Chapter 21

Nano-phytoremediation: The Successful

Combination of Nanotechnology
and Phytoremediation

Melina Borges Teixeira Zanatta, Maycon Lucas de Oliveira,

and Lilian Rodrigues Rosa Souza

Abstract Environmental pollution is a recurrent problem since anthropogenic

actions constantly expose the environment to toxic compounds. In view of this fact,
many decontamination methodologies have been developed such as thermal treat-
ment, oxidation, ion exchange, and others. Among these methods, phytoremedia-
tion has the advantage to be a green methodology (since it is employed plants for the
remediation) and can efficiently degrade, stabilizes, or accumulates both inorganic
and organic pollutants. Nowadays, nanomaterials and some microorganisms have
been used combined with phytoremediation in order to improve the remediation and
this new approach is called nano-phytoremediation. This chapter discusses the
nanomaterials and microorganisms combined with phytoremediation besides
explores the mechanisms of remediation of nano-phytoremediation for some nano-
materials combined with plants.

Keywords Nano-phytoremediation · Nanomaterials · Microorganisms ·

Phytoremediation · Environmental pollution · Remediation

Melina Borges Teixeira Zanatta and Maycon Lucas de Oliveira contributed equally with all other
contributors.

M. B. T. Zanatta
Environmental Studies Center (CEA), São Paulo State University, UNESP,
Rio Claro, SP, Brazil
M. L. de Oliveira · L. R. R. Souza (*)
Department of Chemistry, FFCLRP-USP, University of São Paulo - USP,
Ribeirão Preto, SP, Brazil
e-mail: [email protected]

© The Author(s), under exclusive license to Springer Nature Switzerland AG 2023 443
L. Newman et al. (eds.), Phytoremediation, https://doi.org/10.1007/978-3-031-17988-4_21
444 M. B. T. Zanatta et al.

21.1 Introduction

The environment is constantly being exposed to different chemical elements from

natural and anthropogenic sources. Industrialization and urbanization release a wide
range of toxic elements from anthropogenic sources and due to the continuous
release of toxic substances, environmental contamination remains a recurrent prob-
lem (Souza et al. 2020).
Toxic metals can cause harmful effects on the environment since they can persist
in the long term in soil and aquatic environment. Furthermore, they can be easily
transferred from one environment to another where direct or indirect exposure can
occur, and also be interconverted to different species and become more bioavailable
or toxic, adversely affecting the ecosystem and human health. Due to this, a wide
range of methods has been applied for the removal of toxic metals including precipi-
tation and cementation, liquid-liquid extraction, cloud-point extraction, immobili-
zation, adsorption methods, and phytoremediation (Souza et al. 2020; Khairy
et al. 2014).
Organic pollutants also can cause toxic effects not only for the environment but
also the human health. One of the most used methods for remediation of organic
pollutants is the oxidation and use of the photocatalytic process (Jiang 2007;
McCullagh et al. 2011).
In order to overcome this problem, which affects not only the soil, air, and aquatic
environment, different strategies have been developed for environmental remedia-
tion, according to the pollutant. The methods of remediation can be divided into
physical methods, chemical methods, and biological methods depending on the
environment (soil, water, air) (Fig. 21.1). Physical remediation employs physical
methods such as thermal treatment, and soil replacement (for soil remediation).
Chemical remediation employs chemical reactions to remove the contaminants and

Fig. 21.1 Methods for environmental remediation (Souza et al. 2020; Song et al. 2017)
21 Nano-phytoremediation: The Successful Combination of Nanotechnology… 445

includes ion exchange, oxidation, reduction, adsorption, and catalytical methods.

Biological remediation employs microorganisms and also plants (phytoremedia-
tion) in order to remove the contaminants (Song et al. 2017).
Phytoremediation is a remediation method mediated by plants that can accumu-
late, degrade, or stabilize pollutants such as toxic metals or organic compounds and
this methodology can be applied in water, air, and soil environment (Shah and
Daverey 2020).
Compared with physical and chemical remediation methods, phytoremediation
has the advantage to be less expensive, and environment friendly, and it is consid-
ered a sustainable way to restore the contaminated environment (Shah and Daverey
2020), besides to (i) working with organic and inorganic compounds, (ii) it gener-
ates recyclable metal-rich plant residue, (iii) planting vegetation on a site also
reduces erosion by wind and water, (iv) and practically possible and publicly
accepted. On the other hand, there are some limitations such as: (i) the need for a
spacious location and proper care, (ii) it can take many growing seasons to clean up
a site, (iii) because of the short roots, the plants can clean up the contaminants pres-
ent only in the soil or the groundwater near the surface, and (iv) plants that absorb
toxic materials may contaminate the food chain (Muthusaravanan et al. 2018).
However, the phytoremediation method can be improved by using nanotechnol-
ogy in order to overcome some of these disadvantages and becoming more effective
for environmental remediation.

