Canadian Journal of Basic and Applied Sciences
©PEARL publication, 2015
ISSN 2292-3381
CJBAS Vol. 03(12), 308-321, December 2015
Stabilizing the Various Types of Contaminated Soils Using Different Additives A review
Mohammad Nikookara, Arefeh Jafarpour Lashkamib
a
b
M.S of Geotechnical Engineering, Guilan University, Rasht, Iran
B.S of Civil Engineering, Guilan University, Rasht, Iran
Keywords:
Abstract
Stabilization,
Additives,
Contaminated Soils,
Soil Characteristics.
Stabilization of problematic soils including contaminated soils, peat, silt, and the like
through adding materials such as; cement, lime, bitumen, and etc. is one of effective
methods for improving the geotechnical properties of soils which has been applied for
many years now. There are a great number of techniques for stabilizing that can be
used for various purposes by enhancing some aspects of soil behavior and improving
the characteristics of soil. Most available remediation technologies for treatment of
contaminated soils are very expensive and result in residues requiring further treatment.
This study aims to overview of data published on stabilizing the various types of
contaminated soils such as heavy and toxic metals (As, Cr, Cu, Pb and Zn) using
different additives like ordinary portland cement (OPC), rice husk ash (RHA), lime,
synthesized zeolite, and etc. The consequences of these findings for the stabilization of
contaminated soils by the presence of heavy-toxic metals have been also throughly
discussed.
1. Introduction
Due to the presence of heavy and toxic metals the contamination of soils can result in serious
negative consequences, such as, the loss of ecosystems and, of agricultural productivity, the
deterioration of food chain, tainted water resources, economic damage, and human and animal
serious health problems etc. In several parts of the world the soil contamination represents the most
severe environmental problems [1].
Background knowledge of the sources, chemistry, and potential risks of toxic heavy metals in
contaminated soils is a necessity to select the appropriate remedial options. The fact of the matter is
that remediation of soil contaminated by heavy metals is necessary in order to reduce the associated
risks, make the land resource available for agricultural production, enhance food security, and scale
down land tenure problems as well. To clean up heavy metal contaminated soils In addition

Corresponding Author :
E-mail, nikookar2006@yahoo.com – Tel, (+98) 9111847131
Nikookar and Jafarpour Lashkami- Comput. Res Prog. Appl. Sci. Eng. Vol. 03(11), 308-321, December 2015
immobilization, soil washing, and phytoremediation are frequently listed among the best available
technologies. Needless to say it could have been mostly demonstrated in developed countries. These
technologies are recommended for field applicability and commercialization in developing
countries also where agriculture, urbanization, and industrialization are leaving a legacy of
environmental degradation.
Excavation of contaminated soil was once the solution for soil remediation. Due to the high cost
of excavation, final disposal of landfills, and lack of available landfill sites, these disposal methods
are becoming increasingly less popular [2]. To decrease costs, various technologies are being
developed and implemented for remediation of soils and sediments. In situ treatment of soil is
preferable since they are more cost-effective and less disruptive than ex situ processes. However,
there are very many difficulties with in-situ processes since they are more difficult to be controlled
[3].
Chemical stabilization of problematic soils using chemical admixture is one of the various
methods of stabilization which have been used to improve the soil performance. Stabilization with
chemical additive involves treatment of the soil with some kind of chemical compound, which
when added to the soil, would result in chemical reaction. The chemical reaction modifies or
enhances the physical and engineering aspects of a soil, such as, volume stability and strength of a
soil [4]. Of more recent interest is the stabi¬lization of contaminated soils and sewage sludges for
use in bulk fill operations for highway earthworks [5]. Stabilization must then be considered as
having both a physical aspect involving changes to the mechanical properties of the material, and a
chemical aspect involving changes to the form and mobility of the contaminants present.
Stabilization must therefore be considered as having both a physical aspect involving changes to the
mechanical properties of the material, and a chemical aspect involving changes to the form and
mobility of the contaminants present [6].
