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Rahman 2016

Chapter 8 discusses the contamination of soils and wetlands with toxic metals due to industrial, agricultural, and military activities, highlighting the health risks associated with metal exposure. It emphasizes phytoremediation as a cost-effective and environmentally friendly alternative to traditional remediation methods, detailing its strategies such as phytoextraction and phytostabilization. The chapter also addresses the challenges posed by legislation on genetically modified plants and the urgent need for innovative cleanup solutions.

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0% found this document useful (0 votes)
20 views35 pages

Rahman 2016

Chapter 8 discusses the contamination of soils and wetlands with toxic metals due to industrial, agricultural, and military activities, highlighting the health risks associated with metal exposure. It emphasizes phytoremediation as a cost-effective and environmentally friendly alternative to traditional remediation methods, detailing its strategies such as phytoextraction and phytostabilization. The chapter also addresses the challenges posed by legislation on genetically modified plants and the urgent need for innovative cleanup solutions.

Uploaded by

Nghia Duong
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Chapter 8

Phytoremediation of Toxic Metals in Soils


and Wetlands: Concepts and Applications

M. Azizur Rahman, Suzie M. Reichman, Luigi De Filippis,


Seyedeh Belin Tavakoly Sany, and Hiroshi Hasegawa

Abstract Over centuries, industrial, mining and military activities, agriculture,


farming, and waste practices have contaminated soils and wetlands in many coun-
tries with high concentrations of toxic metals. In addition to their negative effects
on ecosystems and other natural resources, toxic metals pose a great danger to
human health. Unlike organic compounds, metals cannot be degraded, and clean-up
usually requires their removal. Most of the conventional remedial methods have
lost economic favor and public acceptance because they are expensive and cause
degradation of soil fertility that subsequently results in adverse impacts on the
ecosystem. Conventional methods of environmental remediation do not solve the
problem; rather they merely transfer it to future generation. Obviously, there is an
urgent need for alternative, cheap, and efficient methods to clean-up sites contami-
nated with toxic metals.
Phytoremediation, a plant-based green technology, is cost effective, environ-
mental friendly, aesthetically pleasing approach for the remediation of toxic metals.
Due to its elegance and the extent of contaminated areas, phytoremediation
approaches have already received significant scientific and commercial attention.
Two approaches have been proposed for the phytoremediation of toxic metals

M.A. Rahman (*)


Centre for Environmental Sustainability, School of the Environment, University of
Technology Sydney, PO Box 123, Broadway, NSW 2007, Australia
e-mail: Mohammad.Rahman@uts.edu.au
S.M. Reichman
School of Civil, Environmental and Chemical Engineering, RMIT University, G.P.O. Box
2476, Melbourne 3001, Australia
L. De Filippis
School of the Environment, University of Technology Sydney, PO Box 123, Broadway,
NSW 2007, Australia
S.B. Tavakoly Sany
Institute of Biological Sciences, University of Malaya, 50603 Kuala Lumpur, Malaysia
H. Hasegawa
Institute of Science and Engineering, Kanazawa University, Kakuma, Kanazawa 920-1192,
Japan
e-mail: hhiroshi@se.kanazawa-u.ac.jp

© Springer Japan 2016 161


H. Hasegawa et al. (eds.), Environmental Remediation Technologies for Metal-
Contaminated Soils, DOI 10.1007/978-4-431-55759-3_8
162 M.A. Rahman et al.

from soils and wetlands: natural and induced phytoremediation. Natural


phytoremediation refers to the use of hyper-accumulating plants and associated
soil microbes, while the induced phytoremediation refers to the use chemicals,
especially synthetic chelating ligands, for the increase of metal bioavailability and
uptake in plants. Recently, genetically modified plants (GMPs) have been proposed
to use in phytoremediation technology; however, this approach is being hindered by
ideology-driven restrictive legislation over the use of GMPs. We will discuss the
concepts and practical applications of phytoremediation technologies for the restor-
ation of contaminated soils and wetlands.

Keywords Phytoremediation • Heavy metals • Soil • Wetland

8.1 Metal Contamination of Soils and Wetlands


and Human Health Impact

Metals comprise about 75 % of the known elements and have been used from the
beginning of ancient human civilization. Since the beginning of the industrial age,
metals have been emitted to and deposited in the environment (Sparks 2005). In
some cases, metals can be accumulated in terrestrial and aquatic environments in
high concentrations and cause harm to living beings via ingestion of soil and/or
dust, food, and water, inhalation of polluted air, and absorption via the skin from
polluted soils, water, and air (Hillel 2005). Increasing use of metals with population
and economic growth, especially in the developing countries, may contribute to soil
and water contamination causing the deterioration of environmental quality and
posing threats to human health (Sparks 2005).
Toxic metals can be derived from both natural and anthropogenic sources.
Natural (geogenic) sources include rocks and minerals, and anthropogenic sources
include agriculture (fertilizers, pesticides, herbicides, and animal manures), mining,
smelting, and sewage sludge and scrap disposal (Adriano 2001). Anthropogenic
deposition is a major mechanism for toxic metal input in the environment. Soil is
the major recipient of trace elements in terrestrial environment, while sediments are
the major sink in aquatic environment. Leaching of toxic metals or transport via
mobile colloids can contaminate groundwater. On the other hand, runoff and
drainage of toxic metals via sediments can contaminate freshwater environment
(Adriano 2001; Hillel 2005).
For many years across the world, industrial, mining, military, farming, and waste
management have contaminated large areas of soils and wetlands with high con-
centrations of toxic metals and organic pollutants (Peuke and Rennenberg 2005a; Li
et al. 2001; Del Rı́o et al. 2002). The problem of soil and water contamination of
toxic metals is becoming more and more serious with increasing industrialization
and disturbance of natural biogeochemical cycles by human activities and climate
change (Ali et al. 2013). For example, in Europe, an estimated 52 million hectares
of land – more than 16 % of the total land area of the continent – are affected by
some level of soil degradation (Peuke and Rennenberg 2005a). The largest and
8 Phytoremediation of Toxic Metals in Soils and Wetlands: Concepts and. . . 163

probably most heavily contaminated areas are found near industrialized regions in
north-western Europe, but many contaminated areas exist in the vicinity of major
European cities (EEA 2003). In China, over 20 million acres of farmland (almost
one fifth of the total arable farmland area) has been contaminated by toxic metals,
such as Sn, Cr, Pb, and Zn, causing approximately 10 million tons of crop losses per
year (Wu et al. 2010). A total area of 2.9  106 ha of degraded land has been
produced in China as a result of mining and an additional mean area of 46,700 ha of
destroyed land is produced annually. These degraded lands almost completely lack
vegetation due to serious pollution and ultimately cause severe soil erosion and
off-site pollution (Xia 2004). The Campine region in Belgium and the Netherlands
with 700 km2 is diffusely contaminated by atmospheric deposition of Cd, Zn and Pb
(Meers et al. 2010).
Bioaccumulation of toxic elements in the food chain from contaminated soils
and wetlands can be especially dangerous to human health. Toxic metals can enter
the human body by either inhalation or ingestion (Islam et al. 2007). For the
majority of people, the main route of exposure to toxic metals is diet except for
workers with high levels of occupational exposure (Sharma et al. 2008). Exposure
to toxic metals through the food chain has been reported in many countries,
particularly in developing countries, and received significant attention from gov-
ernment and non-government agencies (Åkesson et al. 2008; Al Jassir et al. 2005;
Demirezen and Aksoy 2006; Gulz et al. 2005). Concern over the accumulation of
toxic metals in the food chain and environment has escalated in recent years. Once
metals enter into biological systems they have the potential to disturb normal
biochemical processes, and in extreme cases can be fatal (Pillay et al. 2003).
Many countries have developed regulations for industries and other systems limit-
ing discharges of pollutants into the environment in order to control the emission of
trace elements and their subsequent health effects.
In fact, exposure to high content of toxic metals can cause significant adverse
effects to humans, animals, microorganisms, and plants (Wagner 1993; Gaetke and
Chow 2003; Hernández-Ochoa et al. 2005; Bodar et al. 2005). Regarding their
toxicities, the most problematic toxic metals are Hg, Cd, Pb, As, Cu, Zn, Sn, and Cr
(Ghosh 2010). Hg, Cd, Pb, and As are not essential for living organisms, while Cu
and Zn are essential metals. Exposure of humans to toxic metals may results in
neurobehavioral disorders, such as fatigue, insomnia, decreased concentration,
depression, irritability, sensory, and motor symptoms. Exposure to toxic metals
may also cause developmental retardation, various types of cancers, kidney dam-
age, autoimmunity, and even death in some instances of exposure to very high
concentrations (Glover-Kerkvliet 1995). For instance, at high concentration, Hg
can damage vital organs, such as the lungs and kidneys, may cause fetal brain
damage (Sharma 2003). Accumulation of Cd in human bodies (principally in the
kidney and liver) can cause renal dysfunction and bone disease (e.g., Itai-Itai in
Japan) (Nordberg 1996). Lead poisoning in children causes neurological damage
leading to reduced intelligence, loss of short-term memory, learning disabilities,
and coordination problems (Rai 2008a). The effects of As include cardiovascular
164 M.A. Rahman et al.

