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Nanosized Products for Agriculture

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DOI: 10.13140/RG.2.2.15337.36963

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Nanosized Products for
Agriculture

Reported By Group 2: Course:


Sajad Mohammadi Nanobiotechnology
Mahsa Hakimpour Abyaneh Instructor:
Yue Cao Professor. Marco Bravi

Faculty of Civil and Industrial Engineering


Nanosized Products for Agriculture

Table of Contents
Abstract.......................................................................................................................... 3
1. Introduction ........................................................................................................... 4
1.1 Food Consumption Projection .......................................................................... 4
1.2 Challenges Ahead ............................................................................................. 4
1.3 Nanotechnological Solutions ............................................................................ 5
1.4 Aim and Objective ............................................................................................ 6
2. Plant Diseases ........................................................................................................ 7
2.1 Definition, Control Approaches........................................................................ 7
2.2 Main Symptom Types....................................................................................... 7
3. Fertilizers ............................................................................................................... 9
3.1 Definition and Function .................................................................................... 9
3.2 Soil Fertilization ............................................................................................... 9
3.3 Organic Fertilizers .......................................................................................... 10
3.4 Chemical Fertilizer’s Hazards ........................................................................ 11
3.5 Biofertilizers ................................................................................................... 11
4. Nanofertilizers ..................................................................................................... 12
4.1 Definition, Properties, Applications and Examples ....................................... 12
4.2 Synthesis of Nanofertilizers ............................................................................ 14
4.2.1 Chemical Synthesis ............................................................................... 15
4.2.2 Physical Synthesis ................................................................................. 15
4.2.3 Biological Synthesis .............................................................................. 16
4.3 Formulation and Smart Delivery System ....................................................... 18
4.4 How to Apply Nanofertilizers ........................................................................ 19
4.4.1 Foliar Mode ........................................................................................... 19
4.4.2 Soil Mode .............................................................................................. 20
4.5 Uptake, Translocation, and Fate of Nano-fertilizers ...................................... 20
4.6 Risk and Safety in Using Nanofertilizers ....................................................... 22
5. Nanopesticides..................................................................................................... 23
5.1 Definition and Background............................................................................. 23

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5.2 Nano-enabled Materials and Characteristics .................................................. 23


5.3 Green Synthesis .............................................................................................. 24
5.3.1 Microbe-Based Synthesis ...................................................................... 24
5.3.2 Nanoparticles from Plant Extracts ........................................................ 25
5.4 Risk assessment of Nanopesticides ................................................................ 26
6. Conclusion ........................................................................................................... 26
References ................................................................................................................... 28

Table of Figures
Figure 1. Per capita food consumption kg/person/year (a), kcal/person/year (b)[1] .... 4
Figure 2.schematic of different types of nanoparticles[12] .......................................... 6
Figure 3.Application of nanotechnology in agriculture[4] ........................................... 6
Figure 4.Plant diseases description, examples, and symptoms ..................................... 7
Figure 5.Types of organic fertilizers [11] ................................................................... 11
Figure 6.. Nanofertiliers application area [35] ............................................................ 13
Figure 7.Schematic representation of (a) Top-down and (b) Bottom-up method [56]17
Figure 8.The entry and absorption of nanofertilizers in nanoparticle and nanotube
phases by plant cell via various channels [73] ............................................................ 21
Figure 9.The mechanism of chitosan nanofertilizer provided to Maize plant through
slow release [57] .......................................................................................................... 21
Figure 10.. Toxicity issues of nanoparticles in plants, soil microflora and human
being[71]...................................................................................................................... 22
Figure 11. How pesticides affect human's life [81]..................................................... 23
Figure 12. Biological synthesis process of nanoparticles[83]..................................... 25
Figure 13. Nanoparticles action mechanism ............................................................... 26

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Abstract

The demand for quality food is expected to increase with the rising population across
the globe and it forces the agricultural sector to increase crop productivity to satisfy
the needs of billions of people especially in developing countries. Additionally, plant
diseases significantly impact the global economy, and plant pathogenic
microorganisms such as nematodes, viruses, bacteria, fungi, and viroid’s may be the
etiology for most infectious diseases. In agriculture, the development of disease-free
plants is an important strategy for the determination of the survival and productivity
of plants in the field. Nanotechnology can help to improve agricultural production by
increasing the efficiency of inputs and minimizing relevant losses. Nanomaterials
offer a wider specific surface area to fertilizers and pesticides. In addition,
nanomaterials as unique carriers of agrochemicals facilitate the site-targeted
controlled delivery of nutrients with increased crop protection. Nanotools, contribute
to the advancement of high-tech agricultural farms since they may be employed for
precise input management and control (fertilizers, pesticides, herbicides).
Nanoparticles can be produced by chemical and physical methods however, many
metallic nanoparticles have been successfully synthesized by using different plant
extracts and microbes including bacteria, fungi viruses and microalgae. Some of these
metallic nanoparticles showed strong antimicrobial activities against phytopathogens.
Here, we summarized the applications of nanotechnology to enhance plant’s growth
and in plant protection and the different approaches to synthesis desired nanoparticles
and their utilization in the control of plant pathogens, such as bacteria and fungi.
Keywords: Agriculture, Nanotechnology, Nanomaterials, Plant-Disease, Microorganisms

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1. Introduction
1.1 Food Consumption Projection
The perceived limits to producing food for a growing global population have been a
source of debate and preoccupations for ages. world food production grew faster than
population and per capita consumption increased. Population increased to 6.9 billion
in 2010, up from 2.5 billion in 1950 and 3.7 billion in 1970. The UN population
projections indicate that the world total could reach 9.15 billion in 2050. World
average per capita availability of food for direct human consumption, after allowing
for waste, animal-feed and non-food uses, improved to 2,770 kcal/person/day in
2005/2007. Figure 1. Thus, in principle, there is sufficient global aggregate food
consumption for nearly everyone to be well-fed. Yet this has not happened: some 2.3
billion people live in countries with under 2,500 kcal, and some 0.5 billion in
countries with less than 2,000 kcal, while at the other extreme some 1.9 billion are in
countries consuming more than 3,000 kcal. The reasons are fairly well known mainly
poverty, which has many facets, but is in many low-income countries linked to
failures to develop agriculture and limited access to food produced in other countries
[1].

