Science of the Total Environment 633 (2018) 206–219

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Science of the Total Environment

journal homepage: www.elsevier.com/locate/scitotenv

Review

Remediation techniques for heavy metal-contaminated soils: Principles

and applicability
Lianwen Liu a, Wei Li a, Weiping Song b, Mingxin Guo c,⁎
a
School of Earth Sciences and Engineering, Nanjing University, Nanjing, Jiangsu 210046, China
b
Department of Chemistry, Delaware State University, Dover, DE 19901, USA
c
Department of Agriculture and Natural Resources, Delaware State University, Dover, DE 19901, USA

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Various remediation methods have

been developed for heavy metal-
contaminated soils.
• In-situ, contaminant removal/extraction
remediation techniques are more favor-
able.
• The methods landfilling, soil washing,
and solidification are well established.
• Electrokinetic extraction, chemical sta-
bilization, and phytoremediation are
immature.
• Treatability studies are crucial to
selecting feasible soil remediation
techniques.

a r t i c l e i n f o a b s t r a c t

Article history: Globally there are over 20 million ha of land contaminated by the heavy metal(loid)s As, Cd, Cr, Hg, Pb, Co, Cu, Ni,
Received 1 February 2018 Zn, and Se, with the present soil concentrations higher than the geo-baseline or regulatory levels. In-situ and ex-
Received in revised form 14 March 2018 situ remediation techniques have been developed to rectify the heavy metal-contaminated sites, including sur-
Accepted 15 March 2018
face capping, encapsulation, landfilling, soil flushing, soil washing, electrokinetic extraction, stabilization, solidi-
Available online xxxx
fication, vitrification, phytoremediation, and bioremediation. These remediation techniques employ
Editor: Jay Gan containment, extraction/removal, and immobilization mechanisms to reduce the contamination effects through
physical, chemical, biological, electrical, and thermal remedy processes. These techniques demonstrate specific
Keywords: advantages, disadvantages, and applicability. In general, in-situ soil remediation is more cost-effective than ex-
Heavy metals situ treatment, and contaminant removal/extraction is more favorable than immobilization and containment.
Soil remediation Among the available soil remediation techniques, electrokinetic extraction, chemical stabilization, and
Solidification phytoremediation are at the development stage, while the others have been practiced at full, field scales. Com-
Phytoremediation prehensive assessment indicates that chemical stabilization serves as a temporary soil remediation technique,
Applicability
phytoremediation needs improvement in efficiency, surface capping and landfilling are applicable to small,
serious-contamination sites, while solidification and vitrification are the last remediation option. The cost and
duration of soil remediation are technique-dependent and site-specific, up to $500 ton−1 soil (or $1500 m−3
soil or $100 m−2 land) and 15 years. Treatability studies are crucial to selecting feasible techniques for a soil re-
mediation project, with considerations of the type and degree of contamination, remediation goals, site charac-
teristics, cost effectiveness, implementation time, and public acceptability.
© 2018 Elsevier B.V. All rights reserved.

⁎ Corresponding author.
E-mail address: mguo@desu.edu (M. Guo).

https://doi.org/10.1016/j.scitotenv.2018.03.161
0048-9697/© 2018 Elsevier B.V. All rights reserved.
 L. Liu et al. / Science of the Total Environment 633 (2018) 206–219 207

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
2. Assessment of soil heavy metal contamination. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
3. In-situ remediation techniques for heavy metal-contaminated soils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
3.1. Surface capping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
3.2. Encapsulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
3.3. Electrokinetic extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
3.4. Soil flushing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
3.5. Chemical immobilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
3.6. Phytoremediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212
3.7. Bioremediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
4. Ex-situ remediation techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214
4.1. Landfilling. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214
4.2. Soil washing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214
4.3. Solidification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
4.4. Vitrification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
5. Selection of best soil remediation techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
6. Summary and conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218

1. Introduction existing technologies and provide instructive evaluations on the practi-

cal feasibility of the technologies. This paper was aimed to systemati-
Soil contamination by heavy metals is a worldwide problem for cally review the available remediation techniques for heavy metal-
human health and safe food production. Except for uncommon geogenic contaminated soils in terms of their working principles, technical proce-
origins, heavy metal contaminants are inadvertently introduced to soils dures, applicability, advantages and limitations, and application status.
through anthropogenic activities such as mining, smelting, warfare and The information is expected to assist in selecting appropriate remedia-
military training, electronic industries, fossil fuel consumption, waste tion technology for treatment of heavy metal-contaminated agricultural
disposal, agrochemical use, and irrigation. For example, the common and urban soils within particular scenarios.
fossil fuel coal contains an array of heavy metals including Hg, Pb, Cd,
Cr, Cu, Co, Zn, and Ni in the concentration range of 0.1 to 18 mg kg−1; 2. Assessment of soil heavy metal contamination
these heavy metals are discharged into the environment in vapor, flue
gas particulate matter, fly ash, and bottom ash upon coal combustion In soil, heavy metals exist in different forms: dissolved ions (e.g., Cu2
+
(Nalbandian, 2012). Inappropriate soil disposal of mine spoils, industrial , Cd2+, CrO2− 2− 2−
4 , Cr2O7 , and MoO4 ) and organic complexes (e.g., Cu
2+
,
2+ 2+
waste, and construction waste frequently causes heavy metal contami- Pb , and Hg binding to dissolved organic matter) in soil solution, ex-
nation (USDA, 2000; He et al., 2005). Land application of phosphorus changeable ions (e.g., Cu2+, Zn2+, Cd2+, Ni2+, and Pb2+) adsorbed on
(P) fertilizers, Cu-based pesticides, biosolids, and animal manure and soil solid particles, and (co-)precipitates as part of soil solids (e.g., Cd3
crop irrigation with sewage water and poorly-treated industrial waste- (PO4)2, ZnS, PbCO3, and HgSO4). These three broad forms maintain a
water are major pathways for heavy metals to enter into agricultural thermodynamic equilibrium in activity and concentration between
soils (USDA, 2000; Sharma et al., 2007; Bolan et al., 2014). each other, with insoluble precipitates as the predominant species
Globally there are N5 million sites covering 20 million ha of land in (Roberts et al., 2005). Research has clearly shown that it is not the
which the soils are contaminated by different heavy metal(loid)s total concentration but the reactive fraction of heavy metals in soil
(Wuana and Okieimen, 2011; He et al., 2015). In China alone,
N1.0 million km2 (100 million ha) of land are heavy metal-polluted
(He et al., 2015). The heavy metals in contaminated soils impair the nat-
ural ecosystem services and eventually damage human health via the
food chain (Tchounwou et al., 2012; Jaishankar et al., 2014). Over the
years various in-situ and ex-situ remediation techniques have been de-
veloped to contain, clean up, or restore heavy metal-contaminated soils,
such as surface capping, soil flushing, electrokinetic extraction, solidifi-
cation, vitrification, and phytoremediation (Fig. 1). These techniques
can be classified into five categories: physical, chemical, electrical, ther-
mal, and biological remediation or three divisions: containment-based
(e.g., capping/encapsulation), transformation-based (e.g., stabilization/
immobilization), and transport-based (e.g., extraction/removal)
methods. In general, these soil remediation methods employ different
working mechanisms and demonstrate specific application advantages
and limitations. More important, these techniques vary significantly in
effectiveness and cost in field practices (Khalid et al., 2017). There are
a number of literature documents overviewing the soil heavy metal re-
mediation technologies (Khan et al., 2004; Bradl and Xenidis, 2005;
Jankaite and Vasarevičius, 2005; Dermont et al., 2008; Wuana and
Okieimen, 2011; Yao et al., 2012; Meuser, 2013; Shammas, 2016;
Khalid et al., 2017), yet few are comprehensive to compare all the Fig. 1. Common remediation techniques for heavy metal-contaminated soils.
208 L. Liu et al. / Science of the Total Environment 633 (2018) 206–219

that dictates their toxicity to plants, microbes, and human beings. The
water-soluble and exchangeable forms of heavy metals are much
more reactive and bioavailable than the precipitated species (Roberts
et al., 2005; Leitgib et al., 2007; Kim et al., 2015). Distribution of the
heavy metal species, however, is influenced by a number of environ-
mental factors, particularly the soil pH, redox potential, clay content,
Fe/Mn oxide content, organic matter content, and the presence of
other cations and anions in the soil solution (Rieuwerts et al., 1998;
Pietrzykowski et al., 2014). To precisely evaluate the bioavailability of
heavy metals in soil, these influencing factors have to be considered.
Accumulation of heavy metals in soil causes ecosystem malfunction,
water degradation, and food/feed contamination. Many countries have
surveyed the ambient background concentrations (ABCs; also termed
geochemical baselines) of heavy metals in soils; the information serves
as references for assessing the soil quality status (Karim et al., 2015).
The geoaccumulation index (Igeo) is computed to indicate the degree
of soil contamination by heavy metals:
 