21.2 Nanotechnology for Environmental Remediation

Nanoremediation is a technology that employs different materials with a diameter

of less than 100 nm for remediation of the polluted environment, such as soils,
water, sediments, and air. These materials have the benefits of higher surface area
and small size (Das 2018; El-Ramady et al. 2017). While several nanomaterials are
synthesized, others are naturally found in the environment, including clay mineral
nanoparticles (NPs) and bismuth oxide NPs. Several nanoscale materials can be
applied for environment nanoremediation such as nanotubes, NPs, nanocomposites,
and nanotechnology-based sensors (Borišev et al. 2020).
One of the most commonly used NPs in soil nanoremediation is nanoscale zero-­
valent iron (nZVI). The size range of most nZVI falls from 10 to 100 nm in diameter
and they are composed of Fe, with a noble metal (often palladium) commonly added
as a catalyst (bimetallic nanoparticle). When applied in soils, the second metal is
useful to aid NPs mobility and distribution (Karn et al. 2011). The action modes of
nanomaterials, such as nZVI, can be divided into three: (1) The physical mode—due
to the large surface area of the materials, the contaminants can be adsorbed and
immobilized. (2) The detoxification mode—occurs when chemical degradation of
toxic compounds is induced and/or catalyzed by nanomaterials, leading to their
transformation into less harmful products. (3) The bio-cooperative mode—here, the
446 M. B. T. Zanatta et al.

particles increase the bioavailability and degrading of pollutants into more bioreme-
diate species assisting the biotic degradation (Marcon et al. 2021).
For each category of contaminant, there will be some specific material for its
remediation. For example, remediation of heavy metals is basically done by adsorp-
tion on the surface of metal oxide NPs. On the other hand, redox-active inorganic
anions or chlorinated compounds require reducing conditions, so nZVI (or other
zero-valent metal NPs—Cu, Ni, and Co) should be applied. Polycyclic aromatic
hydrocarbons (PAHs) exhibit a higher redox potential and can be degraded follow-
ing oxidation reactions induced by metal oxide NPs such as CeO2 and MnO2. In this
case, nanoremediation can be integrated with others established PAHs remediation
approaches to enhance remedial efficiency (Marcon et al. 2021; Kuppusamy
et al. 2017).

21.2.1 Inorganic Materials

Recalcitrant or persistent organic pollutants are compounds that are difficult to

degrade and can be bioaccumulative. They have high chemical and photochemical
stability and a very slow biodegradation rate. Since conventional treatment tech-
nologies are ineffective to degrade this type of pollutant, efforts have been made to
reduce the level of environmental pollution (Ganie et al. 2021). Photocatalysis
emerges as an eco-friendly technique for the degradation of various pollutants and
is based on a photochemical process that employs a catalyst to speed up chemical
reactions that requires light. In this process, the photocatalyst is activated by light
(UV and/or visible light) and the electrons are promoted from the valence band to
the conduction band, forming an electron/hole pair (e−/h+). The pair induces the
formation of highly energetic and reactive species (.OH and O2− radicals). Both
radicals can react with organic pollutants, oxidizing them into products that are less
harmful to the environmental (Ganie et al. 2021; Khan et al. 2015).
The use of nanoscale materials for photocatalysis has gained great interest in the
last decade. Different nanomaterials have been developed and TiO2 nanoparticles
have great potential for environmental remediation. They are known for having high
thermal stability, low cost, and good resistance. To improve the photocatalytic activ-
ity of TiO2-based particles some modifications may be necessary, including doping
TiO2 with different metals or TiO2 surface modification with chelating ligands
(Tahir et al. 2020). The use of semiconductor nanomaterials has also been studied as
nanosensors. They are defined as miniature devices capable of converting chemical
interaction into an electrical signal. Ideally, it possesses high sensitivity and repro-
ducibility, fast response, low cost, and low detection limits. These types of devices
are able to quantify the composition and detect the presence or absence of a particu-
lar pollutant. To overcome some of the disadvantages of the technique, which
include high cost, insensitivity, and time-consuming nature, a different method for
environmental remediation is based on the fabrication of metal oxide (MO) nano-
sensors (Ganie et al. 2021; Shafi et al. 2019).
21 Nano-phytoremediation: The Successful Combination of Nanotechnology… 447