problems, skin cancer and other skin effects, peripheral neuropathy, and kidney
damage (Hughes 2002).

8.2 Remediation of Metal-Contaminated Soils


and Wetlands

Low to medium range contamination of lands with toxic metals may induce their
accumulation in the food chain. Therefore, strict environmental laws have been
imposed in many countries to prevent any such occurrence of the toxic metals in
foods by limiting the food production on contaminated lands. For example, a
European Union Council Directive (EC 1986) limited the concentrations of toxic
metals in agricultural soils to be 3 mg kg 1 for Cd, 140 mg kg 1 for Cu, 75 mg kg 1
for Ni, 300 mg kg 1 for Pb, 300 mg kg 1 for Zn, and 1.5 mg kg 1 for Hg (Grčman
et al. 2001). According to the directive, several million hectares of agricultural
lands are considered polluted by toxic metals in Europe (Flathman and Lanza
1998), and between 59 and 109 billion EUR is required to clean-up the contami-
nated sites using conventional techniques such as soil washing using particle size
separation, chemical extraction with aqueous solutions of surfactants and mineral
(EC 2004). Such high costs for land restoration using traditional remediation
methods make the clean-up of many sites unaffordable even in the more developed
nations. For instance, in Germany, only one-third of the total contaminated sites are
cleaned up in soil remediation facilities while the remainder has been left untreated
(Evangelou et al. 2007; Peuke and Rennenberg 2005a). This does not solve the
problem, rather transferring it to future generation.
Aquatic ecosystems (including wetlands) are used directly or indirectly as
recipients of potentially toxic liquids and solids from domestic, agricultural, and
industrial wastes (Demirezen et al. 2007; Peng et al. 2008). Thus, wetland sedi-
ments are the major sink of toxic metals (Marchand et al. 2010). Clean-up of
contaminated soils and wetlands is necessary to reduce the risk of metal toxicity
to human and ecosystems. To date, different physical, chemical, and biological
approaches have been employed for this purpose. The conventional remediation
methods include in situ vitrification, soil incineration, excavation and landfill, soil
washing, soil flushing, solidification, and stabilization of electro-kinetic systems
(Sheoran et al. 2011; Wuana and Okieimen 2011). Generally, the physical and
chemical methods suffer from limitations like high cost, intensive labor, irreversi-
ble changes in soil properties, and disturbance of native soil microflora. Chemical
methods can also create secondary pollution problems. Therefore, there is an urgent
need for alternative, cheap, and efficient methods to clean up heavily contaminated
soils and wetlands. To improve how contaminated sites are remediated, there is a
need to move beyond more traditional remediation practices and include some of
the more novel remediation techniques like phytoremediation. Due to the potential
of phytoremediation and the extent of contaminated sites, this technology has
8 Phytoremediation of Toxic Metals in Soils and Wetlands: Concepts and. . . 165

received significant scientific and commercial attention world-wide (McIntyre


2003; Gleba et al. 1999; Meagher 2000; Dietz and Schnoor 2001; Rahman
et al. 2007; Salt et al. 1998).

8.3 Phytoremediation – A Green Technology


for the Remediation of Contaminated Environment

8.3.1 Phytoremediation Strategies for the Restoration


of Contaminated Soils and Wetlands

Phytoremediation (from ancient Greek “phyto” meaning “plant”, and Latin “reme-
dium” meaning “restoring balance”) defines the remediation of contaminated
environment (soils and wetlands) based on the idea of using natural bioaccumu-
lation abilities of plants without excavating the contaminant material. Phyto-
remediating plants are ideally fast growing, tolerant of toxic metals, and efficient
at transferring toxic metals from roots to above ground biomass. Sometimes,
rhizospheric microorganisms or chemicals (e.g., chelating ligands) are used to
increase of metal bioavailability and uptake. Based on the natural abilities of the
phytoremediating plants, restoration of contaminated soils and wetlands can be
achieved by employing the following phytoremediation strategies.
• Phytoextraction
• Phytostabilization
• Phytovolatilization
• Phytodegradation
• Phytofiltration
• Phytotransformation/detoxification

8.3.1.1 Phytoextraction

Phytoextraction is the uptake of contaminants from soils or waters by plant roots


and their translocation to the harvestable biomass (Sekara et al. 2005; Yoon
et al. 2006; Rafati et al. 2011). Translocation of toxic metals form roots to
harvestable biomass (shoots) is necessary for an effective phytoextraction protocol
because the harvest of root biomass is generally not feasible due to the location of
roots within the soil (Zacchini et al. 2009; Tangahu et al. 2011). In general,
phytoextraction has been tried more often for extracting toxic metals than for
organics. Some of the examples of phytoextraction are sunflower (Helianthus
annuus) (Marchiol et al. 2007) and Chinese brake fern (Pteris vittata)
(Ma et al. 2001) for As; willow (Salix viminalis) Cd, Zn, Ni, Pb, and Cu (Greger
and Landberg 1999; Borišev et al. 2009); Indian mustard (Brassica juncea) for Pb
(Blaylock et al. 1997). The main advantage of phytoextraction is environmental
166 M.A. Rahman et al.

