Science of the Total Environment 863 (2023) 160859

Contents lists available at ScienceDirect

Science of the Total Environment

journal homepage: www.elsevier.com/locate/scitotenv

Nanocomposite-based smart fertilizers: A boon to agricultural and

environmental sustainability
Ranabir Chakraborty a,1, Arkadeb Mukhopadhyay b,1, Subhadip Paul a, Subhasis Sarkar b, Raj Mukhopadhyay c,
⁎
a
Division of Soil Science and Agricultural Chemistry, ICAR-Indian Agricultural Research Institute, New Delhi 110012, India
b
Division of Agricultural Chemicals, ICAR-Indian Agricultural Research Institute, New Delhi 110012, India
c
Division of Irrigation and Drainage Engineering, ICAR-Central Soil Salinity Research Institute, Karnal 132001, Haryana, India

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Synthesis, classification and nutrient de-

livery mechanisms of nanocomposite fer-
tilizers have been discussed
• Nanocomposite-based smart fertilizers in-
crease nutrient use efficiency and improve
environmental quality
• Ecotoxicity and lack of availability of stan-
dard protocols for using nanocomposite
fertilizers limits their application
• Inexpensive synthesis methods, field
study, biodegradability, and toxicity as-
sessment warrant future research atten-
tion

A R T I C L E I N F O A B S T R A C T

Editor: Daniel Alessi Fertilizers are indispensable agri-inputs to accomplish the growing food demand. The injudicious use of conventional
fertilizer products has resulted in several environmental and human health complications. To mitigate these problems,
Keywords: nanocomposite-based fertilizers are viable alternative options. Nanocomposites, a novel class of materials having im-
Nanocomposite
proved mechanical strength, barrier properties, and mechanical and thermal stability, are suitable candidates to de-
Eco-friendly fertilizers
velop eco-friendly slow/controlled release fertilizer formulations. In this review, the use of different nanocomposite
Slow/controlled release
Nutrient management
materials developed for nutrient management in agriculture has been summarized with a major focus on their synthe-
Sustainability sis and characterization techniques, and application aspects in plant nutrition, along with addressing constraints and
future opportunities of this domain. Further detailed studies on nanocomposite-based fertilizers are required to eval-
uate the cost-effective synthesis methods, in-depth field efficacy, environmental fate, stability, etc. before commercial-
ization in the field of agriculture. The present review is expected to help the policy makers and all the stakeholders in
the large-scale commercialization and application of nanocomposite-based smart fertilizer products with greater soci-
etal acceptance and environmental sustainability in near future.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Types of nanocomposites for smart fertilizer development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

⁎ Corresponding author at: ICAR-Central Soil Salinity Research Institute, India.

E-mail address: raj.mukhopadhyay@icar.gov.in (R. Mukhopadhyay).
1
These two authors contributed equally to this work.

http://dx.doi.org/10.1016/j.scitotenv.2022.160859
Received 22 August 2022; Received in revised form 8 November 2022; Accepted 7 December 2022
Available online 13 December 2022
0048-9697/© 2022 Elsevier B.V. All rights reserved.
R. Chakraborty et al. Science of the Total Environment 863 (2023) 160859

2.1. Nanomineral-based nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

2.2. Polymeric nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.3. Porous carbon-based nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3. Controlled release mechanism of nutrients from nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.1. Diffusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.2. Burst release . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.3. Degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4. Nanocomposite-based fertilizers for nutrient management . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.1. Use of nanocomposites as delivery systems of macronutrients . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.2. Use of nanocomposites as delivery systems of micronutrients. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4.2.1. Iron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4.2.2. Copper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4.2.3. Zinc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4.2.4. Manganese . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4.2.5. Boron and molybdenum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4.3. Nanocomposite-based biofertilizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
5. Effect of NCPFs on environmental protection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
5.1. Effect on soil quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
5.2. Effect on water quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
5.3. Effect on air quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
6. Problems and limitations of NCPFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
7. Uptake of nano-nutrients by plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
8. Environmental fate of nano-nutrients . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
9. Safety assessment strategies for nanocomposite-based smart fertilizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
10. Present constraints of adoption of nanotechnology in crop nutrition sector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
10.1. Lack of proper guidelines and legislative framework . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
10.2. Phytotoxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
10.3. Biodegradability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
11. Future prospects of nanocomposite-based smart fertilizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
12. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
CRediT authorship contribution statement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Data availability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

1. Introduction characteristics, including root length, lateral roots, root architecture,

Agricultural production will need to increase by 60 % above 2005 level
to support the anticipated global population of 9.7 billion people in 2050
(Kah et al., 2018). An enormous amount of fertilizers will be required to
reach the food demand and sustain soil fertility (Li et al., 2014; Dubey
and Mailapalli, 2016). However, most of the traditional agrochemicals in-
cluding fertilizers fail to reach the target site in a synchronized manner
and are lost to different environmental compartments through several pro-
cesses such as surface run-off, volatilization, leaching, air-drift, etc. (Guo
et al., 2018). Conventional fertilizers have poor nutrient use efficiency
(NUE). For instance, the nitrogen use efficiency is around 40 % for conven-
tional urea (Chandana et al., 2021). There are various ways to express NUE
such as partial nutrient balance (ratio of nutrients removed by crop harvest
to fertilizer nutrients applied), partial factor productivity (crop yield per
unit of nutrient applied), apparent recovery efficiency (nutrient taken up
per unit of nutrient applied), agronomic efficiency (crop yield increase
per unit of nutrient applied), and physiological efficiency (yield increase
per unit of nutrient taken up). The NUE is also frequently explained in
terms of crop removal efficiency (the percentage of nutrients removed
from harvested crops relative to nutrients applied) (Dobermann, 2007;
Roberts, 2008). The NUE depends on a number of variables; for example,
the NUE decreases with increasing nitrogen (N) dosage (Haile et al.,
2012; Tana et al., 2015). Efficacy is lower when potassium (K) fertilizer is
administered alone or with phosphorous (P), but higher when applied
with N (Burlacu, 2007). The NUE is also influenced by different environ-
mental factors e.g., rainfall, temperature, irradiance (Balasubramanian
et al., 2004); managements factors e.g., tillage, drainage (Darzi-Naftchali
and Mokhtassi-Bidgoli, 2022), crop rotation (Kurtz et al., 1984), pest and
weed infestation (Ghosh et al., 2021) and genotypes (Adeoluwa et al.,
2022). Higher NUE in plants is also associated with a number of plant
canopy height, flowering time, carbohydrate partitioning, and storage,
etc. (Carmo-Silva et al., 2017; Guttieri et al., 2017; Tabbita et al., 2017;
Hawkesford and Griffiths, 2019) According to Ladha et al. (2005), the aver-
age single-year fertilizer N recovery efficiencies for rice, wheat, and corn
were 46 %, 57 %, and 65 %, respectively. Globally, the NUE for cereal
crops was 33 % for N (Raun and Johnson, 1999), and 16 % for P (Dhillon
et al., 2017), while the use efficiency of K ranged between 40 and 60 %
under optimum circumstances (Dobermann, 2007). Cassman et al. (2002)
assessed N fertilizer recovery under various cropping patterns and reported
that corn cultivated in the north-central United States recovered 37 % of its
N fertilizer input. Additionally, they showed 31 % and 40 % N recovery for
rice grown in Asia using standard farmers' techniques and field-specific
management practices, respectively, whereas in India, the average N recov-
ery for wheat cultivated in adverse weather was just 18 %, but it was 49 %
for wheat grown in favorable weather. The NUE varies with soil type also.
For example, soil having high pH suffers from more N loss through volatil-
ization (Arora, 2022). Similarly, Omara et al. (2019) reported that cultiva-
tion increased soil nitrate leaching on sandy loam soil, but not on coarse
sand, hence use efficiency is comparatively lower in sandy loam soil. Re-
gional differences also exist in global temporal trends of NUE. Partial nutri-
ent balance and partial factor productivity for N, P, and K are growing
upwards in Europe, Africa, North America, and the EU-15, whereas these
indices are trending downwards in China, India, and Latin America (Fixen
et al., 2015). Loss of nutrients through various pathways can have negative
impacts on ecosystems on several scales, including soil, water, and air
quality (Solanki et al., 2015). Therefore, the development of target-
specific, environmentally safe approaches is the need of the hour to reduce
unwanted loss of nutrients in different environmental compartments along
with the enhancement of nutrient use efficiency, crop production, and
productivity.