Ci
Igeo ¼ log2
1:5Bi
where Bi and Ci are the background concentration and the present con-
centration (mg kg−1) of a metal element i in soil, respectively. Soils with
an Igeo value ≤0, ≤1, ≤2, ≤3, ≤4, ≤5, and N5 are classified as uncontami-
nated (contamination class 0), slightly to moderately contaminated
(class 1), moderately contaminated (class 2), moderately to strongly
contaminated (class 3), strongly contaminated (class 4), strongly to se-
riously contaminated (class 5), and seriously contaminated (class 6), re-
spectively (Barbieri, 2016). To safeguard natural resources and
minimize pollution risks, many countries have established regulatory
concentrations of heavy metals in agricultural soils (Table 1). Depend-
ing on the protection goals and the jurisdiction framework, the regula-
tory concentrations are phrased as control limits, maximum permitted
concentrations, guideline values, screening values, trigger values, eco-
logical investigation levels, or soil quality standards. In developing soil
quality standards, the regulatory concentrations for heavy metals are
based principally on ecological and health risks and derived primarily
from the ABCs of the trace elements in soils, with comprehensive con-
siderations of land use, soil characteristics, the toxicity levels of the
elements to humans, animals, and plants, and potential economic and
social impacts (Merrington and Schoeters, 2010; Tóth et al., 2016). Dif-
ferent approaches have been used to determine the ABCs of heavy
metals in soils, including regional geological survey, probability function
methods, and geochemical regression methods (Merrington and
Schoeters, 2010). As such, it is understandable that soil quality stan-
dards differ between countries and regions (Table 1). In general, a soil
is considered polluted if the total concentration of a toxic heavy metal
in the soil exceeds the regulatory concentration (Hu et al., 2013).
Prevention is always the most cost-effective option in pollution con-
trol. If the soil in agricultural land or in urban areas is unfortunately con-
taminated by heavy metals, remediation measures have to be
implemented to mitigate the hazardous impacts.
3. In-situ remediation techniques for heavy metal-contaminated
soils
In-situ remediation does not require excavation and transport of the
ð1Þ contaminated soil to off-site treatment facilities and therefore, soil dis-
turbance is minimized, exposure of workers and the surrounding public
to the contaminants is reduced, and the treatment cost may be signifi-
cantly lessened. However, specific field conditions have to be carefully
considered, such as weather, soil permeability, contamination depth,
and potential deep leaching of chemicals (Olexsey and Parker, 2006).
3.1. Surface capping
Surface capping is to simply cover the contaminated site with a layer
of waterproof material to form a stable, protection surface. This
containment-based technique is not truly a soil “remediation” method,
as no efforts are made to remove the heavy metal contaminants or at
least reduce their reactivity in the soil. Nevertheless, the method
works efficiently to eliminate the risk of exposure to the contaminated
soil via skin contact or incidental ingestion. The surface cap serves fur-
ther as an impermeable barrier to surface water infiltration, preventing
soil contaminants from further diffusing to surface water and ground-
water. The capped soil, however, loses its natural environmental func-
tions especially in supporting plant growth. The treated area may be

Table 1
Regulatory concentrations of toxic trace elements in agricultural soils (mg kg−1) of different countries.
(Sources: MEPC, 1995; MEF, 2007; CCME, 2007; Merrington and Schoeters, 2010; Lee and Lee, 2011; He et al., 2015; JPME, 2016)