friendliness. Traditional methods that are used commonly used for cleaning up
metal-contaminated soil disrupt soil structure and reduce soil productivity, whereas
phytoextraction can clean up soil without causing harm to soil quality. Another
benefit of phytoextraction is that it is less expensive than the traditional clean-up
process.
Phytoextraction can be used for phytoremediation of toxic and hazardous metals
as well as for phytomining of precious metals (such as Au, Pd, Tl, and Pt) (Ali
et al. 2013; Brooks et al. 1998). Phytomining has the potential to be an economi-
cally feasible solution to the disposal of used phytoremediation biomass. Plant
biomass containing metals can be combusted to obtain energy and the remaining
ash is considered as “bio-ore”, which can be processed for the recovery or extrac-
tion of precious metals (Rascio and Navari-Izzo 2011). An advantage of
phytomining is that this is a cost-effective and ecofriendly option as compared to
the conventional metal extraction methods (Ali et al. 2013; Rascio and Navari-Izzo
2011). The commercial feasibility of phytomining, however, depends on many
factors like phytoextraction efficiency of precious metals and current market
value of the processed metals. In addition, this technique can only be used to extract
metals from the rhizosphere. Phytomining has been commercially used for Ni and it
was found to be less expensive than the conventional extraction methods for Ni
(Robinson et al. 1997; Nicks and Chambers 1998). Commercial phytomining has
also been used for Au and Tl (Anderson et al. 1999).
The chemical composition and sorption properties of soil influence metal mobi-
lity and bioavailability (Kłos et al. 2012). The bioavailability of toxic metals in soils
is a critical factor affecting the efficiency of phytoextraction of target metals. Low
bioavailability is a major limiting factor for phytoextraction of contaminants such
as Pb (Ali et al. 2013). Strong binding of toxic metals to soil particles or precipi-
tation causes a significant fraction of the toxic metals non-bioavailable, and there-
fore remain unavailable for uptake by phytoremediating plants (Sheoran
et al. 2011). Based on bioavailability, toxic metals in soils can be categorised into
three groups: readily bioavailable (Cd, Ni, Zn, As, Se, and Cu); moderately
bioavailable (Co, Mn, and Fe) and least bioavailable (Pb, Cr, and U) (Prasad
2003). However, many plants have developed mechanisms for solubilizing heavy
metals in soil such as the secretion of metal-mobilizing “phytosiderophores” into
the rhizosphere by members of the Poaceae (Lone et al. 2008; Reichman and Parker
2005), for solubilizing toxic metals in soil.
Phytoextraction is classified into natural and induced based on the bioaccumu-
lation process of the plants species involved. Natural phytoextraction is based on
the idea of the use of natural hyperaccumulators that have exceptionally high metal-
accumulation ability and tolerance to toxic metals (Baker et al. 2000). In induced
phytoextraction, a conditioning fluid containing a chelator or another agent is added
to soil to increase metal solubility or mobilization so that the plants can absorb
higher concentrations of metals.
In the past decade, chelant-enhanced phytoextraction has received much atten-
tion from the scientific community. Chelants, when added to soil, are capable of
forming soluble complexes with both “labile” and “non-labile” metal in the soil
8 Phytoremediation of Toxic Metals in Soils and Wetlands: Concepts and. . . 167

solution via desorption of sorbed species and dissolution of precipitated compounds


(Norvell 1984). Re-precipitation and re-sorption of metals are prevented by the
chelant-metal-complex formation, and the metals become bioavailable (Salt
et al. 1995a). The drawback of metal phytoextraction due to limited bioavailability
of metals is minimized after the unearthing that the translocation of metals from soil
to plants can be increased to maximum with the addition of certain chelants
(Blaylock and Haung 1999). However, the soil properties and the nature of the
applied chelant determine the amounts of bioavailable metals in soil matrix (Kos
and Lestan 2004; Tandy et al. 2004; Luo et al. 2005). Stability constants, Ks, of
chelant-metal-complexes are the decisive feature to select a chelant or rank differ-
ent chelants for the extraction of metals from the metal-contaminated soil. The
chemical characteristics of the chelant itself and the metal speciation in the soil
matrix also influence the effectiveness of different chelant in the separation process
(Elliott and Brown 1989; Luo et al. 2005; Huang et al. 1997).
A wide range of synthetic chelants have been tested for chelant-induced
phytoextraction with aminopolycarboxylate chelants (APCs) among the most
used chelant type. Typically used APCs for metal phytoextraction include
Ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid
(DTPA), N-(hydroxyethyl)ethylenediaminetriacetic acid (HEDTA), nitrilotriacetic
acid (NTA), S,S-ethylenediaminedisuccinic acid (S,S-EDDS), methylglycine-
diacetic acid (MGDA), and glutamic acid diacetic acid (GLDA) . In particular,
EDTA has most often been utilized among the APCs, since EDTA forms strong
water-soluble chelant complexes with most toxic metals (Egli 2001; Nowack and
VanBriesen 2005; Leštan et al. 2008; Salt et al. 1998). Despite the success of the use
of EDTA in phytoextraction of toxic metals, the enhanced mobility of the metals in
soil by EDTA and their potential risk of leaching are important concerns (Cooper
et al. 1999; Wu et al. 2004; Sun et al. 2001). Several studies showed that EDTA
enhanced the leaching of heavy metals during the phytoextraction process
(Sun et al. 2001; Wu et al. 2004; Grčman et al. 2001; Kedziorek et al. 1998).
For example, Wu et al. (2004) found that the mobility and leaching of Cu, Zn, and
Cd increased significantly during the EDTA-enhanced phytoextraction process.
Increased mobility and leaching of Zn, Cu, Cd, and Pb during the EDTA-enhanced
phytoextraction process has also been reported by Sun et al. (2001).
In addition to enhanced mobility and leaching of heavy metals by EDTA, the
persistence of metal-EDTA complexes in contaminated soils and their effects on
soil microbial community are important drawbacks of this technology. Several
studies have indicated that EDTA-metal complexes are resistant to microbial
degradation (N€ ortemann 1999; Oviedo and Rodrı́guez 2003). Palumbo
et al. (1994) found that the bacterial ability to degrade EDTA is rare, since they
could not obtain degrading consortia from places polluted with the chelate. Other
studies also found EDTA to be slowly biodegraded to CO2 in soil, with only 6.7 %
degraded after 4 weeks and a lower rate of degradation in the subsoil than in surface
soil (Tiedje 1975). Means et al. (1980) reported that the EDTA degradation rate was
not rapid enough, even under optimal laboratory conditions, to stop disquiet about
168 M.A. Rahman et al.

its release into the environment. Therefore, biodegradable chelating ligands can be
alternatives to the EDTA for the phytoextraction of toxic metals.
The method of chelant application significantly affects the efficiency of the
phytoextraction process. The chelant can be applied to the soil matrix either in a
single dose after the optimum growth of the accumulator crop, or in small multiple
doses gradually during the growth cycle. Studies showed that application of chelant
in multiple doses is more effective than that of single dose (Wenzel et al. 2003).
Phytoextraction efficiency can also be improved by the combined application of
different chelants to the metal-contaminated soil (Leštan et al. 2008). For example,
Blaylock et al. (1997) showed that the application of EDTA and acetic acid results
in a twofold accumulation of Pb in Indian mustard shoots compared with the
application of EDTA alone. Luo et al. (2006) also found that the combined
application of EDTA and EDDS results in a higher level of efficiency in the
phytoextraction of Cu, Pb, Zn, and Cd than could be obtained by the application
of either chelant alone.
Although phytoextraction of toxic metals can be achieved by using hyper-
accumulators, the technology may not be applicable for remediating sites with
multiple contaminants. Wu et al. (2006) proposed a solution to the phyto-
remediation of soils with multiple contaminants using a combination of microbe-
plant symbiosis within the plant rhizosphere. They showed that inoculation of
sunflower roots with the engineered rhizobacterium resulted in a marked decrease
in Cd phytotoxicity and a 40 % increase in Cd accumulation in the plant root.
Owing to the significantly improved growth characteristics of both the rhizo-
bacterium and plant, they proposed the use of a metal-binding peptide (EC20) in
a rhizobacterium (Pseudomonas putida) with organic-degrading capabilities as a
promising strategy to remediate mixed organic-metal-contaminated sites.

