Nanotechnol Rev 2016; aop
Review
Allah Ditta* and Muhammad Arshad
Applications and perspectives of using
nanomaterials for sustainable plant nutrition
DOI 10.1515/ntrev-2015-0060
Received October 13, 2015; accepted November 5, 2015
Abstract: Nanotechnology opens a large scope of novel
applications in the fields of plant nutrition needed to meet
the future demands of the growing population because
nanoparticles (NPs) have unique physicochemical prop-
erties, i.e. high surface area, high reactivity, tunable pore
size, and particle morphology. Management of optimum
nutrients for sustainable crop production is a priority-
based area of research in agriculture. In this regard,
nanonutrition has proved to be the most interesting area
of research and concerns with the provision of nano-sized
nutrients for sustainable crop production. Using this tech-
nology, we can increase the efficiency of micro- as well as
macronutrients of plants. In the literature, various NPs
and nanomaterials (NMs) have been successfully used for
better nutrition of crop plants compared to the conven-
tional fertilizers. This review summarizes these NPs and
NMs into macro-, micro-, and nanocarrier-based fertiliz-
ers and plant-growth-enhancing NPs with unclear mecha-
nisms, describing their role in improving growth and yield
of crops, concentration/rate of application, particle size,
mechanism of action if known, toxic effects if any, and
research gaps in the present research. Moreover, future
research directions for achieving sustainable agriculture
are also discussed in the appropriate section and at the
end in the concluding remarks section.
Keywords: nanofertilizers; nanonutrition; nanotechnol-
ogy; plant nutrition; sustainable agriculture.
*Corresponding author: Allah Ditta, Department of Environmental
Sciences, PMAS, Arid Agriculture University Rawalpindi, Rawalpindi
46300, Pakistan, e-mail: ad_abs@yahoo.com
Muhammad Arshad: Institute of Soil and Environmental Sciences,
University of Agriculture Faisalabad, Faisalabad 38040, Pakistan
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1 Introduction
The world of agriculture is facing many challenges,
such as changing climate due to the greenhouse effect
and global warming; urbanization due to life pattern
changes; non-judicious use of resources like petro-
leum, natural gas, high-quality rock phosphate, etc.,
that are non-­renewable; and environmental issues like
run off, eutrophication related with the application of
more chemical fertilizers than required. These problems
get more intensified by the world population, which is
increasing at an alarming rate and is expected to reach
9.6 billion by the year 2050 [1]. An increasing demand
for global food production has been observed during the
last two decades due to a change in diet pattern and an
increasing demand for bioenergy crops. An increase by
70% in global grain production is required to feed this
increasing world population [2]. Moreover, to fulfill
the increasing demand for bioenergy, there will be an
additional demand for agricultural production from the
already limited arable land of the world. Of course, it will
create new opportunities for the generation of energy
and electricity from the ­biofuels and agricultural waste
products; however, workable economics and encourag-
ing policy is still pending. The above-mentioned sce-
nario will be critical for the countries, especially the
developing ones where agriculture is the backbone of
their national economy and faces many challenges like
the lack of new arable land and reduction of cultivable
land due to competing demands for economic develop-
ment activities, commodity dependence, poverty, and
malnutrition.
Advancement in the field of science and technology
could be a potential solution for value addition in their
current production systems [3]. A significant increase in
agricultural production could be possible through utili-
zation of current knowledge in the field of nanotechnol-
ogy for efficient nutrient system, good plant protection
practices, efficient photocapturing system in plants,
precision agriculture, and many others [4].
2      A. Ditta and M. Arshad: Nanonutrition for sustainable crop production
In case of plant nutrition, high application rate of fer-
tilizers can boost up the production of agricultural crops
around the world, but it may cause serious threats to the
environment in the form of eutrophication and contami-
nating freshwater sources, thus severely affecting people
using that freshwater sources for drinking and also the
aquatic life due to algal growth [5]. Moreover, the concen-
tration of nitrates in groundwater has increased to a toxic
level due to the intensive use of fertilizers [6]. So, the need
of the hour is to develop an efficient plant nutrient system
with minimum damage to the environment and for global
sustainable development.
For sustainable agriculture, application of nanotech-
nology has been regarded as an innovative and promis-
ing technology to feed the ever-increasing population
of the world. It has not only revolutionized agriculture
with innovative nutrients in the form of nanofertilizers
(NFs) but has also helped in the plant protection field
through the development of nanopesticides, efficient
water management system, and also increasing the effi-
ciency of plant in utilizing the sun’s energy [7]. In case of
conventional fertilizers, low use efficiency (20–50%) and
cost-intensive increase in application rates have urged
scientists around the world to develop and promote the
use of NFs [8]. Many scientists worldwide have focused
on this innovative field and have developed such NPs
and NMs that could serve as nutrients for the plants to
enhance germination rates, growth, yield, and many
physiological parameters [9].
Recently, scientists around the world are focusing on
the potential role of NPs in biotechnology, as these have
the ability to transport DNA and other chemicals into the
plant cells. This breakthrough has opened a new window
for gene manipulation and their expression in the specific
cells of the plants [10]. In this context, a success has been
achieved for plants’ augmented ability to harvest more
light energy by delivering carbon nanotubes (CNTs) into
the chloroplasts. Moreover, these tubes could also serve
as an artificial antenna for capturing wavelengths of light
such as ultraviolet, green, and near infrared, which are
% Increase in surface area
not in their normal range [11].
In this regard, the major objective of this review is to
collate and analyze the most recent nanotechnological
developments/breakthrough in the field of plant nutri-
tion to increase growth and yield of crop plants with
minimum destruction to the environment, mechanisms of
action, factors affecting their efficacy, and future research
gaps, which need to be elucidated for their successful
implementation in sustainable agriculture. The following
sections clearly explain the role of nanotechnology in dif-
ferent aspects of agriculture.
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2 Nanofertilizers
NMs are defined as an ingredient containing particles
with at least one dimension that approximately meas-
ures 1–100  nm (United States Environmental Protection
Agency). Accordingly, the NFs are the NMs that could
serve as macro- or micronutrient(s) for the crop plants
(macro- or micronutrient fertilizers) or help as carriers of
the conventional chemical fertilizers – nanocarriers for
efficient utilization of the nutrient. There are some NMs
that are not included in the list of macro- or micronutri-
ents for plants; however, these have shown an improve-
ment in various growth processes of plants, so these
have been discussed in the later sections of the review as
“others.” NFs have been proved to be comparatively effec-
tive over the conventional chemical fertilizers due to their
novel mechanisms of actions, increased use efficiency,
reduced nutrient loss, and minimum deterioration of the
environment.
Regarding mechanisms, the small size of the NFs
make them possible to be efficiently absorbed by the
plants due to the tremendous increase in the surface area
(Figures 1–3).
Moreover, these have the ability to enter into the
cells directly as these materials are small sized, which
reduces/bypasses the energy-intensive mechanisms of
their uptake/delivery into the cell, as clear from Figure 4
[13, 14]. Similar to the conventional fertilizers, NFs are
dissolved in the soil solution and the plants can directly
take them up. However, their solubility might be more
than that of related bulk solids found in the rhizosphere
due to their small size. These are more efficient compared
to the ordinary fertilizers, as these reduce N loss due to
leaching, emissions, and long-term incorporation by
soil microorganisms. Moreover, controlled-release NFs
120 R2=0.979
100
80
60
40
20
0
20 10 5 2 1
Cluster size (nM)
Figure 1: Relationship between cluster size (nm) and surface area
(%) (modified from Ditta [12]).
 A. Ditta and M. Arshad: Nanonutrition for sustainable crop production      3

in large quantities. These include N, P, K, Ca, Mg, and S.

Nano-size The requirement of macronutrients by the crop plants
with large is increasing with the increase in the demand for more
surface area
food for the ever-increasing population of the world. The
macronutrient demand is expected to increase to 263 Mt
by 2050 [17]. In order to reduce this, macronutrient NFs
Mechanisms of
Enterance have provided the solution in the form of their increased
Nanoscale into the cells
carriers
nano-fertilizer
due to small use efficiency compared to conventional chemical fertiliz-
uptake in plants
size ers with a use efficiency of not more than 20%. NFs com-
prising macronutrients have been developed by scientists
and technicians around the world, and these have shown
Dissolution in a tremendously increased efficiency in increasing the
the soil growth and productivity of crops. So, these have not only
solution
increased the efficiency but also reduced the cost, and
hence were found to be an economical alternative to the
Figure 2: General mechanisms employed by NFs for better uptake existing conventional chemical fertilizers. Their detailed
in plants. description is given in the following sections.

may also improve fertilizer use efficiency (FUE) and soil

deterioration by decreasing the toxic effects associated
with overapplication of traditional chemical fertilizers
[15]. There are also reports about the use of nanoencap-
sulated slow-release fertilizers. Recently, biodegradable,
polymeric ­ chitosan NPs (~78 nm) have been used for
controlled release of NPK fertilizer sources such as urea,
calcium phosphate, and potassium chloride [16]. Other
NMs like kaolin and polymeric biocompatible NPs could
also be utilized for this purpose [14]. The details about NFs
are given in the following sections.
2.1 Macronutrient NFs
These are chemically composed of one or more nano-
sized macronutrients that are required by crop plants
2.1.1 Nitrogen (N)-NPs
N is the most important nutrient involved in many pro-
cesses of crop plants. Various strategies have been
employed to improve its use efficiency. Nitrogenous NFs
have been reported by various scientists around the world
[18–21]. For example, slow release of N was observed
when urea (ammonium) was coated on zeolite chips [18].
Similarly, urea-modified hydroxyapatite NPs were encap-
sulated under pressure into the cavities of soft wood of
­Gliricidia sepium, and were tested for slow and sustainable
release of N into the soil. Interestingly, N supply through
this strategy was found optimum up to 60 days compared
to conventional nitrogenous fertilizers, which gave more
N supply to the plants in the beginning and very low at the
later stage up to 30 days [19].