2
R. Chakraborty et al.
Nanotechnology provides an alternative and viable option to develop
smart agrochemical inputs with sustained-release behavior having both
the advantages of economical convenience and environmental safety
(Shang et al., 2019). Nanotechnology-based agrochemicals provide several
advantages such as targeted delivery, slow degradation, and slow/con-
trolled release of encapsulated inputs rendering them more effective and
environmentally benign as compared to conventional formulations (Abd-
Elrahman and Mostafa, 2015; Usman et al., 2020; Chakraborty et al.,
2021). Different types of materials have been used to date to prepare
slow/controlled release fertilizer nanoformulations such as nanogels
(Umarani and Mala, 2013), amphiphilic polymers (Bindra and Singh,
2021), nano clay-polymer composites (Mukhopadhyay and De, 2014), car-
bon nanotubes (Hasaneen et al., 2016), carbon nanofibers (Kumar et al.,
2018a), etc. The global farming canvas has been vividly changed due to
the revolution of green nanotechnology. Improving macro- and micro-
nutrient deficiency is possible through the enhancement of NUE by using
nanofertilizers (Shukla et al., 2019). Nano-enabled fertilizers may also syn-
chronize the nutrient release with the crop demand. Moreover, it also pre-
vents unfavorable nutrient losses through direct nutrient uptake by crops,
avoiding contact with soil, water, air, and microbes (Dwivedi et al., 2016;
Panpatte et al., 2016). Therefore, the nanoagriculture revolution has re-
sulted from the current trend of developing agr-inputs based on nanotech-
nology (Mukherjee et al., 2016).
Composites are polyphasic heterogeneous solid materials where rein-
forced phases are discontinuous and the matrix phase is continuous
(Hsissou et al., 2021). Nanocomposites are a special type of composite
where nanomaterial having at least one dimension up to 100 nm is rein-
forced into a matrix (Mondal, 2018). This size reduction is responsible for
the distinctive changes in their properties due to the large surface area to
volume ratio. The use of nanocomposites in the agricultural sector has
gained attention due to their promising role in the development of agri-
input products including fertilizers for slow/controlled release, decontami-
nation of wastewater, and preparation of nanosensors for monitoring pur-
poses (Kundu et al., 2021; Sarkar et al., 2021). Several review articles
have been published on the application of nanomaterials in increasing agri-
cultural food production (Ditta, 2012; Chhipa, 2019; Neme et al., 2021;
Ujjwal et al., 2022). These review articles have mainly focused on the
Fig. 1. Advantages of nanocomposite-based smart fertilizers (Modified from Kumar et al., 2021).
3
Science of the Total Environment 863 (2023) 160859
application of nanotechnology in different aspects such as nutrient/pesti-
cide delivery, development of sensors for monitoring crop growth and
health status, pesticide residues in soil and water, etc. Though a brief over-
view of each aspect has been demonstrated in these reviews, a comprehensive
analysis of each sector is necessary for better insights. Moreover, a holistic ap-
proach to the application of nanotechnology in the plant nutrition sector in-
cluding the type of nanomaterials used specifically for this purpose, their
synthesis and characterization techniques, the feasibility of large-scale com-
mercialization for improving soil fertility, quality as well as environmental
sustainability is still lacking. Nanocomposites have emerged as the most
promising class of modified nanomaterials for their biodegradability and hy-
drophilic nature, suitable for multidimensional uses including the develop-
ment of smart fertilizers (Timilsena et al., 2015). The application of
nanocomposites for the preparation of smart fertilizers may not only result
in a targeted, sustained, and synchronized supply of plant nutrients, but
also reduce the chance of contamination in different environmental compart-
ments including soil, water, and air. The United Nation's sustainable develop-
ment goals (SDGs) include sustainable production and consumption patterns
(SDG 12), and sustainable use of water resources (SDG 14) (United Nations,
n.d.). Thus, nanocomposite-based fertilizers (NCPFs) may serve as a tool to
achieve SDGs 12 and 14 along with attaining agricultural as well as environ-
mental sustainability. Therefore, in this review, we have critically discussed
and analyzed the current state-of-art regarding the application of
nanocomposites-based different fertilizers (macronutrients, micronutrients,
and biofertilizers) in crop nutrient management as an eco-friendly alterna-
tive to conventional fertilizers, along with addressing their present limita-
tions, and future opportunities underneath them. The present review also
highlights the synthesis and characterization techniques, nutrient release
mechanisms of nanocomposite-based fertilizers, uptake mechanism, and
environmental fate of nano-sized nutrients.
2. Types of nanocomposites for smart fertilizer development
Materials with internal or surface structure or external dimensions in
the nanoscale are referred to as nanomaterials (NMs), whereas a particle
with at least one external dimension in the nanoscale range (1 nm to less
than 1 μm) is known as a nanoparticle (Buzea and Pacheco, 2017).
R. Chakraborty et al. Science of the Total Environment 863 (2023) 160859

Nanocomposites are the most promising class of modified nanomaterials
generally used in the delivery of agrochemicals. The advantages of the ap-
plication of NCPFs have been represented in Fig. 1. Different types of car-
riers such as polymers of synthetic or natural origin, carbon nanotubes,
carbon nanofibers, layered double hydroxides, liposomes etc. are used as
continuous matrix phases in the preparation of nanocomposites (Guha
et al., 2020). The synthetic routes and characterization techniques of
NCPFs are enlisted in Table 1. Most of the nanocomposites used for crop nu-
trient delivery can be broadly categorized into three classes- Nanomineral-
based nanocomposites, Polymeric nanocomposites, and Porous carbon-
based nanocomposites. The representative examples of different types of
nanocomposites used for the development of smart fertilizers have been
schematically represented in Fig. 2.
2.1. Nanomineral-based nanocomposites
Nanoclays are defined as bi-dimensional layered mineral silicate nano-
particles with remarkable mechanical characteristics having a length of a
few micrometers and a thickness of around 1 nm (de Azeredo et al.,
2011; Huang, 2018). The capacity of nanoclays to safeguard nutrient mol-
ecules through physical barriers produced by their structural constituents,
as well as the intercalation of nutrients into the layers of nanoclay minerals
by ion exchange or non-electrostatic interactions, make them appropriate
as nutrient carriers. Nanomineral-based NCPFs can be prepared either by
direct application of only nano-sized clay minerals or clays as a matrix for
nutrient entrapment; or by reinforcement of nanoclays or clay minerals
with the polymeric matrix for preparation of the matrix for nutrient entrap-
ment. The latter is known as nanoclay-polymeric nanocomposite-based fer-
tilizers and is discussed under Section 2.2 for polymeric nanocomposites.
Nanoclays used for the development of NCPFs can be classified into two
categories- anionic (e.g., LDH) and cationic (e.g., nano-sized montmorillon-
ite) (Kim et al., 2006).
Layered double hydroxides (LDHs), commonly referred to as anionic
clays, or natural or synthetic hydrotalcites have several compositions en-
abling their use in various application arenas, including agriculture
(Singha Roy et al., 2022). LDHs are generally constituted by inorganic
layers containing bivalent and trivalent metal cations (Sharif et al., 2018).
The general formula of LDH is [M2+ (1−x) M3+ x (OH)2]x+ An− x/n·mH2O,
where M3+and M2+ stand for trivalent and divalent metal cations, respec-
tively, and A represents an anion (Sideris et al., 2008). LDHs are of particu-
lar interest due to their nano-raged structure and complete charge
separation between the layers and the ions of the gallery. The most common
method of preparation of LDHs is the co-precipitation method carried out by
the precipitation of the selected M2+and M3+ metal salts in presence of a