Figure 1. Per capita food consumption kg/person/year (a), kcal/person/year (b)[1]

1.2 Challenges Ahead

Due to the growing world population and increasingly varying climate change,
leading to lower yields and increasing harvest losses, feeding global population has
become an international major issue. Farmlands are losing their fertility due to human
activities on them and societal change in lifestyle. This invariably affects the
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production of crops and Nutrient deficiency in food crops is seriously affecting


human health, especially those in the rural areas which could lead to famine and
hunger [2]. The food resources from the field to fork need to be used wisely, with
minimum waste and maximum nutritional efficiency. Accordingly, it has been
anticipated that current crop production needs to be increased by up to 70% to satisfy
future food demands [3]. This great challenge will require combined efforts to
preserve natural resources to support intensive agriculture while limiting detrimental
impact on the environment. To address the increasing challenges of sustainable
production and food security significant technological advancements and innovations
have been made in recent years in the field of agriculture[4]–[6].

1.3 Nanotechnological Solutions

Engineered nanoparticles are materials between 1 and 100 nm and exist as metalloids,
metallic oxides, nonmetals, and carbon nanomaterials and as functionalized
dendrimers, liposomes, and quantum dots. Their small size, large surface area, and
high reactivity have enabled their use as bactericides, fungicides and nanofertilizers.
Furthermore, antimicrobial nanomaterials as nanofilm on harvested products and/or
on packaging materials are suitable for the storage and transportation of vegetables
and fruits. They can be reactive and bind, absorb, and carry compounds such as
small-molecule drugs, DNA, RNA, and proteins with high efficiency[7]. The
application of nanotechnology in the agricultural and food industries was first
reported by the US Department of Agriculture (USDA) roadmap published in
September 2003. The prediction is that nanotechnology will transform the entire food
industry, changing the way food is produced, processed, packaged, transported, and
consumed [8]. It is envisaged that the convergence between nanotechnology, plant
science and agriculture will lead to revolutionary developments and advances in the
next decades to improve food security and sustainability through, for examples, the
re-engineering of crops at cellular level, the precision agriculture leading to water and
nutrient control for more sustainable farming, the identification systems for tracking
plants from origin to consumption or through the precise and the controlled release of
fertilizers and pesticides, etc. In the domain of food technology, nano-biosensors will
contribute to the identification of harmful molecules such as toxins or pesticides and
to quick identification of spoilage processes in food. The development of
nanoscience-based food with improved nutritional and palatable benefits will allow to
increase food nutritional efficiency and the addition of nanoscale materials for food
packaging will extend shelf life and retain quality, both contributing to waste
reduction. Generally, the application of nanotechnology in the agricultural and food
sectors has opened new avenue to understand how physicochemical characteristics of

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nanosized substances can modify the structure, texture, and quality of food stuffs and
agricultural products [9]–[11]. As for all new technologies, their application offers
great potential but raise ethical questions, and when food is concerned, issues on food
safety, risk and benefits, and consumer mistrust become the key ones. Wide spectral
of nanoparticles and nanotechnology applications are illustrated in Figure 2 and Figure 3.

Figure 2.schematic of different types of nanoparticles[12]

Figure 3.Application of nanotechnology in agriculture[4]

1.4 Aim and Objective


Through this report, an attempt has been made to introduce plant disease and factors
which decrease efficiency of agriculture and nanotechnology potential to improve
cultivation and plant protection to fight against pathogens. Furthermore, different

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ways of nanomaterials synthesis and nano-fertilizers, nanopesticides, and their risk


assessment will be discussed.

2. Plant Diseases
2.1 Definition, Control Approaches
Plant diseases caused by infectious pathogens have seriously affected human society
and nature through their damages to food production, economic development,
ecological resilience, and natural landscapes over human history. Plant diseases result
from complex interactions among plants, pathogens, and the environment. In the long
history of agriculture, humans have developed a variety of approaches to manipulate
the interaction to create a system in favor of the growth and development of host
plants but suboptimum to the establishment, reproduction, and transmission of
pathogens. Depending on circumstances of crop, pathogen, geographic location,
technology availability, regulation policy, and other factors, these control approaches
can be agronomic (e.g., crop diversification and field hygiene), regulative (e.g.,
quarantine and eradication), genetic (e.g., disease resistance and tolerance), physical
(e.g., soil solarization and flooding), and chemical (e.g., pesticides and host-immunity
inducer) and can be used individually or in combination (integrated disease
management, IDM) to suppress causal pathogen, promote host immunity, or change
the biotic and abiotic environment where host–pathogen interaction occurs [13]. Plant
disease and examples are shown in Figure 4.