Surface ionic and

week
bond attachments

Encapsulation and Nanoscale Polymers and

entrapment carriers dendrimers

Reduced
avavialabulity to
microbes

Figure 3: Mechanisms of nanocarriers for efficient delivery of nutrients contained in conventional fertilizers.

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4      A. Ditta and M. Arshad: Nanonutrition for sustainable crop production

No silica added (Si-C) 10 g silica added (Si-10) 100 g silica added (Si-100)

Figure 4: Distribution of Si, Ca, and Mn in and on the leaf blades of Phragmites australis subjected to three levels of silicon supply during
growth. Si appears in yellow (top row), Ca appears in red (mid row), and Mn appears in brown (bottom row). Magnification, 350 × . Used with
permission from Brackhage et al. [13].

2.1.2 Phosphorus (P)-NPs 2.1.3 Potassium (K)-NPs

Being an essential component of many metabolites and
having a key role in many metabolic processes of plants,
P is supplied to the crop plants through so-called chemi-
cal fertilizers, of which only up to 20% is taken up by crop
plants and the rest is fixed in the soil and/or accumulates
in water bodies through run off, causing eutrophica-
tion. Nanotechnology has played a key role in increasing
the phosphorus use efficiency (PUE) of crop plants and
decreasing environmental threats through eutrophication.
In this regard, hydroxyl apatite (Ca5(PO4)3OH) NPs were
synthesized using a one-step wet chemical method and
compared with conventional chemical phosphatic fertiliz-
ers for their role in increasing PUE, and ultimately plant
growth and yield [22]. Soybean (Glycine max) was used
as test crop under greenhouse conditions. A significant
increase in growth rate (33%) and seed yield (20%) com-
pared to the conventional chemical phosphatic fertilizers
was observed due to the supply of Ca and P simultane-
ously. Moreover, the product had weaker interaction with
the soil components compared to conventional chemical
phosphatic fertilizers. The product showed no phytotox-
icity effect on the germination rate of lettuce (Lactuca
sativa). Similarly, in another approach, P-NPs were bio-
synthesized using Aspergillus tubingensis TFR-5 from
tri-calcium phosphate (Ca3P2O8) [23]. However, the biosyn-
thesized P-NPs were not tested/reported to have efficacy
in improving growth and yield parameters of crops, and
need to be elucidated in future studies.
Still, there are no reports available in the literature about
the use of K-NPs. However, carrier-based K-NPs have
been developed and tested under controlled conditions
(Table 1).
2.1.4 Calcium (Ca)-NPs
Ca participates in many metabolic processes of plants like
cell elongation, strengthens cell wall structure via the for-
mation of calcium pectate, improves stomatal functions,
induces heat shock proteins, and protects against various
fungal and bacterial diseases. Ca-NPs have also been
­formulated and tested for their role in increasing the crop
growth and productivity. CaCO3 NPs (20–80 nm, 160 mg l-1
as Ca) in Hoagland solution were tested as a source of Ca
for peanut, grown in sand for 80 days [26], and were com-
pared with control (without Ca) and with soluble source
of Ca as Ca(NO3)2 (200 mg l-1). A significant improvement
in fresh biomass compared to the control was observed;
however, this enhancement was similar on a dry weight
basis in comparison to the soluble source of Ca [Ca(NO3)2].
The results were not able to justify why Ca(NO3)2 was com-
pared as a Ca control, as it provides N besides Ca. Ca uptake
by seedling stem and roots was enhanced compared to the
control, which makes it justifiable that Ca-NPs enhanced
Ca uptake and its transport from root to shoot due to their
high surface area for being scavenged by the root surface

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 A. Ditta and M. Arshad: Nanonutrition for sustainable crop production      5

Table 1: Nanoparticles that served as macronutrients and their source to enhance plant growth parameters.

Nutrient   Crop and experimental   Size and rate of application   Growth enhancement   References
provided conditions

N   Lolium multiflorum,   Clinoptilolite NH4, fertilized with   Enhanced yield and NUE possibly due to   [18]
controlled conditions, 0, 60, 120, and 180 kg N ha-1 salt to ion ability to retain and slowly break
sandy loam soil free NH4+ ions
  No crop involved; N release from urea-modified hydroxyapatite   Showed subsequent slow release even on   [19]
NPs day 60 compared to commercial fertilizer,
which released heavily early followed by
release of low and non-uniform quantities
until around day 30
  Zea mays, soil, 120 days,   20 and 60 g NH4-N zeolite kg-1,   N uptake rate (1–1.1), Zea mays yield   [20]
water irrigation, lysimeteric 150 kg N ha-1 commercial fertilizer (1–1.04), N leaching (0.78–0.94)
study
  Zea mays, loamy sand,   23 g N kg-1 zeolite; 112, 224,   N leaching reduced and N-use efficiency   [21]
water irrigation, 45 days, or 336 kg N ha-1; NH4-N soaking improved
greenhouse test in 1 m (NH4)2SO4 for 10 days,
changing solution every 2–3 days

P   Glycine max, 5 months   Apatite, Ca5(PO4)3OH, 16 nm,   Growth and yield was more in case of   [22]
greenhouse test, nutrient 21.8 mg l-1 as P, soluble apatite, Ca5(PO4)3OH compared to soluble
solution Ca(H2PO4)2, 21.8 mg l-1 as P Ca(H2PO4)2

K   Chrysanthemums, potting   K zeolite, 3 g l-1 as K, nutrient   Yield was increased and K leaching was   [24]
medium, 100-days solution reduced
greenhouse test
  Triticum aestivum, soil,   K synthesized by kaolinite,   Aboveground biomass and leaf K content   [25]
25 days greenhouse test KOH, and KCl at 100°C for 6 h, improved significantly
2.8–89 mg kg-1 as K, nutrient
solution

Ca   Arachis hypogaea, 80 days   CaCO3, 20–80 nm, 160 mg l-1 as   Growth, yield, and quality parameters   [23]
greenhouse, sand medium Ca, Ca(NO3)2, 200 mg l-1 as Ca, significantly improved; however,
nutrient solution the highest yield was achieved at a
combination of 1 g l-1 humic acid and Ca NPs

Mg   Vigna unguiculata   Mg-NPs, 500 mg l-1 as Mg   1000-Seed weight and leaf and stem   [26]
subsp. unguiculata, Mg improved compared to regular Mg
foliar application, field salts; the highest yield was achieved at a
experiment combination of 500 mg l-1 Fe and Mg-NPs

of plant in the rhizosphere. Moreover, when there was
combined application of Ca-NPs and humic acid (1 g l-1),
maximum increase in seedling dry weight, i.e. 30% and
14% compared to the control and treated with Ca(NO3)2,
respectively, was observed.
2.1.5 Magnesium (Mg)-NPs
Mg has a key role in photosynthesis as it is an essential
component of chlorophyll, the light-absorbing green
pigment found in plants. It also helps in the synthesis of
amino acids and cell proteins, uptake and migration of P,
and causes resistance against biotic and abiotic stress in
plants. The effect of combined foliar application of Mg-NPs
and Fe-NPs (0.5 g l-1) on the photosynthetic efficiency of
black-eyed pea (Vigna unguiculata) was investigated in
a field experiment [27]. The results clearly showed that
combined application of Fe- and Mg-NPs significantly
improved photosynthetic efficiency, which ultimately
improved growth and yield parameters. Interestingly,
their alone application caused a decrease in grain yield
(8%). However, the authors observed an increase in the
uptake of Mg in different plant tissues compared to the
control and regular application of Mg, which suggests that
Mg uptake increases with the application of Mg-NPs.
2.2 Micronutrient NFs
Micronutrients play an important role in many physi-
ological functions of plants. These are required in a very

