Engineering Geology 60 (2001) 193±207

www.elsevier.nl/locate/enggeo

Remediation technologies for metal-contaminated soils and

groundwater: an evaluation
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 28 March 2000

Abstract
Metals including lead, chromium, arsenic, zinc, cadmium, copper and mercury can cause signi®cant damage to the environ-
ment and human health as a result of their mobilities and solubilities. The selection of the most appropriate soil and sediment
remediation method depends on the site characteristics, concentration, types of pollutants to be removed, and the end use of the
contaminated medium. The approaches include isolation, immobilization, toxicity reduction, physical separation and extrac-
tion. Many of these technologies have been used full-scale. This paper will review both the full-scale and developing tech-
nologies that are available. Contaminants can be isolated and contained to minimize further movement, to reduce the
permeability of the waste to less than 1 £ 10 27 m/s (according to U.S. guidelines) and to increase the strength or bearing
capacity of the waste. Physical barriers made of steel, cement, bentonite and grout walls can be used for isolation and
minimization of metal mobility. Another method is solidi®cation /stabilization, which contains the contaminants in an area
by mixing or injecting agents. Solidi®cation encapsulates contaminants in a solid matrix while stabilization involves formation
of chemical bonds to reduce contaminant mobility. Another approach is size selection processes for removal of the larger,
cleaner particles from the smaller more polluted ones. To accomplish this, several processes are used. They include: hydro-
cyclones, ¯uidized bed separation and ¯otation. Addition of special chemicals and aeration in the latter case causes these
contaminated particles to ¯oat. Electrokinetic processes involve passing a low intensity electric current between a cathode and
an anode imbedded in the contaminated soil. Ions and small charged particles, in addition to water, are transported between the
electrodes. This technology have been demonstrated in the U.S. full-scale, in a limited manner but in Europe, it is used for
copper, zinc, lead, arsenic, cadmium, chromium and nickel. The duration of time that the electrode remains in the soil, and
spacing is site-speci®c. Techniques for the extraction of metals by biological means have been not extensively applied up to this
point. The main methods include bioleaching and phytoremediation. Bioleaching involves Thiobacillus sp. bacteria which can
reduce sulphur compounds under aerobic and acidic conditions (pH 4) at temperatures between 15 and 558C. Plants such as
Thlaspi, Urtica, Chenopodium, Polygonum sachalase and Alyssim have the capability to accumulate cadmium, copper, lead,
nickel and zinc and can therefore be considered as an indirect method of treating contaminated soils. This method is limited to
shallow depths of contamination. Soil washing and in situ ¯ushing involve the addition of water with or without additives
including organic and inorganic acids, sodium hydroxide which can dissolve organic soil matter, water soluble solvents such as
methanol, nontoxic cations, complexing agents such as ethylenediaminetetraacetic acid (EDTA), acids in combination with

* 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)00101-0
194 C.N. Mulligan et al. / Engineering Geology 60 (2001) 193±207

complexation agents or oxidizing/reducing agents. Our research has indicated that biosurfactants, biologically produced
surfactants, may also be promising agents for enhancing removal of metals from contaminated soils and sediments.
In summary, the main techniques that have been used for metal removal are solidi®cation/stabilization, electrokinetics, and in situ
extraction. Site characteristics are of paramount importance in choosing the most appropriate remediation method. Phytoremedia-
tion and bioleaching can also be used but are not as well developed. q 2001 Elsevier Science B.V. All rights reserved.
Keywords: Soil; Remediation technologies; Groundwater; Sediments; Heavy metals