Figure 4.Plant diseases description, examples, and symptoms

2.2 Main Symptom Types

There are three main symptom types that are characteristic of plant disease:

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a. Necrosis or death of infected tissue - e.g., leaf spot of Banana caused by


Mycosphaerella musicola.
b. Hyperplasia and hypertophy increase in cell number and size respectively,
resulting in galls, tumors or witches' broom, e.g., witches' broom disease of cocoa
caused by Crinipellis pernicious.
c. Hypoplasia and hypotrophy reduced growth and stunting characteristic of plants
attacked by plant parasitic nematodes.
The major agents producing these symptom types are either fungi, bacteria, viruses,
mycoplasma, nematodes, insects or so-called physiological disorders or non-parasitic
disease agents. The latter include adverse climatic conditions, lack of a particular
nutrient, phytotoxic atmospheric pollutants, e.g. Sulphur dioxide, fluorine, ozone, etc.
[14]. Below tables indicate 14 common diseases in plants and the way they are
shown. Table 1, Table 2

Table 1.7 common plant disease and their symptoms

Disease Reason Appearance What to do Example

Warm, wet Small dark raised Destroy infected plants and


Bacterial Spot
environments spots apply fungicide

Remove infected plants and


Large yellow spots
Bacterial Blight Cool, wet weather ensure proper spacing
on leaves turn brown
between new plants

Wilted leaves on
plants during Discard infected plant and
Contaminated soil or
Bacterial Wilt daytime, turning replant new in pathogen-free
weeds
yellow and remaining potting soil
wilted
Stunted foliage and
Domp soil with
Thielaviopsis root systems with Use a fungicide
temperature 55-65F
blackened area

Warm environment, Small green or


Wipe with soapy water or
Aphids high nitrogen in early yellow bugs on
rubbing alcohol
growth stage leaves and stem
Cucumber mosaic Yellow spotting or Discard virus infected plant
Aphids
virus streaking on leaves and maintain aphid control

Dark & light brown Remove & dispose infected


Dying or wounded
Botrytis rot forming around
parts part and apply fungicide
wounded plant tissue

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Table 2.7 common plant disease and their symptoms

Disease Reason Appearance What to do Example

Humidity and Varies, typically dark Remove infected plants and pot
cylindrocladium
overhead irrigation brown spotted leaves in sterile soil mixture

Remove infected plants, keep


White mildew
Downey Mildew Prolonged wetness spacing between plants,
underside of leaves
maintain proper air circulation

Plant resistance varieties, grow


Angular leaf spot Seed and plant debris Holes in leaves
in arid climate

Stem rot at soil line


Warm, overly moist remove infected plants and
Rhizoctonia with brown to red
soil apply fungicide
lesions
Isolate the plant and prune
Fine webbing on damaged leaves, clean infected
Spider mites Warm, heated homes
underside of leaves plant with soapy water and
insecticide

Leaf tips turn yellow remove infected plants and


Anthracnose Seed and plant debris
and brown avoid overwatering

Small white insects


Overwatering and Remove manually with rubbing
mealybugs with a white fluffy
high nitrogen soil alcohol or insecticide
coating

a)
3. Fertilizers
c)
3.1 Definition and Function
Fertilizers are compounds given to plants to promote growth. They are usually
applied either via the soil, for uptake by plant roots, or by foliar feeding, for uptake
through leaves. Fertilizers can be organic (composed of organic matter), or inorganic
(made of simple, inorganic chemicals or minerals). They can be naturally occurring
compounds such as peat or mineral deposits or manufactured through natural
processes such as composting or chemical processes such as the Haber process.
Fertilizers typically provide the three major plant nutrients (nitrogen, phosphorus,
and potassium), the secondary plant nutrients (calcium, sulfur, magnesium), and
sometimes trace elements with a role in plant nutrition, boron, chlorine, manganese,
iron, zinc, copper and molybdenum [6].
3.2 Soil Fertilization
Soil Fertilization or Crop Fertilization are methods of improving soil quality with a
view towards improving soil fertility. Fertilization improves crop yield and provides
additional income and profit for farmers. Plants need various elements in order to

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grow and people have known for hundreds of years of the need to improve the quality
of the soil [15]. Nitrogen is the element in the soil that is most often lacking.
Phosphorous and potassium are also needed in substantial amounts. For this reason,
these three elements are included in commercial fertilizers and the content of each of
these items is included on the bags of fertilizer. For example, a 10-10-15 fertilizer has
10 percent nitrogen, 10 percent phosphorous and 15 percent potassium [9]. Increasing
the fertility can be achieved by either using organic fertilizer such as cattle manure,
poultry manure, animal waste and use of compost or by using chemical fertilizers
mainly Potassium and Nitrogen compounds [16]. Some examples of chemical
fertilizers are provided in Table 3.

Table 3.Various types of chemical fertilizers

Type of chemical
Raw material Example Ref
fertilizer
Nitric Acid, Ammonium
Natural gas and
Nitrogen Nitrate, Synthetic, Ammonia [17]
nitric acid
Urea, Sodium nitrate
Ammonium phosphates
Calcium metaphosphates
De-fluorinated, phosphates
Phosphate Phosphate rock [18][19]
Diammonium, phosphates
Phosphoric acid,
Superphosphates
Kainite, Sulfate potash
Potassium potash Magnesia, Potassium chloride [20]
Potassium carbonate
Calcitic lime
calcium Lime Dolomitic lime [21]
Gypsum, Basic slag
Magnesium
Magnesite (40% Sulfate, Sulfate of potash
Magnesium [22]
MgO) Magnesium
Magnesium, oxide
Petroleum
Ammonium sulfate
refining,
Potassium, Sulfate, Gypsum,
sulfur natural gas [23]
Magnesium, sulfate Zinc sulfate,
processing,
Prilled sulfur
coking plants

3.3 Organic Fertilizers


Organic fertilizers are naturally available mineral sources that contain moderate
amount of plant essential nutrients. Figure 5. They are capable of mitigating problems
associated with synthetic fertilizers. They reduce the necessity of repeated application
of synthetic fertilizers to maintain soil fertility. They gradually release nutrients into
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the soil solution and maintain nutrient balance for healthy growth of crop plants.
They also act as an effective energy source of soil microbes which in turn improve
soil structure and crop growth. Organic fertilizers are generally thought to be slow
releasing fertilizers and they contain many trace elements. They are safer alternatives
to chemical fertilizers. However, the improper use of organic fertilizers leads to
overfertilization or nutrient deficiency in the soil. Hence, controlled release of
organic fertilizers is an effective and advanced way to overcome these impacts and
maintain sustainable agriculture yield [10].

