Soil Pollution see Pollution, Soil

Soil Pollution Remediation

MD Fernández Rodrı́guez, MC Garcı́a Gómez, N Alonso Blazquez and JV Tarazona, National Institute for Agriculture and Food
Research and Technology (INIA), Madrid, Spain
Ó 2014 Elsevier Inc. All rights reserved.

Introduction 3. Treatment technologies capable of decreasing the concen-

tration of soil contaminants.
In developed countries, contaminated land is mostly the
Some remedial measures, denominated in situ, manage
outcome of historical industrial use, prior to the implementation
directly the contaminated material in the ground. Other
of environmental protection policies. Currently, ground
measures may require the contaminated material to be exca-
contamination arises from leaks, spills, accidents, poor waste
vated before it can be treated, and they are called ex situ remedial
disposal practice, and uncontrolled discharges. The management
treatment. The subsequent treatment of excavated soils can be
of contaminated lands starts with the identification of soils
performed on the site (‘on-site’ treatment), while other
requiring remediation. The second stage consists of setting the
measures may require the contaminated material is transported
remedial objectives and developing the remedial strategy. Risk
and treated in special facilities (‘off-site’ treatment).
assessment techniques offer support for identifying and priori-
The main advantage of in situ treatments is that soil can be
tizing sites requiring remediation, developing remedial objec-
treated without being excavated and transported resulting in
tives and cleanup standards, and selecting the most appropriate
significant cost savings and additional treatment-related envi-
remedy for a particular location. Currently, cleanup objectives
ronmental impacts. However, in situ treatments generally
are usually based on the target concentration of contaminants
require longer time periods, are less effective, and the moni-
derived from risk-based analysis. However, during remediation
toring of the processes is more difficult because of the vari-
processes, changes in bioavailability and the formation of more
ability in soil characteristics. The ex situ treatments are more
toxic metabolites may challenge the efficiency of remediation in
expensive but also quicker in getting more complete remedia-
lowering soil toxicity. Bioassays performed with soil samples
tion of the contaminated land and providing more certainty
taken from the site can be used to complement chemical anal-
about the uniformity of the treatment.
yses to evaluate the quality of remediated soil. They provide
The main remediation techniques are briefly described
a direct estimation of the toxicity produced by the combined
below. Although the affection of groundwater is a main issue in
effects of identified substances, unknown compounds, and
the remediation of contaminated lands, this article excludes
transformation products. In this article, several different bioas-
technologies for its remediation.
says are presented for the direct ecotoxicological assessment of
remediated soils and biomonitoring of remediation processes.
Containment Technologies
General Considerations in Remediation Processes
Containment technologies use conventional civil engineering
techniques to isolate contaminated media from the surrounding
The choice of remedial technology largely depends on the
environment, that is, blocking the pathways by which contami-
nature and degree of contamination, the intended function or
nants can reach the receptors without destroying them. These
usage of the remediated site, and the availability of innovative
technologies donot require soil excavation and area low-moderate
and cost-effective techniques. The traditional approach to the
cost treatment group despite the required long-term monitoring
remediation of contaminated land has been to excavate and
and maintenance. In general, these technologies are used when
redeposit, usually as landfill. This approach is unsustainable
potential hazards could be produced during excavation and
and increasingly expensive. New techniques are available that
removal of contaminated soil or when other treatment technolo-
help reduce the amount of waste going to landfill and elimi-
gies are not available or have an unrealistic cost. Table 1 summa-
nate the contamination of the site with the aim of reusing the
rizes the main characteristics of these remediation technologies.
land. Generally, several treatment technologies are combined
Containment technologies include covers and barriers.
at each site. The different types of remedial measures that are
Covers are designed to avoid the direct exposure of receptors
available can be categorized into three main groups:
to contaminated soil, minimize the infiltration of rainwater into
1. Containment technologies that seek the isolation of the site, the landfill in order to avoid leachate production and hence
but without acting directly over the contaminants. groundwater contamination, and prevent the emission of vola-
2. Immobilization technologies that reduce the mobility of tile contaminants in the atmosphere. The soil surface is capping
the contaminants in the environment through both physical with low-permeability materials that can be natural (soils and
and chemical means. bentonite), civil engineering (concrete or bituminous asphalt),

344 Encyclopedia of Toxicology, Volume 4 http://dx.doi.org/10.1016/B978-0-12-386454-3.00579-0

 Soil Pollution Remediation 345

Table 1 Summary of remediation technologies based on containment and immobilization strategies

In situ/ Contaminants/
Technology ex situ application Limitations Advantages

Containment technologies
Covers/barriers In situ Organic and inorganic It requires careful design and implementation Applicable to a wide range
contaminants (specially of contaminants, specially
excavation and backfilling of the trench) complex mixtures
It is susceptible to failure or damage Applicable to large or small
It does not treat for the contamination sites
It is not a permanent solution
It requires long-term monitoring (groundwaters and
gases)
Wall materials depend on the type of contaminants
Immobilization
Solidification/ Ex situ/ Inorganics, including Weathering and water infiltration can affect the Reagents are widely available
stabilization in situ radionuclides and integrity of the stabilized mass causing contaminant and inexpensive
heavy metals mobility The maintenance of
The selection of immobilizing agent requires immobilized material can be
treatability studies reduced if proper conditions
Organics in case of The process may increase the waste volume are maintained
asphalt batching In situ, it is difficult to get a complete and uniform mix It greatly reduces the leaching
of the immobilizing agent with the soil of contaminants
In situ, the depth of contaminants may limit the
process
Volatile compound (VOC) may be released during the
process
Vitrification In situ/ Inorganics, including High energy is required Applicable to a wide range
ex situ radionuclides and It needs special equipment and trained personal of contaminants
heavy metals Soil moisture increases the time and cost of the Applicable to a broad range
Organics, although process of media: solids, liquids, and
other methods are The soil must contain enough silica and alkali oxides sludges
preferred to allow the vitreous mass formation The resulting glass structure is
The resulting material may limit future land use durable and resistant to
It does not support a vegetal cover leaching