Another investigated material for environmental remediation is magnetic metal-

lic nano adsorbents. The iron and iron oxide NPs are particularly interesting because
they can be easily retained, separated, and removed from the remedied environment.
These types of nanomaterials can be used for the removal of metals and chlorinated
organic solvents (Guerra et al. 2018). Iron NPs usually have a core-shell structure,
where the core is composed of Fe0 (“zerovalent”) and the shell is formed by mixed
valent oxides (Fe(II) and Fe(III)) (Li and Zhang 2006). The reactivity of these mate-
rials can be significantly affected when aggregation occurs, reducing their efficiency
in the remediation of environmental contaminants. In addition, the toxicity of the
materials involved when using metal and metal oxide NPs is another important fac-
tor that must be considered. To overcome some of the limitations associated with
monometallic NPs, a second metal can be added to the formulation, increasing the
solution stability of the material preventing its aggregation (Guerra et al. 2018).
Mesoporous silica-based adsorbents are a class of materials commonly employed
in water remediation. Its beneficial features for remediation include high specific
surface area, large pore size, facile surface modification, and chemical inertness.
This type of highly porous adsorbent can have its surface functionalized with a wide
variety of chemical components. The presence of hydroxyl groups on the silica
surface is important for adsorption and surface phenomena and modification. A
variety of different materials were synthesized and proved to be efficient for the
adsorption of organic and inorganic pollutants, showing the versatility of mesopo-
rous silica-based adsorbents (Guerra et al. 2018; Diagboya and Dikio 2018).

21.2.2 Carbon-Based Nanomaterials

Carbon-based nanomaterials have unique properties such as small size, high poros-
ity, high reactivity, high thermal and chemical stability, and an active surface. They
are receiving much attention in the field of environmental remediation because their
large surface area creates more active sites for effective interaction of the material
with different chemical species from water or wastewater (Madima et al. 2020;
Madhura et al. 2019). Carbon-based nanomaterials have a structural composition of
elemental carbon with mutable hybridization states, which gives them different
structural configurations such as graphite, diamond, fullerenes, carbon nanotubes,
graphene, etc. (Guerra et al. 2018).
Carbon nanotubes (CNTs) are an allotropic form of carbon composed of cylin-
drical shapes rolled up in a tube-like structure. They are divided into two types:
multi-walled (MWCNTs) and single-walled carbon nanotubes (SWCNTs), depend-
ing on the number of carbon layers (Guerra et al. 2018; Madima et al. 2020). The
presence of impurities that occurs during CNTs preparation as well as the oxygen
content are factors that can affect the adsorption capacity of these materials. Changes
in the surface properties of these nanomaterials can be prevented by functionalizing
carbon nanotubes in the presence of acid and alkali solutions. The new functional
group added to the material surface in this process can be very interesting in
448 M. B. T. Zanatta et al.

environmental remediation, enabling the use of CNTs in the removal of toxic metals
and organic pollutants (Madima et al. 2020).
An allotrope of carbon that has gained significant attention as nanomaterials for
environmental application is graphene. They have unique properties such as high
specific surface area and high thermal conductivity and can be classified into gra-
phene (G), graphene oxide (GO), and reduced graphene oxide (RGO) (Madima
et al. 2020). Compared to carbon nanotubes, graphene-based materials may also
need surface modification, however, they act as a promising adsorbent for environ-
mental application in terms of production costs (Madhura et al. 2019).
Graphitic carbon nitrate (g-C3N4) is the most stable allotrope of carbon nitrides
at ambient conditions and had been reported as a new sorbent for the removal of
metals and organic compounds due to their attractive properties, including high
photocatalytic activity, high thermal and chemical stability, good biocompatibility,
and various available methods for surface modification (Sun et al. 2016).