1. Introduction This phenomenon can lead to extinction or alteration

of plants and animals. Metals can accumulate in the
In the United States, 1200 sites are on the National following order, river sediments, bacteria, tubicids
Priority List (NPL) for the treatment of contaminated and then ®sh and man if one consumes these ®sh.
soils, indicating the extensiveness of this problem. Over the past years, use of metals such as copper,
Approximately 63% of the sites on the NPL include cadmium and zinc have increased substantially
contamination from toxic heavy metals (Hazardous (Table 1). Copper is produced more than any other
Waste Consultant, 1996). For example, lead was metal, whereas more zinc reaches the soil than any
found at 15% of the sites, followed by chromium, other metal. Lead use has decreased due to toxicity
cadmium and copper at 11, 8 and 7% of the sites, concerns. In Canada, according to the National Pollu-
respectively. Therefore, metal contamination is a tant Release Inventory, approximately 13,300 ton of
major problem. copper, 9500 ton of zinc, 1300 ton of lead and 33 ton
Cadmium, copper, lead, mercury, nickel and zinc of cadmium were released to the air, water and soil
are considered the most hazardous and are included on (NPRI, 1995).
the US Environmental Protection Agency's (EPA) list In view of the extensiveness of metals in the
of priority pollutants (Cameron, 1992). Sources of environment, this paper describes the fate and trans-
metals include domestic and industrial ef¯uents, the port of selected metals and technologies for reme-
atmosphere, runoff and lithosphere. Once metals are diation that are full-scale and developing. This
allowed to pass through the municipal waste treatment information will assist in the selection of the appro-
facility, the heavy ones return to the environment priate technology for treatment of metal-contaminated
where they are persistent, cannot be biodegraded soils and sediments.
and can thus follow a number of different pathways.
The metals can adsorb onto the soil, runoff into rivers
or lakes or leach in the groundwater, an important 2. Mobility of metals
source of drinking water. Exposure to the heavy
metals through ingestion or uptake of drinking water In its natural form, cadmium is relatively rare and
(particularly where water is reused) and foods can concentrated in argillaceous and shale deposits as
lead to accumulation in animals, plants and humans. greenockite (CdS) or otavite (CdCO3) and is usually
associated with zinc, lead or copper in sul®de form
Table 1 (Cameron, 1992). It is a bluish-white soft metal or
Global production of metals and the rate of metals reaching the soil
(10 3 ton/year) (adapted from World Resources Institute (1992/
grayish powder. It is more mobile, though, than zinc
1993) and Nriagu and Pacyna (1988)) at low pH, particularly at pH values between 4.5 and
5.5. Above pH 7.5, cadmium is not very mobile. Its
Metal 1975 1980 1985 1990 Emissions to divalent form is soluble but it can also complex with
the soil in
organics and oxides. A natural source of cadmium is
the 1980s
volcanoes that can release cadmium into the atmos-
Cd 15.2 18.2 19.1 20.2 22 phere, spreading it over a wide area. It is only in the
Cu 6739.0 7204.0 7870.0 8814.0 954 last twenty years that cadmium has become a concern
Pb 3432.2 3448.2 3431.2 3367.2 796
due to the extensive use in industrial applications
Zn 3975.4 4030.3 4723.1 5570.9 1372
including steel plating, pigment stabilization and
 C.N. Mulligan et al. / Engineering Geology 60 (2001) 193±207
nickel±cadmium batteries (Fassett, 1980). The aver-
age content of cadmium in soil is less than 1 ppm. In
plants, the normal range is 0.005±0.02 ppm with toxic
levels between 5 and 30 ppm. Sources of cadmium
include alloys, polyvinyl chloride plastic (PVC)
manufacture, solders, fungicides, enamels, motor oil,
textile manufacturing, electroplating and rubber,
sewage sludges and phosphate fertilizers (Matthews,
1984). It enters the environment through industrial
ef¯uents and land®ll leaching, spills and leaks at
hazardous waste sites, mining and household wastes.
Copper is found naturally in sandstones and in
minerals such as malachite and chalcopyrite. It is a
reddish-brown metal that binds strongly to organic
matter and clay minerals, thus decreasing its mobility.
The organic matter, however, can be degraded
through anaerobic or aerobic means releasing the
copper in its monovalent or divalent states, respec-
tively. It has also been demonstrated that bio-
surfactants can release organically bound copper
(Mulligan et al., 1999a). The average content of
copper in rural soils is 2 to 100 ppm. Plants can accu-
mulate copper with average contents in the range of
5±30 ppm while toxic levels vary from 20 to
100 ppm. Increased levels of copper are due to uses
in fertilizers, building materials, rayon manufacture,
pesticide sprays, agricultural and municipal wastes
and industrial emissions (Cameron, 1992).
Lead is found naturally in soils, most commonly in
the form of the ore gelena (PbS) and in smaller quan-
tities in cerussite (PbCO3), anglesite (PbSO4) and
crocoite (PbCrO4). It is a bluish-white, silvery or
gray metal with a high density of 11.4 g/cm 3. Lead
can be found in soils at the surface and organic matter
in higher quantities. Sources of lead include lead±zinc
smelters, ammunition, solder, glass, piping, insecti-
cides, paints and batteries (Jawarsky, 1978). The diva-
lent form is the most common and is capable of
replacing calcium, strontium, barium and potassium
in soils. In general, background levels less than
10 ppm are found, and mobility of lead in soils is
low. Organic matter can adsorb substantial quantities
of lead. Lead is released into the air from burning of
wastes and fossil fuels and subsequently lands onto
the soil. It also reaches the soil from land®lls and
paints.
Although not as toxic as cadmium, zinc is quite
often associated with this metal. Zinc is a soft, white
195
metal with bluish tinge. Soil texture, pH, nature of the
parent rocks and organic content all affect the natural
content of zinc in the soil. Under acidic conditions,
zinc is usually divalent and quite mobile. At high pH,
zinc is bioavailable due to the solubility of its organic
and mineral colloids. Zinc hydrolyzes at pH 7.0±7.5,
forming Zn(OH)2 at pH values higher than 8. Under
anoxic conditions, ZnS can form upon precipitation,
whereas the unprecipitated zinc can form ZnOH 1,
ZnCO3 and ZnCl 1. Natural levels of zinc in soils
are 30±150 ppm. Levels of 10±150 ppm are normal
in plants while 400 ppm is toxic. Sources of zinc
include brass and bronze alloys, galvanized products,
rubber, copying paper, cosmetics, pharmaceuticals,
batteries, televisions, tires, metal coatings, glass,
paints and zinc-based alloys (Cameron, 1992). It can
enter the environment from galvanizing plant ef¯u-
ents, coal and waste burning, leachates from galvan-
ized structures, natural ores and municipal waste
treatment plant discharge. Zinc is commonly found
in wastes as zinc chloride, zinc oxide, zinc sulfate
and zinc sul®de (Agency for Toxic Substances and
Disease Registry, 1995).
3. Metal speciation
The term speciation is related to the distribution of
an element among chemical forms or species. Heavy
metals can occur in several forms in water and soils.
Interest has increased in sequential extraction tech-
niques to relate the degree of mobility with risk
