Pedosphere 25(4): 555–568, 2015

ISSN 1002-0160/CN 32-1315/P

c 2015 Soil Science Society of China
Published by Elsevier B.V. and Science Press

Immobilization of Lead and Cadmium in Contaminated Soil

Using Amendments: A Review

Amanullah MAHAR1,2 , WANG Ping1 , LI Ronghua1 and ZHANG Zengqiang1,∗

1 College of Natural Resources and Environment, Northwest A&F University, Yangling, Shannxi 712100 (China)
2 Centre for Environmental Sciences, University of Sindh, Jamshoro 76080 (Pakistan)
(Received September 9, 2014; revised May 4, 2015)

ABSTRACT
Since the inception of industrial revolution, metal refining plants using pyrometallurgical processes have generated the prodigious
emissions of lead (Pb) and cadmium (Cd). As the core target of such pollutants, a large number of soils are nowadays contaminated
over widespread areas, posing a great threat to public health worldwide. Unlike organic pollutants, Pb and Cd do not undergo chemical
or microbial breakdown and stay likely in site for longer duration after their release. Immobilization is an in-situ remediation technique
that uses cost-effective soil amendments to reduce Pb and Cd availability in the contaminated soils. The Pb and Cd contamination in
the soil environment is reviewed with focus on source enrichment, speciation and associated health risks, and immobilization options
using various soil amendments. Commonly applied and emerging cost-effective soil amendments for Pb and Cd immobilization include
phosphate compounds, liming, animal manure, biosolids, metal oxides, and biochar. These immobilizing agents could reduce the
transfer of metal pollutants or residues to food web (plant uptake and leaching to subsurface water) and their long-term sustainability
in heavy metal fixation needs further assessment.
Key Words: bioavailability, biochar, biosolids, heavy metal, public health, remediation, soil extraction

Citation: Mahar A, Wang P, Li R H, Zhang Z Q. 2015. Immobilization of lead and cadmium in contaminated soil using amendments:
A review. Pedosphere. 25(4): 555–568.

INTRODUCTION pends upon the source, dosage, rate, and magnitude

of plant metal uptake, physico-chemical properties of
The contamination of land resources is a major soil, and the extent of absorption by animals (Adri-
worldwide concern as urban sprawl and industrial units ano, 2001). Worldwide public now becomes vocal on
are continuously rising and leaving negative ecological the detrimental health implications to humans and the
footprints on the natural environment (Wong and Li, natural environment (Marshall, 2001). On a histori-
2004). Lead (Pb)- and cadmium (Cd)-contaminated cal note in human health, metal toxicity has gained
soils are a global environmental concern that results significant attention as a result of serial poisoning at
not only in human health and ecological hazards, but a large scale; i.e., a huge number of human poisoning
also in huge economic implications with respect to tragic cases of Minamata disease due to consumption
reclamation and restoration costs (Semenzin et al., of contaminated fish by toxic metals were recorded, in
2007). Since the last few decades, the distribution and Minamata Bay in Japan in the late 1950s (Knopf and
mobility of heavy metals in various soils have been König, 2010).
documented. While few heavy metals are essential for Many countries have recorded excessive Pb and Cd
living organisms in trace quantities, most are haza- concentrations in their soils. Significant negative effects
rdous in high concentrations. Among the later, Cd and of Pb and Cd on human health have been noted in
Pb, which are naturally present in soils, can accumu- China, India, and Bangladesh with an alarming large
late in humans and cause serious health problems (Ok number of populations at risk from toxic metals (Bhat-
et al., 2004). tacharya et al., 2012). Cadmium is a serious concern
Various unsustainable waste disposal practices for Australia and New Zealand, where it accumulates
have resulted in significant accumulation of a diverse in offal of grazing animals and makes it unsuitable for
range of toxic heavy metals including Cd and Pb. human usage (Loganathan et al., 2008). Likewise, Pb
The contamination of toxic metals in food chain de- in soils resulting from unsustainable use as a compo-

∗ Corresponding author. E-mail: [email protected].

556 A. MAHAR et al.

nent of herbicides and fungicides during urban develop- plied for remediation. For safe disposal of toxic metals
ment of horticultural sites is also an increasing concern from urban soil, phytoextraction process and the sub-
there (Pietrzak and Uren, 2011). sequent recovery are considered for commercial and re-
Toxic heavy metals do not undertake chemical and search implications (Robinson et al., 2009). However,
microbial degradation and their total concentrations when phytoextraction is ineffective, alternate options,
usually do not change due to their persistent nature i.e., in-situ immobilization, are considered as impor-
after being released into the environment (Adriano et tant part of environmental management (Fig. 1). Both
al., 2004). As a result, the scientific community fo- organic and inorganic soil amendments are components
cuses immensely on the development of soil remedia- of remediation techniques applied to manage conta-
tion technologies as global masses are increasingly vo- minated soils.
cal on the animal and human health implications re- The immobilization of Pb and Cd in contaminated
sulting from contaminated soils. Soil remediation tech- soils depends upon the local availability and financial
nologies are of special attention since conventional soil implications of soil amendments. Therefore, the main
reclamation practices, i.e., landfilling and excavation, question to be answered here in this review is that
are often very expansive and environmentally unfea- what types of amendments have been commonly em-
sible, as compared to alternative options. Many soil ployed and are emerging as cost-effective technologies
amendment based-technologies such as soil immobiliza- to immobilize Pb and Cd in contaminated soils by sig-
tion/solidification are cost effective and less environ- nificantly decreasing bioavailability of these metals.
mentally disruptive (Mulligan et al., 2001; Kumpiene
SOURCES OF ENRICHMENT IN SOIL
et al., 2008).
Unlike organic pollutants which can be destroyed, Soil functions as a final sink for heavy metal
heavy metals impair their toxicity and mobility by contamination in terrestrial ecosystems. Both anthro-
triggering the important immobilization process, i.e., pogenic and pedogenic sources contribute to heavy me-
(ad)sorption, precipitation, complexation, and redox tal loads in the soil environment. Most toxic trace ele-
reactions, in the process of soil remediation (Adriano ments are naturally present in the parent material of
et al., 2004). In addition, biological and chemical sta- soil, mainly in forms that are not readily bioavailable
bilization of toxic heavy metals using organic (i.e., for plant absorption or uptake as compared to those
biosolids) and inorganic amendments (i.e., phosphate of pedogenic contribution by anthropogenic sources
compounds and lime) are suitable options to minimize which have extreme bioavailability (Naidu et al., 1996;
metal bioavailability (Park et al., 2011a). In the ur- Lamb et al., 2009). Anthropogenic activities such as
ban environment, as more localized toxic heavy metals manufacturing industrial processes, usage of phospho-
are found, the process of metal stabilization including rus (P) fertilizers, and disposal of domestic and indus-
chemical washing and phytoextraction has been ap- trial wastes are the main sources of toxic heavy metals

Fig. 1 Illustrative diagram showing the relationship between immobilization, bioavailability and remediation of toxic heavy metals
(Bolan et al., 2014). M = metal.
SOIL LEAD AND CADMIUM IMMOBILIZATION 557