or geosynthetic. The design of covers is site specific and is based
on one single layer or a complex multilayer system combining
different materials. To apply this technique, it is necessary that
the site does not undergo continuous periods of wet–dryness,
which can damage the cover. Groundwater should be controlled
through wells. Moreover, gases can be generated due to
contaminant degradation and must be collected and treated.
It is recommended to use this technique in conjunction with
vertical barriers to avoid lateral dispersion of the contaminants.
Barriers are used for restricting the movement of contami-
nant plumes in soil and groundwater. They consist of vertically
excavated trenches filled with highly impermeable materials to
form a subsurface wall. The most commonly used materials are
cement/bentonite or concrete. Another technique for con-
structing vertical barriers is metal sheet piling. They are long
structural sections with a vertical interlocking system that
creates a continuous wall. To seal the wall, the interspace must
be filled with cement/bentonite grout or polyurethane.
Subsurface horizontal barriers are also used to decrease soil
permeability and to control the percolation of contaminants.
The technique may be applied in the saturated and unsaturated
zones. Physical barriers have been used for decades. Therefore,
the equipment and methodology are readily available;
however, the wall materials must be selected for containing the
specific contaminants.
A particular case of physical barriers are the permeable
reactive barriers (PRBs), which are receiving great attention for
in situ cleanup of groundwater contamination. In reality, these
are not containment but treatment techniques. PRBs intercept
the contaminant plume, allowing the movement
of groundwater while contaminants are immobilized or
chemically transformed to less harmful substances. A wide
variety of materials can be used in PRBs, such as zerovalent
metals (e.g., iron metal), humic materials, oxides, surfactant-
modified zeolites (SMZs), and oxygen- and nitrate-releasing
compounds.
Immobilization Technologies
These technologies confine contaminants in soil, reducing
their mobility to prevent migration to other media or the
contact with potential receptors. Immobilization is achieved
by acting directly on the conditions in which contaminants are
346 Soil Pollution Remediation
present in the soil. Processes can be physicochemical or
thermal (Table 1).
Physicochemical Methods
Solidification and Stabilization
Solidification and stabilization, also referred to as waste fixa-
tion, act through both physical and chemical methods. Solid-
ification refers to techniques that physically bind or
encapsulate the contaminants within a stabilized mass of high
structural integrity and does not necessarily involve a chemical
interaction between the contaminants and the solidifying
additives. Stabilization refers to techniques that chemically
reduce the hazard potential of a waste by converting the
contaminants into less soluble, less mobile, or less toxic forms.
The main technologies include cement, asphalt or phosphate,
or alkalis that raise the pH facilitating the precipitation and
immobilization of some heavy metal contaminants.
Solidification and stabilization are performed both ex situ and
in situ. These technologies are used for the unsaturated soil zone.
These technologies have limited effectiveness against
organic substances including pesticides, except asphalt batch-
ing that destroys most organic contaminants. In the long term,
the effects of weathering and water infiltration can affect the
integrity of the stabilized mass resulting in contaminant
mobility.
Thermal Methods
Vitrification
Vitrification uses a powerful source of energy to melt soil at
extremely high temperatures, immobilizing most inorganic
contaminants and destroying organic contaminants by pyrol-
ysis and/or oxidation. Inorganic substances, such as metals and
radionuclides, are incorporated into a glass structure which is
generally strong, durable, and resistant to leaching. Some
volatile metals, radioactive contaminants, and organic
compounds may volatilize by gas treatment. The water vapor
and the products of pyrolysis are collected and led to the gas
treatment system to remove particles and other contaminants.
This technology can be applied both in situ and ex situ. In
ex situ, soil heating can be achieved through various systems
(plasma, direct power, combustion, induction, or microwave),
but the application of electric energy is the most widespread
technique. The soil is placed in a furnace, where it undergoes an
electric power to reach the temperature of 1100–1400
C. The
temperature for in situ treatment is higher (1600–2000
C).
Electrical energy is usually applied through graphite electrodes
inserted into the soil to be treated. Soil vitrification is an
extremely effective technology, destroying or immobilizing
almost all contaminants.
Treatment Technologies
Treatment technologies may be classified into three main
categories according to the processes used to remove, destroy,
or modify the contaminants: (1) physicochemical technolo-
gies, (2) biological technologies, and (3) thermal technologies
(Table 2). An important group of these techniques is based on
the separation processes generating residues, which require
treatment or disposal. Residue management should be added
to the total project costs and may require additional permits.
Physicochemical Treatment
Soil Flushing
Soil flushing is an in situ treatment technology in which an
aqueous solution is injected or infiltrated into the contami-
nated soil. This may occur within the unsaturated zone, the
saturated zone, or both. The flushing solution increases the
mobility or solubility of contaminants sorbed to the soil
matrix. This solution may consist of surfactants, cosolvents,
acids, bases, oxidants, chelants, solvents, or water. Contami-
nated groundwater and extraction fluids are captured and
pumped to the surface using standard groundwater extraction
wells. Finally, extraction fluids with the desorbed contaminants
must be treated. Air emissions of volatile contaminants from
recovered flushing fluids should be collected and treated too.
Soil flushing is generally used in conjunction with other
remediation technologies such as activated carbon, biodegra-
dation, and pump and treat. Physical barriers such as slurry
walls or sheet piles can be installed to prevent uncontrolled
migration of the solvent and the contaminants.
The main disadvantage is the potential risk of spreading
contaminants into uncontaminated areas and the effects of
flushing solution into the soil environment.
Soil Washing
Soil washing is an ex situ technology to remove contaminants
from the soil using two processes: physical separation and
chemical leaching by aqueous solutions. This technique
includes an initial process of homogenization in which the
coarse particles are separated by differences in density.
The physical separation is based on the fact that most
organic and inorganic contaminants tend to bind to clay, silt,
and inorganic particles. Thus, washing processes separate the
fine (small) clay and silt particles from the coarser sand and
gravel soil particles and concentrate the contaminants into
a smaller volume of soil (sludge) that can be further treated by
other methods such as incineration or bioremediation. The
coarse soil fragments can be used as backfill. In the second
process, the contaminants are selectively dissolved and then
chemically transformed or recovered. The additives and
reagents that are added to water depend on the nature of the
contamination to be treated. In soils contaminated by multiple
substances with different characteristics, the application of the
technique usually requires a sequential process using different
washing solutions. The contaminated water is treated with the
technology suitable for the contaminants.
The main advantage of soil washing is that it is a cost-
effective technique because it reduces the amount of the mate-
rial that would require further treatment by another technology.
Chemical Extraction
Chemical extraction is an ex situ process that separates metals and
organic contaminants from soils using chemical extractants,
while soil washing uses water or water with wash-improving
additives. Physical separation steps are often used before chem-
ical extraction to divide the soil into coarse and fine fractions.
Table 2 Summary of remediation technologies based on the treatment of contaminants