assessment, (i.e. the more mobile the metal is,
the more risk associated with it (Bourg, 1995)) and
as a method of designing remediation techniques
(Mulligan et al., 1999b). Not only is total metal
concentration of interest, but is also now accepted
that understanding the environmental behavior by
determining its speciation is of paramount impor-
tance. Based on this information on contaminated
soil, the most appropriate method for soil remediation
can be determined.
To determine the speciation of metals in soils,
speci®c extractants are used. The different extractants
solubilize different phases of metals. By sequentially
extracting with solutions of increasing strengths, a
more precise evaluation of the different fractions
can be obtained (Tessier et al., 1979). A soil or
196 C.N. Mulligan et al. / Engineering Geology 60 (2001) 193±207
sediment sample is shaken over time with a weak
extractant, centrifuged, and the supernatant is
removed by decantation. The pellet is washed in
water and the supernatant removed and combined
with the previous supernatant. A sequence of reagents
is used, following the same procedure, until ®nally,
mineral acid is used to extract the residual fraction.
Heavy metal concentrations are then determined in
the various extracts by atomic absorption or other
means. Numerous techniques and reagents have
been developed and have been applied to soils
(Shuman, 1985), sediments (Lum and Edgar, 1983),
sludge-treated soils (Petrozelli et al., 1983) and
sludges (Lakanen and Ervio, 1971). These methods
are not standardized and the results can even vary
with the same reagents, pH, temperature, extractant
strength and solid sample to volume of extractant
ratio. None of the extractions is completely speci®c.
However, the extractants chosen attempt to minimize
solubilization of other fractions.
To extract the exchangeable fraction, ammonium
acetate, barium chloride or magnesium chloride at
pH 7.0 are generally used (Lake, 1987). They cause
the displacement of the ions in the soil or sediment
matrix bound by electrostatic attraction. Pickering
(1986) showed that magnesium chloride leached low
quantities of other sul®des, organic matter, aluminum
and silicon.
The carbonate phase (calcite and dolomite) is
extracted at pH 5.0 with sodium acetate acidi®ed
with acetic acid. This solubilizes the carbonates,
releasing carbonate-entrapped metals. Organic matter,
oxides or clay components are not solubilized.
The reducible phase (iron and manganese
oxides) is extracted with hydroxylamine hydro-
chloride with acetic acid at pH 2.0. The hydroxy-
lamine hydrochloride reduces the ferrous and
manganese hydroxides to soluble forms. Other
components such as organic matter and clay com-
ponents are not solubilized to any great extent (Tessier
et al., 1979).
Hot hydrogen peroxide in nitric acid is used to
oxidize the organic matter and solubilize sul®des.
The oxidized organic matter then releases metals
that are complexed, adsorbed and chelated. These
agents are used so that the silicates are not affected
by this treatment. In the ®nal step, the silicates and
other materials are dissolved by strong acids at high
temperatures. This fraction is usually used to com-
plete the mass balances for the metals.
In natural soils, Kabata-Pendias (1992) demon-
strated that the speciation of trace metals depends
on the physical and chemical characteristics of the
soil. Soil pH, redox, organic, carbonate, clay and
oxide contents all in¯uence metal speciation and
mobility. Simple and complex cations are the most
mobile, exchangeable cations in organic and in-
organic complexes and are of medium mobility
while chelated cations are slightly mobile. Metals in
organic or mineral particles are only mobile after
decomposition or weathering, and precipitated metals
are mobile under dissolution conditions (e.g. change
in pH). Kabata-Pendias (1992) also showed the
speciation of trace metals such as zinc, copper,
cadmium and lead. Zinc and cadmium are mostly
organically bound, exchangeable and water soluble.
Copper is mainly organically bound and exchange-
able, whereas, lead is slightly mobile and bound to
the residual fraction. Chlopecka (1992) showed,
however, that the cadmium and zinc speciation in
soils depended signi®cantly on the application of
sewage sludge on the soil. Fertilizer addition, water
and air pollution can also affect speciation.
Recently, sequential extraction techniques have
been studied as a tool in various applications. Yong
et al. (1993) examined sequential extraction to obtain
a better appreciation of the ability of clay soil barriers
to contain contaminants in land®ll barriers. The effect
of soil pH, constituents and heavy metal types were
evaluated. In a study by Ramos et al. (1994), sequen-
tial extraction techniques were used to evaluate the
mobility of cadmium, zinc, lead and copper in
contaminated soil in a national park. Cadmium was
found to be the most mobile and would likely be the
most bioavailable.
Ravishankar et al. (1994) evaluated several sludges
for Al, Cu, Fe, Mn and Zn speciation to predict
bioleaching processes. They concluded that more
stabilized sludges contained higher contents of
organically bound metals and that sludges vary
considerably making bioleaching prediction dif®cult.
A potential method to determine if the heavy metals
can be removed by remediation techniques (such as
soil washing) or to predict removal ef®ciencies is to
determine speciation with selective extractive tech-
niques. It is believed that exchangeable, carbonate
 C.N. Mulligan et al. / Engineering Geology 60 (2001) 193±207
and reducible oxide fraction may be amenable to soil
washing techniques (Li et al., 1995). Removal of the
organically and residually bound fraction may not be
economical to recover or necessary, due to lack of
bioavailability. Gombert (1994) used sequential
extraction to determine if cesium, cobalt and chro-
mium could be removed by soil washing. Since less
than 20% was extracted after dissolving 20% of the
soil mass, soil washing was abandoned as an option.
Mulligan et al. (1999a) demonstrated that sequential
extraction techniques could be used prior to soil wash-
ing, to design and monitor the remediation process.
Copper associated with organic matter and zinc asso-
ciated with oxides were successfully removed by
biosurfactant/hydroxide solutions and biosurfactant/
acid solutions, respectively. Clearly, more work is
needed in this ®eld.
4. Remediation techniques
4.1. Isolation and containment
Contaminants can be isolated and contained, to
prevent further movement, to reduce the permeability
of the waste to less than 1 £ 10 27 m/s (as required by
the U.S. EPA) and to increase the strength or bearing
capacity of the waste (USEPA, 1994). Physical
barriers made of steel, cement, bentonite and grout
walls can be used for capping, vertical and horizontal
containment. Capping is a site-speci®c proven tech-
nology to reduce water in®ltration. Synthetic mem-
branes can be used for this purpose.
Vertical barriers reduce the movement of con-
taminated groundwater or uncontaminated ground-
water through a contaminated area. To prevent the
transport of contaminants past the barrier, the barrier
should extend to a clay or bedrock layer of low per-
meability. If this cannot be done, a groundwater
extraction system would be required to avoid the
passage of contaminants below the barrier (Rumer