21.2.3 Polymer-Based Nanomaterials

Polymers are commonly used as a host material to enhance the stability of nanoscale
materials serving as a matrix or support to other types of materials. Despite having
poor mechanical and thermal stability, numerous synthetic and natural polymers are
used due to characteristics such as low weight, the incredible variety of chemical
structures, and the possibility of their recyclability (Bushra 2018). They are used for
the detection and removal of chemical compounds, organic pollutants, gases, and a
wide array of biologics (Guerra et al. 2018).
Polymeric-nanocomposites (PNCs) are another class of adsorbent in environ-
mental remediation and consist of a polymer or copolymer filled with inorganic
compounds. The polymer is called matrix and the filler, when in the nanometer
range, including CNTs, NPs, nanofiber, inorganic filler, and clay (Singh 2018). In
this case, the nanocomposites have their properties improved to the high surface
area and unique microstructures characteristics of nanofillers (Bushra 2018). In
remediation, the polymer is used as a host material and the other constituents of the
composite are responsible for the pollutant removal (Guerra et al. 2018).
Graphene oxides are highly compatible with polymers in the formation of PNC
due to their unique properties. Because they have amphiphilic nature, they can bond
with polar and nonpolar polymers to improve the mechanical properties of the com-
posite. With respect to CNTs, their surface can be modified depending on the desired
application, and it is already recognized that the structural features of MWCNTs
can be improved when used as polymer composite (Bushra 2018).
21 Nano-phytoremediation: The Successful Combination of Nanotechnology… 449

21.2.4 Risks Associated with the Use of Nanoparticles

and Solutions Toward Effective Management

The use of nanoparticles for environmental remediation is a technique that has been
increasingly efficient with a large number of benefits. Although NPs can degrade
pollutants, the same mechanisms can be toxic to biota, so their use in the environ-
ment is not free from risks. Once inside a matrix, nanomaterials can undergo differ-
ent transformations, which are divided into chemical (reduction/oxidation,
dissolution), physical (aggregation), and biotic (redox reactions in bacteria) (Marcon
et al. 2021). Aggregation is one of the most prominent modifications and when NPs
agglomerate, they form clusters losing their effectiveness as a nanoparticle. Because
of their small size and higher mobility, NPs can easily disperse in the environment
and cause ecotoxicity when spread over larger distances (Das 2018).
Since nanoparticles are highly persistent in the environment, potential human
and ecotoxicological risks are associated with the dispersal, ecotoxicity, bioaccu-
mulation, and reversibility of NPs (Ganie et al. 2021). In the case of nZVI nanopar-
ticles, some sulphate-reducing bacteria are able to oxide them. When at a high
concentration of nZVI, this oxidation leads to the formation of reactive oxygen
species (ROS), which can cause oxidative stress, damaging the cell membrane and
possibly leading to death (Diao and Yao 2009). Another report suggests that nZVI
nanoparticles are toxic to plants when present in high concentrations because they
reduce the transpiration rate and translocation to the shoots, which may result in
stunted growth of some plants and depending on the exposure time, can also lead to
death (Das 2018; Ma et al. 2013). In humans, a study showed the toxicity of
SWCNTs assessed in keratinocytes cells. When keratinocytes were treated with
SWCNP particles, the oxidative stress and inhibition of cell proliferation increased
(Manna et al. 2005).
Due to the problems reported above, the disadvantages of employing nZVI
nanoparticles can be overcome by using emulsified zero-valent iron. In this case, the
material is prepared by encapsulating iron nanoparticles in a biodegradable oil
membrane. This surface coating protects the zero-valent iron from other inorganic
compounds or pollutants, preventing the reduction of iron capacity (Hara et al.
2006). The use of greener and more sustainable approaches for the synthesis of
nanomaterials, such as the use of nanoparticles synthesized from plants or plants’
part, reduces ecological toxicity by reducing the release of toxic by-products into
the environment (Machado et al. 2013; Hoag et al. 2009). These approaches are
alternatives that can be used effectively against the disadvantages and risks arising
from the use of nanoparticles in environmental remediation.

21.3 Nano-phytoremediation

Nano-phytoremediation is a process that involves nanotechnology and phytoreme-

diation for the degradation of pollutants in the environment (Verma et al. 2021).
This technique uses plant species and nanoparticles for environmental remediation
450 M. B. T. Zanatta et al.