in the soil environment (Adriano, 2001; Bolan et al., consumption of municipal biosolids (Wuana and Oki-
2003a, b, c, d; Gray et al., 2003). eimen, 2011).
Lead is a natural constituent in the Earth’s crust
SOIL EXTRACTION TECHNIQUES
and is normally available at trace concentrations in
plants, soils, and water bodies. Metallic Pb is rarely Bioavailability of Pb and Cd in soil can be inves-
found in the natural environment (Cheng and Hu, tigated using chemical extraction and bioassay proce-
2010). Galena (PbS) and cerussite (PbCO3 ) are the dures that assess a bioaccessible fraction of these me-
important Pb minerals; anglesite (PbSO4 ) and pyro- tals. Sequential and single extractions using reagents
morphite (Pb5 (PO4 )3 Cl) also frequently occur but in are the methods of chemical extraction (Ruby et al.,
less quantities (Crook, 1921). Lead is commonly found 1996; Basta and Gradwohl, 2000). Animals, plants,
in ores which also contain copper (Cu), zinc (Zn), and and microorganisms are the tools for bioassay (Yang
silver (Ag) and extracted as a co-product of these me- et al., 1991; Domene et al., 2010).
tals. Lead is extremely malleable, ductile, and very Salt solutions (0.01 mol L−1 CaCl2 ), mineral acids
easy to smelt, and its ores are extensive. Lead may e- (1 mol L−1 HCl), chelating agents (diethylene triamine
xist in the Bronze and Copper ages and is considered as pentaacetic acid (DTPA)), and buffer solutions (1 mol
one of the seven antique metals. In 6 500 BC, the first L−1 NH4 OAc ) are chemical extractants used in sin-
Pb object was used and the processing of Pb minerals gle extraction procedure for assessing bioavailability
upgraded significantly around 6 000 years ago (Nriagu, in Pb- and Cd-contaminated soils (McBride et al.,
1983). Due to anthropogenic activities at a global scale, 2009; Bakircioglu et al., 2011). Chelating agents (0.05
Pb has become a widespread toxic metal in the natural mol L−1 DTPA and 0.05 mol L−1 ethylenediamine
environment across the world. Today, Pb is used exten- tetraacetic acid (EDTA)) have been documented as
sively in lead-acid batteries, weights, pewters, fusible more trustworthy in predicting the Pb and Cd availa-
alloys, and bullets, lead shots (pellets), solders, and bility in plants and are more impressive in eliminating
building construction (Cheng and Hu, 2010). soluble metal-organic complexes (Sims and Johnson,
Atmospheric deposition due to emission of Pb- 1991; Zhu et al., 2012).
based petrol is a main problem in various countries Sequential extraction schemes are commonly used
where there is no restriction on consumption of leaded to determine the redistribution or partitioning of Pb
gasoline (Fenger, 2009). On the other hand, biosolids and Cd in different chemical forms, i.e., adsorbed (ex-
are the main source of toxic metals released in North changeable), soluble, occluded, and precipitated (Ta-
America and Europe, and P fertilizers are considered to ble I). With each successive step of the scheme, the
be the main source of heavy metals, especially Cd and bioavailability and solubility of Pb and Cd in soil re-
Pb, in New Zealand, Australia, and China (McLaugh- duces, though the extraction methods differ (Basta and
lin et al., 1996; Bolan et al., 2003a; Loganathan et al., Gradwohl, 2000; Zakir and Shikazono, 2011). Specific
2008; Haynes et al., 2009). The main sources of Pb chemical species measured through chemical extraction
contamination in soil are smelting, mining, industrial, procedures have been successfully linked with plant
coal burning, and waste incineration. metal uptake in assuming the plant availability of me-
Cadmium is odorless, whitish silver in appearance tals in soils (Naidu et al., 1997; Abedin et al., 2012).
and has a firm bioaccumulative tendency. It is easily The relative bioaccessibility leaching procedure
absorbed into animal, human, and plant tissues due (RBALP), physiologically based extraction test (PB-
to its chemical nature similar to Zn (van der Voet et ET), gastrointestinal (GI) test, and potentially bio-
al., 1994). This is a highly toxic metal and usually available sequential extraction (PBASE) are the physi-
found in the industrial work places, extensively used ologically based in vitro chemical extraction proce-
in electroplating, industrial paints, sprays, and manu- dures for assessing bioavailability of Pb and Cd in soil
facturing of batteries, and results from the waste-water (Drexler and Brattin, 2007; Ng et al., 2013). These ad-
discharge of stearate Cd factories. Cadmium contami- vanced schemes predict the bioavailability of Pb and
nation due to P fertilizers used in agricultural soils is Cd in sediment and soil when ingested by human and
of specific concern because Cd originates from phos- animals. With reference to the conventional sequential
phate rocks which are used for P fertilizer manufac- procedures, the capacity of these schemes to solubilize
turing and becomes part of food chain through regular Pb and Cd enhances with each following extraction
use of Cd-containing P fertilizers. The safe limits for P step. Regardless of the identified non-specific nature of
fertilizers have not been set, although various countries these chemical extraction procedures, their analytical
have stipulated threshold levels for Cd in soil due to simplicity and speed prove them to be most potential
558 A. MAHAR et al.

TABLE I
Different methods used for extraction of Pb and Cd in soils or sediments from various parts of the world

Soil(s) or sediments Extraction techniquea) Analytical References

methodb)
Sediments from Barcelona Harbour, Spain Modified BCR three-step sequential extraction ICP-MS Guevara-Riba et al., 2004
method
Sediments from Kranji & Pulau Tekong Modified BCR three-step sequential extraction GFAAS Cuong and Obbard, 2006
Harbour, method
Singapore
Sediments from Townsville Harbour, Qu- Modified Tessier extraction method AAS Esslemont, 2000
eensland, Australia
Sediments from Richards Bay Harbour, Tessier extraction method FAAS Wepener and Vermeulen,
South Africa 2005
Sediments from East China Sea BCR three-step sequential extraction method ICP-MS Yuan et al., 2004
Sediments from Norwegian Sea and Baltic Four-step sequential extraction method AAS Pempkowiak et al., 1999
Sea
Sediments from Huelva Estuarine, Spain Three sequential extraction methods AAS Usero et al., 1998
Sediments from Southwest Coast, Spain BCR-sequential extraction method GFAAS Morillo et al., 2004
Urban Soils from Hangzhou City, China Optimized BCR three-step sequential extraction ICP-MS Zhang and Wang, 2003
method
Polluted soils and sediments from Morocco Optimized BCR three-step sequential extraction FAAS Elass et al., 2004
method
Soils affected by accidental spills from Optimized BCR three-step sequential extraction ICP-MS Pueyo et al., 2003
Spain method
Contaminated soils from Iran Na2 -EDTA (0.1 mol L−1 ) extraction AAS Mahvi et al., 2005
Soil from Moscow Region, Russia Kerstner-Forstner sequential extraction scheme ICP-MS Katasonova et al., 2005
Contaminated soil from Southwest of Sar- Sequential extraction with H2 O, 0.1 mol L−1 ICP-MS Garau et al., 2007
dinia, Italy Ca(NO3 )2 , and 0.05 mol L−1 EDTA
Tropical soils from Sao Paulo State, Brazil Ahnstrom and Parker extraction scheme AAS Silveira et al., 2006
Contaminated soils from Carpiano, Milan, DTPA/TEA method ICP-OES Contin et al., 2008
Italy
Contaminated soil from Chungnam, Korea Deionized water and 0.1 mol L−1 Ca(NO3 )2 ex- ICP-MS Lee et al., 2009
traction
Contaminated soil from Arnoldstein, Aus- DTPA, CaCl2 , EDTA, and ammonium acetate AAS Tica et al., 2011
tria extraction scheme
Smelter site soils from Anghang, Seocheon, USEPA TCLP method 1311 ICP-OES Bade et al., 2012
Chungnam, Korea
Contaminated soils from Hadong Coast, Aqua regia extraction ICP-OES Ok et al., 2011
Gyeongnam, Korea
a) BCR = Community Bureau of Reference; EDTA = ethylenediamine tetraacetic acid; DTPA = diethylene triamine pentaacetic acid;
TEA = triethanolamine.
b) ICP-MS = inductively coupled plasma-mass spectrometry; GFAAS = graphite furnace atomic absorption spectrometry; AAS =

atomic absorption spectrophotometry; FAAS = flame absorption atomic spectrometry; ICP-OES = inductively coupled plasma-optical
emission spectrometry; TCLP = toxicity characteristic leaching procedure.

for regular identification of metal forms and assessment changes. On the other hand, macrofauna (enchytri-
of Pb and Cd bioavailability in situ although the dis- dae, invertebrates, and earthworms) and mesofauna
persal of given metals among different fractions can (microarthropods) have the ability to demonstrate col-
only be measured as a valuation at best because of the lective impacts. There are drawbacks in these met-
subjectivity of the steps involved. hods: they are time consuming and can only give an
As microorganisms are more sensitive to metal overall impact of metal bioavailability to the species
(Pb and Cd) stress than plant flora or soil microfau- tested. In addition, molecular techniques are swiftly
na, determining bioavailability and toxicity of metals developed and applied, but they are generally rela-
in contaminated soils employing microorganisms are tively expensive; thus, the information given by the
gaining more and more focus nowadays (Zhang et al., techniques requires to be well explained (Amaro et al.,
2010; Anyanwu et al., 2011). The procedures using pro- 2011; Frostegård et al., 2011).
tozoa and microflora have showed the capacity to de-
PUBLIC HEALTH RISKS
liver an extent of short-term bioavailability of heavy
metals and even enable the assessment of temporal Soils contaminated with toxic heavy metals not
SOIL LEAD AND CADMIUM IMMOBILIZATION 559