8.3.1.2 Phytostabilization

Phytostabilization is the immobilization of a contaminant in soil through adsorption


onto roots, absorption and accumulation by roots, or precipitation within the root
zone of plants (Brunner et al. 2008). Unlike phytoextraction, phytostabilization
focuses mainly on sequestering pollutants in soil near the roots. This technique is
used to reduce the mobility and bioavailability of pollutants in the environment,
thus preventing their leaching in groundwater and entry into the food chain
(Erakhrumen and Agbontalor 2007).
Phytostabilization occurs through contaminant accumulation in plant tissue and
in the soil around the roots because of changes in the chemistry of the contaminants,
which become insoluble and/or immobilized on soil components. Plants used for
phytostabilization will need to be tolerant of the metals present in the particular site,
but the accumulation of metals in their aerial parts may be positively disadvan-
tageous. If the objective of phytostabilization is purely to prevent erosion and
improve the visual amenity of a derelict site, then the accumulation of metals in
the plants may be irrelevant (Macnair et al. 2000).
8 Phytoremediation of Toxic Metals in Soils and Wetlands: Concepts and. . . 169

Metal immobilizing chemicals (soil amendments) are used for phytostabilization


technology to improve soil conditions for plant growth and to reduce the chemical
mobility in soil and toxicity of the metals to biota (Vangronsveld et al. 2009).
Different soil amendments are used in phytostabilization technology for different
toxic metals. For example, the most promising amendments for phytostabilization
of Pb are phosphate materials, materials containing hydrous iron oxides, steel shot,
inorganic clay minerals, and organic material (Cunningham and Berti 2000). By
excreting special proteins and/or redox enzymes, certain plant species can convert
metals to relatively less bioavailable forms and decrease possible metal bioavail-
ability and toxicity to biota. For example, Cr(III) is less mobile and toxic than
Cr(VI), and the reduction of Cr(VI) to Cr(III) can be a strategy of phytostabilization
(Wu et al. 2010).
Phytostabilization technology influences the mobility of toxic metals in soils in
different ways:
• The amendments directly alter the soil conditions (acidic and/or alkaline condi-
tions, organic matter, oxygen levels) in the rhizosphere that influence metal
mobility.
• Proteins and/or enzymes are released by the roots into the rhizosphere soil,
leading to precipitation and immobilization of the toxic metals either in the
soil or on the root surface.
• The toxic metals are taken up by the plants and sequestered in the root system.
• The surface of the soil is vegetated, and the vegetation acts as a barrier to erosion
and exposure of the contaminated soil to wind, water, and direct contact with
humans or animals.
An example of the application phytostabilization technology is the use of
vegetation cap to stabilize and contain mine tailings (Mendez and Maier 2008;
Conesa et al. 2007).
Phytostabilization technology for the remediation of metal-contaminated soils
has both the advantage and disadvantage. Advantages of this technology include:
• This technology reduces the mobility, and therefore the risk, of toxic metals
without removing them from their location.
• This technology does not generate secondary contamination that needs
treatment.
• Usually this technology enhances the soil fertility. It may combine treatment
with ecosystem restoration.
Disadvantages of phytostabilization technology may include:
• The contaminants are left in place, so the site must be monitored perpetually to
make sure the stabilizing conditions continue.
• If the contaminant concentrations are very high, toxic effects may prevent the
growth of plants until extensive amendments application reduce their bioavail-
ability to plants.
170 M.A. Rahman et al.

• If soil additives are used, they may need to be periodically reapplied to maintain
the effectiveness of the immobilization.

8.3.1.3 Phytovolatilization

Phytovolatilization is the uptake of pollutants from soil by plants, their conversion


to volatile form and subsequent release into the atmosphere (Ali et al. 2013). This
method can be used for organic pollutants and some toxic metals like Hg, Se, and
As that have gaseous forms.
There is some evidence that certain plant species have the ability to accumulate
Hg both from the atmospheric and soil sources; however, no plant species with Hg
hyperaccumulating properties has been identified (Raskin and Ensley 2000). There-
fore, transgenic plants such as Arabidopsis (Arabidopsis thaliana L.) and tobacco
(Nicotiana tobacum) containing bacterial mercuric ion reductase (merA) and organo-
mercurial lyase (merB) genes, responsible for detoxifying methyl-mercury, have
been investigated for their ability of Hg phytovolatilization (Heaton et al. 1998;
Bizily et al. 1999). The advantage of this technology is that the plant may transform
toxic methyl-mercury to a less toxic volatile elemental Hg. However, the important
limitation of Hg phytovolatilization is that the released elemental Hg into the
atmosphere is likely to be recycled by precipitation and then redeposit back into
ecosystem (Henry 2000).
Bacteria containing the As (III) S-adenosylmethionine methyltransferase (arsM)
gene were able to sequentially methylate toxic inorganic As to less toxic penta-
valent methylated arsenicals such as methylarsenate (MAs(V)), dimethylarsenate
(DMAs(V)), and trimethylarsine oxide (TMAs(III)) (Qin et al. 2006, 2009). The
phytovolatilization of the final product, gaseous TMAs(III), could remove arsenic
from polluted water and soil using engineered hyperaccumulator such as Chinese
fern Pteris vittata (Sakakibara et al. 2010; Zhu and Rosen 2009).
The major disadvantage of phytovolatilization is that it does not remove the
pollutants completely from the environment; rather it transfers the pollutants from
soils/waters to atmosphere from where it can be re-deposited through atmospheric
precipitation. Therefore, the use of phytovolatilization for the remediation of
environmental contaminants remains controversial (Padmavathiamma and Li
2007).

8.3.1.4 Phytodegradation

Phytodegradation refers to the microbial breakdown of pollutants, particularly


organic pollutants, in the rhizosphere (Mukhopadhyay and Maiti 2010; Newman
and Reynolds 2004). The main reason for the enhanced degradation of organic
pollutants in the rhizosphere compared to the bulk soil? Is likely the increase in the
numbers and metabolic activities of the microbes in the rhizosphere. Plants can
stimulate microbial activity by 10–100 times higher in the rhizosphere compared to
8 Phytoremediation of Toxic Metals in Soils and Wetlands: Concepts and. . . 171

the bulk soil by the secretion of exudates containing substances such as carbo-
hydrates, amino acids, and flavonoids (Ali et al. 2013). The release of nutrient-
containing exudates by plant roots provides carbon and nitrogen sources to the soil
microbes and creates a nutrient-rich environment in which microbial activity is
stimulated. In addition to secreting organic substrates that facilitate the growth and
activity of rhizospheric microbes, plants also release enzymes that are directly
capable of degrading organic contaminants in rhizosphere (Kuiper et al. 2004;
Yadav et al. 2010).

8.3.1.5 Phytofiltration

Phytofiltration (also known as rhizofiltration), which is related to phytoextraction,


is the removal of pollutants from contaminated wetlands by aquatic plants
(Mukhopadhyay and Maiti 2010; Dushenkov et al. 1995). Gardea-Torresdey
et al. (2004) reviewed phytofiltration technology for the removal of toxic metals
form contaminants from aqueous effluents. Phytofiltration may be rhizofiltration
(use of plant roots) or blastofiltration (use of seedlings) or caulofiltration (use of
excised plant shoots) (Mesjasz-przybyłowicz et al. 2004).
The phytofiltration of toxic metals from contaminated waters using aquatic
plants has been extensively studied (Selvapathy and Sreedhar 1991; Sen and
Bhattacharyya 1993; Low et al. 1994; Alam et al. 1995; Ingole and Ting 2002;
Sen and Mondal 1990; Dushenkov et al. 1995). This cleanup process involves
biosorption and accumulation of pollutants. Many aquatic plants (floating and
sub-merged) have been investigated for the remediation of wastewater contami-
nated with Cu(II), Cd(II), and Hg(II) (Sen and Mondal 1987; Selvapathy and
Sreedhar 1991; Alam et al. 1995). Water fern (Salvinia natans L.) is a free-floating
freshwater macrophyte that has been tested for remediation of Hg(II) (Sen and
Mondal 1987), and Cu(II) (Sen and Mondal 1990) and As(V) (Rahman
et al. 2008c). Other examples of phytofiltration of toxic metals by aquatic plants
are – Medicago sativa (Alfalfa) for Cd, Cr Pb, and Zn (Gardea-Torresdey
et al. 1998); ferns (Pteris vittata and Pteris cretica) for As (Huang et al. 2004);
Yellow burrhead (Limnocharis flava) for Cd (Abhilash et al. 2009); water hyacinth
(Eichchornia crassipes) for Cd and Zn (Hasan et al. 2007); and duckweed
(Spirodela polyrhiza) for As (Rahman et al. 2007) .