Technology In situ/ex situ Contaminants/application Limitations Advantages

Physicochemical
Soil flushing In situ Mainly inorganic contaminants: More effective in coarse-grained soils The equipment is easy to build and operate in
metals, cyanides, radioactive Increased costs as a result of the use and recuperation of the permeable soils
Organic contaminants: NAPLs, surfactant or the cosolvent to be reused It can mobilize a wide range of organic and inorganic
VOCs, SVOCs A long time may be necessary depending on the contaminant sorption contaminants
Fuels, pesticides to soil Costs are moderated depending on the flushing
Flushing fluid must be controlled to avoid the migration of solution
contaminants into uncontaminated areas
Waste generation: flushing fluids and air emissions of
volatile contaminants
Soil washing Ex situ SVOCs More effective in coarse-grained soils Soil washing can remove many types of contaminants
Petroleum and fuel, metals Production of a large amount of washing water to be treated It may not be cost effective for small amounts of
Cyanide Usually, silt and clay after washing processes require to be treated by contaminants
other methods
Chemical Ex situ PCBs, VOCs Soils with high clay content and high moisture levels hinder the It allows to clean chemicals that are difficult to be
extraction Halogenated solvents success of the process removed using other technologies
Petroleum wastes Residual acid and solvent traces in treated soil The extraction of contaminants is generally quicker
Organically bound metals (solvent than
extraction) in situ methods
Heavy metals (acid extraction)
Vapor extraction In situ/ex situ VOCs Concentration reductions greater than 90% are difficult to achieve It treats a large volume of soil at reasonable costs
Certain SVOCs Low effectiveness in low air permeability or stratified soils Minimal disturbance in situ operations
Light fuels High moisture and organic content limit its effectiveness It can be applied at sites with free contaminants
Costly treatment of extracted vapors The wells and equipment are simple to install and
No volatile contaminants present in the site may require additional maintain
technologies for remediation It helps the biodegradation of non-VOCs
Ex situ, air emissions may occur during excavation Addition of reagents is not required
Ex situ, a large amount of space is required Ex situ treatment is uniform and easily monitored
Electrokinetic In situ Mainly metals Effectiveness is reduced if the soil moisture content is less than 10% It is effective for fine-grained soils of low permeability,
Anions Electrolysis of metallic electrodes may introduce corrosive products which are difficult to treat by other methods
Polar organics into the soil. Electrodes of carbon, graphite, or platinum (inert The contaminated soil solution is easily extracted from

Soil Pollution Remediation

materials) avoid this concern the point of collection
Light soluble and strongly adsorbed contaminants limit the success of
the technology
Oxidation/reduction reactions can form undesirable products
Chemical
Chemical In situ (ISCO)/ Inorganics Oxidizing agents are nonselective Contaminants are destroyed
oxidation ex situ Halogenated VOC, cyanide Risk of incomplete oxidation and production of toxic intermediates It can be less costly and quicker than other removal
Fuels Highly adsorbed compounds may limit the degradation process technologies
Phenols and sulfur compounds Treatments may alter soil properties ISCO is particularly useful to remediate sites difficult to
It is not cost effective for high contaminant concentrations treat by other techniques
Potential hazards of chemicals to workers Capability to oxidize DNAPLs
Uncontrolled exothermic reactions in the subsurface

347
(Continued)
 348
Table 2 Summary of remediation technologies based on the treatment of contaminantsdcont'd

Technology In situ/ex situ Contaminants/application Limitations Advantages

Soil Pollution Remediation

Dehalogenation Ex situ Halogenated SVOCs Formation of reaction products that may be more toxic than the The technology is amenable to small-scale
Halogenated pesticides contaminants being treated applications
Soils with high clay and moisture content increase treatment costs APEG dehalogenation is in addition to incineration,
It is not cost effective for high contaminant concentrations one of the few processes available to treat PCBs
Thermal
Thermal Ex situ Nonhalogenated Previous homogenization of particle size is usually required Can be a fast and effective method of cleaning
desorption VOCs PAHs Clay and silty soils and high humic content soils increase reaction time heavily polluted soil
PCBs Dewatering may be necessary (soil moisture > 30%) Equipment cost is lower than other thermal methods
Pesticides Residuals are generated (condensed contaminants, off-gases, Soil structure is not altered at treatment
Fuels wastewater) temperature < 400–500
C
Some SVOCs Corrosion problems in the equipment when the waste contains
halogenated compounds
High metal concentration in the soil may require further treatment
before backfilling
Incineration Ex situ Explosives Previous homogenization of particle size is usually required Incineration can destroy some types of chemicals that
Chlorinated hydrocarbons Residuals are generated (ash, off-gases, wastewater) other methods cannot
PCBs It destroys the soil structure It is quicker than other technologies
Dioxins Heavy metals can produce a bottom ash that requires stabilization It reduces the amount of material that must be moved
Sodium and potassium form low-melting-point ashes that can attack to
the equipment a landfill
Local public opposition
Biological
Phytoremediation In situ/ex situ Metals Time-consuming process Low costs
Chlorinated solvents Treatment is limited to the upper soil profile Aesthetically pleasing technique
Petroleum hydrocarbons, PAHs Plants grow well only in moderately contaminated soil It protects soil against erosion (spreading of
Pesticides and explosives Contaminants may enter the food chain through animals that feed on contaminants)
the plants used in these processes Promising use to remove organic contaminants by
It requires the disposal of the plants used in the treatment of metabolism
metal contaminated soils
Climatic and hydrologic conditions may limit the plant’s growth
Bioremediation In situ/ex situ Biodegradable organic chemicals: High concentrations of contaminants may be toxic to the It is simple to maintain
Petroleum hydrocarbons, microorganisms In situ, it is applicable over large areas
solvents, PAHs Previous feasibility studies are necessary It is cost effective
Pesticides, etc. In situ, successful biological treatment depends on the climatic It leads to the destruction of the contaminants
conditions
Low bioavailability of contaminants limits the success of the process
In situ, microorganisms cannot reach deep contaminants
Recalcitrant behavior of some contaminants (PCBs, polychlorinated
phenols, and PAHs)
Bioremediation slows down at low temperatures