and Ryan, 1995). Slurry walls, grout or geomembrane
curtains, and sheet pile walls are employed. Slurry
walls are the least expensive and are thus the most
common. Although there are many variations, a verti-
cal trench is always constructed under a slurry such as
bentonite and water.
Horizontal barriers within the soil (trenches or
197
wells) are under development and have not been
demonstrated as effective but are potentially useful
in restricting downward movement of metal con-
taminants by acting as underlying liners without the
requirement for excavation. Grout injection by either
vertical boring or horizontal drilling and block dis-
placement are the main types of horizontal barriers.
There have been problems with soil compaction and
vertical boreholes can increase the likelihood of
contaminant migration.
Solidi®cation/stabilization technologies are very
common in the United States (Conner, 1990) as they
contain the contaminants, not the contaminated area
like physical barriers. Solidi®cation is physical encap-
sulation of the contaminants in a solid matrix while
stabilization includes chemical reactions to reduce
contaminant mobility. Some metals such as arsenic,
chromium (VI) and mercury are not suitable for this
type of treatment since they do not form hydroxides
that are not highly soluble. Liquid monomers that
polymerize, pozzolans, bitumen, ¯y ash and cement
are injected to encapsulate the soils. Soils can be
treated in situ or after excavation. However, there
are few vendors of in situ processes while many
exist for ex situ processes since mixing in situ is
dif®cult to evaluate. For ex situ processes, in-drum,
in-plant or area mixing processes are used. Small-
scale pilot plants can treat up to 100 ton per day of
contaminated soil whereas 500±1000 ton of soil per
day can be stabilized in large plants (Smith et al.,
1995).
In situ solidi®cation/stabilization techniques are
preferred since labor and energy costs are lower but
site conditions such as bedrock, large boulders, clays
and oily patches may cause mixing problems. In situ
processes are most suitable for shallow contamination
since conventional equipment including draglines,
backhoes, clamshell buckets and vertical auger mixers
are used (Jasperse and Ryan, 1992). Augers vary from
1 to 3 m in diameter and can reach depths of 13 m. US
regulatory agencies are receptive to this technology
since the contaminants are not transferred to another
medium which would also require treatment. In the
UK, an in situ process called the Colmix process
(slurry including cement, slag-based grout and lime)
was used to immobilize heavy metals and ammonium
at the ICI Explosives' land®ll in Scotland (Wheeler,
1995).
198 C.N. Mulligan et al. / Engineering Geology 60 (2001) 193±207
Graphite and glass
A frit starter path
Electodes
Contaminated
soil area
B Subsidence
Electrodes
Natural soil
C Backfill over monolith
Vitrified monolith
Fig. 1. Diagram showing steps in the vitri®cation process for metal,
including (A) insertion of electrodes and placement of graphite and
glass frit starter path to initiate vitri®cation, (B) subsidence of the
soil during vitri®cation and (C) placement of back®ll over vitri®ed
monolith.
Vitri®cation is a solidi®cation/stabilization process
requiring thermal energy. It involves insertion of
electrodes into the soil which must be able to carry
a current, and then to solidify, as it cools (Fig. 1).
Toxic gases can also be produced during vitri®cation.
Full-scale applications exist for arsenic, lead and
chromium contaminated soils. Mixed wastes can
also be treated in this manner. High clay and moisture
contents and debris can affect the ef®ciency of the
process. These solidi®cation/stabilization processes
are suitable for contamination in shallow depths and
of large volume. Leaching of the contaminants must,
however, be carefully monitored as is the case for
vitri®cation, the formation of a glassy solid.
4.2. Mechanical separation
The aim of the size selection processes is to remove
the larger, cleaner particles from the smaller, more
polluted ones. Characterization in terms of particle
size and contaminant level in each fraction is the
most important parameter in determining the suit-
ability of this process. Bench-scale tests to evaluate
the separation technique are also valuable. To accom-
plish this, several processes are used. They include:
hydrocyclones which separate the larger particles
greater than 10±20 mm by centrifugal force from the
smaller particles, ¯uidized bed separation which
removes smaller particles at the top (less than
50 mm) in the countercurrent over¯ow in a vertical
column, by gravimetric settling and ¯otation which
is based on the different surface characteristics of
contaminated particles. These methods have been
used in mineral ore processing. Addition of special
chemicals such as frothers or ¯otation agents and
aeration causes these contaminated particles to ¯oat.
Magnetic separation, which is based on the magnetic
properties of metals, can also be used to separate these
from ferrous materials. Physical separation techniques
are becoming more common and applications will
continue to increase as they can be used to remove
metal contamination in a particular form or in com-
bination with other processes, to reduce the volume of
soil to be treated by other methods. Most times, off-
the-shelf equipment from the mining industry (hydro-
cyclones, centrifuges, screens, etc.) can be used.
4.3. Pyrometallurgical separation
Pyrometallurgical processes use high temperature
furnaces to volatilize metals in contaminated soil.
Temperatures of 200±7008C are used to evaporate the
contaminants. After volatilization, metals are then
recovered or immobilized. These methods are most
applicable to mercury since it is easily converted to its
metallic form at high temperatures. Other metals includ-
ing lead, arsenic, cadmium and chromium may require
pretreatment with reducing or ¯uxing agents to assist
melting and provide a uniform feed. This type of treat-
ment is usually performed off site due to a lack of mobile
units and is most applicable to highly contaminated soils
(5±20%) where metal recovery is pro®table. The soil
then must be concentrated by physical or soil washing
processes prior to pyrometallurgical processes.
Mercury, however, can be easily recovered at lower
concentrations (Smith et al., 1995). Other valuable
metals such as gold or platinum can also be recovered
 C.N. Mulligan et al. / Engineering Geology 60 (2001) 193±207
from low soil concentrations. Rotary kilns, arc furnaces
or rotary hearth furnaces are the main types of equip-
ment used in this process. They usually produce a slag
with a high concentration of heavy metals that can then
be recovered (USEPA, 1996a,b). The technologies
include ¯uidized bed thermal desorption, high-vacuum
retort, Pittsburgh Mineral and Environmental Techno-
logy's (PMET's) thermal recovery process, Remedial
Technology Group's (Farragut, Tennessee) thermal
screw processor and X-Traxe thermal desorption
system (Hazardous Waste Consultant, 1996).
Mercury levels from 1 to 228 mg/kg were obtained
after treatment of soil contaminated with 1300±
34,000 mg/kg of mercury at a US EPA SITE demonstra-
tion of the X-Traxe process. Rust/OHM has a full-scale
unit that can remediate 10 ton/h of soil for a 20,000±
100,000 ton of contaminated soil. Some of the metals