8.3.1.6 Phytotransformation/Detoxification

Phytotransformation of toxic metals is not a direct remediation technique, rather it


reduce/detoxify the toxicity of toxic metals to the organisms. There are some
microbes (e.g., bacteria, phytoplankton, fungi, etc.) that in the soil and aquatic
environment that have the ability/mechanisms to transform more toxic forms of the
toxic metals and metalloids to their less toxic form (Summers and Silver 1978;
Raab and Feldmann 2003; Bender et al. 1995). This detoxification process of
172 M.A. Rahman et al.

microbes is considered as a promising method for bioremediation of heavy metals


and metalloids.
Higher plants also have detoxification mechanisms of toxic metals (Zenk 1996).
A set of toxic-metal-complexing peptides has been isolated from plants and plant
suspension cultures. The structure of these peptides was established as (γ-glutamic
acid-cysteine)n-glycine and are called phytochelatins (PC) (Zenk 1996; Cobbett and
Goldsbrough 2002). The biosynthesis of PCs proceeds by metal activation of a
constitutive enzyme that uses glutathione ( GSH) as a substrate. In a recent review,
Rahman and Hassler (2014) discussed the rules of PCs and GSH in As resistance
and detoxification by photosynthetic organisms. Other studies also reported the
phytotransformation/detoxification of toxic metals by plants and photosynthetic
organisms (Cobbett and Goldsbrough 2002; Lytle et al. 1998; Ow et al. 1998).
However, more research and knowledge on the natural detoxification mechanisms
of toxic metals by plants are required to improve plant’s performance in removing
these toxicants from the environment.

8.4 Tolerance and Detoxification of Toxic Metals in Plants

8.4.1 Mechanisms of Heavy Metal Uptake in Plants

Plants uptake heavy metals from soil solution and waters into their roots, and then a
fraction of the heavy metal ions are stored in the roots while the rest are translocated
to the aboveground parts primarily through xylem vessels (Prasad 2004; Jabeen
et al. 2009). The uptake of heavy metal ions from soil solution by plants’ roots and
subsequent translocation to the shoots and vacuoles is controlled and regulated by a
variety of molecules. Some molecules are involved in the cross-membrane trans-
port of the heavy metal ions and others are involved in their complexation with
chelating compounds and subsequent sequestration in the vacuoles (Ali et al. 2013;
Tong et al. 2004). Uptake of heavy metal ions into plant’s roots is mediated by
several classes of specialized transporter proteins (channel proteins) in the plasma
membrane (Seth 2012). These include the CPx-type heavy metal ATPases, the
natural resistance-associated macrophage (Nramp) family of proteins, action diffu-
sion facilitator (CDF) family proteins, and zinc-iron permease (ZIP) family proteins
(Williams et al. 2000). The ZIP family proteins contribute to the uptake of Zn2+ and
Fe2+ (Clemens 2001), while CPx-type heavy metal ATPases have been involved in
the transport of essential as well as potentially toxic metals like Cu, Zn, Cd, and Pb
across the cell membranes (Williams et al. 2000). The Nramp family proteins play
an important role in transport of divalent metal ions into the plant’s roots (Seth
2012).
8 Phytoremediation of Toxic Metals in Soils and Wetlands: Concepts and. . . 173

8.4.2 Mechanisms of Metal Tolerance and Detoxification


in Plants

Plants have a range of potential cellular mechanisms in order to tolerate and


detoxify heavy metal stress. These include metal binding to cell walls, exudation
of metal chelating compounds, and a network of processes that take up metals,
chelate them, and transport these complexes to above-ground tissues where they are
sequestered into vacuoles (Peuke and Rennenberg 2005a). Based on these mecha-
nisms, plants can be classified into two groups: (i) non-accumulators that achieve
metal tolerance by preventing toxic metals uptake into roots cells passively through
binding the metal ions onto the cell walls; (ii) accumulators that evolved specific
mechanisms for high levels of metal accumulation and detoxification in cells. The
second group of plants uptake heavy metals in shoots and sequester them in cellular
vacuoles to remove excess metal ions from the cytosol to reduce their interactions
with cellular metabolic processes (Assunção et al. 2003).
The hyperaccumulating or metal-tolerant plant species such as Silene vulgaris,
Thlaspi caerulescens, Alyssum lesbiacum, Arabidopsis halleri, and Brassica spp.
have been investigated by several researchers (Clemens et al. 2002; Kraemer 2003).
The ability of these plants to accumulate high concentrations of metals was
observed for both essential nutrients, such as Cu, Fe, Zn, and Se, as well as
non-essential metals, such as Cd, Hg, Pb, Al, and As (Salt et al. 1998; Meagher
2000; Clemens et al. 2002; McGrath and Zhao 2003). Metal concentrations in the
shoots of accumulating plants can be 100–1000-fold higher than in
non-accumulating plants (Peuke and Rennenberg 2005a). Frequent generation of
free radicals are taking place during heavy metal stress in accumulating plants and it
leads to oxidative stress. Plants have been developed a good tolerance mechanisms
against these heavy metal induced oxidative stress via significant synthesis of
antioxidants and chelating compounds (Mishra et al. 2006; Seth et al. 2007,
2008). The transformation of toxic forms to less harmful forms is also an approach
to detoxifying heavy metals, particularly As, Hg, Fe, Se, and Cr, which exist in a
variety of cationic and oxyanionic species and thio- and organo-metallic forms
(Meagher 2000; Guerinot and Salt 2001).
In antioxidant system, plants have shown significant synthesis of various types
of antioxidants subjected to metal stress, indicating a possible role in defense
mechanisms (Cobbett 2000; Mishra et al. 2006; Seth et al. 2007). The functional
significance of a compound as antioxidant achieved through different mechanisms,
such as metal chelation, activated oxygen species scavenging, recycling of other
antioxidant, inhibition of lipid per oxidation, and repair of damaged DNA mole-
cules caused by oxidative stress (Allen 1995; Seth et al. 2008). Among these,
scavenging and/or removal of free radicals are the most likely mechanisms for
antioxidants mediated tolerance strategy in plants (Seth 2012). Several enzymatic
antioxidants such as super oxide dismutase (SOD), ascorbate peroxidase (APX),
and catalase (CAT) are major types of reactive oxygen species (ROS)-scavenger
that play significant roles in these mechanisms (Mishra et al. 2006). Other than
174 M.A. Rahman et al.

enzymatic antioxidant, some non-enzymatic antioxidants such as cysteine,


non-protein thiols (NP-SH), ascorbic acid and GSH are also playing a very impor-
tant role in plant resistance against oxidative stress (Seth et al. 2007; Hammond-
Kosack and Jones 1996).
Chelating peptides, most notably metallothioneins (MTs) and PCs, have a
significant role in the detoxification of metals, and their synthesis in the plant is
induced by exposure of root cells to heavy metals (Rauser 1999; Cobbett and
Goldsbrough 2002; Cobbett 2000; Hall 2002). These cysteine-rich polypeptides
exploit the property of heavy metals to bind to the thiol-groups of proteins – one of
the toxic effects of heavy metals – for detoxification. Metallothioneins are S-rich
proteins of 60–80 amino acids that contain 9–16 cysteine residues and are found in
plants, animals, and some prokaryotes (Cobbett and Goldsbrough 2002; Cobbett
2000; Rauser 1999). Phytochelatins are a family of γ-glutamylcysteine
oligopeptides with glycine or other amino acids at the carboxy-terminal end, in
which γ-Glu-Cys units are repeated 2–11 times. They are synthesized from GSH
and its derivates by phytochelatine synthase in the presence of heavy metal ions
(Cobbett 2000). It is reported that cells and tissues exposed to a range of heavy
metal ions, such as Cd, Ni, Cu, Zn, Ag, Hg, and Pb, are rapidly synthesized PCs,
with the fact that Cd was the strongest inducer for PCs synthesis (Rauser 1995;
Yang and Yang 2001; Pinto et al. 2003). The functional significance of PCs can be
attributed due to the presence of thiol groups ( SH) which make co-ordination
bond with toxic metal ions (Seth 2012), which are then sequestered into the cellular
vacuoles.
Sequestration of heavy metal ions in cellular vacuoles is an important detoxifi-
cation/tolerance mechanism in metal hyperaccumulators (Tong et al. 2004). Com-
plexation to low molecular weight organic chelators such as organic acids (malate,
citrate), amino acids (O-acetylserine, histidine), and nicotinamine have also shown
to play significant roles in metal detoxification/tolerance in plants (Salt et al. 1995b;
Clemens 2001; Cobbett and Goldsbrough 2002; Hall 2002; Kraemer 2003).