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6      A. Ditta and M. Arshad: Nanonutrition for sustainable crop production
small amount (  ≤100 ppm) but have a very critical role in
various plant metabolic processes. These include chlo-
ride (Cl), iron (Fe), boron (B), manganese (Mn), zinc (Zn),
copper (Cu), molybdenum (Mo), and nickel (Ni). These
are applied to the plants either as Hoagland solution
[28] or as foliar depending on crop species, and also on
the nutrient to be applied. These are also applied to the
crop plants with composite fertilizers containing multiple
macronutrients like NPK. Micronutrients present in these
composites usually provide enough nutrients and cause
little environmental risks. However, their availability is
severely affected by small changes in pH, soil texture, and
organic matter [29]. So, it is most likely that under such cir-
cumstances, their optimum availability could be achieved
through the application of NFs containing these micro-
nutrients. A summary of the studies conducted regarding
the investigation of the efficacy of each micronutrient-­
containing NPs is given below Table 2.
2.2.1 Iron (Fe)-NPs
In a greenhouse study under a hydroponic system, appli-
cation of lower concentrations of Fe-NPs (30, 45, and
60  mg l-1) significantly improved the chlorophyll con-
tents of the subapical leaves of soybean compared to the
regular application of Fe-EDTA [30]. The results suggested
that Fe-NPs could serve as an efficient source of Fe com-
pared to the regular Fe-EDTA applied at  < 45 mg l-1 as Fe,
thereby reducing the chloratic symptoms caused by its
deficiency in soybean. Moreover, the uptake efficiency of
Fe-NPs in the plant body was enhanced, which ultimately
increased the chlorophyll contents of soybean plants.
In another experiment, growth and yield parameters of
black-eyed peas were significantly improved when Fe-NPs
were applied as foliar at 500  mg l-1 [27]. Moreover, the
application of Fe-NPs improved the effect of another fer-
tilizer nutrient applied in the form of Mg-NPs. Previously,
Hoagland and Arnon [28] found that most of the plants
generally require 1–5 mg l-1 Fe in soil solution.
2.2.2 Manganese (Mn)-NPs
A hydroponic culture experiment was conducted to find
out the comparative efficacy of Mn-NPs and commonly
used Mn-salt, i.e. MnSO4, on the growth and yield param-
eters of mung bean [48]. Both were applied at 0.05, 0.1,
0.5, and 1.0 mg l-1. The results showed that application of
Mn-NPs at 0.05 mg l-1 significantly improved growth and
yield parameters compared to the control with no Mn
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applied. At higher doses, Mn-NPs did not show toxicity to
the bean plants, while MnSO4 applied at 1 mg l-1 showed
toxic effects like necrotic leaves, brown roots, and gradual
disappearance of the rootlet after 15  days of treatment.
Moreover, greater oxygen evolution and photophospho-
rylation in Mn-NP-treated chloroplasts was noted com-
pared to the control. Greater oxygen evolution was caused
by enhanced splitting of water in the oxygen-evolving
center located in the chloroplast. The authors concluded
that Mn-NPs could serve as a potential modulator of
­photochemistry in the agriculture sector.
2.2.3 Zinc (Zn)-NPs
Many researchers around the world have focused on
finding the effect of ZnO-NPs on the growth and productiv-
ity of crops. Most important, out of the all micronutrients, it
is the most widely studied in plant science worldwide. For
example, optimal concentration of ZnO-NPs significantly
enhanced the growth and yield parameters of mung bean
and chickpea [31]. Authors found that the optimal concen-
tration of ZnO-NPs to be applied depends on the nature
of the crop. With the application of 20 mg l-1 ZnO-NPs to
mung bean plants, an increase of 42%, 41%, 98%, and
76% in root length, root biomass, shoot length, and shoot
biomass, respectively, was recorded. Moreover, the appli-
cation of higher doses of ZnO-NPs caused a decrease in
the growth rates of mung bean and chickpea. In another
greenhouse experiment, the application of ZnO-NPs at the
rate of 400 and 800 mg kg-1 caused a significant increase
in the growth and yield parameters of cucumber (Cucumis
sativus) [32]. The results clearly showed an increase of
10% and 60% in plant root dry mass with the applica-
tion of 400 and 800  mg kg-1, respectively, as compared
to control (without ZnO NPs). However, the same rates
caused a slight increase of 0.6% and 6% in the dry fruit
weight, respectively, as compared to the control. Similarly,
Lin and Xing [33] reported a significant increase in the
root elongation of germinated seeds of radish (Raphanus
sativus) and rape (Brassica napus) with the application of
ZnO-NPs at 2  mg l-1, in comparison to control (deionized
water). The authors also found a significant improvement
in the growth parameters of ryegrass (Lolium perenne)
with the application rate of 2 mg l-1 metallic Zn-NPs. Seed
germination was improved with the application of lower
concentrations of ZnO-NPs in peanut [34], soybean [35],
wheat [36], pearl millet [37], tomato [38], and onion [39].
In another experiment, a significant improvement in
Cyamopsis tetragonoloba plant biomass, shoot and root
growth, root area, chlorophyll and protein synthesis,
 Table 2: Nanoparticles that served as micronutrients and their source to enhance plant growth parameters.
Nutrient   Crop and experimental conditions  
provided
Fe   Vigna unguiculata subsp. unguiculata,  
foliar application, field study
  Glycine max, greenhouse test 7 days,  
perlite medium, nutrient solution
  Cucurbita pepo cultivated in vitro  
Mn   Vigna radiata, 15 days in growth  
chamber, perlite medium, nutrient
solution
Zn   Vigna radiata and Cicer arientinum,  
incubated 60 h in agar medium
  Cucumis sativus, 53 days greenhouse  
pot study
  Brassica napus and Lolium perenne,  
5 days germination
  Arachis hypogaea, germination and field   nZnO, 25 nm, 1000 ppm, and chelated bulk
trial during 2008–2010
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  Glycine max  
  Triticum aestivum L.  
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  Pennisetum americanum  
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  Solanum lycopersicum L.  
  Allium cepa  
  Cyamopsis tetragonoloba L.  
  Musa acuminata in vitro cultures  
  Arabidopsis thaliana (mouse-ear cress)   nZnO at 400, 2000, and 4000 mg l-1
  Medicago sativa, Cucumis sativus, and  
Solanum lycopersicum
Size and rate of application  
Fe-NPs, 0.25 and 0.5 g l-1  
Superparamagnetic iron oxide NPs, Fe3O4,  
18.9–20.3 nm, 30, 45, and 60 mg l-1
carbon-coated Fe-NPs  
Metallic Mn, 20 nm, 0.05, 0.1, 0.5, and  
1.0 mg l-1, MnSO4
ZnO, 20 nm, 1–2000 mg l-1  
ZnO, 10 nm, 400 and 800 mg kg-1 soil  
ZnO, 20 nm, 1–2000 mg l-1 applied to Brassica   Improved root elongation in both and Zn-NPs at levels higher than
napus and metallic Zn, 35 nm, 1–2000 mg l-1
applied to Lolium perenne
 
zinc sulfate (ZnSO4), a field experiment
with nZnO applied at 15 times lower dose
compared to chelated ZnSO4
nZnO at 0, 0.5,and 1 g l-1  
nZnO 20–50 nm  
Biosynthesized Zn-NPs, 15–25 nm, sprayed  
at 16 l ha-1 after 2 weeks of germination at
10 ppm
TiO2- and ZnO-NPs, 25±3.5 nm, 0–1000 ppm  
ZnO-NPs, at 0.0, 10, 20, 30 and 40 g ml-1  
Biosynthesized nZnO, foliar sprayed at 10 ppm  Improved growth, yield, and quality parameters
nZn and nZnO  
 
nZnO at 0–1600 mg l-1 and Zn2+ at 0–250 mg l-1   Germination in Cucumis sativus increased with nZnO at 1600 mg l-1   [43]
Comments   References
More 1000-seed weight, leaf Fe and chlorophyll content compared to   [26]
regular Fe salt
Chlorophyll contents increased up to 45 mg l-1 but decreased at   [29]
60 mg l-1
–   [20]
Metallic Mn increased growth and physiological parameters more   [30]
compared to MnSO4; Mn-NPs did not show phytotoxicity
Growth and yield parameters in both improved   [31]
Root dry mass, fruit starch, glutelin, and Zn contents significantly   [32]
improved
  [33]
the optimum showed phytotoxicity
Promoted both seed germination and seedling vigor, early flowering,   [34]
higher leaf chlorophyll content, pod yield per plant compared to
chelated bulk ZnSO4; in field experiment, there was higher pod yield
compared to chelated ZnSO4
Increased germination over control; greater radicle length and fresh   [35]
weight in stressed seedling
Significantly increased chlorophyll and protein content   [36]
Improved growth, physiological, biochemical, and yield parameters   [37]
over control in 6-week-old plants
Promoted growth and development   [38]
Low concentrations increased seed germination but decreased under  [39]
higher ones
  [40]
Somaclones accumulated more proline, chlorophyll, antioxidant   [41]
enzymes activity, and developed more dry weight than the control
nZnO was most phytotoxic; inhibition of seed germination depended   [42]
on particle size at equivalent concentrations
while it decreased in Medicago sativa and Solanum lycopersicum,
observed highest Zn content in alfalfa with 1600 mg l-1 nZnO and
250 mg l-1 Zn2+
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 8      A. Ditta and M. Arshad: Nanonutrition for sustainable crop production