The two major chemical extraction processes are acid
extraction and solvent extraction. Acid extraction uses hydro-
chloric acid to extract metal contaminants from soils. The heavy
metals are potentially suitable for recovery. Solvent extraction
uses organic solvents (acetone, hexane, methanol, dimethyl
ether, or triethylamine) as extractants. The extractants are
treated for their regeneration and can be reutilized in site. This
technique is commonly used in combination with other tech-
nologies, such as solidification/stabilization, incineration, or
soil washing, depending on the site-specific conditions. Traces
of solvent may remain within the treated soil matrix, so the
toxicity of the solvent is an important consideration.
Chemical extraction is used to clean up many chemicals that
are difficult to remove from soil using other technologies.
Soil Vapor Extraction
Soil vapor extraction (SVE) is used to remediate unsaturated
zone soil. A vacuum is applied to the soil to induce the
controlled flow of air and remove volatile and some semivolatile
organic contaminants. It is usually an in situ technology;
however, in some cases, it can be used as an ex situ technology.
In in situ SVE, also known as soil venting or vacuum
extraction, vacuum is applied to the soil through the wells near
the source of contamination, creating a negative pressure
gradient to induce the controlled flow of air and remove the
contaminants from the soil through an extraction well.
Extracted vapor is treated before being released into the
atmosphere. The increased airflow through the subsurface can
also stimulate the biodegradation of some of the contami-
nants, especially those that are less volatile. In areas of high
groundwater levels, water depression pumps may be required
to offset the effect of upwelling induced by the vacuum. In situ
SVE can reach greater depth than methods that require
removing the soil, the wells and the equipment are simple to
install and maintain. Ex situ SVE is a full-scale technology in
which soil is extracted and placed over a network of above-
ground piping where a vacuum is applied to volatilize organic
contaminants. The process includes a system for handling
off-gases.
Electrokinetic
Electrokinetic is an in situ innovative technique for the
decontamination of soils contaminated with metals, anions,
and polar organics. The principle of electrokinetic remedia-
tion relies upon the application of a low-intensity direct
current through a porous solid medium between appropri-
ately distributed electrode arrays, causing ions and water to
move toward the electrodes. Contaminants are transported by
two contributive processes: electromigration (migration of
ions) and electroosmosis (movement of liquid containing
ions). Electromigration is the main mechanism for the elec-
troremediation process. Moreover, other electrolysis effects
such as diffusion, adsorption, complexation, and precipita-
tion reactions also contribute to the process. Contaminants
are removed at the electrode by different methods such as
electroplating; precipitation or co-precipitation; water
pumping near the electrode; or complexation with ion
exchange resins.
Apolar organic compounds are transported by the electro-
osmosis-induced water flow. Therefore, the addition of
Soil Pollution Remediation 349
surfactants is necessary to increase their solubility and facilitate
the formation of micelles.
The main advantage of electrokinetic is that it is effective for
fine-grained soils of low permeability that are difficult to treat
by other methods. The effectiveness of this technique has been
demonstrated in laboratory and pilot studies. However, more
field trials are necessary.
Chemical Oxidation/Reduction
Chemical oxidation is applied to treat organic substances that
are almost completely oxidized into H2O and CO2 or trans-
formed into less toxic compounds. This method may be
applied in situ or ex situ. In situ chemical oxidation (ISCO) is an
innovative technology applicable to a wide variety of organic
compounds present in subsurface environments. Several
oxidants have been tried, but most commercial applications
use hydrogen peroxide (typically used together with Fe(II) to
form Fenton’s reagent) or ozone for the vadose zone and
hydrogen peroxide (H2O2) or potassium permanganate
(KMnO4) in the saturated zone. Recently, persulfate salts
(Na2S2O8) are being used for ISCO applications, but they are
relatively expensive and require thermal activation.
The method is based on the direct injection of an aqueous
solution of the oxidant agents into the subsurface using
conventional injection wells or advanced injection techniques,
such as deep soil mixing or hydraulic fracturing, in case of low-
permeability soils.
ISCO is the chosen technique to remediate those sites
considered difficult to treat using other technologies. A serious
potential limitation to the use of oxidizing agents for soil
treatment is that the oxidants are nonselective. A significant
part of these reagents is consumed by oxidizable material
present in the soil and groundwater. This is a major concern
because the concentration of natural organic material in the
soils may be lowered, which would result in a decrease in
the sorption capacity of some organics limiting the efficiency of
the ISCO treatment.
Reductive technologies may also be applied to soil remedi-
ation. The addition of reductive agents to soil can be used as an
in situ treatment technology. They have been successfully applied
in small-scale field experiments to remediate soils contaminated
with organic compounds, Cr(VI) or Se(VI). Organic chemical
constituents in soil may be reduced using catalyzed powder
metals (mainly iron) or sodium borohydride (NaBH4). Metals
are reduced by the addition of acidification agents such as sulfur
or other agricultural acidification agents (leaf litter or acid
compost) and a reducing agent (ferrous sulfate).
Chemical Dehalogenation
Chemical dehalogenation processes use chemical reagents to
degrade hazardous halogenated molecules or to transform
them into other less harmful compounds. Two processes are
employed: alkaline polyethylene glycol (APEG) reagents and
base-catalyzed decomposition (BCD). Both are ex situ processes
requiring excavation.
APEG is used to treat halogenated aromatic compounds in
a batch reactor in which the contaminated soil and the reagent