only possess threats to environmental health but al- diation technologies to minimize or control Pb and
so have huge financial issues, i.e., removal costs and Cd contamination in soil. In general, various reme-
restoration problems (Semenzin et al., 2007; Chapman diation methods are needed to eliminate Pb and Cd
et al., 2013). Lead is susceptible for inhalation or in- from wastes containing exceeding levels of contami-
gestion from different sources, i.e., food items, pollu- nants than stipulated safe limits. Various amendments
ted ambient air, soil, and polluted potable water. A are being employed to immobilize Pb and Cd in conta-
soil contaminated with Pb mostly enters human body minated soils. Immobilization of toxic heavy metals
through inhalation or ingestion and may leave harm- can be achieved mainly through precipitation, com-
ful effects on the central nervous system (Needleman plexation and adsorption, reactions which result in the
et al., 1990). Human adults are vulnerable to lead poi- redistribution of metals from solution phase to solid
soning, causing problems to central and peripheral ner- phase, thus reducing their transport and bioavailability
vous system, blood pressure, and kidney (Needleman, in the soil (Bolan et al., 2003a; Porter et al., 2004).
2004). Mild exposures to Pb may cause increased blood
Phosphate compounds
pressure, decreased neurological functions, weakness,
and tingling in the extremities (Jennings, 2013). High Various studies have reported convincing evidence
Pb exposures may cause kidney damage, miscarriages, for the mitigative value of both water-soluble (diammo-
severe brain impairment, and ultimately, death. Com- nium phosphate, DAP) and water-insoluble (apatite
pared to adults, infants and children are more vulne- from phosphate rock, PR) phosphate compounds (Ta-
rable to Pb poisoning, triggering irreparable impacts ble II), which can immobilize metals in soils, thus
on mental development in their early childhood (God- decreasing their bioavailability for plant and human
win, 2001). Even mild exposures can affect infant’s uptake, mobility, and transport (Bolan et al., 2003b,
neurological and physical development (ATSDR, 2007; d). Phosphate compounds increase the immobilization
NLM, NIH, 2012). Nowadays, Pb contamination is a of metals in soils through different processes, i.e., di-
global issue and the focus has shifted from suscepti- rect metal absorption/substitution by phosphate com-
bility of adults to increases of emissions in industrial pounds and precipitation of metals with phosphate so-
areas to a significant number of children populations lution as metal phosphates.
being more prone to respiratory allergies and asthma Through increased phosphate anion-induced metal
with lesser contacts (Needleman, 2004). A consensus adsorption and increased surface charge, soil applica-
analysis showed that Pb is probably a human carcino- tion of phosphate compounds can cause direct adsorp-
gen and leaves multiple impacts on overall quality of tion of metals on these compounds depending upon the
environmental health (ATSDR, 2007). sources. Precipitation as metal phosphates has been
Without any inhibition of plant growth, Cd can proved one of the main mechanisms for the immobiliza-
accumulate in plant at concentrations harmful to hu- tion of Pb and Cd in soils (Bolan et al., 2014). These
man or animal consumption (Asami, 1984). Cadmium fairly stable metal-phosphate compounds have ex-
is poisonous to all living organisms and can enter in- tremely low solubility over a wide pH range, which
to the human body through various different routes. makes phosphate application an attractive technology
When a human body absorbs Cd, it may show symp- for managing Pb- and Cd-contaminated soils, but
toms such as difficulty in breathing, salivation, vomi- phosphate is also a fossil source and high phosphate ap-
ting, nausea, anemia, abdominal pain, diarrhea, and plication rates cause eutrophication of water resources.
kidney failure. Furthermore, inhaling smoke or dust In typical arable soils, precipitation of Pb and Cd is un-
containing Cd may cause headache, dryness of throat, likely, but in modest Pb- and Cd-contaminated soils,
coughing, chest pain, bronchial complications, and in- this process can play a major role in the immobilization
creased uneasiness. Cadmium may also have harmful of such metals.
effects on the metabolic systems of living organisms The potential of apatite to immobilize Pb in conta-
(Doyle, 1977). Moreover, Cd might cause kidney disor- minated soils or solution by Pb-phosphate precipita-
der or ultimately death at the concentration of 200 mg tion has been well reported (Chrysochoou et al., 2007).
kg−1 in the kidney (Alloway et al., 1990). A total of The precipitants are usually termed as chloropyromo
64 persons died in the Jintsu Valley of Toyama, Japan rphite or hydroxypyromorphite. Two methods have
in 1969 due to Itaiitai disease (Friberg, 1984). been recommended for the reaction of dissolved Pb
with apatite. Firstly, Pb(II) in apatite can be a substi-
IMMOBILIZATION USING SOIL AMENDMENTS
tute for Ca(II). Thereby, through adsorption of Pb or
Many efforts have been made in developing reme- dissolution of hydroxyapatite (Ca10 (PO4 )6 (OH)2 ), (Ca,
TABLE II
Promising soil amendments in the immobilization of Pb and Cd in contaminated soils 560
Soil amendment(s) Target Immobilization result(s) Reference
metal(s)
Liming material(s)
Ca(OH)2 Cd Transforming to less mobile fractions, reduced phytoavailability Bolan et al., 2003c
Lime Cd No reduction in uptake, transferring to the kernels of sunflower Li et al., 1996
Lime Cd Reduced uptake by lettuce Lehoczky et al., 2000
Lime Pb, Cd Decreased Cd uptake, little influence on Pb uptake by radish Han and Lee, 1996
Ca(OH)2 , CaCO3 Cd Phytotoxicity prevented by Ca(OH)2 , but not by CaCO3 Chaney et al., 1977
Lime Cd Reduced uptake of Cd Brallier et al., 1996
Red mud, natural zeolite, lime Pb, Cd Reduced solubility of Pb and Cd, changes in microbial communities Garau et al., 2007
Zeolite, compost, calcium hydroxide Pb, Cd Increased residual fraction of metals in soils, decreased metal uptake by Castaldi et al., 2005
white lupin
Lime, red mud Cd, Pb Reduced metal concentrations in grass Gray et al., 2006
Cyclonic ash, lime Cd Reduced Cd accumulation in plant and concentration in soil pore water Ruttens et al., 2010
Portland cement Cd, Pb Different combinations with cement instead of cement alone as fixing agents Jang and Kim, 2000
Phosphate compound(s)
KH2 PO4 Cd Enhanced immobilization, decreased plant availability Bolan et al., 2003b
Apatite, zeolite, Fe oxide Cd, Pb Reduced mobility and plant uptake Chlopecka and Adriano, 1997
KH2 PO4 Pb, Cd, Zn Reduced Pb level, but not Zn and Cd levels in earthworms Pearson et al., 2000
Phosphate Pb Decreased Pb uptake with increasing phosphate supply, decreased phosphate Wang et al., 2002
concentration in the root with increasing Pb supply
Phosphate Pb, As Increased plant uptake of soil As, but no effect on soil Pb phytoavailability Creger and Peryea, 1994
H3 PO4 , Ca(H2 PO4 )2 , phosphate rock Pb Increased residual fraction, reduced translocation from root to shoot of plant Cao et al., 2003
Phosphate rock, diammonium phosphate Cd, Pb Reduced metal elution Basta and McGowen, 2004
Bonemeal (finely ground, poorly crystalline apatite) Pb Reduced concentration in the leachate and availability in soils Hodson et al., 2000
Hydroxyapatite, phosphate rock, triple superpho- Cd, Pb Reduced plant uptake Chen et al., 2007
sphate, diammonium phosphate
Metal oxide
Hydrous Mn oxide Cd, Pb Reduced mobility and ryegrass uptake Mench et al., 1994
Mn oxide Pb Reduced bioavailable fractions Hettiarachchi et al., 2000
Fe-rich waste (Fe (hydro)oxides) with redox cycles Cd, Pb, Reduced exchangeable fractions Contin et al., 2007
Mn oxide Cd, Pb Reduced exchangeable fraction and Chinese cabbage uptake Cheng and Hseu, 2002
Fe oxide waste byproduct Cd, Pb Reduced uptake by maize and barley Chlopecka and Adriano, 1996
Organic matter
Biosolid Cd Reduced bioavailability Bolan et al., 2003a
Papermill sludge, sewage sludge Cd Increased uptake Merrington and Madden, 2000
Biosolid Cd Reduced plant availability Brown et al., 1998
Biosolid Cd Increased phytoavailability in biosolid-amended soil by chloro-complexa- Weggler-Beaton et al., 2000
tion of Cd
Cow manure Cd No reduction in rice Kashem and Singh, 2001
Chicken manure compost Cd Reduced soluble/exchangeable fractions and phytotoxicity Liu et al., 2009
Compost Cd, Pb Decreased Cd leaching, but increased Pb leaching Ruttens et al., 2006
Coal fly ash, peat Pb Reduced leaching in the field lysimeters Kumpiene et al., 2007
Humus, compost Cd Reduced uptake by rice Ok et al., 2011
Biosolid, wood ash, K2 SO4 Pb, Cd Alleviated phytotoxicity of Pb and Cd and reduced bioavailability of Pb DeVolder et al., 2003
Hard wood biochar Cd Immobilization due to enhanced pH by biochar Beesley et al., 2010
Chicken manure- and green waste-derived biochars Cd, Pb Immobilization due to partitioning from the exchangeable to organic- Park et al., 2011c
bound fraction
Oak wood biochar Pb Sorption due to increases in soil pH Ahmad et al., 2012
A. MAHAR et al.
SOIL LEAD AND CADMIUM IMMOBILIZATION 561

Pb) apatites could be formed, followed by co-precipi-

tation of mixed apatites. Secondly, by precipitation of
pure hydroxypyromorphite (Pb10 (PO4 )6 (OH)2 ), Pb2+
can react with apatite through hydroxyapatite disso-
lution.
A substitute process, which happens to be signifi-
cant in temperate soils, involves metal-ligand com-
plexation in solution and followed reductions in cation
charge, which most likely decreases adsorption (Har-
ter and Naidu, 1995). The formation of soluble Cd-
phosphate complexes reduces Cd(II) sorption onto soils
in the presence of phosphate (Krishnamurti et al.,
1996). The activity of free Cd(II), rather than total
dissolved Cd(II), is a regulatory factor in Cd(II) sorp- Fig. 2 Immobilization of Pb by phosphate amendments with or
tion (O’Connor et al., 1984). The efficacy of phosphate- without phosphate solubilizing bacteria (PSB) as measured by
induced metal immobilization can be improved by the Pb concentration in soil extracted with ammonium nitrate
enhancing solubility of phosphate compounds in the (NH4 NO3 ) (Park et al., 2011b; Bolan et al., 2014). The soils
tested, a naturally Pb-contaminated soil collected from a shoo-
soil. The combination of rock phosphate and phos- ting range and a Pb-spiked soil collected from an uncontamina-
phoric acid has the potential to immobilize Pb (Cao ted site, are a sandy loam with a pH of 5.8, water-holding capaci-
et al., 2003). To enhance Pb immobilization in soil, ty of 38.5%, electrical conductivity of 34.5 μS cm−1 , and organic
matter of 7 g kg−1 and a silt loam with a pH of 5.23, water-
phosphate-solubilizing bacteria (PSB) were used to
holding capacity of 73%, electrical conductivity of 66.9 μS cm−1 ,
slowly release phosphate from insoluble phosphate and organic matter of 109 g kg−1 , respectively. CK = control
rock (Park et al., 2011a, b) (Fig. 2). There are some without phosphate amendment; TP = tricalcium phosphate; HA
concerns related to the usage of phosphate compounds = hydroxyapatite; PR = phosphate rock.

