil than from a silt loam soil and that
sodium dodecyl sulfate (SDS) was less effective than
the biosurfactants in removing hydrocarbons. Recently,
Deschenes et al. (1994) showed that the rhamnolipids
from the same strain in a bioslurry could enhance the
solubilization of four-ring PAHs more signicantly than
three-ring PAHs and that the biosurfactants were ve

Jafvert (1996)

USEPA (1998)

USEPA (1998)

Jafvert (1996)

Jafvert (1996)

Rice University (1997)

times more effective than SDS. The benet of the

addition of the biological and synthetic surfactants in
assisting the biodegradation process was less evident.
Research with another strain, Pseudomonas marginalis,
also indicated that the produced biosurfactants
solubilized PAHs such as phenanthrene and enhance
biodegradation (Burd and Ward, 1996).

C.N. Mulligan et al. / Engineering Geology 60 (2001) 371380

3. Field studies
Several eld studies have also been performed with
surfactant in situ ushing. In 1988, a wood-treating
site was used to test surfactant washing (Sale et al.,
1989). Two blends were tested, one as a prewash and
the other to further lower oil levels. Blend 1 consisted
of 1% Polystep A, 0.7% NaHCO3, 0.1% Na2CO3 and
1000 mg/l xanthan gum and second blend comprised
of 1.4% Makon-10 surfactant, 0.7% NaHCO3, 0.8%
Na2CO3 and 1000 mg/l xanthan gum. Ninety-ve
percent of the oil was reduced and 99% of the surfactants were recovered. The combination of surfactants
and sodium hydroxide has been used in enhanced oil
recovery to reduce interfacial tensions. Alkaline
agents can also react with hydrocarbons to form
surfactants. The combination of these surfactants
and the added surfactants can effectively reduce interfacial tension and enhance oil recovery (Sale and
Pitts, 1988). This same mechanism then can be
responsible for removal of hydrocarbons from a
contaminated soil. The addition of polymer enhances
the mobility ratio (i.e. enables the contaminant to be
pushed instead of ow passing around it).
At a Canadian Forces Base Borden in Ontario, a test
was performed in 199091. The hydraulic conductivity at the site was 1 1024 cm=s with a low cation
exchange capacity (CEC) and organic matter content.
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 pumping and treating groundwater would require 2000 pore
volumes over a period 100 times longer to decontaminate the site (AAEE, 1993). Other examples are
shown in Table 2.
Abdul et al. (1992) examined treatment of PCBcontaminated soils. The hydraulic conductivity was
1 1023 cm=s: A 0.75% solution of Witconol was
applied to the surface. During the test, 1.6 kg of
PCBs and 16.9 kg of carrier oil were recovered.
In 1996, Intera, Radian and the University of Texas
conducted a study where 2.5 pore volumes of an 8%
surfactant solution, 4% isopropanol and sodium
chloride were used to remove mainly TCE. No
conning walls were used. Approximately 99% of
the DNAPL was removed to reach as nal groundwater concentration of 10 mg/l (Brown et al., 1999).
In 1996, the University of Oklahoma and the US