Figure 5.Types of organic fertilizers [11]

3.4 Chemical Fertilizer’s Hazards


Over-use of chemical fertilizer can be harmful to environment by polluting water and
increasing the volumes of farm crops proved to be hazardous to human health. In
organic farming, the soil becomes rich in nutrients, therefore, crops grow healthy and
can be resistant to pests and diseases, making the quality of the products more
nutritious, tastier and contain substances that are good for health [24].
3.5 Biofertilizers
Biofertilizers are eco-friendly inputs that increase soil fertility by forming new plant-
microbe interactions. They are usually the formulations of living or latent cells of
required strains of potential microorganisms (requirement of microbial strain depends
upon the plant and soil need) which on application to seeds, root, or soil helps in the
uptake of nutrients by crop plants. These microbes either colonize the rhizosphere
(e.g., Clostridium pasteurianum, Azotobacter, Azospirillum, Rhodobacter, etc.) or
within the plant (e.g., Rhizobium, Anabaena, Vesicular arbuscular mycorrhiza , etc.)
and assure the availability of important nutrients to plants into available forms [25].
Till date, many plant-microbe interactions/associations discovered have been used in
the production of biofertilizers. Based on their process of bio-fertilization, they are
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classified under various classes. They provide benefits including better nutritional
value, pathogen defense, heavy metal tolerance, salt tolerance, and drought tolerance
[26]. Biofertilizers became a highly compelling alternative when compared with
chemical fertilizers as they can be easily applicable, non-toxic, environment-friendly
and have cost effective in nature. However, there manufacturing process, storage,
strain specificity, inoculums potential, etc. are snags in their smooth production. The
hurdles which come into existence are mainly related to manufacturing on an
industrial basis that needs proper protocol and quality checks at each step which adds
to the labor cost. Regarding to reduce the production rate, several steps should be
involved to bring down their cost so that they can be feasible for farmers to buy.
Several cyanobacterial biofertilizers in open-air production are season dependent
(March to June) and have slow production rate. Not even this, contamination with
other strains is always a problem for specific strain biofertilizer production. Their
storage also demands intensive care as the shelf life of each biofertilizer must be used
before its expiry date for good production rate [27]. To overcome these hurdles,
researchers today are approaching towards nanobiotechnology-based biofertilizers, a
new and advanced addition in the series of nature compatible fertilizers.

4. Nanofertilizers
4.1 Definition, Properties, Applications and Examples
Nanofertilizers are defined as materials in the nanometer scale, containing macro and
micronutrients. The nanofertilizer (NFs) industry is newer as compared to the use of
organic fertilizers which is known to the human beings for more than 1000 years and
phosphate and nitrogen fertilizers for 100 years [28]. After all various fertilizers
focused on plant nutrition, the NFs found and studied as a way to boost nutrient
dosage and plant nutrition along with healthy food, as compared with traditional
fertilizers. NFs have gained the attention of agricultural engineers, environmentalists,
and soil scientists due to increase crop yields, positivity to soil fertility, trimming
down pollution, and mark a burgeon Eco to flourish microorganisms[29]. With
nanofertilizer, there is slow release of the nutrients, which minimizes leaching of the
nutrients among other interesting properties. Nanomaterials are of unique properties
resulting from their low particle size, large surface to volume ratio and excellent
optical properties[30].The incorporation of nano scale objects as pesticides, fertilizers
and sensors in agriculture sector was reviewed by Konappa et al[31]. Application of
nanofertilizers can decrease the nitrogen loss because of the leaching, emissions, and
long-term incorporation by soil microorganisms. Controlled or the slow release of the
fertilizers may also improve soil by reducing the toxicity of fertilizers usage [32].
Figure 6 depicts the application area of nanofertilizers. Scientist found the favorable
effects of nanochitosan-based nitrogen (N), phosphorous (P), and potassium (K)
(NPK) fertilizer on the chemical composition of wheat and showed a significant

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increase in total sugar content, fully grown on varied varieties of soils like clay, clay-
sandy, and sandy soils [33]. In another study, when peanuts were treated by ZnONPs
(25 nm), both seed germination and it’s seedling vigor were promoted, resulted in
early flowering and an elevated content of leaf chlorophyll signifying that these
particles showed effective increment in stem and root growth, while the pod yield per
plant was estimated to be 34% higher when compared with chelated bulk ZnSO4 [34].
Blow, application of nanofertilizers and Some examples of nanofertilizers which are
approved to use in the agriculture are mentioned Table 4.

Figure 6.. Nanofertiliers application area [35]

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Table 4.Some approved nanofertilizers used in the world today and their compositions[36]

Nanofertilizers Constituents Name of Manufacturer


organic matter, 5.5%;
Nano Ultra-Fertilizer Nitrogen, 10%; P2O5, 9%; SMTET Eco-technologies
(500) g K2O, 14%; P2O5, 8%; K2O, Co., Ltd., Taiwan
14%; MgO, 3%
CaCO3, 77.9%; MgCO3,
7.4%; SiO2, 7.47%; K, 0.2%;
Na, 0.03%; P., 0.02%; Fe-7.4
Nano Calcium AC International Network
ppm; Al2O3, 6.3 ppm; Sr,
(Magic Green) (1) kg Co., Ltd., Germany
804 ppm; sulfate, 278 ppm;
Ba, 174 ppm; Mn,
172 ppm; Zn, 10 ppm
N, 0.5%; P2O5, 0.7%; K2O,
3.9%; Ca, 2.0%; Mg, 0.2%;
The Best International
Nano Capsule S, 0.8%; Fe, 2.0%; Mn,
Network Co., Ltd., Thailand
0.004%; Cu, 0.007%; Zn,
0.004%
Zn, 6%; B, 2%; Cu, 1%; Fe,
Nano Micro Nutrient Shan Maw Myae Trading
6%+; EDTA Mo, 0.05%;
(EcoStar) (500) g Co., Ltd., India
Mn, 5%+; AMINOS, 5%
M protein, 19.6%; Na2O,
WAI International
0.3%; K2O, 2.1%;
PPC Nano (120) mL Development Co., Ltd.,
(NH4)2SO4, 1.7%; diluent,
Malaysia
76%
Multiple organic acids
chelated with major nutrients,
Nano Max NPK amino acids, organic carbon, JU Agri Sciences Pvt. Ltd.,
Fertilizer organic micro Janakpuri, New Delhi, India
nutrients/trace elements,
vitamins, and probiotic
Proteino-lacto-gluconate
TAG NANO (NPK,
chelated with micronutrients, Tropical Agrosystem India
PhoS, Zinc, Cal, etc.)
vitamins, probiotics, seaweed (P) Ltd., India
fertilizers
extracts, and humic acid
Extracts of corn, grain,
Nano Green Sciences, Inc.,
Nano Green soybeans, potatoes, coconut,
India
and palm
Combination of organic
Biozar Fanavar Nano-Pazhoohesh
materials, micronutrients,
Nano-Fertilizer Markazi Company, Iran
and macromolecules