are mixed and heated. The reaction between the chlorinated
compounds and APEG replaces the chlorine atoms reducing
the toxicity. A variation of this reagent is the use of potassium
350 Soil Pollution Remediation
hydroxide or sodium hydroxide/tetraethylene glycol, referred
to as alkaline tetraethylene glycol (ATEG) that is more effective
on halogenated aliphatic compounds. The technology is
amenable to small-scale applications and may be used in
combination with other technologies. APEG dehalogenation is
one of the few processes, other than incineration, that has been
successfully field tested for treating polychlorinated biphenyls
(PCBs).
BCD is a two-phase process applied to remediate soils and
sediments contaminated with chlorinated organic compounds,
especially PCBs, dioxins, and furans. The first phase consists of
thermal desorption in a rotary reactor which may include
mixing contaminated material with sodium bicarbonate. In the
second phase, the volatilized contaminants are transferred into
a reactor for dehalogenation by a catalytic hydrogenation. The
process uses sodium hydroxide, hydrogen donor oil, and
temperatures between 250 and 350
C.
Biological Treatments
Biological treatments include two main technologies: biore-
mediation and phytoremediation. Bioremediation exploits the
ability of microorganisms to degrade and detoxify organic
contaminants. Two general approaches are commonly used:
biostimulation and bioaugmentation. The most widely used
bioremediation procedure is biostimulation, which consists of
stimulating the site conditions for the development of indige-
nous microorganisms by optimizing conditions such as aera-
tion, addition of nutrients, pH, and temperature control. In
addition to the stimulation of autochthonous microorganisms,
the technique can also involve the addition of adapted
microbial degraders specific for the contaminants (bio-
augmentation). Bioremediation methods may be used in situ
(e.g., bioventing) or ex situ (e.g., land farming, composting,
slurry bioreactors).
Phytoremediation is the use of green plants and their
associated microbial communities to reduce contaminant
levels in soils, surface and groundwaters, and sediments. It is an
in situ technology that can also be applied ex situ (e.g., hydro-
ponics systems). In soils, some plants can stabilize certain
environmental contaminants (phytostabilization) and uptake
contaminants that can be degraded or transformed into
harmless metabolites (phytodegradation), stored within the
cell structures (phytoaccumulation), and volatilized into the
atmosphere (phytovolatilization). Moreover, plant roots
release a range of organic compounds that stimulate the activity
of microorganisms in the rhizosphere increasing the rates of
biodegradation (rhizosphere degradation). Plants may assist in
the remediation of sites contaminated by a wide range of
chemicals: metals, radionuclides, and organic compounds such
as pesticides, solvents, and petroleum products.
Biological treatments (bioremediation and phytor-
emediation) are now widely used as an alternative to the
equivalent physicochemical methods because of their low cost,
effectiveness, and environmental benefits. Moreover, phytor-
emediation improves the overall quality and texture of the soil
at remediated sites and contribute to the restoration of habitat
quality. These techniques will be more widely dealt within
other articles.
Thermal Methods
Thermal methods are ex situ treatment technologies that
destroy or remove contaminants through exposure to high
temperature in treatment cells, combustion chambers, or other
means used to contain the contaminated media during the
remediation process.
Thermal Desorption
Thermal desorption is a technology of physical separation
based on heating the contaminated soil to volatilize water and
organic contaminants. Soils are heated in a thermal desorp-
tion system, the rotary dryer being the most commonly used
equipment. The systems require the treatment of the off-gas to
remove particles and contaminants. Its effectiveness depends
on the contaminant. Decontaminated soil usually returns to
the original site. Based on the operating temperature, these
processes can be categorized into two groups: high-tempera-
ture thermal desorption ranging from 320 to 560
C and low-
temperature thermal desorption ranging from 90 to 320
C.
Thermal desorption can be used in a place where some other
cleanup methods cannot be used, such as at sites that have
a high soil contamination, and can be a soil remediation
method that is faster than others.
Thermal methods may also be applied as an in situ tech-
nique. In this case, heat is applied to soil to volatilize semi-
volatile organic compounds (SVOCs), which can be extracted
via collection wells and treated. It is a particular case of SVE.
Heat can be introduced into the subsurface by electrical resis-
tance heating, radio frequency heating, or injection of hot air or
steam. Thermal methods can be particularly useful for dense
nonaqueous phase liquids (DNAPLs) or light nonaqueous
phase liquids (LNAPLs).
Incineration
Incineration is a technology for ex situ thermal treatment
based on the application of high temperature (870–1200
C)
to the soil to burn harmful organic chemicals. Metals cannot
be destroyed by this technique. The efficiency of a properly
operated incinerator is very high, especially for PCBs and
dioxins.
Excavated contaminated soils can be incinerated on site or
transported to an incinerator off site, although to burn PCBs
and dioxins only off-site incinerators are permitted. There are
various types of incinerator plant designs: circulating bed
combustor, infrared combustion, rotary kiln, and fluidized
bed that may be applied to soil incineration. The gases
produced in the process must be treated to remove any
remaining metal, acids (HCl, NOx, and SOx), and particles of
ash before they are dispersed into the atmosphere. The soil or
ash remaining in the incinerator after the burning and from
gas treatment may be disposed into a landfill or buried on
site. However, incineration significantly reduces the material
for disposal.
Incineration can destroy some types of contaminants
that are not possible by other methods and is quicker than
other technologies. This is important when a site must be
cleaned up quickly to prevent harm to the people or the
environment.