remain in the solid residues which will have to be
properly disposed of. Pretreatment is often necessary
to reduce the volume of soil to be treated, produce a
uniform feed and increase metal recoveries.
4.4. Chemical treatment
Chemical treatment by reductive as well as oxidative
mechanisms may be used to detoxify or decrease the
mobility of metal contaminants (Evanko and Dzombak,
1997). This method is commonly used for wastewater
treatment. Oxidization reactions which detoxify, preci-
pitate or solubilize metals involve addition of potassium
permanganate, hydrogen peroxide, hypochlorite or
chlorine gas. Neutralization reactions are performed to
adjust the pH of acidic or basic soils. Reduction reac-
tions are induced through the addition of alkali metals
such as sodium, sulfur dioxide, sul®te salts and ferrous
sulfate. Sometimes chemical treatment is used to
pretreat the soil for solidi®cation or other treatments.
For example, chemical reduction of Cr(VI) is performed
during solidi®cation/stabilization. Oxidation is less
commonly used with solidi®cation/stabilization. These
reactions are, however, not speci®c and there is there-
fore, a risk of converting other metals into more toxic or
mobile forms. Arsenic is most applicable for chemical
oxidation since As(V) is less toxic than As(III).
Co-precipitation of high concentrations of As(V) and
Fe(III) forms FeAsO4 while low concentrations of
As(V) co-precipitate with FeHO2 with high concentra-
tions of Fe(III) to form arsenic ferrihydride, a product
199
Source of contaminant
Ground surface
Treatment wall
Remediated
Groundwater groundwater
Impermeable layer
Fig. 2. Permeable reactive treatment barrier placed in the ground-
water to remove metal contaminants.
that is resistant to acid and neutral leaching (Robins,
1992). Mercury, lead, selenium and silver are also
applicable for reduction. These chemical treatments
can be performed in situ by injection into the ground-
water but have the potential to introduce further
contamination.
4.5. Permeable treatment walls
Permeable barriers (Fig. 2) that contain a reactive
substance (physical, chemical or biological or a
combination) are being evaluated for reducing the
mobilization of metals in groundwater at contamin-
ated sites. Various materials have been investigated
and include zeolite, hydroxyapatite, elemental iron
and limestone (Vidac and Pohland, 1996). Prelimin-
ary results have shown that elemental iron can be used
for chromium reduction and limestone for lead preci-
pitation. The advantages of this technique are that it is
in situ, a wide variety of contaminants can be treated
and ¯ow control can be used. Further research is
required in the areas of matching the contaminant
with the media in the barrier, optimization of the
¯ow and retention time through the barrier, and
methods of regenerating the media.
4.6. Electrokinetics
Electrokinetic processes involve passing a low
intensity electric current between a cathode and an
anode imbedded in the contaminated soil (Fig. 3).
Ions and small charged particles, in addition to
water, are transported between the electrodes. Anions
move towards the positive electrode and cations
towards the negative. An electric gradient initiates
200 C.N. Mulligan et al. / Engineering Geology 60 (2001) 193±207
AC/DC Converter
Extraction/processing
of fluids
Clean purge well Extraction well
Anode + Cathode –
Groundwater level
ˇ ing on the strain. Leaching can be performed by direct
˛
ˇ ˛
˛˛
ˇ ˛
Metal-contaminated
soil
Fig. 3. Electrokinetic process for soil remediation. Cations move
towards the cathode and anions towards the anode. Buffer solutions
are added and removed by the purge and extraction wells.
movement by electromigration (charged chemicals
movement), electro-osmosis (movement of ¯uid),
electrophoresis (charged particle movement) and
electrolysis (chemical reactions due to electric ®eld)
(Rodsand and Acar, 1995). Buffer solutions are used
to maintain the pH at the electrodes. The metals can
be removed by electroplating or precipitation/co-
precipitation at the electrodes, using ion exchange
resins or recovering the metals by pumping the
waste to the surface (Smith et al., 1995). The process
can be used in situ or with excavated soil. Metals as
soluble ions and bound to soils as oxides, hydroxides
and carbonates are removed by this method. Other
non-ionic components can also be transported due to
the ¯ow. Large metal objects, rocks, foundations,
rubble or other obstacles can interfere with the process
(Acar and Gale, 1995). Unlike soil washing, this
process is effective with clay soils of low perme-
ability. It is mainly applicable for saturated soil with
low groundwater ¯ow rates. Demonstrations of
this technology have been performed, such as
the Lasagnae technology, but are limited. In
Europe, this technology is used for copper, zinc,
lead, arsenic, cadmium, chromium and nickel.
Electrode duration and spacing is site-speci®c
and may need to be optimized, in addition to the
type of pore ¯uid used.
4.7. Biochemical processes
Techniques for the extraction of metals by micro-
biological means are rather limited at this time. The
main methods include bioleaching and oxidation/
reduction reactions. Bioleaching involves Thiobacil-
lus sp. bacteria under aerobic and acidic conditions
(pH 4) at temperatures between 15 and 558C, depend-
means, oxidation of metal sul®des to produce sulfuric
acid, which then can desorb the metals on the soil by
substitution of protons. Indirect leaching involves
conversion of Fe 21 to Fe 31 which in turn oxidizes
sulfur minerals to Fe 21 producing acidity. Several
options are available for bioleaching including heap
leaching, bioslurry reactors and in situ processes.
Anoxic sediments are more suitable for treatment
since the bacteria can solubilize the metal compounds
without substantially decreasing the pH. Soils require
lower pH values to extract the metals since they have
already been exposed to oxidizing conditions. For
both heap leaching and reactors, the bacteria and
sulfur compounds are added. In the reactor, mixing
is used and pH can be controlled more easily.
Leachate is recycled during heap leaching. Copper,
zinc, uranium and gold have been removed by
Thiobacillus sp. in biohydrometallurgical processes
(Karavaiko et al., 1988). Several feasibility studies
have indicated that contaminated soils can be remedi-
ated by Thiobacilli (Tichy et al., 1992). Sludges from
anaerobic processes that contain metal sul®des could
be treated in this manner (Blais et al., 1992).
Another leaching technique that has potential for
remediation of metal-contaminated soil is through
the production of citric and gluconic acids by the
fungus Aspergillus niger can produce citric and glu-
conic acids. They can act as acids (pH 3.5) and chelat-
ing agents for the removal of metals such as copper
from oxide mining residues (Mulligan et al., 1999c).
Inexpensive carbon substrates will be required to
decrease the costs of this process.
Biosorption is a biological treatment method which
involves the adsorption of metals into biomass such as
algal or bacterial cells that can be dead or alive. If
large-scale, inexpensive production techniques for
the biomass are developed, this heavy metal treatment
is promising (Hazardous Waste Consultant, 1996).
This method is mainly applicable for removal of
 C.N. Mulligan et al. / Engineering Geology 60 (2001) 193±207 201