Table 1
Synthesis and characterization techniques of different NCPFs.
Type Nanocomposite Synthesis procedure Characterization Reference
techniques

Layered double LDH nanosheets and banana peel
hydroxide-based cellulose-based nanocomposite
nanocomposites LDH, polyurethane, montmorillonite-based Ion-exchange method
nano-composite fertilizer
Polymeric nanocomposites
Clay-polymeric Slow-released NPK fertilizer encapsulated
nanocomposite by a superabsorbent nanocomposite
(NaAlg-g-poly(AA-co-AAm)/MMT)
Semi-Inter penetrating network (IPN)
nanocomposites
Biopolymeric nanocomposites Chitosan nanocomposites
Nanozeolite and chitosan/sago starch
biopolymer-based nanocomposite
Nanocomposite with copper oxide and
chitosan/alginate NPs
Cellulose reinforced Alginate-coated gelatin-cellulose
nanocomposites nanocrystal superabsorbent composite
Rice husk cellulose-g- poly(acrylate
acid-co-acrylamide)/bentonite clay
Graft solution polymerization XRD, FT-IR, SEM Lohmousavi et al. (2020)
XRD, TGA, X-Ray Bortoletto-Santos et al. (2020)
Tomography
in-situ free radical polymerization of acrylic FT-IR, XRD, SEM Rashidzadeh and Olad (2014)
acid, sodium alginate, acrylamide, and
montmorillonite in presence of fertilizer
materials
Formation of chemical bonding between FT-IR, SEM, TEM, XRD, Song et al. (2019)
super-absorbent polymer, SAPWS (grafting XPS, TG-DSC
wheat straw (WS) to poly
(acrylic-co-acrylamide)) or SAPHEC (grafting
Hydroxyethyl cellulose (HEC) to poly
(acrylic-co-acrylamide) with NPK-containing
polymeric)
slow-release fertilizer
Solution polymerization of methacrylic acid TEM Hasaneen et al. (2016)
(MAA) with chitosan
Ionotropic gelation technique SEM, EDX, XRD, TEM Pimsen et al. (2021)
Polyelectrolyte complexation SEM, TEM, XRD, FT-IR, Leonardi et al. (2021)
DLS, TGA, ICP-OES
Layer-by-layer process SEM, AFM, FT-IR, XRD, do Nascimento et al. (2022)
TGA
Free radical polymerization FT-IR, XRD, SEM Abbas and Kurniawan (2017)

Porous carbon-based nanocomposites

Carbon nanofiber-based
nanocomposites
Graphene oxide-based
nanocomposites
Biochar-based nanocomposites
PVA–starch-encapsulated Dispersion of Cu\ \Zn nanoparticle and CNFs SEM, EDX, ICP-MS Kumar et al. (2018a, 2018b)
Cu–Zn/carbon nanofiber (CNF) composite in a polyvinyl alcohol and starch polymer
film matrix
Graphene oxide and chitosan Mixing followed by Ultrasonication and FEG-SEM, XPS Li et al. (2019)
nanocomposite film casting
Magnesium biochar nanocomposite Pyrolysis of Mg-enriched leaves of tomato XRD, SEM-EDX, XPS Yao et al. (2013)
plants
Corn cob biochar-based nanocomposite Simple impregnation method FT-IR, powder XRD, Lateef et al. (2019)
SEM/EDX, TGA/DSC,
AFM
Vinasse biochar–dolomite-based Pyrolysis of vinasse with dolomite FT-IR, XRD, SEM-EDX Kamali et al. (2020)
nanocomposite

(Abbreviations: FT-IR: Fourier Transformed Infrared Spectroscopy, XRD: X-ray Diffraction, SEM: Scanning Electron Microscopy, FEG-SEM: Field Emission Gun Scanning
Electron Microscopy, TEM: Transmission Electron Microscopy, AFM: Atomic Force Microscopy, EDX: Energy-Dispersive X-ray Spectroscopy, ICP-MS: Inductively Coupled
Plasma Mass Spectrometry, ICP-OES: Inductively Coupled Plasma Optical Emission Spectrometry, XPS: X-ray Photoelectron Spectroscopy, TG-DSC: Thermogravimetry- Dif-
ferential Scanning Calorimetry, DLS: Dynamic Light Scattering, TGA: Thermogravimetric Analysis)