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[24]

[44]

[45]

[46]

[47]

[24]
rhizospheric microbial population, acid phosphatase,
alkaline phosphatase, and phytase activity in cluster bean
rhizosphere was recorded with the application of ZnO-NPs
[40]. Similarly, Helaly et al. [41] found that ZnO-NPs sup-
 

Reduced biomass, root tips shrank, and root epidermal and cortical  

Improved nodule number/mass, activity of antioxidant enzymes and  

plemented with MS-media promoted somatic embryogen-

decreased the ion content of bulk Cu solution but increased Cu2+ of

cells highly vacuolated/collapsed; nZnO was observed in apoplast

T. aestivum exposed to nCu were 335 and 570 mg l-1, respectively

esis, shooting, regeneration of plantlets, and also induced

Increased photosynthesis rate but leaf Cu at  < 0.5 mg l-1 CuSO4

The 2-day median effective concentrations for P. radiatus and proline synthesis, activity of superoxide dismutase, cata-

Bulk and NP Cu were highly phytotoxic; humic acid (50 mg l-1)

lase, and peroxidase, thereby improving tolerance to

Increased shoot/root ratio, total N, and organic matter at

biotic stress. In contrast to these studies, many researchers
have reported phytotoxicity of the application of Zn-NPs
and protoplast of the root endodermis and stele

in various crop plants [31–33, 42, 49]. However, phytotox-

icity was found to depend on the nature of crop plants.
Overall, most of the crop plants usually require merely
0.05 mg l-1 soil solution. The researchers in these studies
applied metallic Zn-NPs at a very high rate, ranging from
inhibitory at all concentrations

400 to 2000  mg l-1, which was the main reason for their
toxic effects. Even the application of Zn-NPs at 10  mg l-1
to ryegrass proved harmful for normal growth [50]. In
symbiotic bacteria

another study, among cucumber, alfalfa, and tomato, the

NP solutions

application of ZnO-NPs only enhanced seed germination

130 mg kg-1
Comments

of cucumber [43].

2.2.4 Copper (Cu)-NPs

 

70% CuO and 30% Cu2O, 30 nm, 0.025, 0.25,  

 
Mo, 100–250 nm, 8 mg l-1, others unknown
Metallic Cu, b 50 nm, 130 and 600 mg kg-1
Bulk and Cu-NPs and Ag-NPs were directly

Previously, it has been clearly found that the application

rate of Cu-NPs at 0.02  mg Cu l-1 in Hoagland solution is
optimum for normal growth and yield of crops. Scientists
0.5, 1, and 5 mg l-1 as Cu, CuSO4

around the world have found toxic effects of the applica-

Size and rate of application

tion of Cu-NPs, as they have applied them at higher rates

than required [44, 45]. They found that Cu-NPs applied at
the rate of 200–1000  mg l-1 caused toxic effects on seed-
nZnO and nZn2+

ling growth of mung bean, wheat, and yellow squash.

compared

Similarly, reduced biomass of zucchini by 90% com-

pared to that of the control (without Cu) after the seed-
as Cu
nCu

lings were incubated in Hoagland solution for 14  days

was recorded with the application of metallic Cu-NPs at
 

Lactuca sativa, 15-day germination, soil  

Edodea densa planch, 3-day incubation,  

1000  mg l-1. However, researchers like Shah and Beloze-

rova [46] recorded a significant increase of 40% and 91%
Crop and experimental conditions

Cicer arietinum, rhizosphere soil

Phaseolus radiatus and Triticum

in 15-day lettuce seedling growth rate with the application

of Cu-NPs at 130 and 600 mg kg-1, respectively. Similarly,
a 35% increase in photosynthetic rate of waterweed was
recorded in a 3-day incubation study using a low concen-
tration of Cu-NPs applied at   ≤ 0.25 mg l-1 [47].
Lolium perenne

Cucurbita pepo

examination
aestivum
Table 2 (continued)