low concentrations of metals in water. Therefore, the
cells could potentially be placed in permeable barriers
for adsorption of metals in groundwater.
Microorganisms are also known to oxidize and
reduce metal contaminants. Mercury and cadmium
can be oxidized while arsenic and iron can be reduced
by microorganisms. Cr(VI) can be oxidized to Cr(III)
that is less mobile and toxic. Bacteria such as Bacillus
subtilis and sulfate reducing bacteria in the presence
of sulfur can perform this reaction.
Sulfate-reducing bacteria (SRB) form metal (Me)
sul®des that are insoluble as shown in the following
reactions
CH3 COOH 1 SO22 2
4 ! 2HCO3 1 HS 1 H
1
H2 S 1 Me21 ! MeS 1 2H1
As can be seen from the equations, sulfate, low
redox conditions and an electron donor such as metha-
nol are required. Oxygen should not be there and
nutrients must be added. Stimulating sulfate reduction
can increase pH also and form metal hydroxides and
oxides that precipitate and do not migrate in soils and
groundwater. A project proposed by the Flemish Insti-
tute for Technological Research for NATO/CCMS
(1999). It involves bioprecipitation of the heavy
metals (zinc, cadmium, arsenic, lead, chromium,
nickel, and copper) within biological reactive zones
or biowalls. The ®rst site contains zinc (0±150 mg/l),
cadmium (0.4±4 mg/l), and arsenic (20±270 mg/l)
with high concentrations of sulfate (400±700 mg/l),
ideal for SRB activity. The second site has copper
(up to 92 mg/l), chromium (up to 78 mg/l), zinc (up
to 8.3 mg/l), nickel (up to 3.5 mg/l) with high levels of
sulfate (up to 3000 mg/l). Results will be available in
the coming years.
Biomethylation involves the addition of a methyl
(±CH3) group to a metal such as arsenic, mercury,
cadmium or lead. The methylated forms are more
mobile and can migrate into the groundwater.
Although, methylation increases volatility, it is not
likely that methylation of metals such arsenic will
be performed for remediation since the by-products
are more toxic. They are currently under develop-
ment and not commercially available. Volatilization
of selenium from contaminated agricultural soils
has shown some promise (Thompson-Eagle and
Frankenberger, 1990) Therefore, these processes
could be used for soil and sediment treatment. How-
ever, this form of the metal may dif®cult to control in
gas emissions.
Another process (called mercrobes) has been devel-
oped and tested in Germany at concentrations greater
than 100 ppm. Between 95 and 99% of the mercury
was reduced in laboratory tests (Hazardous Waste
Consultant, 1996). Since the mobility is in¯uenced
by its oxidation state, these reactions can affect the
contaminant mobility.
4.8. Phytoremediation
Plants such as Thlaspi, Urtica, Chenopodium,