Stabilization reduces the mobility of hazardous substances and contaminants in the environment
through both physical and chemical means. It physically binds or encloses contaminants within a
stabilized mass and chemically reduces the hazard potential of a waste by converting the
contaminants into less soluble, mobile, or toxic forms.
Currently, several technologies can be employed to clean up the soils and the mining wastes
contaminated by toxic metals, including thermal, biological, and physical/chemical procedures, or
their appropriate combinations. These techniques usually require the removal of contaminated soil,
its subsequent treatment and either replacing it on-site, or disposed in specific landfills, located in
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most cases rather away from the polluted areas; therefore, creating a secondary disposal problem,
due to the presence of lead and of other toxic metals. Such treatment/removal technologies are
generally costly to practice and destructive to the application sites, from which the wastes are
removed. In addition, these removal technologies are often partially effective for the total removal
(efficient clean up) of toxic metals, or for the sufficient reduction of their mobility and
bioavailability to the environment [7].
The purpose of this paper is to summarize the major findings of data published on stabilization
of various types of contaminated soils such as heavy and toxic metals (As, Cr, Cu, Pb and Zn) using
different additives like ordinary portland cement (OPC), rice husk ash (RHA), lime, synthesized
zeolite and etc.
2. Soil Contaminating Materials
‘Heavy metals’ is a widely-used term for elements with metallic properties - it is not, in fact, a
scientifically accurate description, since the definition of ‘heavy’ is not fixed, and some so-called
heavy metals, such as arsenic and antimony, are semi-metals or metalloids. The group ‘heavy
metals’ for the purpose of discussing health risks or impacts generally includes: Arsenic (As), Lead
(Pb), Cadmium (Cd), Chromium (Cr) (although only the form Cr(VI) is toxic), Copper (Cu),
Mercury (Hg), Nickel (Ni) and Zinc (Zn). Several of these elements are necessary for human health,
and are beneficial when taken in to the body in foods or as supplements at appropriate, low levels
[8].
This study is an overview of data published on the stabilization and immobilization of five
materials contaminating soils including one metalloid, As, and four heavy metals, Cr, Cu, Pb and
Zn, in soils.
2.1. Arsenic
Arsenic is one of the most toxic elements. Arsenic is classified as a metalloid (having some
properties of a metal) and, like lead, occurs everywhere in the environment. Arsenic also has many
beneficial uses but can cause human health problems if exposure is sufficient. Environmental
contamination with arsenic because of human activities is less widespread than contamination from
lead but can be of regional and local importance [9].
2.2. Chromium
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Chromium is an important industrial metal used in diverse products and processes [10]. At
many industrial and waste disposal locations, chromium has been released to the environment via
leakage and poor storage during manufacturing or improper disposal practices [11].
2.3. Copper
Copper is the third most used metal in the world [12]. Copper is an essential micronutrient
required in the growth of both plants and animals. In humans, it helps in the production of blood
haemoglobin. In plants, Cu is especially important in seed production, disease resistance, and
regulation of water. Copper is indeed essential, but in high doses it can cause anaemia, liver and
kidney damage, and stomach and intestinal irritation. Copper normally occurs in drinking water
from Cu pipes, as well as from additives designed to control algal growth.
2.4. Lead
Lead (Pb) is one of the most common contaminants found in soils contaminated as a result of
agricultural activities, urban activities and industrial activities such as mining and smelting. It is
toxic both to humans and animals, especially to young children and hence presents a serious
environmental and health hazard [13]. Lead is a heavy, soft, malleable metal. Due to its physical
and chemical properties, industry has found countless uses for lead in our daily lives. While certain
uses of lead are banned, lead is still found in a myriad of products such as, lead in paint, lead in
occupational settings (often brought home on clothes or skin), Lead from industrial emissions, Lead
in drinking water and etc.
