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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
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3 authors, including:
Catherine Mulligan
Concordia University Montreal
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www.elsevier.nl/locate/enggeo
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 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
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
Surfactant
injection
Well
Groundwater level
Physical property
372
Micelle
Solubility
Surface tension
Interfacial tension
Surfactant concentration
Fig. 2. Schematic diagram of the variation of surface tension, interfacial and contaminant solubility with surfactant concentration.
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
373
374
Table 1
Classication and microbial origin of biosurfactants. (Adapted from
Mulligan and Gibbs (1993) and Banat (1995))
Surfactant class
Microorganism
Trehalose lipids
Arthrobacter parafneus
Corynebacterium spp.
Mycobacterium spp.
Rhodococus erythropolis
Rhamnolipids
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
Lipopolysaccharides
Acinetobacter calcoaceticus
(RAG1)
Pseudomonas spp.
Candida lipolytica
Lipopeptides
Arthrobacter sp.
Bacillus pumilis
Bacillus subtilis
Bacillus licheniformis
Pseudomonas uorescens
Thiobacillus thiooxidans
Streptomyces sioyaensis
Gluconobacter cerinus
Phospholipids
T. thiooxidans
Corynebacterium alkanolyticum
Sulfonylipids
Capnocytophaga spp.
Penicillium spiculisporum
Corynebacterium lepus
Arthrobacter paraneus
Talaramyces trachyspermus
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
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
recovery
Injection of 4% Witconol
and Tween 80 and modeling
Fountain (1993)
4% sodium dihexyl
sulfosuccinate surfactant/4%
isopropyl alcohol as
cosolvent and 2% electrolyte
(1:1 NaCl and CaCl2)
Surfactant
Biodegradable nontoxic
surfactant
10 PV of 4.3% surfactant
(Dowfax)
DNAPL (PCE or
perchloroethylene)
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
Jafvert (1996)
Internet report:
www.epa.gov/Superfund/
index.htm
Jafvert (1996)
USEPA (1998)
Jafvert (1996)
Jafvert (1996)
376
Table 2 (continued)
Group
Process
Contaminant removed
Reference
Cell 8, Surfactant/cosolvent
solubilization
AATDF (1998)
OU2-Micellar Flood
Jafvert (1996)
Hydrocarbons, chlorinated
hydrocarbons
(Dichloromethane,
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
Surfactants
Surfactant/cosolvent
(n-butanol, hostapur (SAS),
d-limonene
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)
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
377
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
100
Cu removal (%)
80
60
40
20
0
0
2
3
Time (days)
2
3
Time (days)
2
3
Time (days)
B 30
Zn removal (%)
20
10
Cd removal (%)
378
20
10
0
4
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).
379
380
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