Australia Canada China, Mainland China, Taiwan European Union Japan US

Cd ≤3 ≤1.4 ≤0.30 (pH ≤ 7.5) ≤5 ≤10 ≤0.01 mg/L in soil solution and b 0.4 mg kg−1 in grown rice ≤0.48
≤0.60 (pH N 7.5)
Pb ≤300 ≤70 ≤250 (pH b 6.5) ≤500 ≤200 ≤0.01 mg/L in soil solution ≤200
≤300 (pH 6.5–7.5)
≤350 (pH N 7.5)
Cr ≤50 ≤64 ≤250/150 (pH b 6.5) ≤250 ≤200 Cr(VI) ≤0.05 mg/L in soil solution ≤11
≤300/200 (pH 6.5–7.5)
≤350/250 (pH N 7.5)
In paddy/dryland soils
Hg ≤1 ≤6.6 ≤0.30 (pH b 6.5) ≤2 ≤2 Total Hg ≤0.5 μg/L and alkyl Hg undetectable in soil solution ≤1
≤0.50 (pH 6.5–7.5)
≤1.0 (pH N 7.5)
Cu ≤100 ≤63 ≤50 (pH b 6.5) ≤200 ≤150 b125 mg kg−1 in paddy soil ≤270
≤100 (pH ≥ 6.5)
Zn ≤200 ≤200 ≤200 (pH b 6.5) ≤600 ≤250 ≤1100
≤250 (pH 6.5–7.5)
≤300 (pH N 7.5)
Ni ≤60 ≤50 ≤40 (pH b 6.5) ≤200 ≤100 ≤72
≤50 (pH 6.5–7.5)
≤60 (pH N 7.5)
As ≤20 ≤12 ≤30/40 (pH b 6.5) ≤60 ≤50 ≤0.01 mg/L in soil solution and b 15 mg kg−1 in paddy soil ≤0.11
≤25/30 (pH 6.5–7.5)
≤20/25 (pH N 7.5)
in paddy/dryland soils
Se ≤1 ≤0.01 mg/L in soil solution
 L. Liu et al. / Science of the Total Environment 633 (2018) 206–219
Fig. 2. Examples of various surface capping systems (OhioEPA, 2000).
used for other civil purposes as a parking lot or a sport field (NJDEP,
2014).
Selection of an appropriate capping system is site specific, varying
with site characteristics and remedial objectives. Single-layer caps or
multilayer systems can be used, with many choices of the capping ma-
terials including clay, concrete, asphalt, and high-density polyethylene
(Fig. 2). The surface cover, with adequate structural strength and dy-
namic stability, should extend 60–90 cm beyond the horizontal extent
of the contamination site (Rumer and Ryan, 1995). Water control struc-
tures such as ditches, dikes, and slope are typically installed to divert
runoff and drainage from surface caps. Revegetation can be achieved
in multilayer cap systems if a layer of topsoil is placed over the imper-
meable cover layer (Fig. 2).
Surface capping is a treatment option for highly contaminated soils
(e.g., Igeo N 3). The method is only applicable to correcting small areas
(e.g., b2000 m2). Otherwise construction of the capping surface be-
comes difficult (OhioEPA, 2000). The depth and seasonal fluctuation of
groundwater table at the remediation site and the nearby
hydrogeological features (e.g., ponds, runoff) that may influence the
cap stability need thorough considerations. The sliding risk has to be
evaluated if a cap is placed on sloping ground. If the remediation site
is proximal to residential neighborhoods, parks, or walkways, the com-
munity acceptance needs to take into account. Overall, surface capping
is a simple, rapid, and effective method to eliminate the soil contamina-
tion risks. It is a top choice in terms of project time and budget yet a low
choice in terms of land use and soil ecosystem function changes. The
method has been widely practiced to rectify small areas of soil contam-
inated by heavy metals and organic pollutants (NJDEP, 2014). The cost
for a surface capping project is reflected by the essential engineering de-
sign, materials, labor, and follow-up operations (e.g., inspection, main-
tenance). The recent cost ranges from $20 m−2 to $90 m−2 in the U.S.
(NJDEP, 2014).
3.2. Encapsulation
Encapsulation, also termed “barrier wall”, “cutoff wall”, or “liner”
method, is a remedial alternative paralleling to surface capping. The
technique is to contain polluted soil in a properly designed physical bar-
rier system consisting of low permeability caps, enclosing underground
barriers, and in rare situations, barrier floors. Contaminated sites are iso-
lated and pollutants are enclosed, eliminating off-site dispersion of the
contaminants and on-site bio-exposure to the contaminants (Khan
et al., 2004; Meuser, 2013). The low permeability caps, usually synthetic
textile sheets or clay layers, minimize surface water infiltration and thus
prevent leaching of contaminants into the groundwater. The under-
ground impermeable barriers inhibit the contaminant source from hor-
izontal migration to surrounding areas via potential diffusion and
subsurface interflow.
The main challenge of encapsulation is to construct underground
vertical impermeable walls at contamination sites. A number of con-
struction methods have been developed, including slurry walls, thin
walls, sheet pile walls, and injection walls (Bradl and Xenidis, 2005;
209
Meuser, 2013). In the slurry wall method, for example, a trench is first
excavated in the ground to the desired depth using a trench cutter or
grab bucket. Cement-bentonite-water slurry is then poured into the
trench and solidifies into a 0.4–1 m thick wall. To increase the wall
strength and impermeability, HDPE (high density polyethylene) mem-
branes, sheet piles, and glass tiles can be inserted into the still liquid
slurry. The wall can be constructed in sequential panels at different
times, yet the watertight contact between panels has to be secured to
maintain the wall integrity. In thin wall construction, a narrow trench
is prepared by vibrating a heavy steel beam into the ground using a
pressure jet. Clay-cement-water slurry is then injected into the trench
to create a 0.15-m thin wall. Compaction of the soil during trench prep-
aration provides additional impermeability of the structure. Alterna-
tively, steel/aluminum sheets, precast concrete plates, or wood boards
can be driven into the ground to form impermeable sheet pile walls,
with locks connecting the adjacent piles together. More commonly,
boreholes are executed to the desired depth in the ground using a rotary
casing; grouting materials such as cement suspension and artificial
resins are injected into the boreholes through a high pressure jet; a
“soilcrete” injection wall forms after the grouting slurry fills the pores
of soil between adjacent boreholes and solidifies (Bradl and Xenidis,
2005). Quality barrier walls are of low hydraulic conductivity (b10−
7
cm s−1), low shrinkage, adequate strength, and long-term durability
(Meuser, 2013).
Similar to surface capping, encapsulation is limited to small-area,
shallow yet serious-contamination sites. The technology is commonly
selected to manage sites contaminated by radionuclides, asbestos, poly-
cyclic aromatic hydrocarbons (PAHs), heavy petroleum hydrocarbons,
and mixed wastes, when other cost-effective, excavation-and-
treatment remediation technologies are not available (Meuser, 2013).
It is particularly appropriate for sites with high seasonal groundwater
table, in which vertical barrier walls are constructed below the water
table to prevent further groundwater contamination. The cost of soil en-
capsulation varies with the depth of contamination and the site geology,
but is apparently higher and may double that of surface capping
(National Research Council, 1997).
3.3. Electrokinetic extraction
Electrokinetic extraction is to remove heavy metals from contami-
nated soils by electrical adsorption. When low-density direct current
(DC) electricity is applied via electrodes inserted in the ground, cations
in the solution phase of the contaminated soil migrate to the cathode
while anions migrate to the anode at the attractive force of the
established electrical field. Metal contaminants concentrated at the po-
larized electrodes are subsequently removed by electroplating, (co-)
precipitation, solution pumping, or ion exchange resin complexation
(FRTR, 2012).
Starting from the late 1980s, electrokinetic extraction has been
tested for removing contaminants from soil (Alshawabkeh, 2009). In
general, the technique is effective for decontaminating fine-grained
soils with low hydraulic conductivity and is applicable to both water
210 L. Liu et al. / Science of the Total Environment 633 (2018) 206–219
saturated and unsaturated soils. The success of electrochemical remedi-
ation, however, depends on the specific conditions encountered in the
field, including the types and amount of contaminant present, soil
type, pH, and organic content (Figueroa et al., 2016).
Depending on the overall velocity at which metal ions move in soil,
electrokinetic remediation may take a few days to several years. Migra-
tion of metal ions under a DC electric field is primarily via electroosmo-
sis (movement of water from anode to cathode; even non-ionic species
can be transported along with the electroosmosis-induced water flow),
electromigration (movement of ions to the counterpart electrode), elec-
trophoresis (movement of charged colloidal particles), and diffusion
(transport induced by concentration gradients) (Page and Page, 2002).
The direction, speed, and quantity of heavy metal migration are deter-
mined by the metal species, the mobility of metal ions (by charge den-
sity and the hydrated radius), the aqueous metal concentration, soil
type, soil structure, soil moisture content, and the chemistry of soil solu-
tion. The migration is further influenced by potential sorption, precipi-
tation, and dissolution during the course (Virkutyte et al., 2002). The
migration velocity of a metal ion in an electrical field can be predicted
by the Helmholtz–Smoluchowski equation (Karim, 2015):
εζ ∂δ
uEO ¼
μ ∂x
where uEO is the electroosmotic velocity, ε is the dielectric constant of
soil solution, ζ is the zeta potential of metal ion, μ is the viscosity of
soil solution, and ∂δ/∂x is the electric gradient. Under a unit electric gra-
dient metal ions move in fine-grained soils at rates much higher than
under a unit hydraulic gradient, but the rates are low in the absolute
value (e.g., a few centimeters per day).
Heavy metals are present primarily in adsorbed and precipitate
forms in soils. Electrokinetic extraction of heavy metals involves desorp-
tion/dissolution followed by transport. When the concentration of
heavy metals in the soil solution becomes below the soil sorption capac-
ity, chemical additives are typically needed to help mobilize sorbed
metals. Higher energy consumption is additionally required to facilitate
the transport of low-concentration metal ions. The tested chemical ad-
ditives include ethylene-diamine-tetra-acetic acid (EDTA),
ethylenediaminedisuccinic acid (EDDS), diethylenetriaminepentaacetic
acid (DTPA), nitrilotriacetic acid (NTA), acetic acid (CH3COOH), citric
acid ((HOOC-CH2)2C(OH)(COOH)), and potassium iodide (KI). These