and has excellent potential. As mentioned before, nanomaterials are widely used in
the remediation field and when combined with the phytoremediation technique,
increases their efficiency (Srivastav et al. 2018).
The advantages of using plants to remove contaminants from the environment
include cost-effectiveness, ecologically sound, long-term applicability, and the pos-
sibility of being directly applied at polluted sites, replacing other expensive treat-
ment methods (Romeh and Ibrahim Saber 2020). Some factors can affect chemical
uptake and distribution in living plants: (i) physical and chemical properties of the
compounds; (ii) environmental characteristics such as pH, temperature, and organic
matter; (iii) plant characteristics (Srivastav et al. 2018).
For effective nano-phytoremediation, plants and nanoparticles should possess
some specific characteristics. The plants must have fast growth and well-developed
root systems for greater remediation efficiency. In addition, they should be able to
tolerate or accumulate contaminants. The technique is facilitated when the plants
are easy to harvest, in addition to the need to be nonconsumable for humans and
animals since they can be fatal. Finally, plants susceptible to genetic modification
are generally preferred in this technique. Regarding the selection of nanoparticles,
they should be nontoxic for plants and increase germination, seedling growth, plant
height, and biomass. They must increase significantly phytoenzymes production in
plants and enhance plant growth hormones. These nanoparticles should be capable
to bind contaminants and increase bioavailability for plants. Remediation efficiency
can be dramatically improved when all these factors are considered (Verma et al.
2021; Srivastav et al. 2018).

21.3.1 Nanoparticles and Microorganisms

for Phytoremediation

As discussed in topic 3, the combination of plants (phytoremediation) and nanoma-

terials has attracted attention since some nanomaterials can improve the uptake of
pollutants by plants and, consequently, increase the phytoremediation efficiency.
The nano-phytoremediation can employ inorganic nanoparticles (NPs) and also
microorganisms (Table 21.1).
Reactive NPs of zero-valent iron (nZVI) are one of the most NPs employed for
nano-phytoremediation with alfalfa (Medicago sativa). Recently, Wu et al. used
nZVI for remediation of persistent organic pollutants (POPs) in the soil such as
polychlorinated biphenyl (PCB). They reported that the phytoremediation from
alfalfa increased from 66.7 and 38.5% to 93.1 and 52.3% when is added a concen-
tration of nZVI of 1000 mg kg−1 for PCB28- and PCB180 respectively (Wu et al.
2021). It is also important to take into account that some syntheses of NPs employ
toxic reagents and/or generate toxic residues which can be an issue for the environ-
ment. In order to overcome this, a green methodology can be employed by using
plants to synthesize the NPs and also use these NPs to improve phytoremediation.
A study by Romeh and co-workers employed two different NPs (AgNPs and
21 Nano-phytoremediation: The Successful Combination of Nanotechnology… 451

Table 21.1 Some nanoparticles and microorganisms used for nano-phytoremediation

Nanoparticles/microorganisms employed for
nano-phytoremediation References
Iron nanoparticles (FeNPs) Romeh and Ibrahim Saber
(2020)
Silver nanoparticles (AgNPs) Romeh and Ibrahim Saber
(2020)
TiO2 nanoparticles Singh and Lee (2016)
Rhizophagus irregularis and Pseudomonas fluorescens Mokarram-Kashtiban et al.
(2019)
Acaulospora mellea ZZ Cheng et al. (2021)
Rhodococcus sp. Hou et al. (2019)

FeNPs), synthesized by a green methodology, to enhance the phytoremediation of

chlorfenapyr, an insecticide-miticide, in water and soil. They reported a reduction of
about 90% in chlorfenapyr concentration in water (Romeh and Ibrahim Saber 2020).
Zuo et al. also observed the improvement of phytoremediation of phenanthrene by
Erigeron annuus when it was added SiO2-NPs combined with the surfactant Triton
X-100 (Zuo et al. 2020).
In general, the microorganisms combined with the phytoremediation are organ-
isms found in the rhizosphere such as bacteria, fungi, oomycetes, nematodes, proto-
zoa, and algae. As reported by Hou et al., the bacteria Rhodococcus sp. significantly
increased Cd accumulation in S. plumbizincicola, and the phytoremediation effi-
ciency was strongly correlated with the reshaped bacterial network topology (Hou
et al. 2019).
In order to improve the phytoremediation process, it is also possible to combine
both methods: the use of microorganisms and nanoparticles. Kashtiban and co-­
workers reported that the combination of Rhizophagus irregularis and Pseudomonas
fluorescens, which are mycorrhizal fungus and rhizobacteria respectively, and nano-­
sized zero-valent iron (nZVI) were successfully employed to remediate soil with the
toxic metals Pb, Cu, and Cd by increasing the bioconcentration factor (BCF) of the
metals (Mokarram-Kashtiban et al. 2019). This same behavior was observed by
Cheng et al. who employed Acaulospora mellea ZZ, an arbuscular mycorrhizal, and
nZVI for phytoremediation of Cd, Pb, and Zn in soil by the plant sweet sorghum.
The synergic effect of NPs and mycorrhizal promoted the immobilization of metals,
especially Pb (Cheng et al. 2021).