2.5. Zinc
Zinc is a transition metal. Most Zn is added during industrial activities, such as mining, coal,
and waste combustion and steel processing. Zinc provides the most cost-effective and
environmentally efficient method of protecting steel from corrosion. Zinc is also an essential
element which is indispensable for human health and for all living organisms. This essentiality
makes the interaction between zinc and the environment complex. Despite, in the vicinity of some
old industrial sites, levels of zinc in the soil, usually in combination with other metals, can be
elevated due to high emissions in the past (historical contamination). Such sites need specific
attention and appropriate risk management to limit exposure of the local ecosystem and prevent
contamination from spreading to surrounding areas. Promising results have recently been obtained
with metal immobilising compounds that, when mixed with contaminated soils, fix zinc and other
metals to the soil complex, rendering them less available for uptake by organisms [14].
3. Stabilization / Immobilization Results
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Stabilization involves the addition of reagents to the contaminated soil to produce more
chemically stable constituents. The general approach for stabilization treatment processes involves
mixing or injecting treatment agents to the contaminated soils. Inorganic binders (Table 1), such as
clay (bentonite and kaolinite), cement, fly ash, blast furnace slag, calcium carbonate, Fe/Mn oxides,
charcoal, zeolite [15, 16], and organic stabilizers (Table 2) such as bitumen, composts, and manures
[17], or a combination of organic-inorganic amendments may be used.
Table 1. Organic amendments for heavy metal immobilization [18].
Material
Heavy metal immobilized
Bark saw dust (from timber industry )
Cd, Pb, Hg, Cu
Xylogen ( from paper mill waste water )
Zn, Pb, Hg
Chitosan ( from crab meat canning industry )
Cd, Cr, Hg
Bagasse ( from sugar cane )
Pb
Poultry manure ( from poultry farm )
Cu, Pb, Zn, Cd
Cattle manure (from cattle farm )
Cd
Rice hulls ( from rice processing )
Cd, Cr, Pb
Sewage sludge
Cd
Leaves
Cr, Cd
Straw
Cd, Cr, Pb
Table 2. Inorganic amendments for heavy metal immobilization [18].
Material
Heavy metal immobilized
Lime ( from lime factory )
Cd, Cu, Ni, Pb, Zn
Phosphate salt ( from fertilizer plant )
Pb, Zn, Cu, cd
Hydroxyapatite (from phosphorite )
Zn, Pb, Cu, Cd
Fly ash ( from thermal power plant )
Cd, Pb, Cu, Zn, Cr
Slag (from thermal power plant )
Cd, Pb, Zn, Cr
Ca – montmorillonite ( mineral )
Zn, Pb
Portland cement ( from cement plant )
Cr, Cu, Zn, Pb
Bentonite
Pb
Many of the additives are not effective in immobilizing organic contaminants. Modified clays,
however, are currently being studied for application in the stabilization/immobilization of organic
contaminants. Recent tests with some silicate binders and some organic binders have shown success
in immobilizing and perhaps treating some semivolatile and heavier organic contaminants [19].
The consequences of findings for the stabilization/immobilization of contaminated soils by the
presence of heavy-toxic metals in this study have been discussed.