additives (enhancement fluids) demonstrate varied mobilization effi-
ciencies on different metal species in soil (Zhang et al., 2014;
Sivapullaiah et al., 2015; Song et al., 2016). Under the influence of a
DC electric field, water surrounding the electrodes hydrolyzes to form
a low pH, high redox potential area at the anode (H2O − 2e− → 2H+
+ 1/2O2) and a high pH, low redox potential area at the cathode
(2H2O + 2e− → 2OH− + H2), resulting in an oxidizing acid front and
a reducing base front slowly migrating toward the opposite electrode.
Therefore, across the positive and negative electrodes the profiles of
pH, redox potential, electrical conductivity, and solution chemistry are
transient, nonlinear, and non-uniform (Alshawabkeh, 2009). Especially
the change in pH affects the surface charge of soil particles and metal ion
mobility. The generated acidic conditions help mobilize sorbed metal
ions. An acidic environment further prevents formation of metal hy-
droxide and carbonate precipitates. The in-situ acidification, however,
may not be adequate if the soil possesses high buffering capacity. More-
over, the generated base front causes metal ions to precipitate, imped-
ing their final arrival at the cathode (Reddy, 2013). Evidently, artificial
acidification is necessary in electrokinetic soil remediation (Bahemmat
and Farahbakhsh, 2015). Nevertheless, external addition of inorganic
acids (e.g., HNO3) is not environmentally acceptable and can be costly.
Typically, water or chemical solution (e.g., 0.1 M EDTA or acetic acid)
is continuously injected at the anode to maintain optimal remediation
conditions; contaminated water is removed at the cathode by pumping
(Alshawabkeh, 2009). There are minor electrolytic gases (e.g., Cl2 and
H2S) evolved at the electrodes, yet influencing little the electrokinetic
process if allowed to continuously bubble out without attaching to the
electrode surfaces (Virkutyte et al., 2002; Niroumand et al., 2012).
Electrokinetic extraction targets on heavy metals, anionic pollutants,
and polar organics in soil, sediments, sludge, and dredging. Soils con-
taminated with single or combinations of the heavy metals Pb, Cr, Cd,
Co, Ni, Cu, Zn, Hg and Ur have been tested. The technique is most effec-
tive for remediating saturated or partially saturated (e.g., moisture con-
tent 15–25%), low-permeability, low-electrical-conductivity, fine-
textured soils by removing the water-soluble and exchangeable frac-
tions of metal contaminants (Reddy, 2013). Insulating and conductive
materials such as gravels, ore deposits and metallic objects in soil reduce
the effectiveness of electrokinetic extraction. In practice, arrays of inert
electrodes made of ceramic, carbon, graphite, titanium, stainless steel,
or plastic are installed in ceramic wells in the contaminated soil at
1.0–1.5 m spacing, with imposed DC current at 1.0–1.5 V cm−1 or
100–500 kWh m−3 (FRTR, 2012). Pumps and treatment units are
equipped at the cathode to remove and treat the contaminated water.
The system may have multiple anode/cathode pairs or multi-anodes/
single cathode deployed in parallel or in circle (Fig. 3). The size, shape,
and arrangement of the electrodes impact the distribution and strength
of the established electrical field, and consequently the treatment effi-
ð5Þ
ciency (Turer and Genc, 2005). In addition to the optimal electrode con-
figuration, other measures such as elongating the treatment time,
elevating the electric potential gradient, changing the mode of the elec-
tric field (from continuous to periodic), and adding cation/anion ex-
change membranes to the electrodes can be taken to enhance the
metal removal efficiency (Reddy, 2013). The overall cost of electroki-
netic soil remediation varies drastically with the contamination and
field conditions. The U.S. Federal Remediation Technologies Roundtable
(FRTR) estimated in 2012 based on pilot scale trials that the cost aver-
aged at $117 m−3 in the wide range of $26–295 m−3, with $15 m−3
soil for the electricity expenditure (FRTR, 2012).
Currently electrokinetic remediation is still at the developing stage.
There are a number of demonstration and pilot-scale projects
employing the technique, but full-scale applications are rare (Hansen
et al., 2016). One pilot study in the U.S. showed that electrokinetic treat-
ment of a Pb-contaminated site for 30 weeks decreased the soil Pb con-
tent from 4500 mg kg−1 to below 300 mg kg−1 (FRTR, 2012). In another
U.S. pilot study, 22 weeks of electrokinetic extraction did not remove
significant amounts of Cr and Cd from the contaminated soil, likely
due to the abundant presence of NaCl and metal sulfides in the soil
(Geoengineer, 2013).
3.4. Soil flushing
Soil flushing is to in-situ remove contaminants from soil by passing
an extraction fluid through the soil. The extraction fluid is then recov-
ered, reused, and eventually treated and disposed of. The technique is
applicable to homogenous, coarse-textured soils with high permeability
(CLU-IN, 2017).
In soil flushing, the extraction fluid is typically injected or infiltrated
into the soil. To effectively extract heavy metals from soil, the extraction
fluid has to be designed with particular formula. Various chelating and
acidic solutions have been tested, indicating EDTA is the most effective
agent. Using batch experiments, Wuana et al. (2010) found that at
0.01 M and 1:25 soil/solution ratio, EDTA excelled over citric acid and
tartaric acid in extracting heavy metals from a fortified loamy sand
(pH 6.1, organic matter (OM) content 8.7%). The solutions demon-
strated mobilization efficiencies varying with the metal species in co-
existence: Cu N Ni N Zn N Cd N Pb. Sequential extraction analysis showed
that EDTA mobilized all non-residual fractions of metals, while citric
acid and tartaric acid was not effective for mobilizing organic matter-
bound and residual metal fractions. Reddy et al. (2011) reported that
0.2 M EDTA was the most efficient extraction fluid relative to water, sur-
factants, and cyclodextrin, flushing out 25–75% of the Cu, Zn, and Pb in
 L. Liu et al. / Science of the Total Environment 633 (2018) 206–219
Fig. 3. Exemplified electrode arrangements in electrokinetic soil remediation.
industry-contaminated loam sand (pH 7.0, OM 11.1%) columns. In com-
parison, the biodegradable chelating agent chitosan (pH 3.3) performed
even better than EDTA (pH 3.1) at 2.0 g L−1 to extract Cu and Ni from a
pH 5.0 clay loam (Jiang et al., 2011). The removal efficiency was the
highest for Pb (75%) and the lowest for Cu (25%).
Soil flushing is technically simple, yet it might be challenging and
costly to install solution collection wells or subsurface drains. If the
water table is not deep, groundwater is commonly extracted to recover
the flushing elutriate. The metal extraction efficiency is generally low
for soils with high cation exchange capacity (CEC), high buffering capac-
ity, and high OM and clay contents. Research demonstrates that the
technique is potentially effective for removing Pb from acidic sandy
soils, Cd from low CEC, low clay, and moderately acidic soils, and Cr
(VI) and As from low iron oxides, low clay, and high pH permeable
soils (Shammas, 2009). The applicability of the technique is further in-
fluenced by the soil heterogeneity and layer arrangement. The soil
flushing treatment cost was estimated in the range of $20–104 m−3
soil, increasing as the soil permeability decreases and the water table
deepens (Iturbe et al., 2004; FRTR, 2012). The technique has been prac-
ticed more commonly to remove organic pollutants by flushing
211
surfactant solutions through contaminated sites. A list of the in-situ
soil flushing projects in the North America can be found in USEPA
(2012); the main goal of these soil remediation projects was to remove
organic contaminants and at three of the sites (Lipari Landfill, NJ;
Sprague Road Groundwater Plume, TX; and United Chrome Products,
OR), also the heavy metals Cr, Hg, and Pb.
3.5. Chemical immobilization
In-situ chemical immobilization, sometimes termed as in-situ solid-
ification/stabilization (S/S), is to trap or immobilize pollutants in the
contaminated soil by introducing chemical agents into the original me-
dium to solidify the soil or convert the mobile pollutant fractions
(i.e., soluble and exchangeable forms) into precipitates and/or strongly
sorbed moiety. Chemical immobilization does not remove or extract
contaminants from soil. Instead, the mobility/solubility of heavy metals
and their concentrations in soil pore water are drastically decreased,
minimizing their potential transport to plants, microorganisms, and
water (Tajudin et al., 2016).
212 L. Liu et al. / Science of the Total Environment 633 (2018) 206–219
Solidification is a soil remediation technique feasible to both in-situ
and ex-situ practices. In in-situ solidification, a binding agent, com-
monly cement, asphalt, fly ash, and/or clay, is added to the contami-
nated soil followed by auger spin mixing to transform the soil into a
solid block. If pollutants are deep in the soil, binding slurries can be
injected into subsurface and mixed with the waste using a crane
equipped with an injector head and a large mixer. The solid block is im-
permeable to water and therefore, the entrapped pollutants are not
leachable (Tajudin et al., 2016). Over the long term, however, the
trapped contaminants may become mobile again if the integrity of the
solid block is destructed by natural weathering and uncontrolled me-
chanical disturbance (FRTR, 2012). Furthermore, the solidified site
may be limited in future uses.
Solidification is an established technology that has been practiced in
the U.S. since the 1980s. It has been used in-situ to treat N60 heavy
metal-contaminated sites (USEPA, 2016a). The average operational
time of a solidification project is 1.1 months, much shorter than other
treatment techniques. However, solidification does not destroy or re-
move the contaminants. The solidified areas may inhibit future more
comprehensive restoration. Therefore, solidification is the last option
for soil remediation, only when other methods become impractical.
The applicability of solidification is chiefly influenced by the availability
and the transport cost of the binding agent, as the operation requires a
huge volume of binding agent. The overall cost of solidification is site