2.2.5 Molybdenum (Mo)-NPs

water

Mo is essential for legumes as it is involved in biologi-

Nutrient  

 
provided

cal nitrogen fixation (BNF), being the component part of

Mo

nitrogenase enzyme. For normal metabolism, crop plants

Cu

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 A. Ditta and M. Arshad: Nanonutrition for sustainable crop production      9
usually require ≈0.01 mg Mo l-1 soil solution. Taran et al.
[24] conducted a pot experiment using different combi-
nations of N-fixing bacteria and Mo-NPs (water, Mo-NPs,
microbial inoculation with nitrogen-fixing bacteria, and
a combination of the microbes and Mo-NPs). The control
was treated with distilled water. Chickpea seeds were
soaked in each of the treatments for 1–2 h. The results
clearly showed that the combined application of microbes
and Mo-NPs significantly improved the microbiological
properties of the rhizosphere, including all groups of agro-
nomically important microbes. The same combination
­significantly improved the root number, nodule number
per plant, and nodule mass per plant compared to control.
2.3 Nanocarrier-based fertilizers
These are the fertilizers that contain NMs, which, when
mounted with a plant nutrient, can increase the nutri-
ent efficiency of the plants and/or reduce the detrimental
effect of conventional fertilizers associated with their high
rates of application. These nanocarriers, in themselves, do
not contain any nutrient at all. The most commonly used
nanocarrier-based fertilizers are discussed below.
2.3.1 Nutrient-augmented zeolites
Zeolites are complicated silicate minerals with nanostruc-
tures that are well renowned for their unique nanoporous
properties with high specific surface area (≈1150.5  m2 g-1)
and cation exchange capacity (10 times more than that of
soil). These are highly selective toward plant macronutri-
ents like K+ and NH4+ [51]. These mostly do not occur at
nanoscale but acquire nanostructure during the arrange-
ment of Al and Si in the three-dimensional framework of
SiO4 and AlO4 tetrahedra of zeolites, which creates chan-
nels and voids that are within nanoscales (0.3–10  nm
diameter). The essential nutrients may be mounted onto
the exchange sites of zeolites, which, on their applica-
tion to the field, slowly release nutrients, thereby reduc-
ing their loss through leaching and/or run off. Similarly,
as the nutrients get adsorbed onto the exchange sites of
zeolite, the chances of their availability to the soil microbes
involved in ammonification are also reduced, thereby
decreasing the loss of nutrients through volatilization or
through nitrification and denitrification (NH3, N2, or N2O).
Long ago, zeolites have been well renowned for being
used as carrier for plant nutrients and have been inten-
sively studied around the world [52]. Zeolites have been
mostly used for increasing nitrogen use efficiency (NUE),
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reducing the nutrient loss, and thereby reducing the
detrimental effects on the environment. For example, a
pot experiment was conducted to find out the compara-
tive efficacy of naturally occurring zeolite (Clinoptilolite)
rich in exchangeable K and with regularly used nutrient
­solution containing 234  mg K l-1 using chrysanthemum
(Chrysanthemum morifolium) as a test plant [25]. The
results clearly showed that a single application of natu-
rally occurring zeolite at 33 g l-1 was sufficient to produce
a 3-month yield of chrysanthemum compared to those
recorded with a nutrient solution containing 234 mg K l-1.
The nutrient solution contained about 2.3 times more K
than the potting medium fertilized with K-augmented
zeolite.
Two greenhouse studies were conducted with sweet
corn (Zea mays L.) to find out the effect of ammonium-
loaded clinoptilolite (A-Cp) in reducing N-leaching com-
pared to ammonium sulfate (AS). Pots containing sandy
soil were fertilized with either AS or one of three size frac-
tions of A-Cp at rates of 112, 224, or 336 kg N ha-1 in a first
experiment, and 112 or 224 kg N ha-1 in a second experi-
ment. Soil amended with AS leached 10–73% of the added
N, depending on N rate, whereas  < 5% of added N leached
from A-Cp-amended soil regardless of N rate and Cp par-
ticle size. Plants fertilized with A-Cp assimilated signifi-
cantly more N than AS-fertilized plants. It was concluded
that fertilization with A-Cp would minimize N leaching
from sandy soils while sustaining normal corn growth [21].
In another study, application of NH4-exchanged zeolite-
rich tuff (an equivalent rate of 30 tons ha-1) significantly
decreased nitrification rate by 4% in a silty clay loam and
11% in loamy sand soil [53]. It was suggested that decrease
in nitrification was due to the adsorption of NH4+ on the
exchange sites of zeolite, which ultimately reduced NH4+
exposure to nitrifying bacteria.
In a lysimetric study, 22% reduction in leaching of
NO3-N (13.8 kg ha-1) was recorded with the application of
zeolite amendment (60 g kg-1) compared to the control
(18 kg ha-1). There was 10.3% and 4.9% increase in dry
weight of stoves and grain yield of maize [20]. Moreover,
the zeolite amendment caused a significant increase in
rate of fertilizer uptake from 77% to 86%. Pot experiment
under controlled condition was conducted to compare the
effect of K-augmented zeolite with KCl applied at varying
concentrations on different growth stages of wheat [54].
The results clearly showed that K-augmented zeolite sig-
nificantly improved the aboveground dry biomass by 64%
compared to KCl applied at rate of 89  mg kg-1. Recently,
Li et al. [55] investigated the effect of NH4- and K-loaded
zeolite (NK-Z) on slow release of N and potassium (K).
The results clearly showed a significant increase in total
10      A. Ditta and M. Arshad: Nanonutrition for sustainable crop production
harvest weight of kale (Brassica alboglabra Bailey) com-
pared to that with the application of KCl or KOH. More-
over, higher levels of N and K were detected in soil applied
with NK-Z.
So, nutrient-augmented zeolites significantly improved
the growth and yield of various test crops as discussed
in the above reports. However, their use is constrained by
their extra cost to purchase zeolite and augment it with
nutrient of interest. In the future, there is dire need to find
out an automated system installed in the chemical manu-
facturing unit that automatically ensures the mounting
required nutrient during the prilling process of fertilizer
manufacture.
2.3.2 Other nanocarriers
Several laboratory studies have demonstrated the capa-
bility of several NPs (silica, Fe oxides, C-coated Fe, and
polymers) for efficient DNA transport and chemicals into
the plant tissues/cell [30, 56, 57]. Moreover, their use
might become expensive as plants have a natural ability
to absorb soluble nutrients (e.g. N, P, and K) directly from
soil solution so their use might become an extra effort,
which makes nutrient application more complex and
also expensive. However, there is a possibility to find out
certain NMs/NPs that are economical and more efficient
compared to previously available carriers like zeolite. So,
there is need to find out such NMs comprehensively in
future research.
3 P
 lant-growth-enhancing NPs with
unclear mechanisms
Several studies have reported NPs that could enhance
plant growth with an unknown mechanism as these are
neither a source of macro- or micronutrients nor carry any
nutrient with them. Their detailed description is given in
the following sections Table 3.
3.1 Titanium dioxide (TiO2)-NPs
Traditionally, Ti is not included in the list of essential
plant nutrients. Moreover, most of the soils contain suf-
ficient amount of Ti ranging from 0.1% to 0.9% with an
average of about 0.03  mg l-1 in soil solution [113]. So,
there is no need to apply an external source of Ti to crop
plants. However, several researchers have reported about
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its positive effect on photosynthesis efficacy and enzyme
activities like that of nitrogenase, thereby increasing N
supply to the crop plants via BNF, and ultimately the plant
growth [58–60]. For example, Yang et al. [58] noted a sig-
nificant increase (twofold) in the fresh and dry weights
of spinach (Spinacia oleracea) plants when 2.5 g l-1 Ti-NP
solution was sprayed once a week for 35 days compared
to that of the control (without Ti-NP application). Moreo-
ver, the same treatment caused an increase of 23%, 34%,
and 13% in total N, chlorophyll, and protein contents over
control, respectively. Gao et al. [59] noted similar results
with the application of Ti-NP at 0.3 g l-1, about 10 times less
concentration than that used by Yang et al. [58]. In a 7-day
growth chamber study, a significant increase in plant
height and fresh weight of duckweed (Lemna minor) was
noted with the application of Ti-NP at 0.5 g l-1 compared
to bulk TiO2 solution [61]. Application of Ti-NP  > 0.5 g l-1
showed an inhibitory effect on the plant. Combined appli-
cation of TiO2 and SiO2 at lower concentrations resulted in
a significant increase in the activity of nitrate reductase
in the rhizosphere of soybean, which ultimately improved
germination and growth [62]. Yang et al. [114] and Mishra
et  al. [67] recorded improvement in plant fresh and dry
weights, and suggested this to be due to the improvement
in various enzyme activities (nitrate reductase, gluta-
mate dehydrogenase, glutamine synthase, and glutamic-
pyruvic transaminase) involved in N metabolism. Ti-NPs
favor the conversion of inorganic N to organic N in the
form of proteins and chlorophyll, which results in an
overall increase in plant productivity. Seed germination,
radicle and plumule growth of canola seedlings, tomato
and mung bean [38, 63], spinach (Spinacia oleracea), and
wheat (Triticul aestivum L.) were significantly improved
with the application of Ti-NP [64–70]. Similarly, under
water-deficit conditions, wheat growth and yield param-
eters were significantly improved with the application of
Ti-NPs at 0.01%, 0.02%, and 0.03% [71].
Moreover, these are also effective photocatalysts and
have been extensively used for the production of H2 as
a fuel using solar energy through photocatalytic decom-
position of organic compounds [115, 116]. Yang et  al.
[114] found that Ti-NPs noticeably promote aged seeds’
vigor and chlorophyll formation and stimulate ribulose
1,5-bisphosphate carboxylase (Rubisco) activity, thereby
increasing photosynthesis and ultimately plant growth
and development. It has also been found that Ti-NPs
increase light absorbance, hasten transport and conver-
sion of light energy, protect chloroplasts from aging, and
prolong the photosynthetic time of chloroplasts. Hong
et al. [66, 72] suggested that it might be due to protection
of chloroplast from excessive light by augmenting the
 Table 3: Nanoparticles that enhanced plant growth parameters through partially known mechanisms.

Crop and experimental conditions   Size and rate of application   Comments   References

TiO2-NPs that enhanced plant growth parameters through partially known mechanisms
 Solanum lycopersicum L.   TiO2- and ZnO-NPs, 25±3.5 nm, 0–1000 ppm   Promoted growth and development   [38]
 Spinacia oleracea, greenhouse, 35 days,   Anatase, 5 nm, 2.5 g l-1, seed soak and leaf spray   More biomass, N, chlorophyll, and protein content observed with   [58]
perlite medium anatase compared to bulk rutile
 Spinacia oleracea   Nano-anatase TiO2 (5 nm), bulk TiO2   Greater amount and the activity of Rubisco activase with nano-   [59]
anatase TiO2 compared to bulk TiO2
 Spinacia oleracea   Nano-anatase TiO2   Promoted spectral responses, leading to the improvement of   [60]
primary electron separation, electron transfer, and light energy
conversion of D1/D2/Cyt b559 complex
 Lemna minuta, growth chamber, 7 days,   Anatase, 5–10 nm, 10, 50, 100, 200, 1000, and   More root length, biomass, and chlorophyll content with anatase   [61]
nutrient solution 2000 mg l-1, bulk TiO2 at  < 500 mg l-1 compared to bulk TiO2
 Glycine max     Hastened germination, growth, and prevented from going moldy;   [62]
increased nitrate reductase of root and leaves; ultimately improved
resistance to adversities
 Vigna radiata L.   Biosynthesized TiO2, 12–15 nm, foliar sprayed at   Promoted growth, physiological, biochemical and yield parameters  [63]
10 ppm
 Brassica napus   nTiO2 at 10, 100, 1000, 1200, 1500, 1700, and   Showed larger radicle and plumule growth of seedling at 1200 and   [64]
2000 mg l-1 1500 mg l-1 compared to other concentrations and control
 Spinacia oleracea   nTiO2 (rutile) and non-nTiO2   Increased germination, growth, yield, and physiological functions.   [65]
The best results were found at 2.5% n-TiO2
 Spinacia oleracea under different illumination   nTiO2 (rutile) 0.25% solution   Increased rate of evolution oxygen of chloroplasts in different   [66]

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times (1, 5, 10, 20, 30, and 40 min) illumination times
 Spinacia oleracea   Nano-anatase TiO2   Increased activities of reactive oxygen species (ROS) scavenging   [67]
enzymes

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 Spinacia oleracea chloroplasts under UV-B   Nano-anatase   Improved ROS scavenging system by increasing activities of   [68]
radiation various enzymes involved in defense system under stress