8.5 Phytoremediation of Toxic Metals Using Transgenic


Plants

The efficiency of a remediation strategies depends on many issues including biotic


(e.g., the plant species concerned) and abiotic (e.g., bioavailability of the heavy
metals, speciation of the heavy metals, physico-chemical conditions of the contami-
nated sites, level of contamination) factors. The abiotic factors can be changed to
conditions favorable for a phytoremediation strategy. For example, bioavailability
of heavy metals has been reported to be increased by chelating ligands (Blaylock
et al. 1997; Evangelou et al. 2007). The main challenge of an effective phyto-
remediation strategy for the removal of heavy metals from contaminated sites
is the choice of a potential plant species that has desirable characteristics such as
8 Phytoremediation of Toxic Metals in Soils and Wetlands: Concepts and. . . 175

fast growth rate, high above-ground biomass, widely distributed root systems,
tolerance to the toxic effects of the target heavy metals, adaptive to the target
sites, and easy to harvest (Adesodun et al. 2010; Sakakibara et al. 2011; Ali
et al. 2013). It is difficult to find a plant species with all of these characteristics.
However, some researchers proposed that the phytoextraction potential of a plant
species should be determined mainly by two key factors: (i) shoot metal concen-
tration and (ii) shoot biomass (Li et al. 2010). Other researchers proposed
hyperaccumulation and hypertolerance as more important characteristics than
shoot biomass for a phytoremediation strategy (Chaney et al. 1997).
Most scientific and commercial interest in phytoremediation now focuses on
phytoextraction and phytodegradation, which use selected plant species grown on
contaminated sites. In phytoextraction, the plant species are harvested to remove
the plants together with the pollutants that have accumulated in their tissues.
Two different approaches have been tested for phytoextraction of heavy metals
(Robinson et al. 1998; Tlustoš et al. 2006).
1. The use of hyperaccumulating plant species. In this technique, the idea is to use
hyperaccumulators that produce comparatively less aboveground biomass but
accumulate high amount of the target heavy metals.
2. The use of high biomass producing plant species. This technique aims to use
plant species which is not a hyperaccumulator but produce more aboveground
biomass than the hyperaccumulators so that overall metal accumulation in the
aboveground biomass is comparable to that of hyperaccumulators.
However, in selecting a plant species for phytoremediation based on different
desired characteristics discussed above, it should be carefully considered that the
use of hyperaccumulators will yield a metal-rich, low-volume biomass, which is
economical and easy to handle in case of both metal recovery and safe disposal.
On the other hand, use of non-accumulators will yield a metal-poor, large-volume
biomass, which will be uneconomical to process for recovery of metals and also
costly to safely dispose. However, high biomass yielding plants are usually not
hyperaccumulators. Use of genetically modified plants (GMPs) has been proposed
to be a solution to overcome the limitations of fast growing non-hyperaccumulators
(Rugh et al. 1998; Pilon-Smits and Pilon 2002; Cunningham and Ow 1996; Bennett
et al. 2003).
Unlike plant growth, which depends on numerous genetic and non-genetic
factors, the accumulation of heavy metals is controlled by only a few gene loci
and is more easily accessible for genetic manipulation (Clemens et al. 2002).
Therefore, phytoremediation strategies that have been put into consideration are
the genetic manipulation of GSH and PC production in plant tissues (Song
et al. 2003; Noctor et al. 1998; Cobbett 2000; Yadav 2010).
Initial experiments with transgenic plants have shown that they are indeed
efficient in drawing metals from heavily contaminated soils (Rugh et al. 1998;
Cherian and Oliveira 2005; Tong et al. 2004). Trees are probably the best-suited
plants for transgenic approaches to improve the heavy-metal accumulation. Tree
biotechnology is thus becoming an increasingly important tool for the remediation
176 M.A. Rahman et al.

of contaminated environments (Peuke and Rennenberg 2005b). Fast-growing trees,


such as Populus spp., are good candidates for phytoremediation due to their
extensive root systems, high rates of water uptake and transpiration that is helpful
in efficient transport of contaminants from roots to shoot, rapid growth and large
biomass production (Rugh et al. 1998; Taghavi et al. 2005). Poplars can be grown in
a wide range of climatic conditions and are used with increasing frequency in
‘short-rotation forestry’ systems for pulp and paper production. This raises the
possibility of using plantations of transgenic poplars across several multiyear cycles
to remove heavy metals from contaminated soils (Robinson et al. 2000; Peuke and
Rennenberg 2005a). In addition, a dense tree cover would also prevent erosion and
the spread of contaminated soil by wind. After the first planting, the costs for field
management are relatively low and the products (biomass/wood) can be used for the
production of electricity and heat by burning in wood power stations. Another
important point is that it is very unlikely that poplars will enter the human food
chain or end up as feedstock for animals.
The transformation of gray poplar trees (Populus tremula x P. alba) to
overexpress γ-ECS from Escherichia coli resulted in higher levels of GSH and its
precursor γ-L-glutamyl-L-cysteine compared with wild type (Noctor et al. 1998),
and an elevated capacity for PC production. These new transgenic trees have been
shown a high potential for the uptake and detoxification of heavy metals (Peuke and
Rennenberg 2005b). Results from preliminary trials showed that the transgenic
poplars are genetically stable and there are no indications so far of any impact on
the environment. The transgenic trees have a higher capacity than wild-type trees
for accumulating heavy metals on the heavily contaminated sites (Peuke and
Rennenberg 2005a).
Despite this and other advantages, the progress and application of GMPs in
phytoremediation technology to tackle widespread environmental contamination
problems is being hampered by ideology-driven, restrictive legislation over the use
and release of GMPs in Europe, and many other countries (Peuke and Rennenberg
2005a). However, if genetic engineering is eventually successful in producing
plants that are able to restore/remediate contaminated sites without any potential
impact on the environment in general and in particular on agriculture and human
health, then we may also see a better public acceptance of GMPs in the future.