for metal immobilization. The leaching of phosphate at the same time it is getting wide acceptance as a
induced after the phosphate treatment must be consi- potential option among scientific community to reduce
dered. A mixture of soil with phosphate addition in metal poisoning in soil (Fig. 3). Liming materials are
the molar ratio of H3 PO4 :hydroxyapatite of 0.75:1 is in a diverse range with differences in their potential
suggested to be optimum to reduce phosphorus (P) to neutralize the acidity (Table II). Over the years, li-
leaching (Zupančič et al., 2012). Furthermore, bacte- ming has been employed as a regular traditional prac-
ria affect the stability of pyromorphite. It is assumed tice to decrease levels of Cd and Pb in edible parts
that the microbes enhance the dissolution of mineral P, of agricultural crops. Liming increases sorption of me-
promoting its transformation into pyromorphite. The tals through decreasing the H+ concentration and en-
controversy of the method stems from the need of in- hancing negatively charged ions. Addition of alkaline
troducing a living, extraneous strain of bacteria into an materials such as lime and red mud increases the con-
uncontrolled environment, although the long-term ef- centrations of residual fractions of Cd and Pb in conta-
fect of such a treatment is unknown. Park et al. (2011a, minated soil. The pH increases in red mud and lime
c) showed that PSB can affect the stability of pyro- result in the heavy metal precipitation (Garau et al.,
morphite and the effectiveness of the process depend- 2007).
s on the availability of dissolved phosphates in solu- The competition between Ca(II) and metal ions
tion. However, the interaction between microbes and and the reduced mobility in soils by precipitation and
minerals are complex and some aspects of the potential adsorption result in reduced metal uptake by plants
involvement of PSB in remediation treatments remain with liming on the root surface (Gray et al., 2006). An
unclear. There is some evidence that various organic in-situ field trial of heavy metal remediation in conta-
compounds, microbial metabolites, and plant activity minated soil proved that combing red mud and lime en-
may increase the dissolution of pyromorphite and cause hances soil pH and reduces metal bioavailability, thus
a secondary Pb release (Sayer et al., 1997; Fomina et forming vegetative cover in soil contaminated by Pb
al., 2004; Manecki and Maurice, 2008; Debela et al., and Cd.
2010, 2013; Topolska et al., 2013). Lime can be employed in combination with other
Lime treatment amendments to decrease metal availability. When lime
is mixed with biosolids, it decreases electrical conduc-
Lime is basically used to ameliorate soil acidity but tivity (EC) and enhances pH, precipitating soluble ions
562 A. MAHAR et al.

for solidification/stabilization of Cd- and Pb-contami-

nated soils from a former industrial site (Voglar and
Leštan, 2010a). Soils formed solid monoliths with ce-
ment. Concentrations of Cd and Pb in the water ex-
tracts and the toxicity characteristic leaching proce-
dure (TCLP) extracts were lower in the solidified/sta-
bilized soils than the original soils.
Formulations of 15% (weight/weight) ordinary
Portland cement (OPC), calcium aluminate cement
(CAC), and pozzolanic cement (PC) and additives
including plasticizers cementol delta ekstra (PCDE)
and cementol antikorodin (PCA), polypropylene fibers
(PPF), polyoxyethylene-sorbitan monooleate (Tween
80) and aqueous acrylic polymer dispersion (Akrimal)
Fig. 3 Immobilization of Cd and Pb by eggshell, oyster shell were used for solidification/stabilization of soils from
and calcium carbonate treatments as measured by the Cd and an industrial brownfield contaminated with up to 157
Pb concentrations in soil extracted with 1 mol L−1 calcium chlo- and 32 mg kg−1 Cd and Pb, respectively (Voglar and
ride (CaCl2 ) after treatments (Ok et al., 2011; Ahmad et al.,
2012). The soil tested is a sandy loam with a pH of 6.21, ele- Leštan, 2010b). Based on the model calculation, the
ctrical conductivity of 0.22 dS m−1 , organic matter of 38.69 g most efficient formulation was CAC + Akrimal, which
kg−1 , total N of 1.49 g kg−1 , and cation exchange capacity of greatly reduced the leachability of soil Cd and Pb into
15.11 cmol(+) kg−1 . CK = untreated control; CC10 = calci-
deionized water below the limit of quantification and
um carbonate at 10 g kg−1 ; CC50 = calcium carbonate at 50 g
kg−1 ; ES10 = eggshell at 10 g kg−1 ; ES50 = eggshell at 50 g into TCLP solution and the mass transfer of the ele-
kg−1 ; OS10 = oyster shell at 10 g kg−1 ; OS50 = oyster shell at ments from soil monoliths.
50 g kg−1 .
There are several areas ripe for further investiga-
(Fang and Wong, 1999). Composting with lime addi- tions in the field of cement-based solidification/stabi-
tion also effectively increases pH and decreases leaching lization of Cd and Pb in contaminated soils, for exa-
and bioavailability of metals (Singh and Kalamdhad, mple, the phase development of cement pastes in the
2013). presence of Cd and Pb, the dissolution and precipita-
tion of stoichiometric phases and solid solutions, and
Cement-based solidification/stabilization surface phenomena controlling Cd and Pb immobiliza-
Soil contaminated with Cd and Pb usually needs tion (Akhter et al., 1990).
solidification/stabilization, aiming to lower the leac-
Animal manure and biosolids
hing rate and bioavailability. Cement is the most adap-
table binder currently available for the immobilization Animal manures and biosolids are the signifi-
of Cd and Pb. The selection of cements and operating cant sources of organic composts. Biosolids are consi-
parameters depends upon an understanding of che- dered traditionally as one of the key sources of metal
mistry of the system (Chen et al., 2009). contamination in the soil. Advances in the industrial
Cement-based stabilization/solidification techno- wastewater and sewage treatment technologies are suc-
logy is an attractive option for the management of soil cessfully decreasing metal contamination in biosolids.
polluted with Cd and Pb to facilitate land use and Moreover, alkaline materials are used for stabilizing
reduce the release of contaminants into the environ- metals in biosolids. Zeolites are also valuable as a metal
ment. The efficacy of cement-based solidification/sta- scavenger in the metal-contaminated biosolids. Natu-
bilization can be improved by modifying cement phase ral zeolites stabilize Cd and Pb through transforming
compositions and controlling temperature, water/solid them in the exchangeable and carbonate to residual
ratios, particle size, and other factors that affect set- fractions (Zorpas et al., 2000).
ting and strength development and long-term durabili- Cattle, poultry, swine, and dairy are key sources
ty of solidified waste forms. The potentially deleterious of animal manure byproducts worldwide. The majori-
Cd and Pb may adversely affect the cementing matrix; ty of the manure products are less contaminated with
pretreatment to render such substances harmless, e.g., metals except As in poultry and Zn and Cu in swine
by adsorbent addition, is necessary in some cases (Jang manure. However, recent developments in the manure
and Kim, 2000). byproduct treatment have brought reduction in the
Portland cement (15%, weight/weight) was used bioavailability of metals. For example, treatment of
SOIL LEAD AND CADMIUM IMMOBILIZATION 563