Atmosphere Phytovolatilization

Plant Phytoaccumulation

Soil Phytostabilization

Groundwater level

Mechanisms for
phytoremediation of metals

Fig. 4. Schematic diagram showing the mechanisms of the phytoremediation process for metal uptake.
202 C.N. Mulligan et al. / Engineering Geology 60 (2001) 193±207
Polygonum sachalase and Alyssim have the capability
to accumulate cadmium, copper, lead, nickel and zinc
and can be therefore be considered as an indirect
method of treating contaminated soils (Baker et al.,
1991). This method is limited to shallow depths of
contamination. Rhizo®ltration, the adsorption by
plant biomass, can be used to remediate metal-
contaminated groundwater. Phytoextraction involves
uptake of metals by trees, herbs, grasses and crops and
can be used for soil treatment. Phytostabilization is a
process to excrete components from the plants to
decrease the soil pH and form metal complexes. The
plants will have to be isolated from wildlife and agri-
cultural lands. The climatic conditions and bio-
availability of the metals must be taken into
consideration when using this method. Once con-
taminated, the plants will have to be disposed of in
an appropriate fashion. Some techniques include
drying, incineration, gasi®cation, pyrolysis, acid
extractions, anaerobic digestion, extraction of the
oil, chlorophyll ®bers from the plants (Bolenz et al.,
1990) or disposal since plants are easier to dispose of
than soil. Phytoremediation will be most applicable to
shallow soils with low levels of contamination (2.5±
100 mg/kg) for polishing. Phytoremediation ®eld
demonstrations (Fig. 4) are summarized in Table 2.
The main disadvantage of this method is that longer
times are required compared to other methods. More
research is needed to enhance the extraction of the
metals by the plants through genetic breeding or
other methods and how to correlate bioavailability
with metal uptake. Crop plants that grow fast may
be viable for phytoremediation.
4.9. In situ treatment (soil ¯ushing)
Extracting solutions are in®ltrated into soil using
surface ¯ooding, sprinklers, leach ®elds, basin in®l-
tration systems, surface trenches, horizontal drains or
vertical drains. Water with or without additives is
employed to solubilize contaminants. The ef®ciency
of the extraction depends on the hydraulic con-
ductivity of the soil. High permeability gives better
results (greater than 1 £ 10 23 cm/s). The solubility of
pollutants and if the pollutant was originally solu-
bilized in water or not affects removal ef®ciencies.
Prior mechanical mixing of the soil can disturb the
in®ltration 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 is the controlling removing
mechanism, additives are used to enhance ef®ciencies.
In an analysis of a test site, it was determined that 400
years would be required to treat a site with water alone
compared to 4 years with chemical enhanced ¯ushing
(AAEE, 1993). The research in this area is still quite
limited, particularly where metal removal is con-
cerned (USEPA, 1987) but chemical enhanced ¯ush-
ing has potential for a wide variety of metals. Little
handling of soil is required. Chemical enhanced ¯ush-
ing includes addition of 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 combina-
tion with complexation agents or oxidizing/reducing
agents. 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. Once the
water is pumped from the soil, it must be extracted
and then treated to remove the metals in wastewater
treatment facilities or reused in the ¯ushing process.
Several technologies exist such as sodium hydroxide
or sodium sul®de precipitation, ion exchange, acti-
vated carbon adsorption, ultra®ltration, reverse osmo-
sis, electrolysis/ electrodialysis and biological means
(Patterson, 1985). Metal recovery and recycling must
be improved.
Large-scale treatment has been done mostly for
organic removal and is limited to metals. Full-scale
treatment was performed at United Chrome, a chrome
plating plant (Corvallis, OR), for removal of Cr(VI)
(USEPA, 1996a,b). Water was used as the ¯ushing
solution with three methods of in®ltration, in®ltration
basins, injection wells and an in®ltration trench. The
site had a low permeability silty soil and treatment
was performed for both shallow and deep aquifers.
A clay aquitard was also ¯ushed indirectly by using
deep injection wells. Signi®cant removal of chro-
mium was achieved, in addition to hydraulic contain-
ment of the plume. Levels of chromium were reduced
to 18 from 2000 mg/l. At another site, a 30,000 m 3
volume has been successfully treated in The
Netherlands to decrease the cadmium content in
 C.N. Mulligan et al. / Engineering Geology 60 (2001) 193±207 203

90% of the soil from 10 to less than 1 mg/kg with

Lab, Riverside, CA
Rutgers University
dilute hydrochloric acid (pH 3) (Urlings, 1990).

USDA Salinity
Schnoor, 1997
More demonstrations are needed in this area, in addi-

Brown, 1995
Reference

Phytotech

Phytotech
tion to developing more understanding into the
mechanisms for solution, metal recovery and use of
non-toxic additives.

Uptake of Zn and Cd rapid but 4.10. Soil washing (chemical leaching)

90% reduction 137Cs, 90Sr in 2

soil dif®cult to decontaminate

volatilized but soil dif®cult to

In one season, reached below

Heavy metals can be removed from soils using

95% removal of U in 24 h

Se is partly taken-up and

various agents added to the soil (Fig. 5). This can be
weeks, 8000 X normal
concentration in roots

(350 ppb to ,5 ppb)

done in reactors or as heap leaching. These agents are:

inorganic acids such as sulfuric and hydrochloric
decontaminate

acids with pH less than 2, organic acids including

Performance

action level
In progress

acetic and citric acids (pH not less than 4), chelating
agents such as ethylenediaminetetraacetic acid
(EDTA) and nitrilotriacetate (NTA), and various
combinations of the above (USEPA, 1991). The
cleaned soil can then be returned to the original site.
Soils with less than 10±20% clay and organic content
Indian mustard Brassica juncea
Sun¯owers Helieanthus anuus

Sun¯owers Helieanthus anuus

(i.e. sandy soils) are most effectively remediated with

these extractants. Both organics and metals are
Sun¯owers and mustard

removed. However, modi®cations to the process,

which is commercially used, have to be made for
each type of soil (Hinsenveld et al., 1990). In general,
Thlaspi spp.

Brassica sp.

soils with low contents of cyanide, ¯uoride and

sul®de, CEC of 50±100 meq/kg and particle sizes of
Plants

0.25±2 mm, with contaminant solubility in water of

greater than 1000 mg/l, can be most effectively
cleaned by soil washing (Hazardous Waste Consul-
tant, 1996). In the EPA VISITT 2.0, there are more
Rhizo®ltration of energy wastes

than 20 soil washing vendors and 5 vendors of acid

Phytoextraction of mine wastes
Phytoextraction of 200 £ 300 ft

Phytovolatilization of re®nery
wastes and agricultural soils

extraction.
Rhizo®ltration near nuclear
Phytoremediation demonstration projects (Schnoor, 1997)

Rhizo®ltration of land®ll

The feasibility of using biodegradable biosur-

factants to remove heavy metals from an oil-
contaminated soil was recently demonstrated (Fig.
6) by laboratory scale batch washes with surfactin, a
Application

brown®eld

rhamnolipid and a sophorolipid (Mulligan et al.,

leachate
disaster

1999a). The ®rst two agents are produced by bacteria

while the last is produced by a yeast. The soil
contained 890 mg/kg of zinc, 420 mg/kg of copper
with a 12.6% oil and grease content. A series of ®ve
batch washes removed 70% of the copper with 0.1%
Chernobyl, Ukraine