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 Triticum aestivum  
 Triticum aestivum  
 Triticum aestivum, field experiment  
 Spinacia oleracea  
 Zea mays L. and Vicia narbonensis L.  
 Ulmus elongate, foliar application  
nTiO2 (1, 2, 10, 100, and 500 ppm), bulk (1, 2, 10,  
100, and 500 ppm), and control (without TiO2)
Anatase and rutile TiO2-NPs with diameters ranging  
from 14 to 655 nm
nTiO2 at 0.01%, 0.02%, and 0.03%, control (bulk  
TiO2)
n-TiO2 (rutile) 0.25%  
nTiO2 at concentration range from 0.2% to 4.0%  
Nano-anatase TiO2 at 0.1%, 0.2%, and 0.4%  
solution
nTiO2 improved germination and various growth parameters at   [69]
10 ppm compared to bulk and control
The smallest NPs during the first stages of development caused an   [70]
increase of root elongation
nTiO2 at 0.02% increased almost all agronomic traits including   [71]
gluten and starch content
Accelerated Hill reaction and noncyclic photophosphorylation   [72]
(nc-PSP) activity of chloroplasts, the chloroplast coupling and
activities of Mg2+-ATPase and chloroplast coupling factor I (CF1)-
ATPase on the thylakoid membranes
Delayed germination progression in both materials; reduced   [73]
mitotic index and increased aberration emergence
Enhanced leaf absorbance indicating the synthesis of   [74]
carbohydrate and lipid compounds
A. Ditta and M. Arshad: Nanonutrition for sustainable crop production      11
 Table 3 (continued)

Crop and experimental conditions   Size and rate of application   Comments   References

CNTs that enhanced plant growth parameters through partially known mechanisms
 Cell culture with extracted chloroplasts   SWNTs   Enhanced photosynthetic activity than that of controls and reduced  [10]
concentrations of ROS inside extracted chloroplasts
 Lolium multiflorum, Brassica napus, Zea mays,   MWCNTs with diameter 10–20 nm, length 1–2 μm,   Significantly improved root elongation in Brassica napus,   [33]
5 days incubation study 2 g l-1 ryegrass, and Zea mays
 Solanum lycopersicum, 2 months growth   MWCNTs diameter ~10–25 nm, 50 and 200 mg l-1,   Both increased plant height and fruit number per plant compared   [75]
chamber, soil mixture, water activated carbon (AC) to control and enhanced water uptake and utilization efficiency
 Solanum lycopersicum   Well-dispersed MWCNTs and MWCNTs   Increased plant growth and production of water channel protein   [76]
functionalized with stronger -ve groups compared to control or plants exposed to poorly dispersed and
highly aggregated MWCNTs
 Zea mays   Factory-synthesized MWCNTs   Improved water absorption, plant biomass, and the concentrations   [77]
of the essential Ca, Fe nutrients
 Tobacco cell culture   MWCNTs and AC at 5–500 μg ml-1   Both MWCNTs and AC enhanced growth, expression of aquaporin   [78]
gene, and production of NtPIP1 protein; however, AC stimulated
cell growth only at low concentrations over control. The expression
of marker genes for cell division and cell wall extension was also
upregulated in cells compared to control cells or those exposed to
AC only
 Barley, Zea mays, Glycine max, agar medium,   MWCNTs diameter ~15–40 nm, 50, 100, and   Shoot and root length in barley, Zea mays and Glycine max   [79]
10-day germination study 200 mg l-1 significantly enhanced

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 Triticum aestivum, 7 days of exposure   OMWCNTs with a length 50–630 nm,   Improved growth, yield and dehydrogenase activity at 80 lg ml-1   [80]
12      A. Ditta and M. Arshad: Nanonutrition for sustainable crop production

at 10–160 lg ml-1
 Triticum aestivum under light and dark   Water-soluble carbon nanodots (wsCND)   Enhanced growth of root and shoot both in light and dark   [81]

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conditions conditions
 Allium cepa and Cucumis sativus 2–3-day   SWCNTs, diameter ~8 nm, length 0.1–5 μm, at 104,   Improved root elongation of 1-day-old Allium cepa and Cucumis   [82]

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germination study in growth chamber 315, 1750 mg l-1
 Solanum lycopersicum   CNTs (10–40 μg ml-1)  
 Brassica juncea and Phaseolus mungo   MWCNTs at 10, 20, and 40 μg ml-1  
 Hybrid Bt Gossypium spp., in vitro conditions   MWCNTs  
 Brassica juncea   Oxidized MWCNTs having a diameter of 30 nm  
 Lactuca sativa, hydroponic study for 15 days   MWNTs treated Hoagland’s media, carbon black  
(CB)
 Spinacia oleracea, hydroponic culture   MWCNTs at 0–1000 mg l-1  
 Onobrychis arenaria seedlings   Nano-Taunit containing MWCNTs at 100 and  
1000 μg ml-1
 Cicer arietinum   Water-soluble carbon nanotubes (wsCNTs) at  
6.0 μg ml-1
sativus
Improved germination and growth rates compared to control   [83]
Germination and root growth in both was enhanced at 10 and   [84]
20 μg ml-1 while phytotoxicity was evidenced at 40 μg ml-1
Improved growth and yield parameters both under in vitro and field  [85]
conditions at 60 and 100 μg ml-1, respectively
Improved germination and growth under low concentration   [86]
compared to non-oxidized and higher conc.-treated seeds
Deteriorated root tip and penetrated into plant cell wall, causing   [87]
cell death on root and leaves compared to CB
Exhibited growth inhibition and cell death, suggesting a role of   [88]
ROS in MWCNT-induced toxicity
Stimulated root and stem growth and enhanced the peroxidase   [89]
activity
Increased growth rate, water absorption, and retention; wsCNTs   [90]
are non-toxic to plant cells
 Table 3 (continued)
Crop and experimental conditions  
AG-NPs nanoparticles that enhanced plant growth parameters through partially known mechanisms
 Bacopa monnieri L. Wettst, hydroponically  
 Arabidopsis  
 Corms Crocus sativus  
 Raphanus sativus and Lactuca sativa,  
Hordeum vulgare as a reference, greenhouse
study
 Eleven species of wetland plants in simple   20-nm Polyvinylpyrrolidone-coated AgNPs
pure culture and field soils in greenhouse
experiment
 Boswellia ovalifoliolata  
 Phaseolus vulgaris L., Zea mays L.  
 Brassica juncea, 7-day-old seedlings  
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Au-NPs that enhanced plant growth parameters through partially known mechanisms
 Lactuca sativa, short term  
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 Cucumis sativus, Lactuca sativa, and  
Photobacterium phosphoreum
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 Brassica juncea, field conditions  
 Gloriosa superba  
 Arabidopsis thaliana  
SiO2-NPs that enhanced plant growth parameters through partially known mechanisms
 Glycine max  
 Lycopersicum esculentum Mill.  
 Zea mays  
Size and rate of application  
Biosynthesized Ag-NPs  
Ag-NPs with decahedral (45±5 nm), triangular  
(47±7 nm), and spherical (8±2 nm) shapes
nAg at 0, 40, 80, or 120 ppm  
AgNP, 10 nm PVP, at 1, 2.5, 5 and 10 mg l-1  
 
(PVP-AgNPs), 6-nm gum arabic-coated AgNPs
(GA-AgNPs), and AgNO3 at equivalent Ag conc.
(1, 10, or 40 mg Ag l-1).
Biosynthesized AgNPs at 10–30 mg ml-1 in MS  
basal medium
AgNPs at 20, 40, 60, 80, and 100 ppm  
AgNPs at 0, 25, 50, 100, 200, and 400 ppm  
Silica, palladium, gold, and copper  
Au, 10 nm, germination, and anaerobic toxicity test   In all cases, low or zero toxicity was observed
AuNPs at 0, 10, 25, 50, and 100 ppm  
Spherical biosynthesized Au NPs 25 nm at 500 and   Exposure at 1000 μm concentration had the most significant effect   [101]
1000 μm
Au-NPs, 24 nm, at 10 and 80 μg ml-1  
Unknown nanometer materials  
nSiO2, 12 nm  
Si-NPs, 20–40 nm, at 5–20 kg ha-1, bulk silica at  
15–20 kg ha-1
Comments   References
Enhanced peroxidase and catalase activity; simulated the stress   [91]
conditions induced by the silver nitrate treatment
Increased ROS accumulation and root growth, activated gene   [92]
expression involved in cell proliferation, metabolism, and
hormone signaling pathways
Increased root number, length, and leaves dry weight with 80 ppm   [93]
under flooding stress
Root length was increased for Hordeum vulgare, but was   [94]
dramatically inhibited for Lactuca sativa
The plant growth response differed by taxa with Lolium multiflorum  [95]
growing more rapidly under both AgNO3 and GA-AgNP exposures
Improved germination and growth parameters   [96]
Increasing concentration from 20 to 60 ppm increased growth and   [97]
physiological parameters
Improved growth and physiological parameters involved in ROS   [98]
scavenging, found optimum growth at 50 ppm
Enhanced growth of Lactuca sativa seeds as measured through   [46]
shoot/root ratios of the germinated plant (p < 0.05)
  [99]
Increased growth, yield, and quality parameters up to 25 ppm,   [100]
improved the redox status of the treated plants
on seed germination rate and vegetative growth
Enhanced total seed yield, seed germination rate, vegetative   [102]
growth and free radical-scavenging activity
Increased nitrate reductase activities, water use efficiency, total   [62]
antioxidant capacities, and stimulated the antioxidant system
Among the treatments, 8 g l-1 nSiO2 improved germination and   [103]
growth parameters
SNPs increased growth up to 15 kg ha-1; silica accumulation in   [104, 105]
leaves was high at 10 and 15 kg ha-1 concentrations of SNPs
A. Ditta and M. Arshad: Nanonutrition for sustainable crop production      13
 14      A. Ditta and M. Arshad: Nanonutrition for sustainable crop production