Other Treatment Technologies
Natural Attenuation
Natural attenuation (NA) is an in situ treatment to reduce the
contamination in soil and groundwater using naturally occurring
processes in soil. This treatment acts without human intervention
and the activity focuses on the verification and monitoring
of processes to assure their sustainability over time and their
effectiveness. Moreover, the process must be carefully controlled
and monitored to ensure that unaccepted risk for human health
and ecosystems may appear mainly as a result of the migration of
contaminants. NA may act by three different ways: (1) to destroy
the contaminant by biodegradation or abiotic processes such as
hydrolysis, (2) to reduce the concentrations through dilution or
spreading by diffusion, dispersion, and volatilization, and (3) to
immobilize contaminants (adsorption), and hence to reduce the
bioavailability and toxicity.
The effectiveness of NA highly depends on the site-specific
conditions and the types of contaminants. This technique
requires contaminants that are readily degradable; therefore, it
is being applied mainly to petroleum hydrocarbons and
nonhalogenated solvents.
NA is a relatively simple technology compared to other
remediation technologies. The costs are low and they are asso-
ciated with initial evaluation and monitoring. However, it
presents two main limitations. First, it requires more time than
conventional remediation methods to get the same remaining
concentration. Second, contaminants may migrate into the soil
and groundwater during the remediation process and larger
volumes of groundwater can become contaminated through
dilution. Therefore, before applying this technique, it is neces-
sary to estimate the movement of the contaminant plume and its
extension during the cleanness process.
NA can be used as an alternative to or in combination with
active technologies. Usually, it is used as a complement to an
active system of remediation and it is accepted as the only
approach in a small number of cases.
Nanoparticles
Nanoparticles (NPs) are of interest for environmental applica-
tions because they have larger surface areas per volume of
material, which provides more reactive sites allowing for more
rapid degradation of contaminants compared to the larger
particles of the same bulk material. An increasing variety of
nanoscale materials is being researched and applied as
in situ contamination remediation technologies. The most
widely studied NPs in remediation trials is the nanoscale zer-
ovalent iron (nZVI), although other substances are being
investigated: self-assembled monolayers on mesoporous
supports (SAMMSÔ), dendrimers, carbon nanotubes, metal-
loporphyrinogens, and swellable organically modified silica.
The nZVI are used mainly in the remediation of ground-
water, although they are also applied to soil remediation. Iron
particles are effective for the treatment of contaminants such as
chlorinated organic solvents, organochlorine pesticides, PCBs,
organic dyes, and various inorganic compounds. NPs are
directly injected via gravity or under pressure and need less
infrastructure than traditional techniques. However, there are
some fundamental issues limiting their applications. A main
Soil Pollution Remediation 351
question is the insufficient knowledge about their environ-
mental behavior and their toxicity to the potentially affected
receptors. Another main disadvantage of using NPs is the
agglomeration of particles among them or to the soil surface. It
increases the particle size, reducing the effectiveness of these
materials and their subsurface mobility. Modifications of NPs
have been made to decrease this agglomeration; for example,
adding coatings or encasing in emulsified vegetable oil drop-
lets. More research is needed to understand the fate, transport,
and the potential toxicity of nanoscale materials in the
environment.
Sustainable Issues
Contaminated land management has been traditionally
considered intrinsically sustainable despite the remediation
processes consuming a large amount of energy, generating large
amounts of atmospheric emissions including greenhouse
gases, and creating a risk of injury for its workers. Management
decisions have not taken into account many of these impacts
when selecting the remediation method. However, a more
comprehensive approach to soil remediation should incorpo-
rate sustainability assessments.
Sustainable (green) remediation involves balancing the
benefits of remedial action with the impacts of these actions,
without forgetting the long-term protection of human health
and the environment. It is based on the three elements of
sustainable development: environment (conservation of
natural resources and biodiversity), economy (balancing
economic viability), and society (enhancement of the quality
of life in surrounding communities). Sustainability can be
considered either in decisions that lead to the overall remedi-
ation project including site development and future land use or
targeted to the selection of the most proper remediation
option.
Sustainability evaluation is a key point to be applied in
a comparative sense where the ‘best option’ is selected, gener-
ally based on the assessment indicators. These indicators or
metrics can be qualitative (e.g., wildlife and flora conservation,
worker safety, local residents’ safety and quality of life, and
potential for litigation) or quantitative (e.g., carbon dioxide
emissions, energy consumption, direct costs, water usage,
duration of work, and local job creation). Indicators are
combined using different qualitative or quantitative tools.
Some qualitative methods yield a relative ranking and are
considered hybrids. These approaches include decision tables
and multicriteria analysis that use scores (the magnitude of an
effect) and weighting (the importance), which are mathemat-
ically processed. Some quantitative tools suited to evaluate
sustainability of remediation projects are life-cycle assessment,
net environmental benefit analysis, and cost–benefit analysis.
Biological Tools for the Assessment of Contaminated
and Remediated Soils
Traditionally, remediation objectives are focused on the
concentration of the contaminant that is judged acceptable
based on the established standards or guidelines or following
352 Soil Pollution Remediation
a site-specific risk analysis. The chemical analysis of contami-
nated and remediated soils is carried out with those contam-
inants expected according to the historical use of the site.
However, not all contaminants present in the soil, including
metabolites or transformation products, may be considered
during the analysis. Furthermore, the chemical analysis by
itself does not allow an integration of the combined effects of
the contaminants present at a contaminated site as well as the
bioavailability changes during the remediation process. Bio-
logical tools contribute to identify contaminated soils, to
follow the success of the remediation process in terms of biota,
and to assess the final state of the soil as well as to monitor the
evolution of the ecosystems after its clearness. Monitoring can
be done by simple and cheap standardized bioassays or suit-
able biomarkers. These can verify the decline in toxicity due to
transformation, dissipation, or reduction in the bioavail-
ability, quantifying the impact of the remediation method by
measuring directly the effects on biota. The potential toxicity
of the chemical compounds added or produced during the
remediation process, remaining in the remediated soil, is also
integrated in the measurements. Higher-tier methods would
be restricted to monitor the evolution of the ecosystem after its
clearness, when the intended use of soil is natural. These
methods are briefly described below.
Single-Species Toxicity Tests
Ecotoxicity tests performed at different levels of biological
organization, from molecular level (biochemical changes) to
ecosystem function, can be modified for the direct measure-
ments of soil toxicity. Most assays are performed at the
organism level, constituting the single-species toxicity tests.
The measured end points may be lethal or sublethal effects
(e.g., inhibition of growth or reproduction).
Many single-species assays have been standardized by
different organizations (ISO, OCDE, USEPA, ASTM, etc.) to
harmonize their use, with the aim of reducing the variability
and comparing the results. The OECD list of standardized
methods on soil and water organisms is presented in Table 3.
These methods may be applied with some modifications to
the assessment of contaminated soils for their initial ‘eco-
diagnostic’ and to remediated soils.
The toxicity of contaminated or remediated soils may be
tested using two approaches: at a single concentration of the
test soil and at different dilutions of the test soil. In the first
case, assays are performed with a control or reference soil and
with nondiluted samples of the test soils. The results of the
toxicity assessment are compared using statistical tools such as
ANOVA analysis and are expressed as a percentage of inhibition
with respect to the control. In the second approach, different
dilutions of the test soil are obtained using a control soil or
reference soil obtaining a contamination gradient. Quantitative
dilution–response relationship is determined by regression
analyses (e.g., logit, probit, and Spearman–Karber). The first
approach is fast and cheap and allows obtaining directly the
toxicity results at a percentage of inhibition between 0 and
100% for each sample. Regression models provide estimations
of the parameters of interest with higher sensitivity and preci-
sion. Moreover, the use of different concentrations allows
detecting cross effects such as hormesis or effects due to
different physicochemical properties of the test and control
soils. Differences in soil properties between the control/refer-
ence and the test soils may affect the test results. Ideally, assays
should be performed with a reference soil, which is a soil with
the same characteristics as that of the test soil but non-
contaminated. To find a proper reference soil on the site not
affected by the contamination or far away but with similar
properties can be problematic, making difficult the data inter-
pretation except when toxicity is still observed after a large
dilution.
To correctly assess soils, a battery of tests has to be conducted
with different test species to cover differences in species sensi-
tivity. Typically, soil toxicity is tested on soil invertebrates
(e.g., earthworms), terrestrial plants, and soil microorganisms;
and leachates from the contaminated soil in algae and aquatic
invertebrates. Fish are often not used to diagnose the toxicity of
a soil due to the large volume of leachates required in the assay
and because of the ethical issues intended to reduce testing on
vertebrates. An alternative is the use of in vitro assays with fish cell
lines to overcome these obstacles.
Single-species assays are very good tools for the diagnosis of
the soil at the starting stage in terms of toxicity to identify the
most sensitive organisms and to verify the effectiveness of soil
remediation.
Microcosms
An alternative to the battery of single-species assays is the use of
multispecies systems that account for species interactions.
These systems include simultaneously several organisms in the
same unit allowing not only the interaction among the species
but also evolving them under the same exposure conditions
along with the assay. These systems are more realistic and
complex than single-species test. Usually, the soil microcosm
consists of a column of soil with a device to collect the leachate
from below. Water is applied at regular times to simulate
rainwater percolating through the soil, and is collected using
a funnel. Two types of soil microcosms have been often used:
intact soil cores with autochthonous soil organisms and
artificial assemblages adding test organisms on sieved soil
columns. For ecotoxicological testing of soil quality, the
latter approach seems to be more appropriate. It allows deter-
mining the toxicity in a set of selected organisms cultivated in
the laboratory and therefore not previously exposed to
contaminants.
Biomarkers
Biomarkers measure biological response (biochemical, cellular,
physiological, or behavioral changes), at the organism level or
below, that could be associated with the exposure to one
or more contaminants. This biological response can be specific
or nonspecific. At the present time, specific biomarkers are only
available for a very limited number of chemicals and metals.
Nonspecific biomarkers may be useful as an integrative
measure of a set of stressors (not only chemicals but also
nonchemical factors).
Biomarkers are very sensitive indicators whose main goal
is to serve as early warning signals for predicting adverse
effects at higher biological organization levels (population or
Table 3 Standardized methods that can be applied to the toxicity assessment of contaminated and remediated soils (OECD Guidelines)