4
R. Chakraborty et al.
Fig. 2. Representative examples of different types of NCPFs
(The symbol “ ” denotes nutrients or nano-sized nutrients).
solution of alkaline nature. Other methods of synthesis of LDHs include re-
construction of the calcined structure by applying the so-called ‘memory ef-
fect’ or the anion-exchange properties of LDHs (Saikia et al., 2017). Due to
its attractive traits, including low production cost, biocompatibility, envi-
ronmental friendliness, and abundance, it can be employed as a vector for
different nutrients (Bernardo et al., 2017; Lohmousavi et al., 2020). LDHs
are efficient as phosphate, nitrate, and borate carriers due to their distinc-
tive anion exchange capacity (Guo et al., 2018). Everaert et al. (2016) eval-
uated the efficacy of LDH as a carrier to regulate phosphate release. The
performance of LDH-P (phosphate exchanged Mg\\Al LDHs) was found to
be soil pH-dependent. LDH-P demonstrated up to 4.5 times more P utilization
efficiency in the acid soil than a soluble P fertilizer. In contrast, the value of
phosphorus in calcareous soil was only 20 % higher at low doses than that
of soluble phosphorus fertilizers and further declined at high doses. In another
study, the release behavior and efficacy in grape tomatoes (Solanum
lycopersicum) under pot experiment of boron (B) and zinc (Zn) from LDH
hosts (Zn-Al-LDH-B) were studied (Songkhum et al., 2018). The study re-
vealed that the controlled release of B occurred through desorption and ion
exchange, whereas that of Zn was through the conversion of Zn2+ in the
LDH structure to ZnO and Zn(OH)2. Moreover, the application of LDH pro-
moted plant growth as well as reduced nutrient loss from the soil.
The application of cationic clays is also important to develop nanoclay-
based NCPFs. Nano-montmorillonite and nano-zeolite are the most com-
monly used cationic nanoclays and nanominerals respectively in this re-
gard. Similar to mica-type layered silicates, the nano-montmorillonite
5
Science of the Total Environment 863 (2023) 160859
clays belong to the smectite clay family, and essentially consist of a three-
layered structure of aluminium octahedral layer sandwiched between two
tetrahedral layers of silicon (Ren et al., 2020). The extensive water absor-
bency and cation exchange properties of these nanoclays are of particular
interest to developing NCPFs. The zeolites have a crystalline porous struc-
ture, reversible hydration and dehydration properties, and the ability to ex-
change some of their constituent cations which render them suitable for
application as nutrient carriers (Cataldo et al., 2021). Nano-sized montmo-
rillonite has been used to prepare a slow-release urea nanocomposite fertil-
izer by intercalation of nanoclay and urea, which revealed slow-release
behavior in water even at lower concentrations (20 % w w −1) of nano-
montmorillonite (Pereira et al., 2012). The application of a nano-N fertilizer
utilizing zeolite (nanozeourea) on maize showed a significant increment in
total nutrient content, plant growth, quality as well as yield (Manikandan
and Subramanian, 2016).
2.2. Polymeric nanocomposites
Polymeric nanocomposites are another type of nanocomposites, where
the continuous phase is a polymer and the reinforcing phase is any material
having at least one dimension up to 100 nm (Fu et al., 2019). Polymeric
nanocomposites are synthesized by using several techniques such as solu-
tion processing, intercalation of fillers followed by in situ polymerization,
and melt intercalation (Mondal, 2018). Solution processing is a method
where nanofiller materials are initially dispersed in polymeric or pre-
R. Chakraborty et al.
polymeric solutions (Perveen et al., 2022). Thereafter, the mixture is agi-
tated by physical means to get a homogeneous mass. The feed mass is
then undergone casting and solvent evaporation to get polymeric nanocom-
posites. In the case of in-situ polymerization method, the selected monomer
is used as a solubilizing agent for swelling the filler materials or layered sil-
icate clays (Salabat and Mirhoseini, 2022). Subsequent polymerization re-
actions occur after combining monomer and silicate clays or fillers,
allowing the formation of polymer chains. Melt intercalation is the most
economical and environment-friendly among all these techniques, where
the polymer is first melted and then combined with a definite proportion
of selected clay or filler for intercalation in inert gas conditions (Qian
et al., 2010). Another important method for the development of polymeric
nanocomposite is graft polymerization, where the polymeric chains are
grafted onto the nano-filler surface (Ming et al., 2022).
Clay/nanoclay-based polymeric nanocomposites are the most impor-
tant types of polymeric nanocomposites that have been widely used in the
recent past for the development of nanocomposite-based nanofertilizers
(Kalia et al., 2020). Nanoclay-based polymeric composites can also be
used as nitrification inhibitors. In a study of Saurabh et al. (2019), the load-
ing of urea and different types of nitrification inhibitors inside a nanoclay
polymeric composite revealed potential nitrification inhibition by Schiff
base-loaded nanocomposite matrix. There are two types of clay-polymer-
based-nanocomposites: exfoliated nanocomposites and intercalated nano-
composites. Individual, 1-nm-thick clay layers are exfoliated into the se-
lected polymer matrix to produce exfoliated nanocomposites. On the
other hand, regardless of the clay-to-polymer ratio, intercalated nanocom-
posites are developed due to the penetration of polymer chains in between
the crystalline silicate layers (in the nano range) (Mukhopadhyay et al.,
2020). There are various kinds of polymeric nanocomposites that have
been used in agriculture for nutrient management, where different fillers
such as clay/nanoclay, agri-residues, nanocellulose, etc. have been rein-
forced within the polymeric matrices. The detailed analysis of the effect
of these materials on agriculture has been discussed in Section 4.
2.3. Porous carbon-based nanocomposites
According to the International Union of Pure and Applied Chemistry-
USA, porous materials can be classified based on the diameter of the
pores that make them up (Chaudhary and Sharma, 2017). Microporous ma-
terials contain pores that are less than 2 nm in size, in contrast to mesopo-
rous and macroporous materials, which have pore sizes that range from 2 to
50 nm and more than 50 nm, respectively. In general, porous materials with
high surface areas, such as activated carbons, metal-organic frameworks,
zeolites, graphenes, and mesoporous materials, are prospective adsorbents
since the adsorption mostly depends on the surface area or porosity and the
functioning of the adsorbent (Afreen et al., 2018). Additionally, these
carbon-based nanomaterials, primarily carbon nanofibers (CNFs) and car-
bon nanotubes (CNTs) have the capacity to penetrate seed coats and have
the ability to move inside of plants from roots to shoots to leaves (Ashfaq
et al., 2017). According to several investigations, CNFs and CNTs can be ef-
ficiently translocated within the plants (Mohammad Ashfaq et al., 2019).
Moreover, carbon-based nanomaterials served as a growth promoter by en-
hancing nutrient and water absorption (Sasidharan et al., 2022). CNFs can
govern the release of metal nanoparticles as well as their storage. As metal
nanoparticles, such as Cu, Zn, and Fe, also served as micronutrients for
plants, CNFs may also serve as a vehicle for the delivery of micronutrients
(Talreja et al., 2020). However, the chances of CNFs and CNTs to get trans-
ferred to animals and even to human beings through food chains depend on
different factors such as length, shape, chemical composition, presence of
impurities, aggregation behavior, surface structure, surface charge, solubil-
ity, etc. (Prajapati et al., 2022). Therefore, safety assessment of these mate-
rials are necessary before large scale application to avoid any negative
impacts to non-target organisms including human.
To create a polymer-bi-metal‑carbon composite (PBMC), Kumar et al.
(2018b) produced Cu and Zn-based bi-metallic nanoparticle-dispersed
CNFs encapsulated in the matrix of the polyvinyl alcohol-starch composite.
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Science of the Total Environment 863 (2023) 160859
The created PBMC polymeric composite works well as a fertilizer to accel-
erate plant development. It also showed the controlled release of
micronutrients (Cu/Zn) from the encapsulated matrix. The study revealed
that because of the polymer encapsulation, the release of micronutrients
from the developed PBMC matrix is comparatively delayed when compared
to only CNFs. Additionally, CNFs successfully moved within the plants from
root to shoot to leaves. Therefore, the developed biodegradable PBMC-
based formulation having Cu and Zn micronutrients reveals an effective
method for using nanomaterials in agriculture.
A range of industrial and agricultural biomasses can be pyrolyzed at dif-
ferent temperatures under oxygen-limited circumstances to create biochar,
a carbonaceous solid residue (Chausali et al., 2021). Agricultural wastes, or-
ganic portions of municipal solid waste forestry waste, animal manures,
and industrial biomass by-products are some of the raw materials used to
prepare biochar (Amin et al., 2016). Different biomass feedstock sources
are converted into biochar via pyrolysis (300–700 °C) in oxygen-free or
oxygen-limited environments (Mandal et al., 2017; Kwak et al., 2019).
The specific surface area, unique functional groups, pore characteristics,
and different surface charges of biochar have cumulative impact on its abil-
ity to adsorb substances. The type of raw materials used, the pyrolysis con-
ditions, such as time and temperature of pyrolysis, heating rate, and type of
pyrolysis furnace generally affect the attributes of biochar (Sabzehmeidani
et al., 2021).
3. Controlled release mechanism of nutrients from nanocomposites
A controlled release system has been considered an alternative sustain-
able nutrient delivery approach to conventional fertilizers (Bortolin et al.,
2012; Wanyika, 2014; Carson et al., 2014). The controlled release provides
the nutrients to the soil and plant within the desired period along with re-
ducing the amount of agrochemicals, manpower, and energy resources
(Kumar et al., 2021). Moreover, it is an environmentally benign approach
as it reduces unpredictable loss of nutrients through volatilization,
leaching, infiltration, surface run-off, etc. Controlled release property de-
pends on several factors such as physico-chemical properties of the nano-
composite matrix, the interaction between entrapped nutrients and the
matrix, soil properties (pH, EC, soil moisture content, soil temperature,
soil microbial population, mineral composition, texture, etc.), environmen-
tal factors (temperature and rainfall), cultural practices (time, dosage, and
method of application), etc. (Carson and Ozores-Hampton, 2013). Different
mechanistic approaches, empirical (“Higuchi model”, “Generalized Neural
Network Model”), and semi-empirical models (“Korsmeyer–Peppas” and
“Ritger–Peppas” models) are also available to predict the release mecha-
nism from controlled release fertilizers (CRFs) (Lawrencia et al., 2021).
Most of the NCPFs developed to date have reported their sustained
nutrient-release behavior. However, the material-specific in detail analysis
of the controlled release mechanism of these fertilizers is still limited. In
general, the controlled release of nutrients from the NCPFs may occur
through diffusion, burst release, degradation, or a combination of any of
these. Different mechanisms involved in the controlled release of nutrients
from NCPFs have been summarized below and schematically represented
in Fig. 3.
3.1. Diffusion
This is the most common approach to releasing the encapsulated or
loaded nutrient through swelling or relaxation of the matrix in the applied
environment (Bortolin et al., 2016). This is a concentration gradient phe-
nomenon, whereby nutrients are released when the nutrient-loaded nano-
composite gets diluted due to irrigation or rainfall. The nanocomposite
matrices used for the encapsulation of nutrients could be hydrophilic
(LDH clays, nano-montmorillonites, nano-zeolites, superabsorbent nano-
composites, CNFs, graphene oxides, etc.) or hydrophobic (CNTs, biochar,
etc.) in nature. In case of hydrophilic matrices of CRFs, the release is carried
out by simple diffusion, whereas in case of hydrophobic matrices, the re-
lease is governed by erosion or swelling of the matrix (Bruschi, 2015).
R. Chakraborty et al.
Fig. 3. Nutrient release mechanisms from NCPFs
(The symbol “ ” denotes nutrients or nano-sized nutrients.
The lag phase, continuous release phase, and decay phase are the three
stages through which nutrients are typically released from
nanocomposite-based CRFs. In case of hydrophilic NCPFs, as compared to
the soil solution, the NCPFs have a higher nutrient-specific osmotic poten-
tial. As a result, the osmotic potential difference between the soil solution
and the NCPF determines how quickly nutrients are released from these
materials. Water, mostly in vapor form, enters the fertilizer during the lag
phase of nutrient release. The driving force is the vapor pressure gradient,
and no fertilizer is released at this stage. The lag phase is followed by a lin-
ear phase of constant release of nutrients by equilibrating the vapor pres-
sure gradient, and finally enters a decay phase during which the majority
of the nutrients have been released, which reduces the vapor pressure gra-
dient as well as nutrient release rate. At the end of nutrient release, the ma-
trices with certain low concentrations of nutrients are left behind in the soil.
In case of hydrophobic nanocomposite matrices, the swelling and shrinking
7
Science of the Total Environment 863 (2023) 160859
processes may result in fractures or interstices on their surfaces that facili-
tate surface erosion and subsequent nutrient release. The incorporation of
more barrier properties within the nanocomposite matrix may retard the
diffusion rate. Bortoletto-Santos et al. (2020) proposed a nanocomposite-
based delivery system comprising castor oil-derived polyurethane and
montmorillonite/hydrotalcite for coating urea and monoammonium phos-
phate (MAP) granules, which showed reduced diffusion release of nutrients
due to barrier properties of the hydrotalcite present in the matrix.
3.2. Burst release
In this mechanism, the undesirable and rapid release of nutrients occur
from the matrix due to unfavorable application to the target (Kumar et al.,
2021). The development of more cross-link points within the encapsulation
matrix may reduce this kind of release. In a study by Li et al. (2019), the
R. Chakraborty et al. Science of the Total Environment 863 (2023) 160859