4.2 Synthesis of Nanofertilizers


The approach of nanoscale fertilizers involves the use of nanoparticles that contain
nutrients. The nanomaterial may be produced by using both physical (top-down) and
chemical (bottom-up) approaches. Figure 7. These nanoparticles are directly used to
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improve plant growth and productivity. The top-down approach involves the use of
physical or chemical processing to convert bulk for of material into nano scale. This
could be achieved by grinding, etching, and milling. Bottom-up nanotechnology
involves the self-assembly and self-organization of smaller building blocks of
material to create functional nanoscale materials. The nanoscale fertilizer thus
achieved gives high production, nutritious food, save natural resource, enhance soil
biological health, more microbial diversity, enhance native nutrient mobilization and
reduce the demand of fertilizers [37]. The top-down and bottom-up synthesis
approach could further be described in to three categories as chemical, physical and
biological synthesis methods. The Bottom-up approach mostly involves the chemical
synthesis of nanoparticles while Top-down approach involves the physical synthesis
and biological synthesis (biosynthesis). There are numerous reports on nanomaterial
being synthesized and used as nanofertilizers[38]–[40]. Ahmed Shebl et al.
synthesized Manganese, Zinc, and Iron nanofertilizers with the particle size 20 to 60
nm via green microwave assisted hydrothermal method using nitrate precursors [41].
The identical synthesis route was practiced in producing manganese – zinc ferrite
nanofertilizers for the squash plant growth were also reported by the same group [42].
The various pros and cons of planetary ball mill techniques in view of commercially
viable and optimal reaction time for the synthesis of nanofertilizers were discussed by
Pohshna et al [43]. The next step in synthesis of nanofertilizers is to consider the
novel dosage mechanisms such as slow release and controlled release. The ionotropic
gelation method for Silicon encapsulating Chitosan nanofertilizers supplemented to
Maize plant resulted in better seedling vigor index and overall well-being of crops
[44].
4.2.1 Chemical Synthesis
The most common approaches used for synthesis of nanoparticles, which further
could be used as nanofertilizers are chemical reduction by organic and inorganic
reducing agents. The chemical synthesis approaches like chemical vapor deposition
(CVD), chemical precipitation, sol–gel technique is used to produce different metal
oxides, borides, sulphides and various other nanoparticles [45]. Chemical synthesis
approaches are molecular or atomic scale procedures and are called as bottom-up
approach as the synthesis begins at atomic scale to build up nanoparticles by using
chemical reaction. The atoms are scaled up to nanoparticles by different chemical
reactions. These methods provide better control over particle size, reduce impurities,
involve low temperature process and makes controlled synthesis possible [46].
4.2.2 Physical Synthesis
There are various physical synthesis techniques such as gas condensation method
planetary ball mill, vibrating ball mill low energy tumbling mill, high energy ball mill
explored by researchers for the synthesis of nanomaterial. The physical synthesis

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process mainly suffers from the drawbacks like source-precursor incompatibility,


lower control in the size distribution, the greater quantity of impurities, introduced
stresses, defects and imperfections and cost involved in the equipments. Physical
synthesis methods are generally used as the basic method in the production of
nanofertilizers because of ease in synthesis, lesser time consumed in synthesis of the
nanoparticles and possible large-scale production. The nanoparticle oxides of cobalt,
aluminum, titanium, chromium synthesized by the physical synthesis methods are
used as nanofertilizers[47]–[49].
4.2.3 Biological Synthesis

The current focus of nano-biotechnology is on environmentally benign biosynthesis


processes wherein microorganisms such as bacteria and fungi are employed as
promising bio-manufacturing units to carry out nano-synthesis. The biosynthesis
synthesis of NPs mainly involves different plant extracts or microorganisms. It is also
reported that the plant waste could be the best material as reducing agent for the
synthesis. The applications of biosynthesized nanoparticles extend beyond
nanofertilizers and finds suitability in antimicrobial coatings, medical imaging and
drug delivery to catalytic water treatment and environmental sensors. These
biosynthesis routes involving green chemistry reduce pollution risk at source level
where the reagents are eco-friendly. Nanoparticles or nanomaterials synthesized from
plants produced or extracted from readily available plant material and from nontoxic
nature of the plant. Various plant parts including leaves, roots, stems, fruits, and their
extracts are used in the synthesis of nanoparticles or nanomaterials to produce
nanofertilizers. This biological synthesis method is highly advantageous than
physical and chemical synthesis also cost effective and environmentally friendly
process of synthesis. Also have easy availability of plants extracts and
microorganisms can give bulk or large-scale production of nanoparticles with help of
effective enzymes and various microbial activities. Also, the synthesized
nanoparticles are nontoxic and can also be nutrients based. The biosynthesis modifies
inorganic crystals with the nano-fractional, phase, orientation, and topography in
biological systems. Such biosynthesis processes are the biomimetic routes that have
many advantages in comparison with other chemical and physical methods. There are
reports on the biosynthesis of silver, gold, titanium, lead, copper, cadmium sulfide,
zinc, and iron synthesized from plants [50]–[55]. compares the different approaches
to synthesis fertlizers and provides information on the benefits and drawbacks of each
one. Table 5 Table 6.