specific and can be as high as $1500 m−3 (averagely $520 m−3 in the
U.S. in 2012), covering material, drilling, and mixing expenditures
(FRTR, 2012).
Stabilization (also termed “in-situ fixation”) immobilize contami-
nants but does not solidify the soil. In stabilization, precipitation
reagents/stabilizing chemicals other than binding agents are incorpo-
rated into the contaminated soil to induce physiochemical interactions
between the stabilizing reagents and heavy metals to reduce their mo-
bility (Tajudin et al., 2016). An array of materials have been evaluated
for the purpose, including carbonates (e.g., lime), phosphates
(e.g., bone meal, ammonium phosphate, apatite, and hydroxyapatite),
alkaline agents (e.g., fly ash, and calcium hydroxide), clay and iron-
containing minerals (e.g., bauxite, red mud, goethite, greensand, molec-
ular sieves, palygorskite, silica gel, vermiculite, and zeolites), and or-
ganic matter (e.g., chitosan, starch xanthate, peat, compost, manure,
activated carbon, and biochar) (Basta and McGowen, 2004; Gray et al.,
2006; Kumpiene et al., 2008; Farrell and Jones, 2010; He et al., 2013;
Bolan et al., 2014; Ali et al., 2017; Seshadri et al., 2017). In general,
these soil amendments reduce the bioavailability and leaching potential
of heavy metals by inducing a variety of physiochemical processes in-
cluding precipitation, surface precipitation, co-precipitation, complexa-
tion, and surface adsorption. The specific agents, however, were
selectively effective in immobilizing different metal species through
particular mechanisms. For example, Castaldi et al. (2005) reported
that relative to vegetable waste/sewage sludge, compost applied at
100 g kg−1 and calcium hydroxide spiked at 0.5 g kg−1, zeolite
(b0.02 mm) applied at 100 g kg−1 was the most effective treatment at
reducing Cd uptake by lupin plants from a contaminated sandy loam
(pH 4.4); whereas the former treatments were more efficient at reduc-
ing Pb and Zn uptake. Phosphate-based treatments could effectively re-
duce the bioavailability and leachability of Pb in contaminated soils for
N10 years by forming the thermochemical stable mineral pyromor-
phites (Pb5(PO4)3(Cl,F,OH)) (Tang et al., 2009).
Phosphates- and carbonates-containing materials are the most prom-
ising agents for efficiently stabilizing heavy metals in contaminated soils.
These two types of materials are widely available at low costs and are reg-
ularly applied to farmland as a fertilizer or acidity conditioner. In-situ
chemical stabilization is implemented by mixing treatment agents with
the contaminated soil at appropriate rates and timing pre-determined
through previous field experiments. If the treatment agents are water sol-
uble, they can be sprayed in aqueous solutions over the site to allow free
soil infiltration. Insoluble treatment materials are generally broadcast
over the site surface followed by plow incorporation. Chemicals in fine
powders can also be injected in suspension into soil. The remediated
soil can be used to grow crops, as uptake of the metal contaminants by
plants has been minimized to below the risky level.
Chemical stabilization serves an effective, affordable method for
temporarily “fixing” heavy metals in less contaminated farmland soils
(e.g., Igeo b 3). Since heavy metals are not removed, the chemical stabi-
lization effect needs to be regularly monitored and evaluated. “Well-
mixing” of stabilizing chemicals with contaminated soils is crucial to
achieve satisfactory soil remediation effects. As well-mixing cannot be
secured in large-scale field practices, the USEPA has not adopted this
technique in superfund site cleaning.
3.6. Phytoremediation
Phytoremediation is to grow plants in contaminated soils, re-
lying on green plants to remove heavy metals (phytoextraction
and phytovolatilization) or stabilize them into harmless status
(phytoimmobilization and phytostabilization) (Mahmood et al.,
2015). This plant-based technology is operationally simple, aes-
thetically preferable, economically viable, and widely accepted.
Unlike physical and chemical treatments that irreversibly alter
soil properties, phytoremediation generally improves the physi-
cal, chemical, and biological quality of contaminated soils.
Since the 1970s, plants have been tested and used in treating heavy
metal contamination in soils and wetlands. Governmental and commer-
cial adoption of the technology for contaminated site cleaning up
started in 1980s. Over the years the technology has been intensively ex-
plored and rapidly developed. There are comprehensive reviews on the
principles and application feasibility of phytoremediation of metal-
contaminated soils (Van Nevel et al., 2007; Vamerali et al., 2009; Pinto
et al., 2015; Sarwar et al., 2017). In general, phytoremediation is classi-
fied into two broad techniques: Phytoextraction, through which heavy
metals are absorbed by plants from soil and accumulated in shoots
and leaves and phytostabilization, through which heavy metals are
immobilized in soil by plant roots.
In phytoextraction, heavy metals are removed from soil by
hyperaccumulators, macrophytes capable of concentrating N10 g kg−1
(1%) Mn or Zn, N1 g kg−1 (0.1%) As, Co, Cr, Cu, Ni, Pb, Sb, Se or Tl, and
N0.1 g kg−1 (0.01%) Cd in the aerial organs from soils without suffering
phytotoxic damage (Verbruggen et al., 2009). The metal(loid)s As, Hg,
and Se may be discharged by accumulator plants (e.g., Astragalus
racemosus) in gaseous species into the atmosphere. The process is
termed phytovolatilization. So far 721 species of plants have been iden-
tified as metal hyperacculators (Reeves et al., 2017). These plants toler-
ate high concentrations of heavy metals, grow well in metalliferous
soils, and possess distinct capabilities to efficiently absorb particular
metal ions from soil, translocate the metals from roots to shoots, and de-
toxify and sequester the metals in leaf tissues. For example, Sebertia
acuminate is a Ni hyperaccumulator tree native to New Caledonia, able
to accumulate Ni in its latex up to 26% dry mass (Jaffré et al., 2013).
Tobacco (Nicotiana tabacum L.) is a Cd hyperaccumulator.
Arabidopsis halleri, Thlaspi goesingense, and Sedum alfredii are Zn
hyperaccumulators. A. halleri, S. alfredii, Thlaspi caerulescens, and Thymus
praecox are both Cd and Zn hyperaccumulators (Rascio and Navari-Izzo,
2011; Y. Yang et al., 2017).
Successful phytoextraction is evaluated as cleaning up of contami-
nated soils to a level that meets environmental regulations at a cost
lower than using other optional techniques or the cost of inaction. To es-
timate the time required for successful phytoextraction, the following
equations are commonly used (Chandra et al., 2017):
M ¼ Adρb ΔC ð6Þ
where M is the amount of metal to be removed (mg), A is the area of the
contaminated site (m2), d is the soil depth of contamination (m), ρb is
 L. Liu et al. / Science of the Total Environment 633 (2018) 206–219
soil bulk density (kg m−3), and ΔC is the expected concentration de-
crease (mg kg−1).
M the ecological risks of contaminated sites, especially for the areas lacking
t¼
APB
where t is time (yr), P is metal concentration in plant tissue (mg kg−1),
and B is annual plant biomass production (kg m−2).
Research and development have not overcome the major technical
challenges that prevent commercial utilization of heavy metal
hyperaccumulators in soil remediation. Field soil is spatially heteroge-
neous and plant production is temporally variable. The identified
hyperaccumulators are typically metal-selective, limited to their native
habitats, and have shallow root system, slow growth rate, and low
biomass yield. The knowledge of cultivating the hyperaccumulators is
generally lacking (Chaney and Baklanov, 2017). Furthermore,
phytoaccumulation of heavy metals is correlated with the available con-
centration in the soil. With successive croppings, heavy metals demon-
strate linear or even logarithmic decreases in bioavailable concentration
in soil, and so in the phytoextracted amount (Van Nevel et al., 2007).
The plant biomass yield may also decrease over time due to nutrient de-
pletion or pest infection. All these factors indicate that phytoextraction
is an inefficient, impractical technique. Even under theoretical condi-
tions, to reduce 1 mg kg−1 Cd from a contaminated soil using
hyperaccumulators requires 15 years (Li et al., 2012). The time is clearly
unacceptable in remediation practices (expected b 10 yr). To accelerate
phytoextraction, many approaches have been proposed, including che-
lating agent enhancement and plant genetic manipulation. Neverthe-
less, metal chelates (e.g., with EDTA and DTPA) are resistant to
biodegradation and may be leached to deep soil and groundwater. Arti-
ficial chelate assistance should not be considered in phytoextraction
(Evangelou et al., 2007). Genetically engineered hyperaccumulators
may demand tremendous efforts and time to develop (Fasani et al.,
2017). Overall, the current phytoextraction technique needs significant
improvement to achieve practical feasibility. To be more realistic,
phytoextraction may shift the remediation goal from reducing total
soil metal concentrations to minimizing the labile, bioavailable metal
pool (e.g., water soluble and exchangeable forms). In this case, the re-
plenishment kinetics of the bioavailable pool over a long term have to
be assessed. In recent years, fast-growing plants such as Indian mustard
(Brassica juncea), shrub willow (Salix spp.), and hybrid poplar (Populus
spp.) have been explored for heavy metal phytoextraction (Mleczek
et al., 2010; Pinto et al., 2015). These plants, though not metal
hyperaccumulators, have significantly higher aerial biomass yield and
demonstrate overall comparable metal extraction capability. More im-
portant, the produced biomass can be harvested as biofuel feedstocks.
To minimize potential ecological risks, phytoextraction areas should
be fenced to avoid entrance of heavy metals into the food chain through
wildlife consumption of the hyperaccumulator plants. Phytoextraction
biomass should be combusted after harvesting and the ashes be proc-
essed for recovering the metals or simply landfilled. Uses as animal
feed or human food are prohibited (Ali et al., 2013; Fedje et al., 2015).
If trees are used for metal extraction, the roots are required to be exca-