coating of potassium nitrate beads by chitosan-graphene oxide cross-linked
films reduced the burst release duration and amount of released nutrients as
compared to only chitosan-coated fertilizer beads.
3.3. Degradation
Nutrients from nanocomposite matrices may also get released due to
degradation by physical, chemical, and biological means (Kumar et al.,
2021). Various factors such as hydrolysis, exposure to light, pH, tempera-
ture, enzymatic activities, etc. may trigger the release through matrix deg-
radation. For instance, the hydrophilicity of a ternary nanocomposite
based on urea-formaldehyde, polybutylene succinate, and potassium
dihydrogen phosphate got increased due to more amount of hydrophilic
urea-formaldehyde components inside the matrix resulting in faster hydro-
lytic degradation and release of nutrients (Zhang et al., 2020).
4. Nanocomposite-based fertilizers for nutrient management
Nanocomposites serve as a suitable matrix for encapsulating nutrients
or microorganisms and provide a barrier to the encapsulated nutrient
(s) or microorganisms to enable their sustained release. Long-term avail-
ability of nutrients with more use efficiency is the major difference in nutri-
ent management with these materials over conventional ones. Several
materials such as nanominerals (LDH, nano-zeolite, etc.); polymeric mate-
rials (polymers of natural, synthetic, or semi-synthetic origin, polymeric
nanocomposites with different fillers such as clay/nanoclay, crop-

Table 2
NCPFs and their role in plant growth/nutrient release.
Nutrient Nanocomposite type Test plant Observed effects Reference
associated species/matrix

N Novel superabsorbent hydrogel with
poly-acrylamide, methyl-cellulose, and
calcic-montmorillonite
Exfoliation of clay over urea matrix.
Formaldehyde was added to increase
interaction.
Extruded thermoplastic starch and urea
blend, hydroxyapatite was dispersed
@20–50 %
Nano zeolite modified by hexadecyl trimethyl
ammonium bromide loaded with N
Urea-montmorillonite-polyacrylamide
hydrogel and paraformaldehyde
nanocomposite
Urea-hydroxyapatite nanohybrids
Urea-montmorillonite intercalated
nanocomposite
P Sugarbeet Vinasse biochar-dolomite
nanocomposite
Sepiolite-chitosan nanocomposite coated
diammonium phosphate granules
Starch- rock phosphate nanocomposite
bioactivated by Aspergillus niger
NK Carbon nanoparticles loaded with N and K
fertilizers
NPK Carbon nanotubes loaded NPK fertilizer
Chitosan poly-methacrylic acid
nanoparticles loaded with NPK
N and Ca Calcium-nitrate gelatin-coated urea
nanocomposite
NPK and Fe Maize bran-g-poly(acrylic
acid-co-acrylamide)/montmorillonite
hydrogel nanocomposite loaded with NPK
and Fe
Fe and Zn FeO and ZnO Nanocomposites based on
mesoporous silica and reduced graphene
oxides
Mn MnO2-perlite nanocomposite
Mg and Mn Biochar-based metal oxide nanocomposite
N and Zn Urea- paraformaldehyde nanocomposite
loaded with Zn
N/P and Zn Zinc-layered hydroxide-phosphate and
Zinc layered hydroxide-nitrate
nanocomposites
B Sodium alginate- g- poly
(acrylate-co-acrylamide)/montmorillonite
superabsorbent nanocomposite loaded
with boric acid
N and B Superabsorbent nanocomposite loaded
with urea and boric acid
– Enhanced absorption of urea, increase N load,
Ryegrass, Greenhouse
condition
Ocimum kilimands-charicum,
Field condition
Ipomoea Aquatic, Pot study
(30 days)
Lolium multiflorum, Pot study
under greenhouse condition
Oryza Sativa, Field condition
Release study in water
Setaria Viridis, Pot experiment
Zea mays L., greenhouse
experiment
– Increased solubilization of P resources
Phaseolus vulgaris L.
French bean, Pot study
Triticum aestivum, Pot study
(till maturity)
Sorghum, Pot experiment
Water and soil
Oryza Sativa, Pot experiment
Hypericum perforatum L.
Carthamus tinctorius L., Pot
experiment
Zea mays L., Pot condition
Release study in water
Release study in water
Release study in water
Liu et al. (2006)
controlled release about 200 times for 50 % Ca
montmorillonite
Increase in yield and N uptake, reduction in NH3 Sekhon (2014)
volatilization
Controlled release of urea, decrease in NH3 Acharjee et al. (2015)
volatilization and increase in citrate soluble P
Increased Plant growth and biomass with higher N Rajonee et al. (2016)
concentration and uptake
Higher N uptake (43 %), Increased dry matter Pereira et al. (2017)
yield (53 %)
Yield was increased by 0.6 t ha−1 as compared to Kottegoda et al. (2017)
conventional urea application
Slow-release behavior of Nitrogen up to 150 h Golbashy et al. (2017)
67 % increase in dry weight of biomass and 49 % Kamali et al. (2020)
increase in above soil height
Improved P-use efficiency Mohammadi and Shariatmadari
(2020)
Klaic et al. (2018)
Improved seed yield and plant growth parameters Salama et al. (2021)
(plant height, number of leaves per plant, number
of flowers per plant, and plant fresh weight)
Improved growth parameters Hasaneen et al. (2016)
Increase in yield (10 %) and growth Aziz et al. (2016)
Increased TOC, OM, MBC, and MBN after soil Khan et al. (2021a, 2021b)
application; Improved plant height and leaf
chlorophyll content
pH-dependent swelling in water and excellent slow Gharekhani et al. (2018)
release of loaded nutrients in aqueous and soil
matrices
53 % increased grain yield as compared to Durgude et al. (2022)
conventional fertilization
Improved plant growth parameters Jafarirad et al. (2021)
Improved root and shoot growth; increased oil and Ghassemi-Golezani and
seed yield Farhangi-Abriz (2021)
Altered root morphology, reduced N loss Giroto et al. (2022)
Sustained release of nutrients following a Khadiran et al. (2021)
pseudo-second-order release kinetics
Slow-release property of boric acid with the Helmiyati and Nugraha (2020)
optimal release of 25.56 % for about 6 days
Improved macronutrient (74.2 g of urea per g of Bortolin et al. (2016)
nanocomposite) and micronutrient (7.29 g of
boron per g of nanocomposite) loading, and
release properties