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Figure 7.Schematic representation of (a) Top-down and (b) Bottom-up method [56]

Table 5.The advantages and disadvantages of various synthesis methods of nanofertilizers [57]

Type Method Advantage Disadvantage


Wide particle size
Gas phase
distribution
condensation/deposition Ease in conduct
curve, source-precursor
incompatibility
Physical Controlling size, shape
Mass production with of the
High energy ball milling high product. Impurities,
yield stresses, and
defects in the product
Cost of precursor, weak
Aspect ratio, precisely bonding,
Sol–gel method controlled in size, and distillation/purification
internal structure of the
product is required
the synthesis of high
untainted,
Chemical Chemical coprecipitation Simple and effective precise stoichiometric
phase is
difficult
Reaction condition
Control over particle
requirements
size
Hydrothermal are high pressure and
and shapes are easily
reaction
controllable
temperature
Higher reproducibility,
scalability, and lesser
Microbial incubation Reaction time and labor
cost
Biological
involved
Ease in infusion and
Plant based biosynthesis Poor and uneven quality
biocompatible

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Table 6.Comparison between Biofertilizers, Chemical Fertilizers and Nanofertilizers [58]–[62]

Parameter Chemical Fertilizer Biofertilizer Nanofertilizer


The deposition of bio-
fertilizers is
biocompatible.
Drifting, leaching, surface Low loss of fertilizers and
Unused component The challenges with
runoff causes higher losses nutrients due to lesser
losses organic matter
due to lesser bioavailability bioavailability.
imbalance and heavy
metal deposition need to
be addressed.
Individual fertilizer dosage
Specific and combined
Less control over dosage is possible. The rate of
Optimized fertilizer dosage is possible.
optimization or release and dosage pattern
dosage/Controlled Not practiced properly and
controlled could be effectively
release excess causes toxicity,
release. controlled through
deposition, and imbalance.
Encapsulation mechanisms.
Solubility and Almost all the nutrients
Fine particle nature leads to
supplement Coarse grains leads to lower are
higher solubility and
micronutrients solubility. provided via bio-
dispersion.
dispersion fertilizers.
The available quantity at the
Pattern of release site and at the time of The uptake occurs at
and uptake application is either slower rates with lesser Effective and extended
(Nutrient uptake consumed or mostly nutrient density duration
efficacy) converted into insoluble availability.
deposits.
Highest environmental
Relatively lower
concerns in terms of soil
Safe and do not give rise environmental concerns in
Environmental adsorption, fixation, water
to any environmental terms of soil adsorption,
concerns reservoir contamination
concerns. fixation, and water
along with weed and disease
reservoir contamination.
resistance.
Definite shelf life and Relatively higher shelf
Shelf life and High shelf lives and ease at
careful storage is lives and careful storage is
storage storage.
required. required.
4.3 Formulation and Smart Delivery System
The formulation of any nano-fertilizer should be in such a way that they possess all
desired properties such as high solubility, stability, effectiveness, time-controlled
release, enhanced targeted activity with effective concentration, and less eco-toxicity
with safe, easy mode of delivery and disposal. Nanoparticles have great potential to
deliver nutrients to specific target sites in living systems. The loading of nutrients on
the nanoparticles is usually done by (a) absorption on nanoparticles, (b) attachment
on nanoparticles mediated by ligands, (c) encapsulation in nanoparticulate polymeric
shell, (d) entrapment of polymeric nanoparticles, and (e) synthesis of nanoparticles
composed of the nutrient itself [63]. Mesoporous silica nanoparticles (150 nm) have
been reported to entrap urea. It has been observed that 15.5 % of urea was loaded
inside the nanoparticles pores and demonstrated a controlled urea release profile in
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soil and water. The study revealed at least fivefold improvement in release
period[64]. Zinc solubility and dissolution kinetics of ZnO nanoparticles and bulk
ZnO particles coated on macronutrient fertilizers (urea and monoammonium
phosphate) have been compared. It has been reported that coated monoammonium
phosphate granules show faster dissolution rate[65]. Multi-walled carbon nanotubes
(MWCNTs) have been reported to have the ability to increase the seed germination
and growth of tomato and to enhance the growth in tobacco cells [66]. The mode of
fertilizer application influences their efficiency and impact on plant systems. The
following methods can be used for nano-fertilizer delivery to plants.

4.4 How to Apply Nanofertilizers


nanoparticle (NP) in the form of new formulations of fertilizers is done by
nanoencapsulation which assists in the slow chemical release under controlled
situations. They usually reduce the required application dosage and improve fertilizer
efficiency. However, detailed efforts are still needed to reveal the interaction between
plants, microbes, and soil and nanofertilizers. Thus, the nanofertilizers should be
applied in a way that they do not lose their vital properties like stability, solubility,
efficiency, time-controlled release, improved targeted activity, and most important
less toxicity due to their safe, simple mode of deliverance and disposal, though their
impact and effectiveness is mainly influenced by their mode of application. The
delivery of these nanofertilizers to plants can be done by the methods listed below.
4.4.1 Foliar Mode
To investigate the delivery of various nanoparticles in combination with nitrogen,
potassium, and phosphorus (NPK) are studied by foliar mode. Chiotsan-NPK
nanoparticles when applied on leaf surfaces entered with the help of stomata via
gaseous exchange. Their uptake inside plants was further investigated by
transmission electron microscopy (TEM) and the results revealed that NPs
translocated through phloem tissues. Nanochitosan-NPK fertilizer, when applied on
wheat, significantly results in crop index, harvest index, and mobilization index
increment. Similar results were also observed by Wang et al in watermelon after
foliar uptake of nanocomposite[67]. It has been observed that nanofertilizers alleviate
the increase within the plasma membrane permeability and cell mortality. Similarly,
foliar spray of gold nanofertilizers on plants again showed a positive effect resulting
in enhanced height, stem diameter of stem, number of branches, pods, and seed
yield[68]. For successful foliar uptake, in addition to particle size other various
factors should also be considered such as working environment (light, water and gas),
plant species, and nanoparticle application methods [69]. Thus, an increase in
productivity and in plant growth by nanofertilizers application led to open novel
perspectives in sustainable agricultural practices [70].
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4.4.2 Soil Mode