3.1. Arsenic
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The mobility of As in soil is mainly controlled by adsorption/desorption processes and coprecipitation with metal oxides. Therefore the most extensively studied amendments for As
immobilization are oxides of Fe and, to a lesser extent, Al and Mn. Iron salts are commonly used
for As stabilization purposes. Ferrous, Fe(II), sulfate was demonstrated to effectively reduce As
mobility. Precipitation of Fe oxides, followed by the Fe sulfate application, causes acid (H2SO4)
release. Co-mixing of lime is usually used to avoid soil acidification. Application rates based on
As/Fe molar ratio can be more informative seeing as different soils have different contamination
levels requiring different amounts of reactive Fe [20]. Moreover, pH and the type of organic matter
might play a role in its varying effect on As mobility. Grafe et al. in 2002 [21] studied adsorption of
As on synthetic ferrihydrite under the influence of three types of OM: peat humic acid (HA),
Suwannee River fulvic acid (FA) and citric acid (CA). According to their results, FA and CA
adsorption to ferrihydrite outcompeted As(III) adsorption at low pH, while only CA was able to
reduce As(V) adsorption on ferrihydrite. HA and As sorption were not interfering and was
suggested to be independent of each other. The authors also observed that goethite had a higher
affinity for dissolved organic carbon (DOC) with a higher surface coverage and stronger bonds than
ferrihydrite. Organic matter can change As speciation by reducing As(V) to more toxic and mobile
As(III). Studies on nine artificially CCA-contaminated soils revealed that in mineral soils on
average 92% of total As was As(V), while in highly organic soils the proportion of As(III)
significantly increased to one third of the total soil As [22].
Stabilization is an established treatment technology often used to reduce the mobility of arsenic
in soil and waste. The most frequently used binders for stabilization of arsenic are pozzolanic
materials such as cement and lime. Stabilization can generally produce a stabilized product that
meets the regulatory threshold of 5 mg/L leachable arsenic as measured by the TCLP. However,
leachability tests may not always be accurate indicators of arsenic leachability for some wastes
under certain disposal conditions.
The stabilization process involves mixing a soil or waste with binders such as Portland cement,
lime, fly ash, cement kiln dust, or polymers to create a slurry, paste, or other semi-liquid state,
which is allowed time to cure into a solid form. When free liquids are present the S/S process may
involve a pretreatment step (solidification) in which the waste is encapsulated or absorbed, forming
a solid material. Pozzolanic binders such as cement and fly ash are used most frequently for the
stabilization of arsenic.
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Figure1. Model of a Solidification/Stabilization System
Besides other stabilization techniques, acid-washing process used for arsenic contaminated
soils. Results obtained from Tokunaga and Hakuta in 2002 [23], laboratory investigation on acid
washing and stabilization of an artificial arsenic-contaminated soil indicated that:
Acid-washing and stabilization processes have been developed for the remediation of
arsenic(V)-contami¬nated soil. Kuroboku soil, a model soil, sorbed arsenic ions in the pH range
2~7 with the maximum sorption capacity of 3150 mg/kg. The arsenic desorption from the modelcontaminated soil (2830 mg As/kg soil) became appreciable in the pH range of <1. Phosphoric acid
is the most promising extractant, and its effectiveness can be attributed to the synergetic function as
a donor of phosphate ions which displace arsenic through ligand exchange mechanism as well as its
function as an acid dissolving metallic components of the soil. Arsenic extraction with phosphoric
acid reached a maximum within 2 h, indicating that arsenic sorbed in the soil can be rapidly
extracted. Acid-washed soil can be further stabilized by the addition of lanthanum, cerium, and
iron(III) salts or their oxides or hydroxides. Both salts and oxides of lanthanum and cerium were
effective in immobilizing arsenic in the soil attaining less than 0.01 mg/l As in the leaching test.
3.2. Chromium
The mobility of Cr in soil depends on its oxidation state. Therefore, Cr stabilization mainly
deals with Cr reduction from its toxic and mobile hexavalent form Cr(VI) to a rather stable in
natural environments Cr(III). In the recent studies, Cr was not a contaminant in focus and the effects
of soil amendments on the Cr stabilization were observed in a context of the other contaminants.
The reduction of Cr in soils is accelerated by the presence of organic matter and divalent iron. Also,
alkaline materials like fly ash, hydroxyapatite, CaCO3 that increase soil pH above neutral favor the
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oxidation of Cr(III) to Cr(VI) [24]. This can cause a higher Cr mobility and uptake by vegetation
[25].