21.4 Soil Nano-phytoremediation: Association

of Nanotechnology and Remediation

The maintenance of soil with appropriate physicochemical characteristics and prop-

erties is essential for the support and quality of life. It is through the soil that nutri-
ents necessary for autotrophic organisms that are essential to plant and animal
nutrition are obtained and biogeochemical cycles are regulated.
452 M. B. T. Zanatta et al.

However, land occupation and use have grown proportionally to technological

advances and human scientific development. Although this development has enabled
the growth of society, the exacerbated use of soil associated with inadequate dis-
posal of pollutants has attracted the attention of researchers due to the accumulation
of heavy metals and toxic compounds in the environment. These contaminants are
not biodegradable and pose a threat to public health due to the possibility of accu-
mulation in the human body by the biomagnification process (Yan et al. 2020). In
this sense, many technologies have been studied to prevent these contaminants from
being dissected by water, air, and land, and to remedy contaminated areas as a way
of mitigating the possible damage to the affected region (Gerhardt et al. 2009).
In this sense, phytoremediation, a process in which plants are used for the
removal of a wide range of contaminants, stands out as a low-cost strategy of opera-
tion, application, and adaptation to a multitude of elements (Gerhardt et al. 2009).
The processes associated with the mechanisms and strategies of plants to eliminate
soil pollution are well known and are based on phytovolatilization, phytoextraction,
phytodegradation, phytostabilization, and phytostimulation (Fig. 21.2).
Phytoextraction is the phytoremediation process that consists of the bioaccumu-
lation of a contaminant by a plant. Economically, this process has been reported by
researchers as the most economical method when compared to conventional tech-
niques since the phytoextraction plants have rapid growth, high performance,

Fig. 21.2 Strategies to phytoremediation of soils by plants

21 Nano-phytoremediation: The Successful Combination of Nanotechnology… 453

extended roots system, and high biomass production (Zand et al. 2020). However,
this application for the toxic elements’ neutralization can take years depending on
the climatic condition, physicochemical properties, and the phytotoxicity of the pol-
lutant. For this reason, many strategies are employed to improve the phyto and envi-
ronmental efficiency as agronomic management, chemical additives, and
nanomaterials application (Song et al. 2019). The association between nanoparticles
and environmental phytoremediation is identified as nano-phytoremediation. Nano-­
phytoremediation consists of a green and ecological technology that involves the
application of nanomaterials with chemical properties that stand out when associ-
ated with plant metabolism. Recent studies show these materials through adsorption
processes or redox reactions lead to the bioavailability of contaminants in plants
stimulating healthy growth and removal of heavy metals in soil and water (Alka
et al. 2021; Rai et al. 2020).

21.4.1 Nano-phytoremediation: Arsenic in the Soil and Water

Arsenic is a toxically metalloid that combines with other elements to form organic
and inorganic compounds. Inorganic arsenic is a worldwide problem as it is the
most prevalent form in soil and the most toxic when compared to organic forms
found in living organisms (Shrivastava et al. 2015) (Fig. 21.3).
The remediation of contaminated soils with arsenic has been studied for decades
and several technologies have developed (Alka et al. 2021). The phytoremediation
of arsenic inorganic consists of the hyperaccumulation of the metalloid in the plant
tissue (phytoextraction) or the phytostabilization through redox reactions in the
roots. The fern Pteris vittata (brake fern) is the most popular plant for removing As.

Fig. 21.3 Arsenic organic and inorganic compounds

454 M. B. T. Zanatta et al.

This plant is extremely efficient in converting As(V) to As (III) and translocating to

roots and fronds (Saffari et al. 2009; Ma et al. 2001). In the aquatic environment,
Pistia stratiotes, often named water lettuce, is an alternative plant to remediate in
the aquatics system. However, different from plants used in the soil, Pistia stratiotes
have the potential to remediate low concentrations of arsenic (Paul et al. 2019).
Although these phytoremediation processes are auxiliary in the treatment of con-
taminated areas, the necessity to understand mechanisms that accelerate this proce-
dure is fundamental to combat the increasing contamination of arsenic in
environmental matrices. The Isatis cappadocica Devis associated with salicylic acid
nanoparticles showed significant results in plant growth and a good response to stress
caused by As. Preliminary studies show that the metalloid aggregates to the root
surface and decreases the concentration of the element available for metabolization
and accumulation in the shoot (Souri et al. 2017). The use of extracts from leaves of
Quercus virginiana (Oaktree), Punica granatum (Pomegranate), and Eucalyptus
globulus (Eucalyptus) suggest that the presence of iron oxide nanoparticles can be
used as mechanisms for nano-phytoremediation of water due to the high affinity of
NPs for Arsenic (V). In addition, among these species, Eucalyptus leaves have a high
adsorption capacity of 40 mg of As/mg of leaves (Kamath et al. 2020).