Soil application is the most common method of nutrient supplement using chemical
and organic fertilizers. The factors that need attention while choosing this method of
fertilizer applications are how long the fertilizer will last in the soil, soil texture, soil
salinity, and plant sensitivities to salts, salt content, and pH of the amendment [71].
Presence of saline water in irrigation or saline soil is considered to be a main factor in
limiting plant growth. Nanofertilizers proved to diminish the drastic effect of salinity.
results of one of studies in this field indicated an enhance in N and P content while
reduction in Na content which signified a special enhancing effect of SiO2
nanofertilizers on the plant growth and yield [72].
4.5 Uptake, Translocation, and Fate of Nano-fertilizers
The uptake, translocation, and accumulation of nanoparticles depend on the plant
species, age, growth environment, and the physicochemical property,
functionalization, stability, and the mode of delivery of nanoparticles. The entry of
nanoparticles through the cell wall depends on the pore diameter of the cell wall (5–
20 nm). Hence, nanoparticles or nanoparticle aggregates with diameter less than the
pore size of plant cell wall could easily enter through the cell wall and reach up to the
plasma membrane. Functionalized nanoparticles facilitate the enlargement of pore
size or induction of new cell wall pore to enhance the uptake of nanoparticles.
Several reports have discussed the uptake of nanoparticles into plant cell via binding
to carrier proteins through aquaporin, ion channels, or endocytosis. Further,
nanoparticles can also be transported into the plant by forming complexes with
membrane transporters or root exudates. After entering the cell, nanoparticles can
transport apoplastically or symplastically. They may be transported via
plasmodesmata from one cell to the other [73].Figure 8. In the cytoplasm, nanoparticles
approach to different cytoplasmic organelles and interfere with different metabolic
processes of the cell. Various other studies reported that nanoparticles could enter
through stomata or the base of trichome in leaf. Kurepa et al reported uptake and
translocation of TiO2-alizarin red S complex in Arabidopsis thaliana seedling. They
observed that mucilage released by roots develops pectin hydrogel complex around
the root and found to be responsible for the entry of nanoparticle-dye complex[74].

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Figure 8.The entry and absorption of nanofertilizers in nanoparticle and nanotube phases by plant cell via various
channels [73]

Figure 9.The mechanism of chitosan nanofertilizer provided to Maize plant through slow release [57]

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4.6 Risk and Safety in Using Nanofertilizers


The fast growth of nanotechnology industries and their attendance on certain markets
create it essential to assess their ecological and health effects. There are dangers of
adverse and accidental significances with nanotechnology, and it is significant to pay
care to communal views concerning new approaches in agro-production in the
product improvement phases [75]. One of the major questions faced by the world is
whether the unknown risks of nanoparticles involving their environmental and health
impact prevail over their potential benefits. The risks associated with the application
of nanoparticles are yet to be evaluated. This consideration has developed
“nanotoxicology,” which is responsible for assessing toxicological potential as well
as promoting safe design and use of nanoparticles [76]. Figure 10. This hazard is due to
the small size and great surface area of NPs, which allow easy dispersal, may rise the
risk for bioaccumulation inside body organs, tissues and exhibiting potential toxicity
[73], [77]. In the agro-production area, millions of small-scale agriculturalists can be
a foremost health risk by usage of nanofertilizers and nanopesticides [78]. The NPs
could enter the food chain via nutrient or through treated foods rising worries of
toxicity in the environment[78], [79]. So, life cycle study, particle uptake by plants,
bio dissemination and entry into the food chain, etc. need a thorough examination
earlier these tools are used as produces in agro-production area [80].

Figure 10.. Toxicity issues of nanoparticles in plants, soil microflora and human being[71]

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5. Nanopesticides
5.1 Definition and Background
Based on the United States Environmental Protection Agency (EPA), a pesticide is
defined as any substance or a mixture of substances intended for (i) preventing,
destroying, repelling, or mitigating any pest; (ii) plant regulation, defoliant, or
desiccant; and (iii) use as a nitrogen stabilizer. Pesticides are usually composed of an
active ingredient (AI) to prevent, destroy, repel, or mitigate a pest, or is a plant
regulator, defoliant, desiccant, or nitrogen stabilizer. Together with the AI are inert
ingredients (II), which are important for product performance and usability[81].
Conventional application of synthetic pesticides leads to ground water contamination
and the pollution of the environment. The toxic substances released and / or degraded
from the pesticides have degenerated in the environment via biodegradation, photo-
degradation, and hydrolysis. Figure 11. Due to these issues, only 1% or less than 1% of
the applied pesticide reached the targeted sites. The nano-enabled pesticides try to
overcome these shortcomings with its characters of high durability, more target and
power mobility. Engineered nanomaterials (ENMs) with their characteristic
properties like small size and large surface to volume ratio, greater permeability,
thermal stability, solubility, and biodegradability are becoming more widely accepted
for use in the agricultural sector[82].