8.6 Phytoremediation of Toxic Metals by Aquatic Plants

Phytoremediation of the heavy metals can be achieved by aquatic plants since the
process involves biosorption and bioaccumulation of the soluble and bioavailable
metals from water (Brooks and Robinson 1998). The aquatic plants can be floating,
emergent, and submerged. The floating aquatic plants accumulate metals by their
roots from water, while the submerged plants accumulate metals from the sedi-
ments by their roots and from the water by their shoots (Rahman and Hasegawa
2011; Rahman et al. 2011).
8 Phytoremediation of Toxic Metals in Soils and Wetlands: Concepts and. . . 177

Provably, Hutchinson (1975) reviewed, for the first time, the ability of aquatic
macrophytes to concentrate elements from the aquatic environment and described
that the levels of toxic elements in these plants were at least an order of magnitude
higher than that in the supporting aqueous medium. Later on, Outridge and Noller
(1991) reviewed the accumulation of toxic trace elements by aquatic vascular plants
and discussed the pathways and rates of elemental uptake and excretion, environ-
mental factors that control uptake of elements, and the significance of trace
elements uptake for the field of wastewater treatment and biomonitoring of pollu-
tants. To date, numerous papers have been published in leading international
journals on different aspects of biogeochemistry, mechanisms and uptake of toxic
metals by different aquatic macrophytes. The aim of these studies was to develop an
efficient and cost-effective phytoremediation technology. A list of aquatic plants
that have been studied for the phytoremediation of toxic metals is listed in
Table 8.1.
Microspora and Lemna minor were studied for Pb and Ni phytoremediation
(Axtell et al. 2003). Five common aquatic plant species (Typha latifolia, Myrio-
phyllum exalbescens, Potamogeton epihydrus, Sparganium angustifolium, and
Sparganium multipedunculatum) were tested for Al phytoremediation (Gallon
et al. 2004). Parrot feather (Myriophyllum aquaticum), creeping primrose
(Ludwigina palustris), and water mint (Mentha aquatic) have shown to remove
Fe, Zn, Cu, and Hg from contaminated water effectively (Kamal et al. 2004).
L. minor was reported to accumulate Cu and Cd from contaminated wastewater
(Kara 2004; Hou et al. 2007). The submerged aquatic plant Myriophyllum spicatum
L. was found to be efficient for metal-contaminated industrial wastewater treatment
(Lesage et al. 2007). The aquatic plants Rorippa nasturtium-aquaticum (L.) and
Mentha spp. have been reported to accumulate significant amount of As from
contaminated freshwater (Robinson et al. 2006). Based on the outcomes of
many studies, aquatic plants have been used for the remediation of contaminated
constructed wetlands.

8.6.1 Constructed Wetlands for Phytoremediation of Toxic


Metals

Wetlands are often considered sinks for contaminants, and there are many cases in
which wetland plants are utilized for removal of pollutants, including metals.
Constructed wetlands offer a cost-effective and technically feasible method and
have proven effective and successful in remediation of heavy metal pollution (Weis
and Weis 2004; Williams 2002). Aquatic macrophytes have been shown to play
important roles in wetland biogeochemistry through their active and passive circu-
lation of elements including heavy metals (Weis and Weis 2004). Active uptake
into the wetland plant tissues may promote phytofiltration and immobilization of
heavy metals in plant tissues, as seen in constructed wetlands for wastewater
178 M.A. Rahman et al.

Table 8.1 Aquatic plants studied for the phytoremediation of toxic elements from wetlands
Common
name Scientific name Trace elements References
Duckweed Lemna gibba L. As, U, Zn Mkandawire and Dudel (2005),
Mkandawire et al. (2004a, b), and
Fritioff and Greger (2003)
Lesser Lemna minor L. As, Zn, Cu, Hg Alvarado et al. (2008), Fritioff and
duckweed Greger (2003), Kara (2004), Miretzky
et al. (2004), Mishra et al. (2008), and
Robinson et al. (2005)
Star Lemna trisulca Zn Huebert and Shay (1992)
duckweed L.
Water Eichhornia As, Fe, Cu, Zn, Alvarado et al. (2008), Vesk
hyacinth crassipes Pb, Cd, Cr, Ni, et al. (1999), Wolverton and McDonald
Hg (1978), Chandra and Kulshreshtha
(2004), Cordes et al. (2000), Delgado
et al. (1993), Dixit and Dhote (2010),
Espinoza-Qui~ nones et al. (2008), Junior
et al. (2008), Mishra et al. (2008),
Odjegba and Fasidi (2007), and
Muramoto and Oki (1983)
Water- Callitriche Cr(V) Augustynowicz et al. (2010)
starwort cophocarpa
Petries Callitriche As Robinson et al. (2005)
starwort petriei
Common reed Phragmites Cr, Cu, Ni, Baldantoni et al. (2009), Deng
australis Pb, S, V, Zn, Cd et al. (2004), and Ghassemzadeh
et al. (2008)
Butterfly fern Salvinia Pb(II) Banerjee and Sarker (1997) and Dhir
rotundifolia (2009)
Salvinia natans As, Ni, Cu, Rahman et al. (2008c), Sen and
Hg(II) Bhattacharyya (1993), and Sen and
Mondal (1987, 1990)
Salvinia minima As, Pb, Cd, Cr Sanchez-Galvan et al. (2008), Hoffmann
et al. (2004), and Olguin et al. (2003)
Salvinia Cd, Cr Maine et al. (2004) and Su~ ne
herzogii et al. (2007)
Eared Salvinia Zn, Hg, Cr Wolff et al. (2009), Molisani
watermoss auriculata et al. (2006), and Espinoza-Qui~ nones
et al. (2008)
Greater Spirodela Cu, Zn, Mn,Cr, Miretzky et al. (2004)
duckweed intermedia Pb
Spirodela As, Hg Rahman et al. (2007, 2008b), and Mishra
polyrhiza L. et al. (2008)
Indian/Sacred Nelymbium Cr, Cu, Ba, Ti, Vardanyan and Ingole (2006)
lotus speciosum Co, Pb
Ludwigia Vardanyan and Ingole (2006)
perennis L.
(continued)
8 Phytoremediation of Toxic Metals in Soils and Wetlands: Concepts and. . . 179

Table 8.1 (continued)


Common
name Scientific name Trace elements References
Arrowhead Sagittaria Vardanyan and Ingole (2006)
sagittiflia L.
Nymphoides Vardanyan and Ingole (2006)
ceristatum
Shoreline Sasuvium Vardanyan and Ingole (2006)
seapurslane portulacastrum
L.
- Nymphae Vardanyan and Ingole (2006)
stellata
Water spinach Ipomoea As, Cd, Pb, Hg, Wang et al. (2008), G€othberg
aquatica Cu, Zn et al. (2002, 2004), Hu et al. (2008), and
Lee et al. (1991)
Eelgrass/ Vallisneria Cu, Cd, Hg Wang et al. (2010) and Rai and Tripathi
Eelweed spiralis L. (2009)
Esthwaite Hydrilla As, Pb, Zn, Cr Dixit and Dhote (2010) and Lee
waterweed verticillata et al. (1991)
Mosquito fern Azolla As Zhang et al. (2008)
caroliniana
Water fern Azolla As, Hg, Cd Zhang et al. (2008), Rahman
filiculoides et al. (2008a), Rai and Tripathi (2009),
Azolla pinnata and Rai (2008b)
Elephant’s ear Colocasia Cd, Cu, Pb, Zn Cardwell et al. (2002)
esculenta
Umbrella Cyperus Cardwell et al. (2002)
sedge eragrostis
Spike rush Eleocharis Cardwell et al. (2002)
equisitina
Parrot’s Myriophyllum Cardwell et al. (2002)
feather aquaticum
Miriophyllum Myriophyllum As Robinson et al. (2005)
propinquum
Water lily Nymphaea Cd, Cu, Pb, Zn Cardwell et al. (2002)
violacea
Nymphaea Cd Schor-Fumbarov et al. (2003)
aurora
Marshwort Nymphoides Cd, Cu, Pb, Zn Cardwell et al. (2002)
germinata
Knotweeds Persicaria Cardwell et al. (2002)
attenuatum
- Persicaria Cardwell et al. (2002)
orientalis
- Persicaria Cardwell et al. (2002)
subsessilis
- Potamogeton As Robinson et al. (2005)
orchreatus
(continued)
180 M.A. Rahman et al.