poultry manure with alum (Al2 (SO4 )3 ) reduced the Oxides of Mn (birnessite and phyllomanganates
concentration of water-soluble Cd. Manure byproducts group of minerals), oxyhydroxides (goethite, ferrihy-
lowly contaminated with metals can be employed in drite, lepidocrocite, feroxyhite, and akaganeite), and
stabilizing metals in soil (Bolan et al., 2014). oxides of Fe (magnetite, hematite, and maghemite)
Various studies have assessed the role of biosolids mostly occur in soil. Arsenat (AsO3− 4 ) and Pb(II)
in the heavy metal contamination in the soil; howe- form inner-sphere surface complexes with hydrous fer-
ver, only few have documented the advantageous im- ric oxides and Pb and Cd form mononuclear comple-
pact of organic amendments as a sink for stabilization xes on goethite and ferrihydrite surfaces (Knox et al.,
of toxic metals in the soil (Li et al., 2000; Brown et 2001). The surfaces of Fe hydrous oxides play a signifi-
al., 2003). Alkaline-stabilized biosolids, known as de- cant role in metal retention; Pb and Cd were immo-
signer sludge with exceptional quality of being low in bilized with amalgamation of Fe(II) and (III) sulfates
metal bioavailability, can be employed as a potential (Hartley et al., 2004). The re-use of Fe oxide-based
sink for decreasing metal bioavailability in sediment drinking water treatment residuals may be a beneficial
and soil (Table II). Complexation, redox reaction, and retention of heavy metals and suitable soil amendment
adsorption are the immobilization processes accom- for various cations and anions (Impellitteri and Schec-
plished through such amendments. kel, 2006).
Metals form both soluble and insoluble complexes Manganese oxide minerals such as cryptomelane,
with organic constituents in soil; the mechanisms spe- todorokite, hausmannite, and birnessite exist in soil
cially depend on the type of the organic matter. The (Hettiarachchi et al., 2000). Birnessites exhibit the
organic constituents in soil have a great affiliation to highest adsorption capacity of Cd and Pb among these
metal cations due to the existence of functional groups Mn oxide minerals. The sequence of birnessite sorption
or ligands which can form chelates with metals. The capacity is Pb(II) > Cd(II) and the maximum adsorp-
alcoholic, phenolic, carbonyl, and carboxyl functional tion of metals by birnessite is attributed to hydroly-
groups dissociate due to increasing pH, thus enhancing sis which shows metal adsorption through Mn oxides
ligand ion affinity towards metal cations. Through pre- present primarily in the form of hydroxylation cations
vention of sulfide oxidation/hydrolysis, the decreases (Feng et al., 2007). Oxides of Mn(IV) are well known to
in the metal concentration can be credited to an in- precisely adsorb Pb. Cryptomelane is representative of
crease in soil pH (Hartley et al., 2004). Likewise, com- Mn oxides and was employed to decrease Pb bioavaila-
post amendment increased the growth of white lupin bility.
and decreased uptake of Pb through reducing metal Fungi and bacteria enzymatically oxidize Mn(II),
bioavailability in the soils (Castaldi et al., 2005). High produce insoluble oxides of Mn(III, IV), and form bio-
fulvic and humic acid concentrations of compost are genic Mn oxides, which have a great sorption poten-
credited for the high metal-binding capacities of com- tial for metals including oxidation of metals (Miyata
post (Perminova and Hatfield, 2005; O’Dell et al., et al., 2007). Sorption of metals by manganese oxides
2007). is through complexation above or below the structural
vacancies and at structural sheet edges, and incorpo-
Oxides of metals ration into the vacancies by isomorphical substitution
Oxides of metals such as iron (Fe), aluminum (Al), for Pb oxidation by biogenic Mn oxide produced by
and manganese (Mn) play an important role in metal bacteria.
geochemistry in soils. Atmospheric nature and highly Nanosized metal oxides such as Mn oxides, ferric
active surface area make them potential for immobi- oxides, titanium oxides, aluminum oxides, cerium o-
lization and sorption of diverse soil pollutants (Table I- xides, and magnesium oxides are referred to as poten-
I). Co-precipitation, formation of inner-surface comple- tial adsorbents for metal remediation due to their high
xes, and specific sorption result in a strong metal bin- activities and surface areas (Hua et al., 2012). Am-
ding by metal oxides. Synthesized, industrial bypro- monium acetate fuel has been used for the synthesis of
ducts and naturally occurring oxides have been docu- nanosized alumina and is effective in the Pb adsorption
mented in their potentiality to be employed for soil in soil, but there are limited available studies which
remediation objectives (Kumpiene, 2010). Recent de- employed metal oxides in soil environment (Rahmani
velopments in the application of metal oxides and their et al., 2010).
precursors for chemical immobilization of metals in Biochar
contaminated soils have been studied well (Komárek
et al., 2013). Recent research development has proved that bio-
564 A. MAHAR et al.

char has the capacity to adsorb metals in contaminated soil are summarized. More research studies are de-
soil and serves as a green environmental sorbent. Vari- sirable on the influence of immobilizing agents on
ous parameters are involved in assessing the main the physiological processes of the plant, i.e., photo-
role of biochar for environmental protection. Feedstock synthetic activity, hydrolysis, plant nutrient uptake,
types and pyrolysis conditions are the important fac- tropism, development of plant hormones including
tors affecting the sorption capacity of biochars (Joseph their functions, nastic movement, photomorphogene-
et al., 2010; Kookana et al., 2011). However, research sis, circadian rhythms, photoperiodism, plant response
studies have documented the reduction of Cd and Pb to environmental stress, seed dormancy, germination,
in contaminated soils amended with biochar (Table osmotic pressure, turgor potential and stomata func-
II). Therefore, the assessment of the biochar efficien- tion in relation to plant-water nexus. Further studies
cy in immobilization of contaminants in multi-metal- are required on the chelate-assisted phytoremediation
contaminated soils should be conducted including the and the root-soil interface. Further phytotoxicity re-
metal immobilization mechanism of biochar to examine search is required with focus on the effects of Pb- and
the long-term efficacy. Cd-contaminated soils amended with solidifying agents
Hardwood-derived biochar is effective in immobi- on the crop plants in both field and laboratory condi-
lizing Cd in contaminated soils. Cadmium solubility tions and the activity of enzymes required for photo-
decreases at alkaline pH induced by biochar (Beesley et synthesis, cell division and respiration, water absorp-
al., 2010). However, biochar produced at low pyrolysis tion and transpiration, and chlorophyll, carotenoid,
temperature regimes immobilizes Pb (Uchimiya et al., and adenosine triphosphate (ATP) synthesis. More in
2011). Remarkable Pb immobilization by biochar pro- situ studies are needed to validate the significance of
duced at low temperature results in the augmented re- a diverse range of immobilizing soil amendments to
lease of available Ca, K, and P in the soil environment. restore contaminated soils. These kinds of field-based
Biochar derived from dairy manure having a great experiments are essential to assess the effects of soil
quantity of available P stabilizes Pb through making amendments on co-contaminants. There is a dire need
insoluble hydroxypyromorphite (Pb5 (PO4 )3 (OH)) in to develop procedures to determine immobilization ef-
soil (Cao et al., 2011). The cotton seed hull-derived ficacy that could be used to assess the in-situ short and
biochar produced at 350 ◦ C contains a high oxygen long-term environmental stability of metal immobiliza-
concentration, resulting in high uptake of Pb and Cd tion. Additional in-situ studies should be conducted
due to the role of oxygen-containing functional groups to determine phyto-poisoning, ecological receptor end-
on biochar surfaces in metal binding (Uchimiya et al., points, and human biomagnification to demonstrate
2011). the heavy metal risk management efficiency resulting
from soil amendments.
CONCLUSIONS
REFERENCES
Unlike organic contaminants, Pb and Cd do not
Abedin J, Beckett P, Spiers G. 2012. An evaluation of extrac-
undergo microbial or chemical degradation and persist
tants for assessment of metal phytoavailability to guide recla-
for a long time after their introduction. Bioavailability mation practices in acidic soilscapes in northern regions. Can
of Pb and Cd plays a vital role in the remediation of J Soil Sci. 92: 253–268.
contaminated soils. This paper reviews the remedia- Adriano D C. 2001. Trace Elements in Terrestrial Environments:
tion of Pb- and Cd-contaminated soils through ma- Biogeochemistry, Bioavailability, and Risks of Metals. 2nd
Ed. Springer-Verlag, New York.
nipulating their bioavailability using a range of soil a- Adriano D C, Wenzel W W, Vangronsveld J, Bolan N S.
mendments. Metal-immobilizing amendments such as 2004. Role of assisted natural remediation in environmental
precipitating agents and sorbent materials decrease cleanup. Geoderma. 122: 121–142.
the bioavailability of Pb and Cd. Immobilizing agents Agency for Toxic Substances and Disease Registry (ATSDR).
2007. Lead. CAS#7439-92-1. Available online at http://ww-
can be used to reduce the transfer of Pb and Cd to
w.atsdr.cdc.gov/tfacts13.pdf (verified on July 25, 2012).
food chain via plant uptake and leaching to groundwa- Ahmad M, Lee S S, Yang J E, Ro H M, Lee Y H, Ok Y S.
ter. One of the major limitations of the immobilization 2012. Effects of soil dilution and amendments (mussel shell,
technique is the long-term stability of the immobilized cow bone, and biochar) on Pb availability and phytotoxici-
Pb and Cd that needs to be monitored. ty in military shooting range soil. Ecotox Environ Safe. 79:
225–231.
In the current review, the immobilization options
Ahmad M, Hashimoto Y, Moon D H, Lee S S, Ok Y S. 2012. Im-
with regards to engineering the bioavailability Pb mobilization of lead in a Korean military shooting range soil
and Cd and following the remediation of polluted using eggshell waste: an integrated mechanistic approach. J
SOIL LEAD AND CADMIUM IMMOBILIZATION 565