8
R. Chakraborty et al.
residues, nanocellulose, etc.); porous carbonaceous materials (CNFs, CNTs,
graphene oxides, biochar, etc.) are generally used to develop chemical
(macro-and micro-nutrients) as well as bio-fertilizers for nutrient manage-
ment. Different types of fertilizers developed using this novel class of nano-
materials have therefore been discussed in the following subsections and
the representative nanocomposite fertilizers for slow/controlled release of
macro/micronutrients and their effects on crop growth or nutrient release
behavior have been enlisted in Table 2.
4.1. Use of nanocomposites as delivery systems of macronutrients
Different types of nanocomposite fertilizers have been developed to
date to enhance the nutrient use efficiency and effective transfer of macro-
nutrients in a synchronized manner to the agricultural fields. Most of
the nanocomposite-based macronutrient fertilizers-related studies reported
so far have given more emphasis on the development and application of pri-
mary nutrients i.e. nitrogen (N), phosphorous (P), and potassium (K) based
fertilizers comprising individual nutrient species or their combination. In
some studies, secondary and/or micronutrients have been incorporated
along with primary nutrients to broaden the application spectrum.
Direct application of nanominerals for the development of the NCPFs is
nowadays in practice due to their non-toxicity, cost-effectiveness, and
abundant availability in nature (Merino et al., 2020). In agricultural sector,
nanoporous zeolite is gaining popularity as it helps crops to utilize the en-
capsulated fertilizer material more effectively while reducing the harm
that conventional chemical fertilizers do to environmental compartments
(Thirunavukkarasu and Subramanian, 2014). It was previously reported
that nonporous zeolite's use as slow-release nanocarriers boosted the nutri-
ent retention capacity of the soil because of its high nutrient loading capac-
ity, mesoporous structure, and high surface area (Mikhak et al., 2017). In an
experiment by Khan et al. (2021a, 2021b), the nanozeolite was utilized as a
carrier to generate a slow-release nano-fertilizer using macronutrient salts.
The co-precipitation technique was used to produce the nanozeolite. The
developed nanozeolite-based controlled-release fertilizer increased the
soil's nutrient availability and further strengthened its physical, chemical,
and biological qualities. Additionally, the prepared fertilizer material dem-
onstrated improved lettuce plantation growth at a reduced concentration.
The pH of the soil may have an impact on LDH instability. According to
a study on LDH-Phosphate (P), the soil pH got increased in both sandy and
clayey soils, after the tested maize plants were harvested 25 days after
seeding (Benício et al., 2017). The authors hypothesized that the pH in-
crease made it easier for plants to absorb P rather than soil minerals. More-
over, as frequent soil ploughing could increase soil pH and enhance LDH
dissolution in the field, Dorante (2007) proposed that LDH was not accept-
able for usage in these places. Another study used an in-situ graft solution
polymerization to create a novel, pH-sensitive hybrid nanocomposite of
Layered Double Hydroxides (LDH) nanosheets and Banana Peel Cellulose-
g-Poly(acrylic Acid)/PVA hydrogel for slow release of NP (nitrogen, phos-
phorous) fertilizers and water retention (Lohmousavi et al., 2020). When
compared to neutral conditions, nitrogen fertilizer was released at a quicker
pace under both strongly alkaline and strongly acidic conditions, while
phosphorus was released at a higher rate at pH 7.0.
Polymeric nanocomposites such as superabsorbent hydrogel-based
nanocomposite fertilizers provide a two-way advantage by supplying
water as well as nutrients for crop growth (Essawy et al., 2016; Liu et al.,
2022), and thereby hydrogel-based nano-polymer composites are emerging
as a promising carrier for crop nutrient delivery systems. For instance, one
hydrogel-based NPK fertilizer-loaded nutrient delivery system was devel-
oped by polymerizing clinoptilolite zeolite, acrylic acid, acrylamide, and so-
dium alginate which showed excellent retention properties with a fertilizer
release rate of about 75 % after the end of one month (Rashidzadeh and
Olad, 2014). Olad et al. (2018a) prepared a novel superabsorbent nano-
composite with maize bran, acrylic acid, acrylamide, and montmorillonite
for loading NPK with surprising retentive properties. Another unique
slow-release fertilizer material was developed by using in-situ polymeriza-
tion of acrylic acid, and sulfonated-carboxymethyl cellulose in presence of
9
Science of the Total Environment 863 (2023) 160859
some silica nanoparticles and polyvinylpyrrolidone that served as an excel-
lent carrier for N, P, and K fertilizers (Olad et al., 2018b).
The hydrophilic polymer's ability to adsorb water and chemical com-
pounds, for example, may be enhanced by the addition of layered silicate
clays like montmorillonite. In-situ solution polymerization of sodium algi-
nate, acrylic acid, acrylamide, and montmorillonite with NPK fertilizer
was demonstrated by Kabiri et al. (2011). The developed material was
then enclosed in a superabsorbent nanocomposite with a slow-release pro-
file and improved water retention capabilities. In the context of the con-
trolled release of nutrients, this experiment determined montmorillonite
as the most effective ingredient. Bortolin et al. (2013) prepared a new nano-
composite for application as a nitrogen-loaded fertilizer having a slow-
release property by using montmorillonite to exfoliate in the matrix of the
urea-formaldehyde polymer. The developed nanocomposite demonstrated
improved slow-release behavior and mechanical resistance in the water im-
mersion tests. In another study, the effectiveness of microspheres devel-
oped using chitosan/clay hybrids for evaluating the release profile of
potassium nitrate in lettuce cultivation was observed by Souza et al.
(2017). According to this finding, soils treated with the prepared nanocom-
posites had increased electrical conductivity and moisture levels. Addition-
ally, a gradual and uniform release performance was observed as compared
to conventional fertilization.
The rate of release of nutrients from clay-based polymer nanocompos-
ites hinges on the stability of coatings which prevent the dissolution of fer-
tilizers (Abuchenari et al., 2020). One experiment was conducted by
encapsulating urea-modified hydroxyapatite nanoparticles into Gliricidia
sepium cavities. The results showed a controlled release of N even on the
60th day after application (Ghormade et al., 2011). Another clay-polymer
nanocomposite (CPU) was developed using Sepiolite and chitosan with dif-
ferent clay mineral/polymer ratios as a coating material for urea
(Mohammadi et al., 2020), where the rate of nitrogen release was delayed,
as evident from the release of 75 % of N of CPU in 25 days against the stan-
dard urea (3 days). To minimize environmental pollution, a new
palygorskite nanocomposite adsorbent was developed, which was utilized
for the recovery and reuse of NH+ 4 in agricultural practices found in
wastewaters containing ammonium in the form of a multifunctional
slow-release ammonium fertilizer (Wang et al., 2014). The phosphate
found in natural rocks has a very low solubility, which restricts its
field application. To solve this problem, a nanocomposite phosphatic
fertilizer was developed by dispersing nanoparticulate rock phosphate
in starch and adding the acidulant bacterium, Aspergillus niger (Klaic
et al., 2018). The results revealed solubilization of the total available
phosphate up to 70 % and 100 % in very poor solubility test phosphatic
rocks and hydroxyapatite mineral respectively as a result of the
bioactivation of the nanocomposite.
Cellulose, which is the primary component of plant-based materials in-
cluding hemp, wood, and cotton, is the most prevalent biopolymer on
earth. This is a linear polysaccharide and is composed of β-(1–4) linked D-
glucose units (Siró and Plackett, 2010). The glucose units have several hy-
droxyl groups that can interact wholly or partially with other reagents to
generate additional derivatives, such as cellulose esters and cellulose
ethers. The use of cellulose and its derivatives as carriers for fertilizing com-
pounds has received interest due to its capacity to form films, biodegrade,
and regenerate. Recently, to create a slow-release NPK fertilizer with