Besides Cr oxidation state, Chromium mobility depends on sorption characteristics of the soil,
including clay content, iron oxide content, and the amount of organic matter present. Chromium can
be transported by surface runoff to surface waters in its soluble or precipitated form. Soluble and
un-adsorbed chromium complexes can leach from soil into groundwater. The leachability of Cr(VI)
increases as soil pH increases. Most of Cr released into natural waters is particle associated,
however, and is ultimately deposited into the sediment [26]. Chromium is associated with allergic
dermatitis in humans [27].
3.3. Copper
Clays, carbonates, phosphates and Fe oxides were the common amendments tested for Cu
immobilization. The suggested mechanisms of Cu retention were precipitation of Cu carbonates and
oxyhydroxides, ion exchange and formation of ternary cation–anion complexes on the surface of Fe
and Al oxy-hydroxides.
Industrial by-products, like coal and biofuel combustion fly ashes (CFA), are alkaline materials
with high sorptive capacity, mainly composed of ferroaluminosilicates, and can be used as
ameliorants for acidic soils. Fly ashes are suggested to solve problems related to acid mine drainage
and metal solubility [28, 29, 30]. Fly ashes increase the surface area available for element
adsorption, improve the physical properties of soil, neutralize the pH of acidic soils and render most
cationic metals less mobile [31].
According to Kumpiene et al, studies in 2007 [32], Soil amendment with coal fly ash and peat
reduced the leaching of Cu from contaminated soil by an average of 96% in laboratory batch
experiments and by 96% during the two-year field observation period.
3.4. Lead
Most of the studies on the Pb stabilization were performed using various phosphorus-containing
amendments, such as synthetic and natural apatites and hydroxyapatites [7], phosphate rock [33],
phosphate-based salts [34, 35], diammonium phosphate [36], phosphoric acid [37, 38, 39, 40, 41]
and their combinations. In general, the treatment efficiency of soil contaminated with Pb by
phosphorus compounds is very high.
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Based on Dermatas, 1994 [42]; Kim et al., 1997 [43] investigations about the effectiveness of
different additives on Pb immobilization, among the different additives tried, lime-based
stabilization technique showed high efficiency on Pb metal. Moreover, Ma et al. in 1995 [44]
reported that rock phosphate were very effective for immobilization of Pb in contaminated soils.
According to Alpaslan and Yukselen in 2002 [45] laboratory investigation on the effectiveness
of different additives on Pb, following consequence were obtained:
• Although a significant decrease (82%) on mobility of Pb was observed through activated
carbon addition at 1:5 additive:soil ratio, application of this mixing ratio will not be economical in
practice and volume of treated soil matrix will increase as a result of huge amount of activated
carbon addition. Thus, activated carbon was determined as inefficient additive for immobilization of
Pb.
• Since no decrease in Pb mobility was observed due to clay, zeolite and sand addition, it was
concluded that these additives have no effect on Pb immobilization. If the pH of soil is somehow
increased above 6 however, clay can be effective due to adsorption of Pb on clay surfaces.
• Lime was determined as very effective additive for lead immobilization through precipitation
of lead hydroxides formed and entrapment of them in cementitious compounds resulted from
pozzolonic reactions occurring with lime addition. The optimum mixing ratio of lime:soil was
found as 1:21 ratio showing 88% immobilization efficiency on Pb at pH 12.6.
• Cement showed very high efficiency on immobilization of Pb through formation of insoluble
lead hydroxides and microencapsulation of them in resultant hardened mass. The determined 1:15
cement: soil ratio provided significantly higher Pb immobilization efficiency (99%) at pH 8.3 than
that was provided by optimum lime:soil ratio under 12.6.