Effect/
Exposure concentration
Assay Reference Organism period data End point (measured variables)

Terrestrial compartment
Earthworm, acute toxicity OECD 207 Eisenia fetida 2 Weeks LC50 Mortality (adult survival)
tests Eisenia andrei
Terrestrial plant test: seedling OECD 208 Terrestrial plants 2 or 3 Weeks LC50 Seedling emergence and inhibition of growth
emergence and seedling NOEC (biomass, shoot height, etc.)
growth test
Soil microorganisms: nitrogen OECD 216 Soil microbial 4 Weeks EC50 Nitrogen transformation activity of soil
transformation test autochthonous microorganisms
populations
Soil microorganisms: carbon OECD 217 Soil microbial 4 Weeks EC50 Carbon transformation activity of soil
transformation test autochthonous microorganisms
populations
Earthworm reproduction test OECD 222 E. fetida 8 Weeks NOEC Reproductive output (cocoon production and
E. andrei viability, juvenile hatching)
Enchytraeid reproduction test OECD 220 Enchytraeus albidus 6 Weeks ECx Reproductive output (number of juveniles/
Enchytraeus sp. NOEC adult)
Collembolan reproduction OECD 232 Folsomia candida 4 Weeks ECx Reproductive output (number of juveniles/
test in soil Folsomia fimetaria 3 Weeks NOEC adult)
Aquatic medium
Freshwater alga and OECD 201 Pueraria subspicata 72 h ErCx Growth inhibition of cultures (number of cells,
cyanobacteria, growth Desmodesmus fluorescence, optical density, etc.)
inhibition test subspicatus
Anabaena flos-aquae

Soil Pollution Remediation

Daphnia sp., acute immobilization OECD 202 Daphnia magna 48 h EC50 Mortality (immobilization)
test
Daphnia magna Reproduction OECD 211 Daphnia magna 21 Days NOEC Reproductive output (number of living
Test offspring/parent alive)
Fish, acute toxicity test OECD 203 Onchorhynchus mykiss 96 h LC50 Mortality (adult survival)
Conchita carpio
Pimephales promelas