water-retention properties, new aqueous waterborne and biodegradable
coated nanocomposite-based formulations were prepared from polyvinyl
alcohol (PVA) reinforced with cellulose nanocrystals (CNC). Using a hydro-
lysis process involving sulfuric acid, CNC was obtained from hemp stalks.
The addition of CNC to PVA-based coatings increased the N-P-K nutrient re-
lease period from 3 days for uncoated fertilizer to 10 and 30 days for neat
PVA- and CNC/PVA-coated fertilizer, respectively, in soil medium, demon-
strating the beneficial effects of CNC (Kassem et al., 2021). In another
study, chemical crosslinking with citric acid was used to create carboxy-
methyl cellulose hydrogels, which were then filled to various degrees
with nanocellulose (NC), vermiculite, or montmorillonite. The NPK fertil-
izer was added to the optimized formulations, and the results showed
R. Chakraborty et al.
successful encapsulation as well as a slow-release profile of the test nutri-
ents (Bauli et al., 2021).
The application of porous carbon materials for the development of
nanocomposite fertilizers is also in practice. For example, the volatile mat-
ter, elemental, and ash contents of biochar are further noteworthy chemical
characteristics that affect its usage as a vector system of different agri-inputs
(Sashidhar et al., 2020). The amount of nutrients is easily available for the
inoculants to survive depending on the amount of volatile matter, such as
the labile C. Based on the pyrolysis conditions, it is known that the volatile
matter content of biochar can range from 13.2 to 70 %. (Downie et al.,
2009). Contrarily, the interaction between the biochar and the inoculum
is controlled by the elemental makeup. Since biochar includes a lot of inor-
ganic substances like Ca2+, NH+ 4 , and P, they help the inoculum to chemi-
sorb and act as a source of nutrients. In a study by Lateef et al. (2019), a corn
cob biochar-based polymeric nanocomposite material loaded with multiple
nutrients (N, P, K, Ca, Mg, Fe, Zn, and Na) was developed by a simple im-
pregnation method. The material revealed slow release behavior of loaded
nutrients up to 7 and 14 days for tap water and soil. Another porous carbo-
naceous material, graphene oxide, based nanocomposite fertilizer was de-
signed by Li et al. (2019) in which fertilizer beads of potassium nitrate
were coated with chitosan-graphene oxide film to encourage slow release.
4.2. Use of nanocomposites as delivery systems of micronutrients
Several approaches have been tried to develop micronutrient-based
nanocomposite fertilizers based on a single micronutrient or in combina-
tion with other nutrient(s). The different approaches attempted for this pur-
pose have been summarized below under specific micronutrient
subheadings.
4.2.1. Iron
One hydrogel-based nanocomposite composed of Na-montmorillonite
with acrylamide as monomer and methylene bisacrylamide as crosslinker
was designed for controlled release of Fe (Bahrami and Mahdavinia,
2016). For constructing the nanocomposite, the cellulose was oxidized to
carboxyl cellulose and these carboxyl groups enabled the attachment of
Fe2+ ions, developing Fe-coated microfibers, which were further coated
with attapulgite. The pH-dependent mechanism is attained due to
attapulgite coating as it loses at low pH thus favoring the release of
entrapped Fe.
The development of agri waste-based hydrogel nanocomposites is also
popular these days to improve their biodegradability and retentive proper-
ties (Olad et al., 2018a). One NPK fertilizer product and a soluble ferric che-
late were added to a maize bran-g-poly (acrylic acid-co-acrylamide)/
montmorillonite superabsorbent nanocomposite to develop a novel slow-
release multi-nutrient fertilizer formulation (Gharekhani et al., 2018). A
better pH-sensitive swelling behavior and good re-swelling ability were
demonstrated by the developed superabsorbent nanocomposite. The
multi-nutrient-loaded superabsorbent nanocomposite has also exhibited
outstanding slow-release behavior in both soil and water.
Several researchers have also tried liposomes (sphere-shaped double-
layered phospholipid vesicles) as a nano-carrier for magnesium and iron.
This type of carrier was used due to its translocation through the leaf and
potential to release the loaded micronutrients in the cytoplasm or nucleus
of the test plant alleviating Fe and Mg deficiency to recover from chlorosis
and epinasty (Karny et al., 2018).
4.2.2. Copper
The copper-loaded carbon nanofiber nanocomposite fertilizer was
prepared from activated carbon microfibers impregnated with 0.4 M
Cu(NO3)2.3H2O salts in presence of sodium dodecyl sulfate as a surfactant
(Ashfaq et al., 2017). A test on the germination of chickpea seeds in water
revealed that the nanofiber formulation improved the plants' ability to ab-
sorb water, their rate of germination, the length of their shoots and roots,
and the protein and chlorophyll contents. The authors also noticed the
movement of the prepared material from the roots to the shoots. The
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Science of the Total Environment 863 (2023) 160859
authors proposed that a substrate or covering material, such as a biodegrad-
able polymer to encase the nanofertilizer, would increase the stability of
the nanoformulation in field applications. Kalinichenko et al. (2016)
showed a technology for the preparation of nanocomposites with acrylic
hydrogel and sludge biogel. Owing to the activity of sludge microorgan-
isms, the entrapped heavy metals were released by bioleaching. The au-
thors reported prolongation of Cu release due to interaction with the
biopolymer and a substantial increase in plant vigor and yield. In order to
transport Cu\\Zn nanoparticles, Kumar et al. (2018b) looked into a poly-
mer film (PVA-starch) and carbon nanofiber combination. The polymeric
formulation prevented the quick release of Cu and Zn nanoparticles into
the soil. It was also demonstrated that the nanofertilizer produced in this
approach improved chickpea growth.
4.2.3. Zinc
One approach was followed to develop Zn nanocomposite fertilizer by
Kumar et al. (2018a), where a nanocomposite consisting of multi-walled
carbon nanotubes (MWCNT) and zinc oxide (ZnO) nanoparticles was devel-
oped and its effect was tested on the onion. Besides acting as a perfect car-
rier, MWCNT safeguarded the easy penetration and further delivery of Zn in
the plant cell of the test plant as well as preventing aggregation of ZnO
nanoparticles. Zinc aluminosilicate (ZnAl2Si10O24), a slow-release nano-
composite for Zn was synthesized via the co-precipitation method (Fizza
et al., 2020). The authors used rice husk as a source of silica to make the
process green and economical. This nanocomposite was then loaded with
urea for simultaneous and slow delivery of both zinc and nitrogen.
In another study, mixed nanofertilizers (MNC) containing Zn, Cu, Fe,
nanozeolite, and hydroxyapatite particles were developed and evaluated
in terms of rice−endophyte symbiosis, biochemical properties, and growth
and development of rice plants (Rahman et al., 2022). The obtained find-
ings indicated the application of MNC fertilizers as an effective fertilization
management strategy for significantly increasing the beneficial endophytes
(Aspergillus fumigatus, Penicillium spp., Rhizopus spp., and Fusarium spp.), im-
proved growth and nutritional parameters in case of the test plant.
Several authors used layered double hydroxide (LDH), as a matrix to de-
velop nanocomposite-based slow-release micronutrient fertilizers. Differ-
ent Mg-Fe-LDH doped with Zn was developed for studying the release
behavior of Zn in solutions having different pH values (Imran et al.,
2016). The results predicted that greater release was correlated with
lower pH and suggested this material could be utilized as a potential source
of Zn for plants.
Another novel multi-nutrient (N, P, K, Ca, Mg, S, Zn, Fe, Cl, and Na)
loaded nanocomposite has been designed using nano zeolite as a carrier
(Lateef et al., 2016). The material was synthesized by co-precipitation
followed by impregnation of different macro and micronutrient salts
(NaNO3, NaH2PO4.2H2O, Ca3(PO4)2, KCl, MgSO4.7H2O, FeCl2.4H2O, and
ZnSO4.7H2O). The release study of the prepared material revealed a slow
release profile of the doped nutrients in soil and water for up to 14 and 7
days respectively.
4.2.4. Manganese
The application of nanocomposites for the preparation of manganese-
based fertilizers is still in a nascent stage. Recently, Khutsishvili et al.