Table 8.1 (continued)


Common
name Scientific name Trace elements References
Willow Persicaria Cd, Cu, Pb, Zn Cardwell et al. (2002)
smartweed lapathifolium
- Potamogeton Cardwell et al. (2002)
javanicus
Fennel Potamogeton Cd, Pb, Cr, Ni, Demirezen and Aksoy (2004)
pondweed pectinatus Zn, Cu
Curled dock Rumex crispus Cd, Cu, Pb, Zn Cardwell et al. (2002)
River Schoenoplectus Cardwell et al. (2002)
clubrush validus
Cumbungi Typha Cardwell et al. (2002)
domingensis
Cumbung Typha Cardwell et al. (2002)
orientalis
Lesser Typha Cd, Pb, Cr, Ni, Chandra and Kulshreshtha (2004) and
Bulrush angustifolia Zn, Cu Demirezen and Aksoy (2004)
Bulrush Typha latifolia Cr, As, Zn, Pb, Chandra and Kulshreshtha (2004), Ye
Cd, Cu. Ni et al. (1997, 1998), Blute et al. (2004),
Deng et al. (2004), Hozhina et al. (2001),
Pratas et al. (2007), and Sasmaz
et al. (2008)
Waterweed/ Elodea As, Pb, Cr, Zn, Chandra and Kulshreshtha (2004),
Pondweed canadensis Cu, Cd Dogan et al. (2009), Fritioff and Greger
(2003), Mal et al. (2002), Mayes
et al. (1977), and Robinson et al. (2005)
Brazilian Veronica As Robinson et al. (2005)
Waterweed aquatica
Water-milfoil Myriophyllum Co, Cr, Cu, Pb, Chandra and Kulshreshtha (2004),
spicatum Zn, Ni Keskinkan et al. (2003), and Lesage
et al. (2007)
Fragrant Nymphaea Cr Chandra and Kulshreshtha (2004)
water lily odorata
Pickerelweed Pontederia Chandra and Kulshreshtha (2004)
cordata
Tape grass/ Vallisneria Hg Gupta and Chandra (1998)
Eel grass spiralis
Wild celery Vallisneria Cr Chandra and Kulshreshtha (2004)
americana
- Nymphaea Cr(VI) Choo et al. (2006)
spontanea
Shichito Cyperus Pb, Zn, Cu, Cd Deng et al. (2004)
matgrass malaccensis
Lam.
Swamp rice Leersia Deng et al. (2004)
grass hexandra
Swartz.
Burma reed Neyraudia Deng et al. (2004)
reynaudiana
(continued)
8 Phytoremediation of Toxic Metals in Soils and Wetlands: Concepts and. . . 181

Table 8.1 (continued)


Common
name Scientific name Trace elements References
Flagroot Acorus calamus Deng et al. (2004)
L.
- Eleocharis Deng et al. (2004)
valleculosa
Water pepper Polygonum As Robinson et al. (2005)
hydropiper
Reed canary Phalaris Pb, Zn, Cu, Cd Deng et al. (2004)
grass arundinacea L.
- Equisetum Deng et al. (2004)
ramosisti Desf.
Soft rush Juncus effusus Deng et al. (2004)
L.
- Polypogon Deng et al. (2004)
fugax Steud.
- Egeria densa As Robinson et al. (2005)
Alligatorweed Althernanthera As, Pb Elayan (1999)
philoxeroides
Water lettuce Pistia stratiotes As, Cr, Pb, Ag, Espinoza-Qui~ nones et al. (2008, 2009),
Cd, Cu, Hg, Ni, Lee et al. (1991), Maine et al. (2004),
Zn and Miretzky et al. (2004)
Floating Potamogeton Zn, Cu, Cd, Pb Fritioff and Greger (2003, 2006)
pondweed natans
Willow moss Fontinalis Cu, Zn Goncalves and Boaventura (1998) and
antipyretica Martins and Boaventura (2002)
Needle Eleocharis As, In, Ag, Pb, Ha et al. (2009a, b, 2011)
spikerush acicularis Cu, Cd, Zn, Sb,
Ni, Mg
Rigid Ceratophyllum As, Pb, Zn, Cu Keskinkan et al. (2004) and Robinson
hornwort demersum et al. (2005)
New Zealand Lepidium As Robinson et al. (2003)
watercress sativum L.
- Najas indica Pb Singh et al. (2010)
Watercresses Nasturtium Cu, Zn, Ni Kara (2005)
officinale
Curly Lagarosiphon As Robinson et al. (2005)
waterweed major
This table was previously published in Rahman and Hasegawa (2011), and reused here with the
permission of the publisher

treatment and in the use of wetland plants in phytoremediation. Aquatic macro-


phytes are more suitable for restoration of water quality of wetlands due to their
faster growth rate and relatively higher ability of pollutant uptake than terrestrial
plants (Ali et al. 2013; Sood et al. 2012).
182 M.A. Rahman et al.

Water hyacinth (Eichhornia crassipes) has been one of the widely studied
wetland plants for the phytoremediation of heavy metals in constructed wetlands
(Jayaweera et al. 2007, 2008; Zhu et al. 1999; Liao and Chang 2004). It is a fast
growing and easily adaptable to various aquatic conditions floating plant with a
well-developed fibrous root system and large biomass that can accumulate signifi-
cant amount of heavy metals from water (Liao and Chang 2004).
Cheng et al. (2002) investigated a twin-shaped constructed wetland comprising a
vertical flow (inflow) chamber with Cyperus alternifolius followed by a reverse-
vertical flow (outflow) chamber with Villarsia exaltata for phytoremediation of
artificial wastewater polluted by heavy metals. Results showed that the system was
very effective in removing toxic heavy metals from wastewater. From a field study
with 12 emergent-rooted wetland plant species including different populations of
Leersia hexandra, Juncus effusus and Equisetum ramosisti, Deng et al. (2004)
proposed that these plants can be used in constructed wetlands for effective removal
of toxic metals like Pb, Zn, Cu, and Cd. Removal of Cu, Ni, and Zn by Phragmites
australis using a horizontal subsurface flow constructed wetland model for domes-
tic wastewater treatment was studied by Galletti et al. (2010). Several other studies
showed that engineered/constructed wetlands can be an effective model for
phytoremediation of toxic metals (Liu et al. 2007, 2010; Rai 2008a; Sobolewski
1999; Yang and Ye 2009; Zhang et al. 2010).

8.7 Conclusion

Over the past two decades, phytoremediation technology has become increasingly
popular and has been employed to restore sites including soils and wetlands
contaminated with toxic metals. While this technology has the advantages that
environmental concerns may be treated without harming the ecosystems; one major
disadvantage of phytoremediation is that it requires relatively longer time com-
pared to traditional physical or chemicals methods as the process is dependent on a
plant’s ability to grow and thrive in an environment that is not ideal for normal plant
growth. There are other limitations (listed below) of phytoremediation approaches
for the restoration of contaminated soils and wetlands, which need to be considered
for commercial application of this technology:
• Long operational time required for clean-up.
• Phytoremediation efficiency of most metal hyperaccumulators is usually limited
by their slow growth rate and biomass production.
• Difficulty in mobilization (bioavailability) of tightly bound fraction of
metal ions from soil.
• Phytoremediation is limited to the surface area and depth occupied by the
roots of the hyperaccumulators.
8 Phytoremediation of Toxic Metals in Soils and Wetlands: Concepts and. . . 183

• With plant-based systems of remediation, especially in the case of chemically-


induced phytoremediation, it is not possible to completely prevent the leaching
of contaminants into the groundwater.
• It is ideal for sites with low to moderate levels of metal contamination. In heavily
contaminated sites, high concentrations of toxic metals can hamper the normal
growth of the hyperaccumulators.
• The survival of the hyperaccumulating plants is affected by the toxicity of the
contaminants and the general condition of the soil. Therefore, this approach may
not be applicable an environment where the conditions are completely unfavor-
able for plant growth.
• There is a risk of food chain contamination in case of mismanagement and lack
of proper care. Bioaccumulation of contaminants, especially the toxic metals,
into primary producers (e.g., phytoplankton) can be passed on to the higher
trophic levels of the food chain. Therefore, safe disposal of the used plants or
organisms is required.

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