Figure 11. How pesticides affect human's life [82]

5.2 Nano-enabled Materials and Characteristics


The polyacrylate nanocarriers are typical and widely used these decades. The
polyacrylate hydrogels, which are a class of materials that have been investigated for

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Nanosized Products for Agriculture

delivery of many different poorly soluble bioactive pharmaceuticals as well as


agrochemical molecules. They put Pendimethalin into the matrix of hydrogel
nanocarrier to form a composite structure. This composite can release the drug in soil
for uptake by plants. These properties are determined by the hydrogel composition,
method and degree of the cross-linking. Engineered nanomaterials (ENMs) have
other characteristic properties like small size and large surface to volume ratio,
greater permeability, thermal stability, solubility, and biodegradability are becoming
more widely accepted for use in the agricultural sector. The behavior of the
nanopesticides in soil depends on the functional characteristics of the matrix and the
durability of the carrier. So, the shortcomings of traditional pesticides such as non-
target can be overcome by these matrix’s characteristics. The most sensitive fate
descriptors are expected to be the mobility. The combination of nanocarrier and
pesticides can increase the persistence of the nanopesticides, to make sure that the
pesticides will not be reduced before they are being released from the nanocarrier. So,
the impact of the formulation on the transport of the matrix in this case depends upon
the mobility of the nanocarriers. Mobile carriers are likely to increase the mobility of
the matrix. While the immobile nanocarriers tend to decrease the mobility of the
matrixes. This can lead to greater exposure concentrations in the surface soil for
longer periods[83].
5.3 Green Synthesis
Green synthesis of nanoparticles is a cost-effective and eco-friendly technique that
does not use toxic chemicals. This technique uses microbes, plants, and other
resources to produce NPs. Most of this synthesis are the cooperation between the
organisms (or their extracts) and metallic salts. The green synthesis can be divided
into two parts depending on their composition method: Plant-Based and Microbe-
Based. The microbes provide templates for synthesis as a potential technique. But as
the plants can reduce the metallic ions more quickly, the synthesis through plants is
more convenient.
5.3.1 Microbe-Based Synthesis
Microbe-Based Synthesis is an alternative method of nanoparticles’ design and
development. Metallic NPs like gold, silver, copper, zinc, titanium, palladium, and
nickel can be carried out both extracellularly and intercellularly [3]. The
extracellularly synthesis is the culture filtrate is collected by centrifugation and mixed
with an aqueous metallic salt solution. The step of synthesis can be monitored by the
color of the mixed solution. The intercellular synthesis, the biomass is washed
thoroughly with sterile water after culturing microorganism under best growth
conditions and mixed with metal ion solution.

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5.3.2 Nanoparticles from Plant Extracts


Plants are well known for their ability to reduce metal ions on the surface and
different organs or tissues at distance from the penetration sites of ions. The study of
the accumulation of metal ions in plants suggested the transformation of metals to
NPs. A variety of acids and metal salts, such as copper, gold, silver, platinum, and
iron are produced through the Plant Extracts. The plant materials are better than the
microbes or chemical method because there are no effects on themselves or chemical
contamination. And lower energy is required. The plant extracts prepared from their
different parts such as roots, stems, barks, leaves, flowers, fruits, and seeds have been
used for green synthesis of NPs[84]. The schematic of biological processes for
nanoparticle synthesis are mentioned in Figure 12.

Figure 12. Biological synthesis process of nanoparticles[84]

The adhesion of NPs with microbial cell membrane occurs due to the electrostatic
attraction between the negatively charged cell membrane of microbes and NPs with
positive or low negative charges Figure 13. But the NPs that have been used for plant
pathogen management may be dispersed from the crop lands to the soil, water, and
atmosphere. The dispersion may take place through leaching, surface run-off by rain,
and transport by air current or trophic transfer. Different studies on this subject have
suggested that NPs may be absorbed by microbes in the soils, sediments, and plant
roots. Later, these NPs are migrated from roots to other parts of the plants, and
accumulation occurs. Shifting of NPs from one trophic level to another trophic level
takes place as the microbes, plant products or their waste materials are utilized or
consumed by various organisms such as fish, insects, birds and mammals[84].

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Figure 13. Nanoparticles action mechanism

5.4 Risk assessment of Nanopesticides


Nanotechnology has become one of the important tools in modern agriculture.
Numerous novel nanomaterials (NM) have been developed for improving food
quality with safer environmental conditions. Nanopesticides is a very important
branch of modern nano products for agriculture. The aim of this tool is to improve the
stability and target properties of the pesticides and try to minimize the effects on the
environment. The traditional pesticides with the surfactant, have been increased the
solubility in the water. So, it contributes to the contaminations of the river. The
development of nanopesticides is a good breakthrough to reduce the amount of the
surfactants as well as the quantities of pesticides applied to the crops. This nano
formulations can be formed through polymers or metals, according to the desired
application. But the rapid development and utilization of the nanotechnology result
in a high uncertainty. To evaluate its environmental and health impacts, scientists do
some tests on animals, plants, insects, water, and soils. As it is known that we use
different materials to build up the carriers, so it is also very important to evaluate
their toxicity. And we also need to consider its dispersion in the environment effects
area and the non-target organisms[85].

6. Conclusion
Delivery of agrochemical substance like plant food provision macro- and
micronutrients to the plants is a crucial facet of application of nanoscience in
agriculture. Nanoscale or nanostructured materials as fertilizer carrier or controlled-
release vectors for building of the supposed sensible fertilizers will enhance the
nutrient use potency and cut back the price of environmental pollution. Nano-
fertilizers can exactly unleash their active ingredients in responding to environmental
triggers and biological demands. each in vitro and in vivo strategies will be used for
nanofertilizer delivery to the plants. Their manipulation ability, which improves the
physico-chemical properties; high carrier system utilization, bioavailability and ease
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of processing and technique; and its low toxicity compared to other compounds make
this field of study more lucrative and applicable for agriculture. However, there
should be regulations for nano-products to protect the environment, the health of
users of such products and public health. Nanotechnology industries should be
required to provide information about the products of their nanomaterials.

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