Hazard Mater. 209/210: 392–401. Brown S, Chaney R L, Hallfrisch J G, Xue Q. 2003. Effect of
Akhter H, Butler L G, Branz S, Cartledge F K, Tittlebaum M E. biosolids processing on lead bioavailability in an urban soil.
1990. Immobilization of As, Cd, Cr and Pb-containing soils J Environ Qual. 32: 100–108.
by using cement or pozzolanic fixing agents. J Hazard Mater. Brown S L, Chaney R L, Scott Angle J, Ryan J A. 1998.
24: 145–155. The phytoavailability of cadmium to lettuce in long-term
Alloway B J, Jackson A P, Morgan H. 1990. The accumulation biosolids-amended soil. J Environ Qual. 27: 1071–1078.
of cadmium by vegetables grown on soils contaminated from Cao R X, Ma L Q, Chen M, Singh S P, Harris W G. 2003.
a variety of sources. Sci Total Environ. 91: 223–236. Phosphate-induced metal immobilization in a contaminated
Amaro F, Turkewitz A P, Martı́n-González A, Gutiérrez J C. site. Environ Pollut. 122: 19–28.
2011. Whole-cell biosensors for detection of heavy metal ions Cao X D, Ma L, Liang Y, Gao B, Harris W. 2011. Simulta-
in environmental samples based on metallothionein promo- neous immobilization of lead and atrazine in contaminated
ters from Tetrahymena thermophila. Microbial Biotech. 4: soils using dairy-manure biochar. Environ Sci Technol. 45:
513–522. 4884–4889.
Anyanwu C U, Nwankwo S C, Moneke A N. 2011. Soil bacterial Castaldi P, Santona L, Melis P. 2005. Heavy metal immobiliza-
response to introduced metal stress. Int J Basic Appl Sci. tion by chemical amendments in a polluted soil and influence
11: 73–76. on white lupin growth. Chemosphere. 60: 365–371.
Asami T. 1984. Pollution of soils by cadmium. In Nriagu J O Chaney W R, Strickland R C, Lamoreaux R J. 1977. Phytotoxi-
(ed.) Changing Metal Cycles and Human Health. Dahlem city of cadmium inhibited by lime. Plant Soil. 47: 275–278.
Workshop Reports, Life Sciences Research Report, Springer, Chapman E E V, Dave G, Murimboh J D. 2013. A review of me-
Berlin and Heidelberg. pp. 95–111. tal (Pb and Zn) sensitive and pH tolerant bioassay organisms
Bade R, Oh S, Sik Shin W. 2012. Assessment of metal bioavaila- for risk screening of metal-contaminated acidic soils. Environ
bility in smelter-contaminated soil before and after lime ame- Pollut. 179: 326–342.
ndment. Ecotox Environ Safe. 80: 299–307. Chen Q Y, Tyrer M, Hills C D, Yang X M, Carey P. 2009.
Bakircioglu D, Kurtulus Y B, Ibar H. 2011. Comparison of ex- Immobilisation of heavy metal in cement-based solidifica-
traction procedures for assessing soil metal bioavailability to tion/stabilisation: a review. Waste Manage. 29: 390–403.
wheat grains. Clean-Soil Air Water. 39: 728–734.
Chen S B, Xu M G, Ma Y B, Yang J C. 2007. Evaluation of
Basta N, Gradwohl R. 2000. Estimation of Cd, Pb, and Zn
different phosphate amendments on availability of metals in
bioavailability in smelter-contaminated soils by a sequential
contaminated soil. Ecotox Environ Safe. 67: 278–285.
extraction procedure. J Soil Contam. 9: 149–164.
Cheng S F, Hseu Z Y. 2002. In-situ immobilization of cadmium
Basta N T, McGowen S L. 2004. Evaluation of chemical immo-
and lead by different amendments in two contaminated soils.
bilization treatments for reducing heavy metal transport in
Water Air Soil Poll. 140: 73–84.
a smelter-contaminated soil. Environ Pollut. 127: 73–82.
Cheng H F, Hu Y. 2010. Lead (Pb) isotopic fingerprinting and
Beesley L, Moreno-Jiménez E, Gomez-Eyles J L. 2010. Effects
its applications in lead pollution studies in China: a review.
of biochar and green waste compost amendments on mo-
Environ Pollut. 158: 1134–1146.
bility, bioavailability and toxicity of inorganic and organic
contaminants in a multi-element polluted soil. Environ Pol- Chlopecka A, Adriano D C. 1996. Mimicked in-situ stabilization
lut. 158: 2282–2287. of metals in a cropped soil: bioavailability and chemical form
of zinc. Environ Sci Technol. 30: 3294–3303.
Bhattacharya S, Gupta K, Debnath S, Ghosh U C, Chattopad-
hyay D, Mukhopadhyay A. 2012. Arsenic bioaccumulation in Chlopecka A, Adriano D C. 1997. Influence of zeolite, apatite
rice and edible plants and subsequent transmission through and Fe-oxide on Cd and Pb uptake by crops. Sci Total Envi-
food chain in Bengal basin: a review of the perspectives for ron. 207: 195–206.
environmental health. Toxicol Environ Chem. 94: 429–441. Chrysochoou M, Dermatas D, Grubb D G. 2007. Phosphate ap-
Bolan N S, Adriano D C, Duraisamy P, Mani A. 2003a. Im- plication to firing range soils for Pb immobilization: the un-
mobilization and phytoavailability of cadmium in variable clear role of phosphate. J Hazard Mater. 144: 1–14.
charge soils. III. Effect of biosolid compost addition. Plant Contin M, Mondini C, Leita L, De Nobili M. 2007. Enhanced
Soil. 256: 231–241. soil toxic metal fixation in iron (hydr)oxides by redox cycles.
Bolan N S, Adriano D C, Duraisamy P, Mani A, Arulmozhisel- Geoderma. 140: 164–175.
van K. 2003b. Immobilization and phytoavailability of cad- Contin M, Mondini C, Leita L, Zaccheo P, Crippa L, De Nobili
mium in variable charge soils. I. Effect of phosphate addition. M. 2008. Immobilisation of soil toxic metals by repeated ad-
Plant Soil. 250: 83–94. ditions of Fe(II) sulphate solution. Geoderma. 147: 133–140.
Bolan N S, Adriano D C, Mani P A, Duraisamy A. 2003c. Im- Creger T L, Peryea F J. 1994. Phosphate fertilizer enhances ar-
mobilization and phytoavailability of cadmium in variable senic uptake by apricot liners grown in lead-arsenate-enriched
charge soils. II. Effect of lime addition. Plant Soil. 251: 187– soil. HortScience. 29: 88–92.
198. Crook T. 1921. Economic Mineralogy: A Practical Guide to the
Bolan N S, Adriano D C, Naidu R. 2003d. Role of phosphorus in Study of Useful Minerals. Longmans, Green and Co., Lon-
(im)mobilization and bioavailability of heavy metals in the don.
soil-plant system. Rev Environ Contam T. 177: 1–44. Cuong D T, Obbard J P. 2006. Metal speciation in coastal marine
Bolan N, Kunhikrishnan A, Thangarajan R, Kumpiene J, Park sediments from Singapore using a modified BCR-sequential
J, Makino T, Kirkham M B, Scheckel K. 2014. Remediation extraction procedure. Appl Geochem. 21: 1335–1346.
of heavy metal(loid)s contaminated soils—To mobilize or to Debela F, Arocena J M, Thring R W, Withcombe T. 2010. Or-
immobilize? J Hazard Mater. 266: 141–166. ganic acid-induced release of lead from pyromorphite and its
Brallier S, Harrison R B, Henry C L, Dongsen X. 1996. Liming relevance to reclamation of Pb-contaminated soils. Chemo-
effects on availability of Cd, Cu, Ni and Zn in a soil amended sphere. 80: 450–456.
with sewage sludge 16 years previously. Water Air Soil Poll. Debela F, Arocena J M, Thring R W, Withcombe T. 2013.
86: 195–206. Organic acids inhibit the formation of pyromorphite and
566 A. MAHAR et al.