vated and disposed of at the end of the process (Pinto et al., 2015).
An alternative technique is phytostabilization (also termed as
phytoimmobilization), through which heavy metals are immobilized
in soil by plants via root absorption, root adsorption, exudate complex-
ation/precipitation, rhizospheric reduction, and soil stabilization.
Phytostabilization plants are tolerant to heavy metals, have high root
biomass production, and barely translocate absorbed heavy metals
from roots to aboveground tissues. The plants Sibth (Agrostis tenuis),
Red Fescue (Festuca rubra L.), wiregrass (Gentiana pennelliana),
thatching grass (Hyparrhenia hirta), Syrian bean-caper (Zygophyllum
fabago), and hippo grass (Vossia cuspidate) are excellent candidates for
phytostabilizing soils contaminated by Pb, Zn, Cr, and Cu (Yoon et al.,
2006; Galal et al., 2017; Radziemska et al., 2017). Phytostabilization
213
has proved effective for reducing the mobility of Pb, As, Cd, Cr, Cu, and
Zn in contaminated soils and stabilizing disturbed metalliferous sites
via efficient revegetation. It serves as an interim strategy for mitigating
ð7Þ
natural vegetation due to high metal concentrations. The technique,
however, is not applicable to extremely contaminated sites in which
plant growth and survival is barely possible. Frequently in practice,
the technique is employed in combination with chemical stabilization
to restore abandoned mining sites. Chemical amendments (e.g., lime,
phosphates, compost) added to soil reduce the bioavailability and
biotoxicity of the inherent heavy metals, providing a better environ-
ment for phytostabilization plants to establish (Chaney and Baklanov,
2017).
Phytoremediation is particularly suitable for treating large, diffusely,
and superficially polluted areas with fine-textured, high organic matter
content soils (Chaney and Baklanov, 2017). Currently the technique is
still at its fledging stage. Further research and development is warranted
to understand the soil–metal–chelate–plant interactions in the rhizo-
sphere and the mechanisms of plants absorbing, translocating, and ac-
cumulating heavy metals. The success of phytoremediation is
determined by a number of environmental factors including soil proper-
ties (e.g., pH, buffering capacity, texture, clay minerals, organic matter
content, fertility, and cation exchange capacity), contaminant
(e.g., metal species, content, and speciation), chemical amendments ap-
plied (e.g., type, rate, and application method), plant (species, growth
stage), climate (e.g., precipitation, temperature), and geography
(e.g., slope and aspect) (Vamerali et al., 2009; Chaney and Baklanov,
2017). Globally there have been over 100 reported soil heavy metal re-
mediation pilot/field projects using the phytoremediation technology
(USEPA, 2016b). For instance, the 317/319 Area Soil Remediation
Project in Lemont, IL, USA was started in 1999 with an original budget
of $1.2 million, in which 1.6 ha of land were planted with hybrid
poplar, willows, and Eastern Gamagrass to remove As, Pb, Zn, and or-
ganic contaminants by phytoextraction, phytostabilization, and
phytodegradation.
3.7. Bioremediation
Bioremediation is to decontaminate soil using microorganisms in-
stead of plants. The technique is more commonly applied to detoxify or-
ganic pollutants in soil and groundwater (FRTR, 2012). Microorganisms
can also detoxify metals by valence transformation (e.g., Cr(VI) to Cr
(III), SeO2−
4 to Se), biosorption (to cell surface), extracellular chemical
precipitation (e.g., by S2− from sulfur-reducing bacteria), and volatiliza-
tion (e.g. dimethylselenide, trimethylarsine, and Hg vapor) (Garbisu
and Alkorta, 2003). In cleaning up heavy metal-contaminated soils, bio-
remediation is typically employed together with other techniques such
as soil flushing and phytoextraction to promote solubilization of heavy
metals prior to extraction. For example, Diels et al. (1999) found that
Alcaligenes eutrophus produced siderophores that could form complexes
with metals; addition of the bacteria significantly improved water ex-
traction of Cd, Zn, and Pb from a sandy soil. The presence of the iron-
reducing bacterium Desulfuromonas palmitatis greatly enhanced the re-
lease of As in a calcareous soil (Vaxevanidou et al., 2008). Many bacteria
(e.g., Bacillus subtilis, Torulopsis bombicola) could produce biosurfactants
such as surfactin, rhamnolipids, sophorolipids, aescin, and saponin to
solubilize metals in soils (Acikel, 2011). Certain rhizosphere microbes
promote the tolerance of plants to heavy metals and enhance their
growth in contaminated soils (Mishra et al., 2017). In-situ soil bioreme-
diation to remove Hg via microbial enhanced volatilization is feasible, in
which bacteria transform methyl mercury into Hg(II) and reduce it to
Hg(0) (Dash and Das, 2015). Genetically engineered microorganisms
capable of hyperaccumulating heavy metals have been developed
(Ruta et al., 2017). A list of the tested bacteria, algae, yeasts, and fungi
potentially useful to soil heavy metal remediation can be found in
Yadav et al. (2017a). The concept “nanobioremediation” has just
214 L. Liu et al. / Science of the Total Environment 633 (2018) 206–219
emerged, referring to the techniques for removing heavy metals and or-
ganic contaminants from wastewater and soil using nanoparticles
(e.g., nanoiron, nanosillicates, and nanousnic acid) generated by partic-
ular plants, bacterial, algae, and fungi and bacteria under controlled con-
ditions (Yadav et al., 2017b).
In practice, the contaminated soil is inoculated with selected micro-
organisms by spray irrigation or infiltration galleries. Injection wells can
be used if the contaminants are deep in soil. Nutrients, oxygen, and
other amendments are usually co-applied to stimulate microbial activ-
ity and enhance the bioremediation process. The technique has been
utilized to treat organic pollutants (e.g., PAHs, non-halogenated volatile
organic compounds, and petroleum) in soils and aquifers (FRTR, 2012).
Up to date no heavy metal-contaminated soil remediation projects
using bioremediation have ever been reported.
4. Ex-situ remediation techniques
Ex-situ soil remediation involves excavation of soil from the contam-
inated site, transport of the contaminated soil to an off-site treatment
facility, and disposal of the treated soil at permitted locations. Relative
to in-situ remediation, ex-situ treatment requires additional costs for
soil excavation, transport, disposal, and site refilling, but the treatment
can be controlled and accelerated, achieving better results in shorter
time.
Fig. 4. The cross-sectional structure of a secure landfill (Weil and Brady, 2017).
4.1. Landfilling
Landfilling, or “dig and haul,” is the simplest soil remediation tech-
nique through which the contaminated soil is removed from its original
site and transported to a secure landfill for disposal. A secure landfill is
an engineered structure with impermeable liners, leachate drains, and
dike enclosures (Fig. 4). The double liners (a plastic layer and a clay
layer) and the leachate collection and monitoring system are integral
components of the facility to prevent potential leakage and groundwa-
ter contamination. The top cap/liner system is to minimize rainfall infil-
tration and keeps surface runoff away from the fill. Design, construction,
and use of a secure landfill are subject to governmental laws and
regulations.
Landfilling is a well-established technique for cleaning up hazardous
waste sites. It was the most common waste disposal method used in the
U.S. before 1984. Depending on the distance between the contaminated
site and the secure landfill, the overall U.S. cost of soil landfilling ranges
from $300 ton−1 to $500 ton−1 (FRTR, 2012). To reduce the disposal
cost, landfilling should be considered only for soils excavated from the
high-contamination areas (“hotspots”).
4.2. Soil washing
Soil washing is a mixed physical and chemical process to remove
heavy metals from contaminated soil by washing the soil ex-situ with
 L. Liu et al. / Science of the Total Environment 633 (2018) 206–219
Fig. 5. A typical soil washing procedure for removing heavy metal contaminants.
specially-formulated solutions. In operation, soil excavated from a con-
tamination site is first crushed and screened to remove coarse materials
such as plastic residues, woods, and stones. Magnetic materials in the
soil are removed using magnets. The screened soil (e.g., b5 mm) is thor-
oughly mixed with a washing solution by sonication or mechanical ag-
itation and then sieved or hydrocycloned to separate coarse sand and
gravels (N0.05 mm) from the fine silt and clay fraction (b0.05 mm).
The coarse fraction is less contaminated and is typically returned to
the original site after water rinsing. The silt and clay particles
suspending in the washing solution are recovered by settling, rinsed
with water, and returned to the original site. The waste washing solu-
tion and rinsing water are reused, recycled, or conveyed to a wastewater
treatment facility for disposal. The wastewater treatment sludge is fur-
ther treated by solidification/stabilization prior to landfilling (Fig. 5).
Soil washing relies on washing solutions to mobilize heavy metals by
altering soil acidity, solution ionic strength, redox potential, or complex-
ation. An ideal washing solution should dramatically improve the solu-
bility and mobility of heavy metal contaminants yet interact weakly
with soil constituents and should be nontoxic and biodegradable. An
array of chemicals have been tested to formulate effective washing solu-
tions: hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid,
fluorosilicic acid, formic acid, acetic acid, oxalic acid, citric acid, tartaric
acid, polyglutamic acid, EDTA, DTPA, NTA, EDDS, carbonate/bicarbonate,
sodium hydroxide, calcium chloride, ferric chloride, ammonium chlo-
ride, ammonium acetate, dithionite, isopropyl alcohol, subcritical
water, and etc. (Moutsatsou et al., 2006; Fedje et al., 2013; Zhu et al.,
2015; Alghanmi et al., 2015; Bilgin and Tulun, 2016; Z. Yang et al.,
2017). The metal extraction efficiency of a washing solution also varied
with the metal species and further influenced by the soil pH, texture,
and organic matter content (FRTR, 2012). Overall, hydrochloric acid,