21.4.2 Nano-phytoremediation of Organochlorine Compounds

Organochlorine compounds (OCCs) are organic molecules with high molecular

weight, low solubility in water, highly lipophilic, containing halogens or condensed
aromatic rings in its composition (Flores et al. 2004). These compounds attract the
attention of public agencies because they are involved with the progressive increase
of toxic elements and substances in the animal trophic status, a process known as
biomagnification. The remediation of contaminated areas with OCC occurred
simultaneously with the development of potential synthetic organic pesticides
(Romeh and Ibrahim Saber 2020). The DDT (dichlorodiphenyltrichloroethane) is
the precursor of the “Organochlorine Age”, the period where agricultural and chem-
ical development has yielded to the discovery and synthesis of chlorine-based com-
pounds for agricultural purposes.
The nano-phytoremediation of OCC is mainly based on the improvement of phy-
toextraction and phytodegradation processes. Pesticides such as Clorfenapir are
quickly and efficiently removed from water and soil by Plantago major L. in the
presence of iron (ZVIs) and silver nanoparticles adsorbed in activated charcoal by
mobilization of roots to leaves through metabolization and stabilization in leaves.
Moreover, it is observed that this process of nano-phytoremediation is associated
with agents that increase the solubility of OCC in the soil uptake the dispersion of
the compound in order to increase the capture process by the roots (Flores
et al. 2004).
Although for P. major L. the nZVIs act mainly as mediators of the adsorption/
absorption process, this nanoparticle can also act in a pre-interaction step with the
21 Nano-phytoremediation: The Successful Combination of Nanotechnology… 455

Fig. 21.4 A conceptual model for dehalogenation of Endosulfan by nZVIs with Mg0 (sub-­products
in green) and nZVIs in anoxic or aerobic conditions (the process in red). (Adapted from Abbas
et al. (2019), Schrick et al. (2002), Singh and Bose (2017))

plant. The high surface area of nZVIs and concentration of Fe2+ are the properties
responsible for the dichlorination of Endosulfan by Alpinia calcarata (the
Endosulfan hyperaccumulator) (Pillai and Kottekottil 2011). As shown in Fig. 21.4,
the degradation process of Endosulfan by reductive reaction with iron is well known
and described in the literature. However, Romeh and Ibrahim Saber (2020) observed
that the combination of nZVIs with compounds that allowed the pesticide to be solu-
bilized in the soil was essential for plants to absorb dehalogenation residues through
the incorporation of these substances into the biomass of the phytoremediator.

21.4.3 Potentially Toxic Metals

Potentially toxic metals (PTMs) are metals often found in rocks and potentially
toxic to the human body after mobilizing these elements to the biosphere through
anthropogenic activities (Chojnacka and Mikulewicz 2014). Due to the similarity of
the physical and chemical properties of these elements with the micronutrients
essential to human development, PTM can be related to several diseases and short-
and long-term problems in human health.
However, just as for humans the chemical similarity of these metals is a problem
for the organism’s absorption, a similar process is observed in plants. In this aspect,
the nano-phytoremediation processes stand out in terms of reducing the toxicity of
this contaminant to people as well as reducing the toxicity to the plant.
Chromium (Cr), for example, is a metal widely used in industry (mainly textile)
and is considered an essential trace element for humans due to its insulin
456 M. B. T. Zanatta et al.