References

[106]

[107]

[108]

[109]

[110]

[111]

[112]
activity of antioxidant enzymes (catalase, peroxidase,
superoxide dismutase). However, more comprehensive
studies are required to elucidate how photocatalysis of
these NPs coordinate with plant’s biochemical process,
 

1 mm nSi+25 mm NaCl improved germination, root length, and dry  

Improved quality and nutrient contents, stimulated SOD and POD  

 
i.e. photosynthesis to improve its growth and produc-
tivity [7, 9]. These studies would also help elucidate the
500 μl l-1 produced the best result, compared to that of control

Improved germination, growth, and physiological parameters;

Adsorbed 4.7 and 15 mg PSII g SBA-1 with 15 nm (SBA15) and
increased, which was due to tolerance induction in the plant

Improved physiological and photochemical parameters; the

mechanisms/process behind why plants do not utilize
Promoted seedling growth and improved seedling quality,

Leaf dry and fresh weight, chlorophyll and proline content

Ti, sufficiently present in the soil, for their biochemi-

optimal concentration of 300 mg l-1 compared to control

cal processes. Above all, there are also reports about the

activities, and decreased MDA content at 300 mg l-1

negative effects of Ti-NPs on seed germination applied
weight while higher conc. reduced germination

at 4 g l-1 [73].

3.2 Carbon nanotubes

23 nm (SBA23), respectively

CNTs have acquired an important position due to their

induced ROS scavenging

unique mechanical, electrical, thermal, and chemical

properties. However, there has been scant information
available on the efficacy of CNTs in plant nutrition and
Comments

their relation with plant metabolism. Various studies

have reported magically positive effects of multiwalled
CNTs (MWCNTs) on the seed germination of various
crops and ultimately plant growth [75–77]. The proposed
 

mechanism behind this plant growth improvement

involves the induction of water channel proteins due to
nSi at 1 and 2 mm and NaCl at 25 and 50 mm

the presence of surface charges of CNTs, thereby enhanc-

TMS (nSiO2) at 2000, 1000, 500, 250, 125,

ing water and essential nutrient (Ca and Fe) uptake effi-
SBA, 15 nm (SBA15) and 23 nm (SBA23)
No Si, Si fertilizer, and nSi, salinity 1, 3,

ciency that could enhance seed germination and plant

nSiO2 at 0, 150, 300, and 450 mg l-1

nSiO2 at 150, 300, and 450 mg l-1

growth and development [77, 78, 117]. In another study,

embedded single-walled CNTs (SWCNTs) in isolated chlo-
Size and rate of application

roplast augmented photosynthetic activity (three times)

compared to control and enhanced electron transport
rates [10]. Moreover, SWCNTs enabled plants to sense
nitric oxide, a signaling molecule. The authors sug-
and 6 dS m-1
and 62 μl l-1

gested that a nanobionics approach to engineered plants

would enable new and advanced functional properties
nSiO2

in photosynthetic organelles. For this purpose, extensive

research is required to elucidate the impact of CNTs on
 

 Indocalamus barbatus McClure, foliar spraying 

 Indocalamus barbatus McClure, foliar spraying 

ultimate products of p­ hotosynthesis such as sugars and

glucose.
 Ocimum basilicum under salinity stress in
 Cucurbita pepo L. cv. white bush marrow

Seed germination of barley, soybean, and corn was

significantly enhanced with the addition of MWCNTs
Crop and experimental conditions

in agar medium [79]. The authors found that MWCNTs

 Larix olgensis soaked for 6 h

have the ability to penetrate into seed coats as nanotube

agglomerates were detected through Raman spectros-
 Solanum lycopersicum

greenhouse condition

copy and transmission electron microscopy. Moreover,

Table 3 (continued)

they also found that MWCNTs regulated the expression

of genes encoding several types of water channel pro-
teins in soybean, corn, and barley seed coat. In another
study, Khodakovskaya et al. [78] found an upregulation in
marker genes for cell divisions (CycB), cell wall formation