San Francisco, CA

surfactin/1% NaOH while 4% sophorolipid/0.7% HCl

Rocky Flats, CO
Ashatabula, OH

was able to remove 100% of the zinc. The results

Pennsylvania
Trenton, NJ

clearly indicated the feasibility of removing metals

Location
Table 2

with the anionic biosurfactants tested even though

the exchangeable metal fractions were very low.
204 C.N. Mulligan et al. / Engineering Geology 60 (2001) 193±207

Contaminated soil

Surfactant Well
injection

Groundwater level

Low permeability zone

Contaminant plume

Fig. 5. Diagram of soil ¯ushing process using injection of water or solution containing chemicals including acids, chelating agents or
surfactants.

These biosurfactants were also able to remove metals
from sediments (Mulligan et al., 1999c). Since these
agents are biodegradable, can enhance hydrocarbon
removal and can potentially be produced in situ,
they have a great potential for soil washing and soil
¯ushing applications.
4.11. Treatment of sediments
Since sediments contain large quantities of water,
de-watering is frequently necessary after dredging to
enable treatment. Methods include draining of the
water in lagoons with or without coagulants and ¯oc-
culants or using presses or centrifuges. Treatment
methods are similar to those used for soil such as
hydrocyclone pretreatment, solidi®cation/stabiliza-
tion and chemical extraction (acids). Few of these
techniques in comparison to soil treatment have
been used commercially.
5. Conclusions
A summary of the various remediation techniques
is shown in Table 3. Physical containment is the least
expensive approach but this leaves the contaminants
in place without treatment. Since metals are considered
relatively immobile, methods for metal decontamin-
ation have focused on solid-phase processes such
as solidi®cation/stabilization and vitri®cation. These

A B
Total copper removal (%)

Total zinc removal (%)

100 100
80 Soph Soph
80
Surf Surf
60 60
Rham Rham
40 40
Control1 Control1
20 20 Control2
Control2
0 0
0 1 2 3 4 5 0 1 2 3 4 5
Number of washings Number of washings

Fig. 6. Cumulative copper (A) and zinc (B) removal after ®ve washes using different biosurfactants and controls. Experiments were performed
as batch washes in 50 ml centrifuge tubes according to Mulligan et al. (1999a). Control 1, 1%; surf, 0.1% surfactin/1% NaOH; rham, 0.1%
rhamnolipid/1% NaOH; control 2, 0.7% HCl; soph, 4% sophorolipid/0.7% HCl.
 C.N. Mulligan et al. / Engineering Geology 60 (2001) 193±207 205

Table 3
Summary of remedial technologies

Technology Description Applicability Costs ($US/ton)

Containment
Physical Prevent movement by Land®ll covers and slurry walls 10±90
preventing ¯uid ¯ow
Encapsulation Creation of an inert waste Injection of solidifying 60±290
chemicals
Vitri®cation Application of electrical energy Shallow metal-contaminated 400±870
to vitrify contaminant soil, low volatility metals
Ex situ treatment
Physical separation Includes, froth ¯otation, gravity For high metal concentrations 60±245
separation, screening, etc.
Soil washing Addition of surfactants and other For water soluble contaminants 25±300
additives to solubilize
Pyrometallurgical Elevated temperature extraction Highly-contaminated soils 200±1000
and processing for metal (5±20%)
removal
In situ
Reactive barriers Creation of a permeable barrier Sorption or degradation of 60±245
contaminants in barrier
Soil ¯ushing Water ¯ushing to leach For soluble contaminants 100±200
contaminants
Electrokinetic Application of electrical current Applicable for saturated soils Little info
with low groundwater ¯ow
Phytoremediation Use of plants for metal Shallow soils and water Good (50,000±200,000/acre)
extraction

processes can be performed in situ which reduces
handling costs. Costs depend on presence of debris,
excess moisture, contaminant dept, and soil homo-
geneity. They are bene®cial where the area of contam-
ination is shallow but large. Long-term stability of the
solidi®ed/stabilized matrix is the major unknown.
Vitri®cation is expensive but applicable to mixed
wastes where few technologies are available. Electro-
kinetics and in situ ¯ushing have been used at a few
sites but results are promising. More ®eld demonstra-
tions are needed for both of these technologies. Elec-
trokinetics is particularly promising for contamination
at moderate depths in clays but R&D is required to
optimize pore ¯uids and electrode con®guration. In
situ ¯ushing is most effective for homogeneous,
permeable, sandy and silty soils. Site hydrology
must be understood to avoid the movement of
contaminants into undesirable areas. More develop-
ments are needed in the area of non-toxic additives
for in situ ¯ushing. Economics also could be improved
by recovery of metals. Phytoremediation and
bioleaching are not as well developed but could be
useful for areas of low contamination although longer
treatment times may be necessary. Numerous issues
still need to be resolved and more demonstrations are
required. Some of the issues include enhancing the
accumulation of metals by plants, developing methods
to extract meals from plants and determining correla-
tions between soil components and bioavailability.
Treatment walls are low cost, passive treatment
methods that have potential. More research is
required to match reactive media with contamin-
ants, model lifetime performance, optimize reten-
tion times and develop methods for regeneration
of reactive media. The selection of each technol-
ogy is site-speci®c. Overall, metal-contaminated
groundwater is treated above-ground. Metal-
contaminated soils are excavated and are treated
ex situ by solidi®cation/stabilization. In situ tech-
niques are under development. Our research has
206 C.N. Mulligan et al. / Engineering Geology 60 (2001) 193±207
indicated that biosurfactants, biologically produced
surfactants, may be viable agents for the enhanced
removal of metals from contaminated soils and
sediments.
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