potentiating activity. However, Cr is a metal that presents various oxidation states,

and Cr (VI) is extremely toxic and harmful to the human body. For plants, recent
research have shown that Cr(VI) is directly associated with changes in physiologi-
cal, biochemical, and molecular processes in order to alter growth procedures until
the generation of reactive oxygen species. Tripathi et al. (2015) observed that the
application of silicon nanoparticles (SiO2) to soil contaminated with chromium can
help combat the phytotoxicity of this metal (Tripathi et al. 2015). The authors con-
cluded that an application of SiNPs was essential to reduce metal phytostabilization
in the roots and to control oxidative stress since there was a decrease in the number
of reactive oxygen species (ROS). In contrast, Brasili and collaborators (2020)
observed that this metal can be removed from soil and water through a redox pro-
cess with nZVIs associated with the germination of Solanum lycopersicum (tomato)
(Brasili et al. 2020). They found that the seeds treated with the metal and the
nanoparticle had better results in terms of growth, germination, and color
development.
Cadmium (Cd) is considered to be the most toxic trace metal among PTMs.
Despite being mostly associated with zinc minerals, anthropogenic activity has
enabled its mobilization and migration to the surface and, consequently, its disposal
in aquatic environments. As a very water-soluble metal, Cd easily travels through
trophic levels and when absorbed by a plant promotes oxidative reactions that gen-
erate stress and cellular damage. However, Singh and Lee (2016) presented a mech-
anism for phytoextraction and bioaccumulation of this metal through the association
of TiO2 nanoparticles with Glycine max (Singh and Lee 2016). Gong et al. (2017)
also evaluated the Cadmium remediation process using as a premise the equilibrium
between the metal’s phytotoxicity and the observable adaptations for the mainte-
nance of the metabolic activities of Boehmeria nivea L. Gaudich. However, contrary
to the study by Singh and Lee (2016), the researchers observed that just as the con-
centration of the contaminant in the soil was a determining factor for the generation
of ROS, the nZVIs used aggravated the cellular damage to the phytoremediator
plant when in high concentrations. At low concentrations, the nano-phytoremedia-
tion process is a promising technique for environmental decontamination of
Cadmium (Gong et al. 2017) (Fig. 21.5).
Copper (Cu) is also characterized as an element that at the trace level has a bio-
logical function (in the electron transport chain) but which in excess has toxicity by
generating free radicals. The Copper surplus in the soil, however, needs to be con-
trolled before being taken up by the plants. Two main natural biological mecha-
nisms are observed in plants exposed to excess copper to control oxidative stress:
hyperaccumulation in shoots or metal stabilization in roots (Manceau et al. 2008).
Manceau et al. (2008) analyzed the response of Phragmites australis and Iris pseu-
doacorus located in an environment contaminated for 10 years with sewage resi-
dues with high levels of Zn, Cu, and Cd. The study revealed that the association of
the roots of these plants with endomycorrhizal fungi was able to synthesize ascorbic
acid and promote the conversion of Cu2+ ions into copper nanoparticles. This
biomining process of a contaminant corresponds to a nano-phytoremediation
method mediated by the phytostimulation of the roots. Plant response mechanisms
21 Nano-phytoremediation: The Successful Combination of Nanotechnology… 457

Fig. 21.5 Phytostabilization and phytoextraction of S-nZVIs adsorbed with Cd and oxidative
stress caused by iron ions. In this figure: SOD superoxide dismutase; POD guaiacol peroxidase;
CAT catalase; GSH reduced glutathione; GSSG oxidized glutathione. (Adapted from Gong
et al. (2017))

were already described in the literature since biomolecular reactions to oxidative

stress were already known for Oryza sativa (in the roots), Cannabis sativa (upper
leaves), and Allium sativum (in the root tip) (Manceau et al. 2008; Lidon and
Henriques 1994; Arru et al. 2004; Liu and Kottke 2004).

21.5 Challenges and Future Perspectives

of Nano-phytoremediation

Considering the advances in phyto and nano-phytoremediation it is clear the great

potential of remediation of this method. However, there are some challenges to face
in order to improve this method such as: (i) long-term experiments are required to
see the effects of the nanomaterials in soils and the phytoremediation process, (ii)
before the application of nanomaterials it is important to study their transformation
in the environment (aggregation, dissolution, complexation, and mobility), (iii) it is
necessary to evaluate the potentially toxic effects of nanomaterials employed for
458 M. B. T. Zanatta et al.

Fig. 21.6 Future challenges and perspectives in nano-phytoremediation method

nano-phytoremediation to the environment, and (iv) perform experiments in large

scale/in real environment in order to ensure the efficiency of the methodology
(Srivastav et al. 2018).
In face of these challenges to overcome, future studies about nano-­
phytoremediation are expected the use of green nanomaterials, the selection of suit-
able plant species with the best synergism for improve the remediation (preferably
using local species of plant), and also use the biotechnology to improve the phytore-
mediation by using transgenic plants (Fig. 21.6).

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