EDTA, and subcritical water demonstrated the highest washing effi-
ciency over a wide range of heavy metals and soils. The optimal washing
conditions including the effective concentration of the washing solution
(e.g., 0.1–1.0 M HCl or 0.05–0.2 M EDTA), the soil/solution ratio
(e.g., 20–50 g L−1), and agitation time (e.g., 0.5–5 h) are case-specific
and have to be determined by small-scale trials. If a single washing so-
lution cannot be formulated to reliably remove complex contaminants
from a soil, sequential washing with different solutions can be practiced.
Soil washing can utilize the equipment (e.g., trommels, screens,
hydrocyclones, and centrifuges) developed for mineral processing. To
reduce the soil transportation costs, the U.S. and some European coun-
tries such as Sweden developed mobile soil washing systems in the
1980s and employed the device in field sites to clean up contaminated
soils (FRTR, 2012). Pilot- and field-scale soil washing projects
215
(0.2–10 ton/h treatment capacity) have been carried out in the U.S.,
Canada, Australia, Korea, and the European countries since 1995
(USEPA, 2013). Soil washing is of short-duration and can be cost-
effective. In 2010 the U.S. cost ranged from $70 m−3 soil (at large
scale) to $183 m−3 soil (at small scale) (FRTR, 2012).
4.3. Solidification
In ex-situ soil solidification, metal-contaminated soil is removed
from site, transported to a treatment facility, screened to exclude coarse
materials (e.g., N5 cm), and mixed with a binding substance in an ex-
truder. The binding substance disperses through the soil, forming a
water-proof solid entity that encases the contaminants. The technology
is sometimes termed “micro encapsulation.” If a stabilizing agent is used
instead of a binding substance to immobilize contaminants through
chemical reactions, the method is referred to as ex-situ stabilization
(FRTR, 2012).
The binding materials for contaminant encapsulation include mol-
ten bitumen, emulsified asphalt, modified sulfur cement (a thermoplas-
tic material melting at 127–149 °C), polyethylene, pozzolan cement (fly
ash, kiln dust, pumice, or blast furnace slag), and Portland cement. If sol-
uble phosphate/lime is used, the material immobilizes the heavy metals
in soil instead of solidifying the soil itself. Another option is to directly
encapsulate contaminated soils in polyethylene or bitumen wraps to
form solid waste blocks that can be disposed of in a nonhazardous land-
fill (FRTR, 2012).
Ex-situ solidification is a well-established soil remediation technol-
ogy that has been implemented in N200 U.S. soil remediation projects
at a treatment cost ranging from $120 to $220 m−3 soil (USEPA,
2016a). It is timely efficient but relatively expensive. At scale-up opera-
tions, up to 1000 kg/h of waste processing rate can be achieved. A nota-
ble drawback of the technology is that solidification significantly
increases the waste volume, sometimes doubling the original volume
of to-be-treated soil. The resultant material from ex-situ solidification
requires additional disposal. Under the U.S. Comprehensive Environ-
mental Response, Compensation, and Liability Act of 1980 (CERCLA),
the material can be placed on site with regular inspection.
4.4. Vitrification
Vitrification is a thermal remediation technique that uses heat to
transform contaminated soil into glasslike solids. The technology has
been developed and tested since 1980. In practice, intensive energy is
applied to contaminated soil to form a high temperature zone (N1500
216 L. Liu et al. / Science of the Total Environment 633 (2018) 206–219
°C). The soil in the zone is then melted into molten “lava” and becomes
glasslike material upon cooling (Meuser, 2013). The heavy metals are
encapsulated in the glassy matrix while any organic contaminants are
destroyed. The resultant vitrification structure is strong, durable, chem-
ically inert, and resistant to leaching. Dependent on the energy source,
vitrification has three main types: electrical vitrification (high voltage
electricity is imposed to graphite electrodes inserted in the contamina-
tion site at pre-determined spacing to generate heat), thermal vitrifica-
tion (an external heat source such as microwave radiation or natural gas
is used to heat a rotary retort containing contaminated soil), and plasma
vitrification (high temperature is achieved via electrical discharge-
induced gas plasma) (Khan et al., 2004). Overall, vitrification is destruc-
tive, the processed soil no longer able to support agricultural uses.
Though both in-situ and ex-situ applicable, the technique has been ap-
plied more often in-situ (e.g., electrical and plasma vitrifications) than
ex-situ (e.g., thermal and plasma vitrifications). Ex-situ vitrification is
easier to control, but harmful exposure to dust and other fugitive emis-
sions can be great, especially when the contaminants are radioactive or
dispersive (Bradl and Xenidis, 2005).
In ex-situ vitrification, the contaminated soil is continuously fed into
a refractory-lined rotating container in a furnace equipped with plasma
torches, electric arcs, natural gas burners, or microwave radiation emit-
ters. Examples of ex-situ vitrification reactors include Horsehead Re-
sources flame reactor, Babcock and Wilcox cyclone furnace, and
Vortec Corporation combustion and melting system. At temperature
N1100 °C, the processed soil fuses into molten slag and flows out from
the furnace bottom opening to form a glassy solid. Any gaseous effluents
from the furnace are captured and further treated (Bradl and Xenidis,
2005).
Vitrification is not applicable to soils with high organic matter con-
tent (e.g., 7%) and high moisture content (e.g., 10%). Nor is it applicable
to soils heavily contaminated by volatile or flammable organics. Ade-
quate presence (2–5%) of monovalent alkaline cations (Na+ and K+)
in the soil is necessary. Though the glassy material from soil vitrification
is durable and stable, de-vitrification does occur from slow weathering
during field storage of the waste. Over a long period of time
(e.g., thousands of years), dissolution and subsequent leaching of chem-
ical elements in silicate glasses ranges 0.1–25% of their initial contents,
dependent on the elemental species (Meuser, 2013).
Vitrification is a proven and commercially available technology. The
USEPA evaluated the technology as the “best demonstrated available
technology” for disposal of radioactive and heavy metal wastes
(Meegoda et al., 2003). In-situ vitrification is typically limited to a
small area up to 12 m (length) × 12 m (width) × 6 m (depth). To pro-
mote field operations, the U.S. Department of Energy has developed a
transportable vitrification system consisting of an electrical distribution
unit, off-gas treatment unit, and process-control components. To date,
there are four in-situ vitrification projects in the U.S. at both pilot and
full scales. For ex-situ vitrification, existing metal-processing apparatus
Fig. 6. A phase chart of typical soil remediation projects showing feasible technology selection through treatability studies.
can serve the purpose (CPEO, 2016). The Handford Vit Plant, for exam-
ple, is a commercial facility in Handford, WA to treat radioactive waste
using ex-situ vitrification. The U.S. cost of vitrification has been esti-
mated at $330–425 per ton of soil treated, with ex-situ operation at
the lower end (FRTR, 2012).
5. Selection of best soil remediation techniques
The currently available remediation techniques as discussed above
for heavy metal-contaminated soil demonstrate different advantages
and disadvantages. The applicability of these individual techniques in
a specific soil remediation project is determined primarily by the con-
tamination site geography, contamination characteristics, the remedia-
tion goal, cost-effectiveness, financial budget, implementation
readiness, time requirement, and public acceptability (USEPA, 2017).
All these factors have to be considered and comprehensively evaluated
to select the best techniques for a specific soil remediation project. Inte-
grated uses of two or more of the available soil remediation techniques
at different stages and locations of a project may be necessary. For ex-
ample, chemical stabilization can be practiced at severely contaminated
sites to reduce the bioavaility and toxicity of high-concentration
heavy metals in soil and allow plants to establish, followed by
phytoremediation to gradually restore the ecosystem functions of the
contaminated soil.
As illustrated in Fig. 6, a successful, well-managed soil remediation
project involves a number of essential steps: 1) technology
prescreening and treatability study scoping, 2) remedial investigation
(RI) of the contaminated site, 3) feasibility study (FS) of prescreened re-
mediation techniques, 4) determination of best remediation methods
(ROD), 5) design and implementation of remediation practices (RD/
RA), and 6) evaluation of remediation performance (AEIC, 2018).
Prescreening for feasible soil remediation techniques should be con-
ducted at the very beginning of a project by searching the technology
literature and consulting with experts. The feasibility of a prescreened
remediation technique is then evaluated through treatability studies
after the contaminated site is carefully characterized for geographic
and contamination information (USEPA, 2017). A treatability study
has typically three sequential tiers: 1) screening tests at bench/small
scales, 2) selection tests at small/pilot scales, and 3) treatability tests
at pilot/full scales (Leigh, 2012). Bench/small scale screening tests are
conducted under conditions similar to those in the field operation sce-
nario to initially assess the feasibility of the prescreened soil remedia-
tion techniques. Feasibility is measured by how well a remediation
technique achieves the performance goals that are pre-set based on
the cleanup/remediation criteria. If all prescreened techniques are
rejected in the screening tests, the performance goals and even the re-
mediation criteria need to be adjusted. Remedial alternatives are then
identified and tested. A technology passing the screening tests needs
to be further evaluated by selection tests to assure its performance
 L. Liu et al. / Science of the Total Environment 633 (2018) 206–219 217