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 A. Ditta and M. Arshad: Nanonutrition for sustainable crop production      15
(NtLRX1), and water transport (aquaporin, NNtPIP1) in
tobacco cell culture with the application of MWCNTs,
hence resulting in better seed germination and ultimately
plant growth. Similarly, MWCNTs improved water reten-
tion capacity and biomass, flowering, and fruit yield,
and increased the medicinal properties of tomato [75].
Wang et  al. [80] applied oxidized MWCNTs and found a
significant improvement in dehydrogenase activity and
cell elongation of the root system. The presence of water-
soluble CNTs inside wheat plants using scanning electron
and fluorescence microscope was also confirmed, which
resulted in improved root and shoot growth under light
and dark conditions [81]. Improvement in root growth
of germinated seeds of ryegrass with the application of
MWCNTs and in onion (Allium cepa) and cucumber seeds
with the application of SWCNTs was recorded [33, 83] in
comparison to control (0 CNTs). Many researchers have
confirmed the role of CNTs in improving seed germination
and ultimately the growth of various crops like hybrid Bt
cotton, Brassica juncea, Phaseolus mungo, tomato (Lyco-
persicum esculentum Mill.), mustard (Brassica juncea),
black gram (Phaseolus mungo), and rice (Oryza sativa L.),
etc. [75, 76, 79, 83–86, 118].
However, some researchers have reported the inhibi-
tory effect of MWCNTs at higher concentrations on the
growth of various crop plants [77, 82, 87, 88, 119]. Similarly,
Lin and Xing [33] in radish, lettuce, or cucumber seeds
have reported no effect even at higher concentrations.
The exact mechanism behind this enhancement is
still unknown. However, various researchers have sug-
gested that improvement in plant growth and enzyme
activities (peroxidase and dehydrogenase) through the
application of MWCNTs might be due to their uptake and
accumulation in roots followed by translocation to leaves,
which ultimately induces gene expression [78–80, 89].
From these reports, it might be concluded that effect of
SWCNTs and MWCNTs varies from plant to plant, within
and across species, and depends on growth stage, con-
centration, and nature of CNTs. So, more field research
is needed to confirm the positive effect of CNTs on yield
of various crops. Studies to elucidate responsible mecha-
nisms are also required to be conducted.
3.3 Silver (Ag)-NPs
The available data show that a few studies regarding
the effect of Ag-NPs have been conducted. Their posi-
tive/neutral/negative effect was entirely dependent on
the plant species exposed, their particle size, and the
rate of application [91]. Recently, exposure of Ag-NPs
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with three different morphologies to physiological and
molecular response of Arabidopsis suggested that deca-
hedral Ag-NPs showed the highest degree of root growth
promotion (RGP); however, spherical Ag-NPs had no
effect on RGP but triggered the highest levels of antho-
cyanin accumulation in Arabidopsis seedlings [92]. The
spherical and decahedral Ag-NPs resulted in the highest
and lowest yield of Cu/Zn superoxide dismutase, respec-
tively. Moreover, three different sizes and shapes of
Ag-NPs regulated protein accumulations, gene expres-
sion involved in cellular events, activated the aminocy-
clopropane-1-carboxylic acid (ACC)-derived inhibition of
root elongation in Arabidopsis seedlings, and reduced
the expression of ACC synthase 7 and ACC oxidase 2, sug-
gesting that Ag-NPs acted as inhibitors of ethylene per-
ception and could interfere with ethylene biosynthesis.
Similarly, Rezvani et  al. [93] also reported that Ag-NPs
induced root growth of Crocus sativus by blocking eth-
ylene signaling. Recently, Gruyer et al. [94] reported root
length increase in barley but was inhibited in lettuce.
Also, Yin et  al. [95] studied the effects of Ag-NPs on
germination of 11 wetland plant species (Lolium mul-
tiflorum, Panicum virgatum, Carex lurida, C.  scoparia,
C.  vulpinoidea, C. crinita, Eupatorium fistulosum, Phy-
tolaca americana, Scirpus cyperinus, Lobelia cardinalis,
and Juncus effusus) and found improved germination
rate only in one species (E. fistulosum). In another hydro-
ponic study, a significant improvement in germination
rate of Bacopa monnieri was recorded with the applica-
tion of biologically synthesized Ag-NPs [91]. Moreover,
the same treatments enhanced protein and carbohydrate
synthesis, while total phenol contents and catalase and
peroxidase activities were reduced. Similar results were
reported in Boswellia ovalifoliolata [96], Brassica juncea,
common bean, and corn [97, 98].
3.4 Gold (Au)-NPs
Similar is the case with Au-NPs that a few studies have
been conducted regarding their effect on plant productiv-
ity. Various researchers around the world reported posi-
tive effects of Au-NPs application on seed germination
of various crops like lettuce and cucumber [99], Brassica
juncea [100], Boswellia ovalifoliolata [96], and Gloriosa
superba [101]. Moreover, Au-NPs application improved
seed germination and antioxidant system in Arabidopsis
thaliana and altered levels of expression of miRNAs that
regulate various morphological, physiological, and meta-
bolic processes in plants [102]. On the other hand, Shah
and Belozerova [46] reported a toxic effect of Au-NPs on
16      A. Ditta and M. Arshad: Nanonutrition for sustainable crop production
the function of aquaporins, a group of proteins involved
in the transportation of a wide range of molecules includ-
ing water. So, a comprehensive study involving the growth
and physiological aspects of plants needs to be conducted
in the future to make the positive effects of Au-NPs on
plant more authentic.
3.5 Silicon dioxide (SiO2)-NPs
Plant growth and development starts from the germi-
nation of seeds followed by root elongation and shoot
emergence as the earliest signs of growth and develop-
ment. Although silicon is not an essential nutrient for
plant growth, it has played an important role in germi-
nation and growth through its effect on metabolism of
various nutrients like carbon, N, and P [13, 120–122]. The
reported data from various studies suggested that the
effect of ­SiO2-NPs on seed germination was concentra-
tion dependent. Their lower concentrations improved
the seed germination of tomato [103]. Similarly, SiO2-
NPs improved seed germination through better nutri-
ent availability to maize [104, 105]. Bao-shan et al. [106]
also reported improved seedling growth and quality
of Changbai larch (Larix olgensis) through exogenous
application of SiO2-NPs. Haghighi et al. [107] in tomato
and Siddiqui et al. [108] in squash reported that SiO2-NPs
enhanced seed germination and stimulated the anti-
oxidant system under NaCl stress. Exogenous applica-
tion of SiO2-NPs and nano-­titanium dioxide (nano-TiO2)
improved seed germination of soybean by increasing the
activity of nitrate reductase [62] and also by enhancing
seeds’ ability to absorb and utilize water and nutrients
[65]. Under salinity stress, SiO2-NPs improve leaf fresh
and dry weights, chlorophyll content, and proline accu-
mulation. An increase in the accumulation of proline,
free amino acids, content of nutrients, antioxidant
enzymes activity results due to the SiO2-NPs, thereby
improving the tolerance of plants to abiotic stress [107–
110]. Wang et al. [123] found silica coated with quantum
dots promoted markedly increased rice root growth.
SiO2-NPs enhance the plant growth and development by
increasing gas exchange and chlorophyll fluorescence
parameters [108, 111]. Similarly, Noji et al. [112] reported
that a nano-mesoporous silica compound (SBA) bound
with photosystem II (PSII) induced stable activity of a
photosynthetic oxygen-evolving reaction, indicating the
light-driven electron transport from water to quinone
molecules, and suggested that the PSII-SBA conjugate
might have properties to develop for photosensors and
artificial photosynthetic systems.
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4 C
 oncluding remarks and future
directions
The world population is expected to reach 9.6 billion or
more in 2050. To feed this ever-increasing population of
the world, more pressure will be on land, which is not
extendable. The conventional fertilizers might not be
helpful under this situation as these have become expen-
sive due to high energy requirements and being envi-
ronmentally unsafe. Recent advancement in the field of
nanotechnology has revolutionized the world with special
NPs and NMs that could serve not only a source of macro-
and micronutrients but also act as carriers for them, and
improve growth and productivity of crops. It is evident
from compiled information that the effect of NPs varies
from plant to plant and depends on their mode of appli-
cation, size, morphology, and concentrations. So, the
following are some future directions that may be kept in
mind while planning future research:
i. More and more efforts might be focused on N- and
P-NFs as these have the largest application rate and
also availability problem. The research might be
focused on the comparison of Ca-NPs from CaCO3 with
other Ca sources like CaCl2 or CaSO4 or multinutrient
comparison like that of Ca- and N-NPs using soluble
Ca(NO3)2 as control.
ii. In case of micronutrients, comprehensive research
might be conducted to elucidate the effect of factors
affecting their availability under field conditions.
Their role in biofortification in comparison to con-
ventional fertilizers may also be tested. Application
strategies through fertigation may also be tested in
comparison to commercially available micronutri-
ent fertilizers. Nanotoxicity is the main problem with
these types of fertilizers, so optimum dose calculation
for each and every crop without any toxic effects may
also be investigated.
iii. In the case of nanocarrier-based fertilizers, there is
still no solid report about their role in increasing the
FUE through improvement in transportation of nutri-
ents into the plant tissues/cells or reducing environ-
mental risks associated with traditional fertilizer use.
There is a possibility to find certain NMs like SiO2-NPs,
Fe2O3-NPs, and CNTs, which are economical and more
efficient compared to previously available carriers like
zeolite. These advances would help in the slow uptake
of active ingredients, thereby reducing the amount of
inputs to be used and also the waste produced. Nano-
carriers could be designed in such a way that these
can anchor the plant roots or to the surrounding soil
 A. Ditta and M. Arshad: Nanonutrition for sustainable crop production      17
structure and organic matter. This can only be pos-
sible through the understanding of molecular and
conformational mechanisms between the delivery
nanoscale structure and targeted structures and mat-
ters in soil [124].
iv. It has been clearly found out that higher concentra-
tions of various NPs/NMs are toxic for plant growth,
which is ultimately dependent on their particle size.
So, a checkpoint might be worked out in future stud-
ies to elucidate the critical concentration of certain
NPs/NMs with a particular size and possible combi-
nations might be searched out.
v. More studies are required to elucidate the responsible
mechanisms behind the improved growth and pro-
ductivity of crop plants caused by the application of
TiO2-NPs, Ag-NPs, SiO2-NPs, or CNTs.
vi. In the future, there is vast scope for greener nanon-
utrition of crop plants keeping in view the nano-
toxicological effects of NMs/NPs reported. So, for
environmental sustainability, green NMs/NPs could
also be utilized as a source of nutrients for the crops
and could play a key role in greener nanonutrition.
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 A. Ditta and M. Arshad: Nanonutrition for sustainable crop production      21

Bionotes Muhammad Arshad

Institute of Soil and Environmental Sciences,
University of Agriculture Faisalabad,
Allah Ditta Faisalabad 38040, Pakistan
Department of Environmental Sciences,
PMAS, Arid Agriculture University
Rawalpindi, Rawalpindi 46300, Pakistan,
ad_abs@yahoo.com

Muhammad Arshad (TI and DNP) is currently a Tenured Professor in

Allah Ditta is currently an Assistant Professor at the Department
of Environmental Sciences, PMAs, Arid Agriculture University,
­Rawalpindi, Pakistan. He received his BSc (Hons) Agriculture in
2007, MSc (Hons) Agriculture Soil Science in 2009, and PhD Soil
Science (Environmental Microbiology) in 2014 from University of
Agriculture, Faisalabad, Pakistan. During his PhD, he went for IRSIP
fellowship at University of Western Australia, Australia. His research
focuses on nanonutrition for sustainable crop production and
carbon sequestration through algal biochar.
the Institute of Soil and Environmental Sciences and Dean, Faculty
of Agriculture at University of Agriculture, Faisalabad. He received
his PhD in Soil Microbiology from University of California, River-
side, USA. He has received a number of national and international
awards. His work focuses on the development of organic fertilizers,
pesticide biodegradation, novel biofertilizers, and industrial waste-
water treatment technology and renewable energy system (biofuels)
and published over 180 peer-reviewed papers.

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 Nanotechnol Rev   2016 | Volume x | Issue x

Graphical abstract

Allah Ditta and Muhammad Arshad Review: Certain robust

Applications and perspectives of ­nanomaterials/nanoparticles are
Research gaps
Improved physiological
parameters

using nanomaterials for being used as a source or carrier of

Optimum dose of each nutrient ......?

Improved growth and

sustainable plant nutrition macro- and micronutrients, having

Toxic level of each nutrient .....?
yield parameters
Economical nano-carriers ......?

a potential role in the promotion of Mechanisms behind growth promotion ......?

DOI 10.1515/ntrev-2015-0060 the germination and various growth,

Nanotechnol Rev 2016; x(x): xxx–xxx yield, and physiological param-

surf ke due
area
ace
eters of different crops depending

ta
to la ved up
on their application rate, size, and

rge
Improved germination

ro
Imp
experimental conditions. Small size with large
surface area

Keywords: nanofertilizers;
­nanonutrition; ­nanotechnology; Macronutrient NFs Micronutrient NFs

plant nutrition; sustainable

Nano-carrier based Plant-growth enhancing NPs
fertilizers with unclear mechanisms

­agriculture.
Nanomaterials/nanoparticles used as Nanofertilizers (NFs)

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