Zn-phosphate in phosphorous amended Pb- and Zn-con- Hettiarachchi G M, Pierzynski G M, Ransom M D. 2000. In situ
taminated soil. J Environ Manage. 116: 156–162. stabilization of soil lead using phosphorus and manganese
DeVolder P S, Brown S L, Hesterberg D, Pandya K. 2003. Metal oxide. Environ Sci Technol. 34: 4614–4619.
bioavailability and speciation in a wetland tailings repository Hodson M E, Valsami-Jones É, Cotter-Howells J D. 2000. Bone-
amended with biosolids compost, wood ash, and sulphate. J meal additions as a remediation treatment for metal conta-
Environ Qual. 32: 851–864. minated soil. Environ Sci Technol. 34: 3501–3507.
Domene X, Mattana S, Ramı́rez W, Colón J, Jiménez P, Bala- Hua M, Zhang S J, Pan B C, Zhang W M, Lv L, Zhang Q
nyà T, Alcañiz J M, Bonmatı́ M. 2010. Bioassays prove the X. 2012. Heavy metal removal from water/wastewater by
suitability of mining debris mixed with sewage sludge for land nanosized metal oxides: a review. J Hazard Mater. 211-212:
reclamation purposes. J Soil Sediment. 10: 30–44. 317–331.
Doyle J J. 1977. Effects of low levels of dietary cadmium in Impellitteri C A, Scheckel K G. 2006. The distribution, solid-
animals—A review. J Environ Qual. 6: 111–116. phase speciation, and desorption/dissolution of As in waste
Drexler J W, Brattin W J. 2007. An in vitro procedure for esti- iron-based drinking water treatment residuals. Chemosphere.
mation of lead relative bioavailability: with validation. Hum 64: 875–880.
Ecol Risk Assess. 13: 383–401. Jang A, Kim I S. 2000. Technical note: solidification and stabi-
Elass K, Laachach A, Azzi M. 2004. Three-stage sequential ex- lization of Pb, Zn, Cd and Cu in tailing wastes using cement
traction procedure for metal partitioning in polluted soils and fly ash. Miner Eng. 13: 1659–1662.
and sediments. Ann Chim-Rome. 94: 325–332. Jennings A A. 2013. Analysis of worldwide regulatory guidance
Esslemont G. 2000. Heavy metals in seawater, marine sediments values for the most commonly regulated elemental surface
and corals from the Townsville section, Great Barrier Reef soil contamination. J Environ Manage. 118: 72–95.
Marine Park, Queensland. Mar Chem. 71: 215–231. Joseph S D, Camps-Arbestain M, Lin Y, Munroe P, Chia C
Fang M, Wong J W C. 1999. Effects of lime amendment on H, Hook J, van Zwieten L, Kimber S, Cowie A, Singh B P,
availability of heavy metals and maturation in sewage sludge Lehmann J, Foidl N, Smernik R J, Amonette J E. 2010. An
composting. Environ Pollut. 106: 83–89. investigation into the reactions of biochar in soil. Soil Res.
Feng X H, Zhai L M, Tan W F, Liu F, He J Z. 2007. Adsorption 48: 501–515.
and redox reactions of heavy metals on synthesized Mn oxide Kashem M A, Singh B R. 2001. Metal availability in conta-
minerals. Environ Pollut. 147: 366–373. minated soil: II. Uptake of Cd, Ni and Zn in rice plants grown
Fenger J. 2009. Air pollution in the last 50 years—From local under flooded culture with organic matter addition. Nutr Cy-
to global. Atmos Environ. 43: 13–22. cl Agroecosys. 61: 257–266.
Fomina M, Alexander I J, Hillier S, Gadd G M. 2004. Zinc Katasonova O N, Fedotov P S, Karandashev V K, Spivakov B
phosphate and pyromorphite solubilization by soil plant- Y. 2005. Application of rotating coiled columns to the frac-
symbiotic fungi. Geomicrobiol J. 21: 351–366. tionation of soil particles and to the sequential extraction of
Friberg L. 1984. Cadmium and the kidney. Environ Health Pe- heavy-metal species from silty, dusty, and sandy fractions. J
rsp. 54: 1–11. Anal Chem. 60: 684–690.
Frostegård Å, Tunlid A, Bååth E. 2011. Use and misuse of PLFA Knopf B, König H. 2010. Biomethylation of heavy metals in soil
measurements in soils. Soil Biol Biochem. 43: 1621–1625. and terrestrial invertebrates. In Sherameti I, Varma A (eds.)
Garau G, Castaldi P, Santona L, Deiana P, Melis P. 2007. In- Soil Heavy Metals. Springer-Verberg, Berlin, Heidelberg. p-
fluence of red mud, zeolite and lime on heavy metal immobi- p. 315–328.
lization, culturable heterotrophic microbial populations and Knox A S, Seaman J C, Mench M J, Vangronsveld J. 2001. Re-
enzyme activities in a contaminated soil. Geoderma. 142: mediation of metal- and radionuclides-contaminated soils by
47–57. in situ stabilization techniques. In Iskandar I K (ed.) Envi-
Godwin H A. 2001. The biological chemistry of lead. Curr Opin ronmental Restoration of Metals-Contaminated Soil. Lewis
Chem Biol. 5: 223–227. Publishers, Boca Raton, London, New York, Washington.
Gray C W, Dunham S J, Dennis P G, Zhao F J, McGrath S pp. 21–60.
P. 2006. Field evaluation of in situ remediation of a heavy Komárek M, Vaněk A, Ettler V. 2013. Chemical stabilization
metal contaminated soil using lime and red-mud. Environ of metals and arsenic in contaminated soils using oxides—A
Pollut. 142: 530–539. review. Environ Pollut. 172: 9–22.
Gray C W, McLaren R G, Roberts A H C. 2003. Atmospheric Kookana R S, Sarmah A K, Van Zwieten L, Krull E, Singh B.
accessions of heavy metals to some New Zealand pastoral 2011. Chapter three—Biochar application to soil: agronomic
soils. Sci Total Environ. 305: 105–115. and environmental benefits and unintended consequences.
Guevara-Riba A, Sahuquillo A, Rubio R, Rauret G. 2004. Asse- Adv Agron. 112: 103–143.
ssment of metal mobility in dredged harbour sediments from Krishnamurti G S R, Huang P M, Van Rees K C J. 1996. Studies
Barcelona, Spain. Sci Total Environ. 321: 241–255. on soil rhizosphere: speciation and availability of Cd. Chem
Han D H, Lee J H. 1996. Effects of liming on uptake of lead and Spec Bioavailab. 8: 23–28.
cadmium by Raphanus sativa. Arch Environ Con Tox. 31: Kumpiene J. 2010. Trace element immobilization in soil using
488–493. amendments. In Hooda P S (ed.) Trace Elements in Soils.
Hartley W, Edwards R, Lepp N W. 2004. Arsenic and heavy John Wiley and Sons Ltd., Chichester. pp. 353–380.
metal mobility in iron oxide-amended contaminated soils as Kumpiene J, Lagerkvist A, Maurice C. 2007. Stabilization of
evaluated by short- and long-term leaching tests. Environ Pb- and Cu-contaminated soil using coal fly ash and peat.
Pollut. 131: 495–504. Environ Pollut. 145: 365–373.
Harter R D, Naidu R. 1995. Role of metal-organic complexation Kumpiene J, Lagerkvist A, Maurice C. 2008. Stabilization of
in metal sorption by soils. Adv Argon. 55: 219–263. As, Cr, Cu, Pb and Zn in soil using amendments—A review.
Haynes R J, Murtaza G, Naidu R. 2009. Chapter 4—Inorganic Waste Manage. 28: 215–225.
and organic constituents and contaminants of biosolids: im- Lamb D T, Ming H, Megharaj M, Naidu R. 2009. Heavy me-
plications for land application. Adv Agron. 104: 165–267. tal (Cu, Zn, Cd and Pb) partitioning and bioaccessibility in
SOIL LEAD AND CADMIUM IMMOBILIZATION 567

uncontaminated and long-term contaminated soils. J Hazard National Institute of Health, U.S. National Library of Medicine
Mater. 171: 1150–1158. (NIH, NLM). 2012. Hazardous substances data bank. Avai-
Lee S H, Lee J S, Choi Y J, Kim J G. 2009. In situ stabilization lable online at http://toxnet.nlm.nih.gov/cgi-bin/sis/search
of cadmium-, lead-, and zinc-contaminated soil using various (verified on June 27, 2012).
amendments. Chemosphere. 77: 1069–1075. Needleman H L, Schell A, Bellinger D, Leviton A, Allred E N.
Lehoczky É, Marth P, Szabados I, Szomolányi A. 2000. The cad- 1990. The long-term effects of exposure to low doses of lead
mium uptake by lettuce on contaminated soils as influenced in childhood: an 11-year follow-up report. New Engl J Med.
by liming. Commun Soil Sci Plan. 31: 2433–2438. 322: 83–88.
Li Y M, Chaney R L, Schneiter A A, Johnson B L. 1996. Effect Ng J C, Juhasz A, Smith E, Naidu R. 2013. Assessing the
of field limestone applications on cadmium content of sun- bioavailability and bioaccessibility of metals and metalloids.
flower (Helianthus annuus L.) leaves and kernels. Plant Soil. Environ Sci Pollut R. 2013: doi: 10.1007/s11356-013-1820-9.
180: 297–302. Nriagu J O. 1983. Lead and Lead Poisoning in Antiquity. John
Li Y M, Chaney R L, Siebielec G, Kerschner B A. 2000. Re- Wiley & Sons, New York and Chichster.
sponse of four turf grass cultivars to limestone and biosolids- O’Connor G A, O’Connor C, Cline G R. 1984. Sorption of cad-
compost amendment of a zinc and cadmium contaminated mium by calcareous soils: influence of solution composition.
soil at Palmerton, Pennsylvania. J Environ Qual. 29: 1440– Soil Sci Soc Am J. 48: 1244–1247.
1447. O’Dell R, Silk W, Green P, Claassen V. 2007. Compost ame-
Liu L N, Chen H S, Cai P, Liang W, Huang Q Y. 2009. Immo- ndment of Cu-Zn minespoil reduces toxic bioavailable
bilization and phytotoxicity of Cd in contaminated soil a- heavy metal concentrations and promotes establishment and
mended with chicken manure compost. J Hazard Mater. biomass production of Bromus carinatus (Hook and Arn.).
163: 563–567. Environ Pollut. 148: 115–124.
Loganathan P, Hedley M J, Grace N D. 2008. Pasture soils con- Ok Y S, Lee H, Jung J, Song H, Chung N, Lim S, Kim J G.
taminated with fertilizer-derived cadmium and fluorine: live- 2004. Chemical characterization and bioavailability of cad-
stock effects. Rev Environ Contam T. 192: 29–66. mium in artificially and naturally contaminated soils. Agr
Mahvi A H, Mesdaghinia A R, Naghipoor D. 2005. Comparison Chem Biotechnol. 47: 143–146.
of heavy metals extractions efficiency in contaminated soils Ok Y S, Lim J E, Moon D H. 2011. Stabilization of Pb and
by various concentrations of EDTA. Pakistan J Biol Sci. 8: Cd contaminated soils and soil quality improvements using
1081–1085. waste oyster shells. Environ Geochem Hlth. 33: 83–91.
Manecki M, Maurice P A. 2008. Siderophore promoted dissolu- Park J H, Bolan N S, Chung J W, Naidu R, Megharaj M. 2011a.
tion of pyromorphite. Soil Sci. 173: 821–830. Environmental monitoring of the role of phosphate com-
Marshall A. 2001. The State of World Population 2001. Foot- pounds in enhancing immobilization and reducing bioavaila-
prints and Milestones: Population and Environmental bility of lead in contaminated soils. J Environ Monitor. 13:
Change. United Nations Population Fund, New York. 2234–2242.
McBride M B, Pitiranggon M, Kim B. 2009. A comparison of Park J H, Bolan N, Megharaj M, Naidu R. 2011b. Comparative
tests for extractable copper and zinc in metal-spiked and value of phosphate sources on the immobilization of lead, and
field-contaminated soil. Soil Sci. 174: 439–444. leaching of lead and phosphorus in lead contaminated soils.
McLaughlin M J, Tiller K G, Naidu R, Stevens D P. 1996. Re- Sci Total Environ. 409: 853–860.
view: the behaviour and environmental impact of contami- Park J H, Choppala G K, Bolan N S, Chung J W, Chuasavathi
nants in fertilizers. Aust J Soil Res. 34: 1–54. T. 2011c. Biochar reduces the bioavailability and phytotoxi-
Mench M, Vangronsveld J, Didier V, Clijsters H. 1994. Evalua- city of heavy metals. Plant Soil. 348: 439–451.
tion of metal mobility, plant availability and immobilization Pearson M S, Maenpaa K, Pierzynski G M, Lydy M J. 2000. Ef-
by chemical agents in a limed-silty soil. Environ Pollut. 86: fects of soil amendments on the bioavailability of lead, zinc,
279–286. and cadmium to earthworms. J Environ Qual. 29: 1611–
Merrington G, Madden C. 2000. Changes in the cadmium and 1617.
zinc phytoavailability in agricultural soil after amendment Pempkowiak J, Sikora A, Biernacka E. 1999. Speciation of heavy
with papermill sludge and biosolids. Common Soil Sci Plan. metals in marine sediments vs their bioaccumulation by mus-
31: 759–776. sels. Chemosphere. 39: 313–321.
Miyata N, Tani Y, Sakata M, Iwahori K. 2007. Microbial man- Perminova I V, Hatfield K. 2005. Remediation chemistry of hu-
ganese oxide formation and interaction with toxic metal ions. mic substances: theory and implications for technology. In
J Biosci Bioeng. 104: 1–8. Perminova I V, Hatfield K, Hertkorn N (eds.) Use of Hu-
Morillo J, Usero J, Gracia I. 2004. Heavy metal distribution in mic Substances to Remediate Polluted Environments: From
marine sediments from the southwest coast of Spain. Chemo- Theory to Practice. NATO Science Series. IV: Earth and En-
sphere. 55: 431–442. vironmental Series. Springer, Dordrecht. pp. 3–36.
Mulligan C N, Yong R N, Gibbs B F. 2001. Remediation tech- Pietrzak U, Uren N C. 2011. Remedial options for copper-
nologies for metal-contaminated soils and groundwater: an contaminated vineyard soils. Soil Res. 49: 44–55.
evaluation. Eng Geol. 60: 193–207. Porter S K, Scheckel K G, Impellitteri C A, Ryan J A. 2004.
Naidu R, Kookana R S, Oliver D P, Rogers S, McLaughlin M Toxic metals in the environment: thermodynamic considera-
J. 1996. Contaminants and the Soil Environment in the Au- tions for possible immobilization strategies for Pb, Cd, As,
stralasia-Pacific Region. Kluwer Academic Publishers, Do- and Hg. Crit Rev Env Sci Tec. 34: 495–604.
rdrecht, Boston, London. Pueyo M, Sastre J, Hernández E, Vidal M, López-Sánchez J
Naidu R, Kookana R S, Sumner M E, Harter R D, Tiller K G. F, Rauret G. 2003. Prediction of trace element mobility in
1997. Cadmium sorption and transport in variable charge contaminated soils by sequential extraction. J Environ Qual.
soils: a review. J Environ Qual. 26: 602–617. 32: 2054–2066.
Needleman H. 2004. Lead poisoning. Annu Rev Med. 55: 209– Rahmani A, Zavvar Mousavi H, Fazli M. 2010. Effect of nanos-
222. tructure alumina on adsorption of heavy metals. Desalina-
568 A. MAHAR et al.