Table 2
Mechanisms, advantages, disadvantages, and application status of the available remediation techniques for heavy metal-contaminated soils.

Remediation technique Applicability Working mechanisms Advantages Disadvantages Application status

Surface capping In-situ, high Physical containment Easy to install, low in cost, high Limited to small areas and certain Widely practiced
contamination security geographic locations, loss of land
cropping function
Encapsulation In-situ, high Physical containment and High security, fast to install Limited to small, shallow Remediation of
contamination isolation contamination areas, high cost, radionuclide and
loss of land cropping function mixed waste
contamination
Electrokinetics In-situ, fine soil, Contaminant removal by Contaminant removal, minimal Time consuming, low efficiency, Under development
moderate to high electricity soil disturbance best for fine-textured soils with with pilot
contamination low permeability demonstrations
Soil flushing In-situ, coarse soil, Contaminant removal by Contaminant removal, minimal Best for coarse-textured soils with Limited number of
moderate to high chemical solutions soil disturbance, low cost, simple high permeability, potential applications to mixed
contamination to install groundwater pollution waste remediation
Immobilization/stabilization In-situ, high Contaminant deactivation Affordable, easy to implement, Metal-specific, temporary Temporary
contamination by physiochemical immediate effects effectiveness, contaminants remediation, not
transformation remaining in soil officially approved
Phytoremediation In-situ, low to Contaminant removal High public acceptance, low cost, Limited to shallow contamination, Under development
moderate and/or stabilization by easy to implement, suitable for metal-specific, time-consuming, with pilot
contamination plants large, low contamination areas low efficiency demonstrations
Bioremediation In-situ, low to Contaminant Low cost, simple to implement, Low efficiency, merely Not practiced for
moderate transformation by minimal soil disturbance supplemental to principal heavy metal
contamination microorganisms remediation techniques remediation
Vitrification In-situ and Contaminant deactivation High efficiency High cost, limited to small soil Regularly practiced
ex-situ, high by thermally vitrifying area/volume, treated land and soil
contamination soil losing environmental functions
Solidification In-situ and Contaminant deactivation Fast to implement, high efficiency High cost, treated land and soil Regularly practiced
ex-situ, high by physically solidifying losing environmental functions
contamination soil
Landfilling Ex-situ, high Physical containment and Immediate cleanup, high security High cost, requiring additional Widely practiced
contamination isolation land for waste storage
Soil washing Ex-situ, moderate Contaminant removal by High efficiency, fast effects Extreme soil disturbance Regularly practiced
to high mechanical separation
contamination and chemical extraction

and to estimate the costs associated with full-scale implementation. Se-
lection tests are normally performed with pilot or full-scale equipment
to confirm the feasibility of the screened remediation technique and in-
vestigate the optimal, equipment-specific operational parameters
(Shammas, 2016). Prior to intensive implementation, the feasibility of
the selected remediation technique is further validated by treatability
tests, which are mostly performed by remediation contractors and tech-
nology vendors in the field with pilot- or full-scale equipment. The
treatability tests also generate detailed design, cost, and performance
data, helping select the best contractor and remediation process. A
treatability study may not be necessary when sufficient data are avail-
able in the literature and treatability databases to perform the feasibility
assessment of a prescreen remediation technique (Shammas, 2016).
The treatability study reports of many soil remediation projects can be
found in the literature (PNNL, 2006; Gupta et al., 2010; Lamichhane
et al., 2012; Kalb et al., 2012).
6. Summary and conclusions
Unintentional discharge of heavy metals to the environment
through various human activities has caused different levels of soil con-
tamination at globally N5 million sites stretching to 20 million ha of
land. An array of remediation techniques have been developed to re-
duce the hazardous effects and restore the ecosystem functions of
the contaminated soils. These techniques involve physical, chemical,
biological, electrical, and/or thermal processes to rectify soil contam-
ination by containing (e.g., surface capping, encapsulation, and land
filling), immobilizing (e.g., solidification, stabilization, and vitrifica-
tion), and extracting (e.g., phytoextraction, electrokinetics, soil
flushing, and soil washing) the heavy metal contaminants. Advan-
tages, disadvantages, and application status of the techniques are
summarized in Table 2. Most of the techniques are in-situ applicable,
while landfilling and soil washing are ex-situ based, with soil
treatment requiring excavation and transportation. Solidification
and vitrification can be implemented both in-situ and ex-situ. In gen-
eral, the available and emerging soil remediation techniques possess
different “correction” mechanisms and demonstrate specific benefits
and drawbacks in terms of applicability, performance, cost competi-
tiveness, implementation duration, and site/soil disturbance. Over-
all, in-situ soil remediation is more cost-competitive than ex-situ
treatment, and removal/extraction of contaminants from soil is pre-
ferred over containment/solidification of pollutants inside soil, as the
cleaned soil can be returned to agricultural uses. Nevertheless, soil
remediation through contaminant removal/extraction takes much
longer time than soil containment and solidification/vitrification.
Among the remediation methods, chemical stabilization is an effi-
cient, affordable choice for temporary remediation of low to moder-
ately contaminated soils; surface capping, encapsulation, and landfill
are feasible to rectify small, high-contamination sites; solidification
and vitrification are the last options only when other remediation
techniques are not achievable due to time, budget, and geographic
constraints. Phytoremediation, especially phytoextraction, is a
promising method for remediating sites of large extension with rel-
atively low concentrations of contaminants at shallow depths. Com-
pared with other remediation techniques, phytoremediation is cost-
effective and with additional ecological benefits and high public ac-
ceptance. Nevertheless, phytoremediation is time-consuming and
of low efficiency. Currently the technique remains at the develop-
ment stage. More research is needed to search for cultivable broad-
metal-hyperaccumulators with high biomass potential.
The applicability of a soil remediation technique is project-specific,
influenced by a number of factors including the site and contamination
characteristics, remediation objectives, remediation efficiency, cost-
effectiveness, time, and public acceptability. Treatability studies help se-
lect best feasible remediation techniques and should be conducted prior
to the full-scale remediation implementation.
218 L. Liu et al. / Science of the Total Environment 633 (2018) 206–219
Acknowledgements
This work was financially supported by the National Key Technolo-
gies R&D Program of China (Grant No. 2017YFD0800305) and the
USDA-AFRI competitive grant No. 2014-38814-22561.
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