353
354 Soil Pollution Remediation
community), indicating the presence of unacceptable levels of
contamination. The use of biomarkers in soil characterization
has some main limitations. In some cases, it is difficult to relate
the physiological response to the effects at a higher level
(e.g., impacts on survival, growth, or reproduction, or other end
points related to population decline).
The application of biomarkers in actual field assessment has
not been validated yet. Effects are usually measured at the
subcellular or suborganism level. Several biomarkers are asso-
ciated with stress responses. Examples in case of earthworms
are the measurement of the lysosomal membrane stability of
coelomocytes, the lysosomal accumulation of lipofuscin in
chloragogenous tissue and of neutral lipids in coelomic cells,
and the determination of plasma membrane Ca2þ-ATPase
activity or metallothionein content. In plants, biomarkers are
related to the photosynthetic activity (decrease in chlorophyll
fluorescence), the activation and synthesis of stress proteins,
phytohormones, or phenolic compounds, and the production
of high quantities of reactive oxygen species. For microbial
function, the measurement of enzymatic activities (e.g., phos-
phatase and dehydrogenase) is very common.
Biomarkers at suborganism or organism level are related
with damage on tissues, biological fluids, or alterations in the
behavior. In earthworms, histopathological makers such as
bruising, swelling, tissue necrosis, and extrusion of coelomic
fluid have been reported, especially in clitellum region.
Avoidance of media can also be shown as an example of
behavioral changes. In plants, different reactions to stress
situations can be considered biomarkers of contamination such
as inhibition of stomatal opening and respiration rate and
chlorosis.
Biological Field Observations
Biological field observations are another biological alternative
for the direct assessment of contamination effects in situ. They
can be used in the last stage of remediation process to control
the recuperation of the natural abundance of communities in
situ, in those cases where the future land use of remediated soil
is natural use. The selection of the group of organisms for the
monitoring program is based on the ecological relevance and
practicability (e.g., sampling and identification). Microorgan-
isms and soil invertebrates (enchytraeids, nematodes, earth-
worms, and mites) are frequently used. These organisms are
responsible for key ecological processes. Information on the
community may be desirable. Unusual species assemblages are
recognized by comparing with reference sites. If a proper
reference location is not available, only major ecosystem
changes can be detected. Bioaccumulation of contaminants in
the lowest food chains (producers and primary consumers) can
also be studied. It provides information on the transfer of
contaminants through the food web. Biomarkers may also be
used in monitoring programs.
In summary, the integration of chemical analysis and bio-
logical tools is required to manage the remediation of
contaminated lands. There are a variety of biological tools for
the assessment of both contaminated and remediated soils.
Currently, there is an increased interest in the application of the
bioassays for the risk assessment of contaminated soils.
However, the use for remediation purposes is more limited due
to the low sensitivity of these assays. The use of long-term
assays using more sensitive parameters such as sublethal effects
is recommended for the observation of toxicity differences
between initial soils and samples obtained after remediation
treatments. The use of biomarkers can provide warnings of
biological impact despite that for most of them there is not
a relationship between physiological response and population-
level parameters. Finally, the biological field observation of the
site should be desirable to study the natural evolution of the
site, when the intended use of the soil is natural use.
See also: Environmental Risk Assessment, Terrestrial;
Site-Specific Environmental Risk Assessment; Pollution, Soil;
Environmental Biomarkers; Multispecies Environmental
Testing Designs; Environmental Toxicology; Ecotoxicology;
Toxicity Testing, Aquatic.
Further Reading
Calow, P. (Ed.), 1997. Handbook of Ecotoxicology, vol. I. Blackwell Science, Oxford.
Fernández, M.D., Babín, M., Tarazona, J.V., 2010. Application of bioassays for the
ecotoxicity assessment of contaminated soils. Methods Mol. Biol. 599, 235–262.
Hugget, R.J., Kimerle, R.A., Mehrle, P.M., Bergman, H.L., 1992. Biomarkers,
Biochemical, Physiological and Histological Markers of Anthropogenic Stress.
Lewis, Boca Raton, FL.
Khan, F.I., Husain, T., Hejazi, R., 2004. An overview and analysis of site remediation
technologies. J. Environ. Manage. 71 (2), 95–122.
Keddy, C.J., Greene, J.C., Bonnell, M.A., 1995. Review of whole-organism bioassays:
soil, freshwater sediment, and freshwater assessment in Canada. Ecotoxicol.
Environ. Saf. 30, 221–251.
Knacker, T. (Ed.), 2004. Ring-Testing and Field-Validation of a Terrestrial Model
Ecosystem (TME). Ecotoxicology, vol. 13, pp. 5–176 (special issue).
Loibner, A.P., Szolar, O.H.J., Braun, R., Hirmann, D., 2003. Ecological assessment
and toxicity screening in contaminated land analysis. In: Thompson, K.C.,
Nathanail, C.P. (Eds.), Chemical Analysis of Contaminated Land. Blackwell
Publishing Ltd, Oxford, UK, pp. 229–267.
McCarthy, J.F., Shugart, L.R., 1990. Biomarkers of Environmental Contamination.
Lewis, Boca Raton, FL, USA.
Schaeffer, A., Van den Brink, P.J., Heimbach, F., Hoy, S.P., de Jong, F.M.W., Römbke, J.,
et al., 2010. Semi-Field Methods for the Environmental Risk Assessment of Pesti-
cides in Soil. CRC Press, Boca Raton, FL.
Sheppard, S.C., 1997. Toxicity testing using microcosms. In: Tarradellas, J., Bitton, G.,
Rosell, D. (Eds.), Soil Ecotoxicology. Lewis, Boca Raton, FL, pp. 345–373.
Smith, L.A., Means, J.L., Chen, A., Alleman, B., Chapman, C.C., Tixier Junior, J.S.,
et al., 1995. Remedial Options for Metals-Contaminated Sites. Lewis Publishers
by CRC Press Inc. ISBN 1-56670-180-5.
Stephenson, G.L., Kuperman, R.G., Linder, G.L., Visser, S., 2002. Toxicity Tests for
Assessing Contaminated Soils and Ground Water. In: Sunahara, G.I., Renoux, A.Y.,
Thellen, C., Gaudet, C.L., Pilon, A. (Eds.), Environmental Analysis of Contaminated
Sites. John Wiley and Sons Ltd, New York, NY, pp. 25–43.
Swartjes, F.A., 2011. Dealing with Contaminated Sites: From Theory Towards Practical
Application. Springer, NY.
Van Gestel, C.A., Van Der Waarde, J.J., Derksen, J.G., van der Hoek, E.E.,
Veul, M.F.X.W., Bouwens, S., et al., 2001. The use of acute and chronic bioassays
to determine the ecological risk and bioremediation efficiency of oil-polluted soils.
Environ. Toxicol. Chem. 20, 1438–1449.
Walker, C.H., Hopkin, S.P., Sibly, R.M., Peakall, D.B., 2001. Principles of Ecotox-
icology. Taylor and Francis, New York.
Relevant Websites
http://www.nicole.org/WorkingGroups/WGSustainableRemediation/ NICOLE (Network
for Contaminated Land in Europe)
http://www.sustainableremediation.org/ The Sustainable Remediation Forum
(SURF.USA)

http://www.cluin.org/ Contaminated Site Clean-Up Information (CLU-IN)
CLU-IN - The Hazardous Waste Clean-up Information (CLU-IN) Sponsored by the U.S.
EPA Office of Superfund Remediation and Technology Innovation
http://www.frtr.gov/matrix2/top_page.html. Remediation technologies screening
matrix.The Federal Remediation Technology Roundtable (FRTR)
http://oecd.org/ OECD (Organization for Economic Cooperation and Development). The
OECD's Online Library of Statistical Databases, Books and Periodicals.
Soil Pollution Remediation 355
http://www.oecd-ilibrary.org/environment/oecd-guidelines-for-the-testing-of-
chemicals_chem_guide_pkg-en Organization for Economic Cooperation and
Development (OECD). Guidelines for testing of chemicals. Section 2: Effects on
biotic systems. Last updated July 2011.
http://nepis.epa.gov/Exe/ZyPURL.cgi?Dockey¼200083PQ.txt USEPA (1990). Hand-
book on in situ treatment of hazardous-wastes contaminated soils. Rapport. EPA/
540/2-90/002. pp. 169.