tion. 253: 94–100. Voglar G E, Leštan D. 2010a. Solidification/stabilisation of me-

Robinson B H, Bañuelos G, Conesa H M, Evangelou M W H, tals contaminated industrial soil from former Zn smelter in
Schulin R. 2009. The phytomanagement of trace elements in Celje, Slovenia, using cement as a hydraulic binder. J Hazard
soil. Crit Rev Plant Sci. 28: 240–266. Mater. 178: 926–933.
Ruby M V, Davis A, Schoof R, Eberle S, Sellstone C M. 1996. Voglar G E, Leštan D. 2010b. Efficiency modeling of solidifica-
Estimation of lead and arsenic bioavailability using a physi- tion/stabilization of multi-metal contaminated industrial soil
ologically based extraction test. Environ Sci Technol. 30: using cement and additives. J Hazard Mater. 192: 753–762.
422–430. Wang J, Zhao F J, Meharg A A, Raab A, Feldmann J, Mc-
Ruttens A, Adriaensen K, Meers E, De Vocht A, Geebelen W, Grath S P. 2002. Mechanisms of arsenic hyperaccumulation
Carleer R, Mench M, Vangronsveld J. 2010. Long-term sus- in Pteris vittata. Uptake kinetics, interactions with phos-
tainability of metal immobilization by soil amendments: cy- phate, and arsenic speciation. Plant Physiol. 130: 1552–1561.
clonic ashes versus lime addition. Environ Pollut. 158: 1428– Weggler-Beaton K, McLaughlin M J, Graham R D. 2000. Salini-
1434. ty increases cadmium uptake by wheat and Swiss chard from
Ruttens A, Colpaert J V, Mench M, Boisson J, Carleer R, soil amended with biosolids. Aust J Soil Res. 38: 37–45.
Vangronsveld J. 2006. Phytostabilization of a metal conta- Wepener V, Vermeulen L A. 2005. A note on the concentra-
minated sandy soil. II: Influence of compost and/or inorgan- tions and bioavailability of selected metals in sediments of
ic metal immobilizing soil amendments on metal leaching. Richardsi Bay Harbour, South Africa. Water SA. 31: 589–
Environ Pollut. 144: 533–539. 596.
Sayer J A, Kierans M, Gadd G M 1997. Solubilisation of some Wong C S C, Li X D. 2004. Pb contamination and isotopic
naturally occurring metal-bearing minerals, limescale and composition of urban soils in Hong Kong. Sci Total Environ.
lead phosphate by Aspergillus niger. FEMS Microbiol Lett. 319: 185–195.
154: 29–35.
Wuana R A, Okieimen F E. 2011. Heavy metals in contaminated
Semenzin E, Critto A, Carlon C, Rutgers M, Marcomini A. 2007.
soils: a review of sources, chemistry, risks and best available
Development of a site-specific ecological risk assessment for
strategies for remediation. ISRN Ecol. 2011: ID 402647.
contaminated sites: part II. A multi-criteria based system for
Yang J E, Skogley E O, Georgitis S J, Schaff B E, Ferguson A
the selection of bioavailability assessment tools. Sci Total
H. 1991. Phytoavailability soil test: development and verifi-
Environ. 379: 34–45.
cation of theory. Soil Sci Soc Am J. 55: 1358–1365.
Silveira M L, Alleoni L R F, O’Connor G A, Chang A C. 2006.
Yuan C G, Shi J B, He B, Liu J F, Liang L N, Jiang G B.
Heavy metal sequential extraction methods—A modification
2004. Speciation of heavy metals in marine sediments from
for tropical soils. Chemosphere. 64: 1929–1938.
the East China Sea by ICP-MS with sequential extraction.
Sims J T, Johnson G V. 1991. Micronutrient soil test. In
Environ Int. 30: 769–783.
Mortvedt J J, Cox F R, Shuman L M, Welch R M (eds.)
Micronutrients in Agriculture. 2nd Ed. Soil Science Society Zakir H M, Shikazono N. 2011. Environmental mobility and geo-
of America, Madison. pp. 427–476. chemical partitioning of Fe, Mn, Co, Ni and Mo in sediments
Singh J, Kalamdhad A S. 2013. Effects of lime on bioavailability of an urban river. J Environ Chem Ecotox. 3: 116–126.
and leachability of heavy metals during agitated pile com- Zhang F P, Li C F, Tong L G, Yue L X, Li P, Ciren Y J, Cao
posting of water hyacinth. Bioresource Technol. 138: 148– C G. 2010. Response of microbial characteristics to heavy
155. metal pollution of mining soils in central Tibet, China. Appl
Tica D, Udovic M, Lestan D. 2011. Immobilization of potentially Soil Ecol. 45: 144–151.
toxic metals using different soil amendments. Chemosphere. Zhang M K, Wang M Q. 2003. Potential leachability of heavy
85: 577–58. metals in urban soils from Hangzhou City. Acta Pedol Sin
Topolska J, Borowicz P, Manecki M, Bajda T, Kaschabek S, (in Chinese). 40: 915–920.
Merkel B J. 2013. The effect of gluconic acid secretion by Zhu Q H, Huang D Y, Liu S L, Luo Z C, Zhu H H, Zhou B, Lei
phosphate-solubilizing Pseudomonas putida bacteria on dis- M, Rao Z X, Cao X L. 2012. Assessment of single extraction
solution of pyromorphite Pb5 (PO4 )3 Cl and Pb remobiliza- methods for evaluating the immobilization effect of amend-
tion. Annal. Soc. Geol. Pol. 83: 343–351. ments on cadmium in contaminated acidic paddy soil. Plant
Uchimiya M, Chang S, Thomas Klasson K. 2011. Screening Soil Environ. 58: 98–103.
biochars for heavy metal retention in soil: role of oxygen func- Zorpas A A, Constantinides T, Vlyssides A G, Haralambous I,
tional groups. J Hazard Mater. 190: 432–441. Loizidou M. 2000. Heavy metal uptake by natural zeolite and
Usero J, Gamero M, Morillo J, Gracia I. 1998. Comparative stu- metals partitioning in sewage sludge compost. Bioresource
dy of three sequential extraction procedures for metals in Technol. 72: 113–119.
marine sediments. Environ Int. 24: 487–496. Zupančič M, Lavrič S, Bukovec P. 2012. Metal immobiliza-
van der Voet E, van Egmond L, Kleijn R, Huppes G. 1994. Cad- tion and phosphorus leaching after stabilization of pyrite
mium in the European Community: a policy-oriented analy- ash contaminated soil by phosphate amendments. J Environ
sis. Waste Manage Res. 12: 507–526. Monitor. 14: 704–710.