Yin et al., 2006 [46] study results indicated that usage of OPC with RHA as an overall binder
system for stabilization of lead-contaminated soils showed tremendous potential as evident in the
regulatory compliance of two predominant post-treatment test parameters, namely UCS and
leachability of metals. Incorporation of RHA in the binder system was justified as leachability of
lead from the treated samples was reduced corresponding to incorporation of RHA increments from
0 to 30%. Even though partial replacement of OPC with RHA in the binder system reduced the
UCS of solidified samples, it was still high enough to exceed the mortar limit of 20 N/mm2, which
was more than sufficient to be reused as construction materials. The presence of lead(II) nitrate
increased the initial and final setting times of mortar mixtures. Initial incorporation of 10 wt% RHA
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into the binder system significantly increased the mixture’s initial setting time while subsequent
RHA incorporations conversely reduced the mixture’s initial setting times. Moreover, Soil
amendment with coal fly ash and peat reduced the leaching of Pb from contaminated soil by an
average of 99.9% in laboratory batch experiments and by 97% during the two-year field observation
period.
3.5. Zinc
A number of studies have been done attempting to stabilize Zn in soil by phosphorus
amendments [47, 36, 48, 39, 49]. Results indicated that Zn was immobilized as metal-phosphate
precipitates with low solubility and high resistance to soil acidification. The treatment efficiency
using a 4% clay dose reduced the readily extractable (water soluble + exchangeable) Zn fraction by
76% (palygorskite) and 99% (sepiolite) from highly polluted mining soils. Alkaline materials like
coal fly ash and red mud also decreased Zn leaching by 99.7% and 99.6%, respectively [50].
Based on Houben and Sonnet study in 2010 [51], the amendment of iron grit in soil was very
effective in reducing Zn up to 98%. Likely mechanisms are, among others, a pH increase and the
sorption of ionic free metals and organometal complexes.
According to Yan-Jun Du et al. laboratory tests in 2014 [52] , the effects of high levels of zinc
concentration on the compressibility of natural clay stabilized by cement additive have been
evaluated. Several series of laboratory compression (oedometer) tests were conducted on the soil
specimens prepared with the zinc concentrations of 0, 0.1, 0.2, 0.5, 1, and 2 %, cement contents of
12 and 15 %, and curing time of 28 days. The results show that the yield stress and compression
index at the post-yield state decrease with an increase in the zinc concentration regardless of the
cement content. The observed results are attributed to the decrease in the cement hydration of the
soil. Overall, this study demonstrates that the cementation structure of the soils is weakened, and the
compressibility increases with the elevated zinc concentration, particularly at relatively high levels
of zinc concentration.
3.6. Stabilization of multi-element contaminated soil
The presence of one contaminant (e.g. Cu or Pb) can decrease the stabilization efficiency of the
other (e.g. Zn) due to competition for sorption sites. Contrary to that, several contaminants of an
opposite charge can have a synergistic effect on each other and significantly increase the retention
capacity by, for example, forming complex As – Zn precipitates on Fe oxy-hydroxides [20]. Lime
can effectively reduce the mobility of Cu and Pb in contaminated soils by raising the soil pH.
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Alkaline industrial by-products like fly ashes can neutralize soil acidity arising from acid mine
drainage generation in sulfide-rich waste and prevent contaminant spread [29, 30]. Fly ashes have a
more sustained neutralizing effect than lime [53], but increasing soil pH to alkaline region can
increase the risk of Cr(III) transformation to Cr(VI) and As(V) to As(III). Both transformed species
are much more mobile and toxic, and therefore undesirable.
4. Conclusions
Based on conducted investigation on stabilizing contaminated soil, stabilization/ immobilization
and acid-washing reduces the hazard potential of a waste by converting the contaminants into less
soluble, mobile, or toxic forms. To achieve the best stabilized/immobilized soli, different additives
including: inorganic binders, such as clay (bentonite and kaolinite), cement, fly ash, blast furnace
slag, calcium carbonate, Fe/Mn oxides, charcoal, zeolite and organic stabilizers such as bitumen,
composts, and manures, or a combination of organic-inorganic amendments may be
used.conclusions.
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