EPA R.S. Kerr Laboratory conducted a surfactant

ood by pumping 6.5 pore volumes of a 4.3% surfactant through a 3 5 m sheet piling cell at Hill, AFB,
Utah. In this case, the contamination was mainly a
8.5% saturation of LNAPL consisting of weathered
jet fuel and other components. The surfactant was
able to remove 90% of the LNAPL by mobilization.
In the same year at the same site, the University of
Florida conducted a test by injecting 9 pore volumes
of 3% surfactant and 2.5% pentanol followed by a
pore volume of 3% surfactant and then 6.5 pore
volumes of water. Core data indicated that 90% of
the NAPL was removed while partitioning tracer
data indicated that 72% removal was achieved (Jawitz
et al., 1998). In this case, solubilization was the main
mechanism of removal.
In general, high permeability soil is favored for
surfactant ushing since numerous pore volumes can
be passed through the contaminated area. Layered
systems are difcult to remediate due to limited
contact in less permeable areas. Also, fractured rock
is extremely challenging due to the ow complexity in
the fractured media. However, these challenges are
relevant for all remediation technologies. Comparisons under the same conditions in these difcult
media should be performed to determine if surfactant
ushing is able to remove contaminants faster than
other technologies.
4. Metal removal by surfactants
The research in the area for metal removal is still
quite limited, particularly where metal removal is
concerned (USEPA, 1987). They include organic
and inorganic acids, sodium hydroxide, which can
dissolve organic soil matter, water-soluble solvents
such as methanol, displacement of toxic cations with
nontoxic cations, complexing agents such as EDTA,
acids in combination with complexation agents or
oxidizing/reducing agents. Soil pH, soil type, CEC,
particle size, permeabilities and contaminants affect
removal efciencies. High clay and organic matter
contents are particularly detrimental.
At Superfund sites, with signed Records of
Decision (ROD), the combination of hydrocarbons
and metals is found at 49% of the sites (USEPA,
1997). Even though organic and metal contamination

C.N. Mulligan et al. / Engineering Geology 60 (2001) 371380

5. Conclusions
It has been demonstrated that high contaminant
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 surfactants can accelerate remediation work and potentially
a wide variety of contaminants in the vadose and
saturated zones can be remediated.
However, limited studies have been performed over
a long period of time to determine the levels of
residual contamination that are achievable at full
scale. Some of the limitations may include low soil
permeability, heterogeneity and extremely insoluble
contaminants. For example, low permeability clays
with hydraulic conductivities in the order of
10 24 cm/s may signicantly increase the time for the
surfactant to permeate through the contaminated zone.
Heterogeneities could cause some sections of the


Cu removal (%)


Time (days)

Time (days)

Time (days)

B 30

Zn removal (%)

are major concerns, very few technologies are capable

of dealing with both types of contaminants. As
previously mentioned, surfactants can be used to
assist in the remediation of numerous types of hydrocarbon contaminants. Only recently, has it been
shown that surfactants can be used to enhance metal
removal (Mulligan et al., 1999a,b). Biologically
produced surfactants, surfactin, rhamnolipids and
sophorolipids (Mulligan et al., 1999a) were able to
remove copper and zinc from a hydrocarbon-contaminated soil. This is due to the anionic character of these
surfactants. A series of washings was performed with
surfactin and compared to a control. Initial concentrations of oil and grease were 12.6% and the initial
copper content of the soil was 550 mg/kg. Five consecutive washings were performed each lasting 24 h
(Fig. 3). For copper, the control showed a nal cumulative removal of 20% while approximately 70% was
removed by the surfactin. At the same time, approximately 50% of the hydrocarbons were removed by
surfactin compared to 30% by the control. Therefore,
these results seem very promising. Other advantages
of these biosurfactants are that they are biodegradable
and low in toxicity. In addition, they potentially can
be produced in situ using the organic contaminants as
substrates for their production. Larger scale studies,
however, are required to determine their potential.



Cd removal (%)





Fig. 3. Series of washings for (A) copper, (B) zinc and (C) cadmium
by 0.25% surfactin with 1% NaOH (B) and the control (1% NaOH)
(A) according to Mulligan et al. (1999b).

treatment zone to receive more solution than others

and thus increase solution requirements. Control of
mobility by the addition of polymers or foam can
reduce this problem. Another potential factor in
surfactant ushing that must be taken into consideration is that since the NAPLs are mobilized by the

C.N. Mulligan et al. / Engineering Geology 60 (2001) 371380

surfactant, there is the potential for downward or

horizontal movement of the contaminant and subsequent groundwater contamination. Research is underway to minimize this possibility (Fountain, 1998).
Another concern of the regulators is the toxicity of
the ushing solutions. Therefore, it is very important
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The development of the use of biosurfactants both for
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