(2021) developed manganese-containing nanobiocomposites using differ-
ent biopolysaccharides namely k-carrageenan, arabinogalactan sulfate,
and arabinogalactan for application as novel multi-purpose low-dose
organomineral fertilizers. The application of the prepared
nanobiocomposites fertilizer revealed that the test potato plants grown in
a medium containing nanobiocomposite had higher biometric metrics as
compared to the control medium, and no accumulation of manganese was
observed in plant tissues.
4.2.5. Boron and molybdenum
A recent development in hydrogel-based nanocomposite is the effective
delivery of B along with urea (Bortolin et al., 2016). This nanocomposite is
composed of polyacrylamide and methylcellulose along with calcium
R. Chakraborty et al.
montmorillonite as a modifier. Recently, a superabsorbent nanocomposite
was developed for regulated B release using sodium alginate grafted by
poly(acrylate-co-acrylamide) loaded with montmorillonite (MMT), and fi-
nally the addition of boric acid (Helmiyati and Nugraha, 2020). The swell-
ing property was increased by increasing MMT as well as boric acid content.
The maximum swelling i.e. 426.337 g water per g material was found with
20.0 % MMT and 0.1 g boric acid. The optimal release rate for B was re-
corded 25.561 % after 6 days.
Intercalation of molybdenum anions in a Mg-Al-LDH nanocomposite
deploying different methods of synthesis was also performed to analyze
the release behavior of the molybdenum anion in different reaction condi-
tions (Bendinelli et al., 2016). However, any molybdenum-loaded nano-
composite for application as fertilizer material is not developed yet .
4.3. Nanocomposite-based biofertilizers
The application of nanocomposites as a matrix for the immobilization of
different biofertilizers has resulted in the development of nanobiofertilizers
in the present day. However, this strategy is still at early stage. Recently, a
bio-nanocomposite that can stimulate the growth of lettuce plants was pre-
pared by immobilizing a nitrogen-fixing bacteria of Streptomyces spp. in a
layered double hydroxide-based nanocomposite matrix (Velázquez-
Herrera et al., 2022). In comparison to the individual components used
for the nanocomposite matrix development, with or without microorgan-
isms, the bio-nanocomposite with a specific surface area of 375 m2 g−1
was particularly successful because, in only 14 days, the lettuce plants
grew to a length of 36 mm, whereas the individual components were
found to be almost inactive. In another study by He et al. (2015), the
Raoultella planticola Rs-2 was enclosed in sodium alginate and bentonite
composites to prepare a slow-release biofertilizer with good efficacy and
cheap production costs. About 88.9 % of the Rs-2 in dried bentonite/algi-
nate microcapsules survived after six months of storage. In comparison to
alginate alone, the effective amount of alginate for the creation of suitable
composite microcapsules was significantly lower. Moreover, the release
rate, swelling, and biodegradability all decreased as bentonite content in-
creased while improved as sodium alginate concentration increased.
In another study, Pandey et al. (2022) developed one acylated
homoserine-coated iron‑carbon nanofiber with the aim of enhancing the
soil rhizomicrobiome. On application to the Triticum aestivum and Cicer
arietinum, the nanocomposite-based biofertilizer resulted in increased
plant biomass, crop output, and plant resilience to biotic stress. In a similar
study by Gahoi et al. (2021), a physical blend of bacterial (Panebacillus
polymyxa) endospores trapped in activated carbon beads and Fe‑carbon
nanofibers (Fe-CNFs) coated with acylated homoserine lactone (AHL) was
prepared. While the endospores remained in the soil, AHL/Fe-CNF was
found to be transported to plants by an apoplastic pathway through roots
to shoots and leaves, promoting plant growth through the generation of in-
dole acetic acid and siderophore. Moreover, the application of the prepared
nanobiofertilizers to the Triticum aestivum and Cicer arietinum showed an in-
crease in root length, biomass, and protein as well as chlorophyll contents.
Bio-fertilizer is an interesting area for agricultural sustainability
(Mahapatra et al., 2022). However, the safety concerns related to the appli-
cation of nanocomposite-based biofertilizers include assessment of the ef-
fect of the microorganism(s) used in the development of the biofertilizers
on different non-target soil microorganisms for maintaining ecological
safety. Several test methods are already available in this regard (Sharma
et al., 2012). For instance, genetic and physiological experiments have
been carried out to evaluate the impact of biofertilizers on non-target com-
munities using both culture-dependent and culture-independent (Finger-
printing methods like “Denaturing Gradient Gel Electrophoresis” (DGGE),
“Amplified Ribosomal DNA (rDNA) Restriction Analysis” (ARDRA), “Ribo-
somal RNA (rRNA) Intergenic Spacer Analysis” (RISA) for microbial com-
munity profiling; estimation of different enzymes like dehydrogenase,
chitinase, esterase, nitrogenase, phosphatase; “Phospholipid fatty acids”
(PLFAs) analysis) methods. The assessment of microbial community struc-
tures using plating and cytochemical techniques is a useful tool for
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determining how biofertilizer affects indigenous microflora. DNA is consid-
ered as an effective marker to evaluate community variety and potential.
The messenger RNA (mRNA) extraction from the soil is also significant
enough to include the experiment for efficiency as well as risk assessment
studies with biofertilizers (Mahanty et al., 2017). Moreover, the shelf-life
of the prepared bioformulations is an important issue to exploit the poten-
tial of these microorganisms for a longer period of time. To achieve a long
and sustainable shelf-life behavior of nanocomposite-based biofertilizer
products at ambient temperature, the selection of a suitable matrix compat-
ible with the physiological behavior of the entrapped microorganisms
along with maintaining proper pH and moisture content of the biofertilizer
formulation is therefore paramount (Brar et al., 2012). The shelf life of
biofertilizers may also be enhanced by pre-sterilizing the carrier matrix
and enriching it with nutrients so that the microorganism may survive
and/or develop in a non-competitive microenvironment (Yardin et al.,
2000). Quality control of nanocomposite-based biofertilizer products is an-
other important criterion to achieve maximum benefits at the field level in
terms of improving soil health, and increasing crop yield and quality.
Proper packaging, absence of contaminating microorganisms, presence of
an adequate quantity of viable microorganisms, and appropriate user infor-
mation are the key parameters to be maintained for getting maximum out-
put from the use of biofertilizers for a long time (Atieno et al., 2020).
5. Effect of NCPFs on environmental protection
Nanocomposite intervention in smart nutrient delivery systems over-
comes the lower nutrient use efficiency challenges in intensive agricultural
practices. However, the question remains on its effect on soil and plant
health, environmental quality (Oberdörster et al., 2005; Iavicoli et al.,
2017). Because of its reinforcement technology, the persistence of nano-
composite materials in the natural ecosystem comes to the researchers' at-
tention a decade ago. Different pieces of literature questioned its
environmental safety standards as prescribed by its manufacturers but its
promising results were shown by the majority of researchers from different
sectors of agriculture along with some difficulties in its handling
(Oberdörster et al., 2005; Kah, 2015; Iavicoli et al., 2017; Zulfiqar et al.,
2019; Avila-Quezada et al., 2022). Due to providing a barrier to the loaded
nutrients by the nanocomposites to get sustained release results in lesser
sudden exposure of chemicals to different environmental compartments.
Sustained release of chemical nutrients promotes fewer chances of accumu-
lation of chemical species at a particular time point to contaminate the soil;
less chance of leaching and therefore, reduced possibility of surface as well
as groundwater contamination; and reduced chance of volatilization and
hence, lesser possibility of air pollution. The followings are summarized ex-
planations of the effects of the materials used for the preparation of
nanocomposite-based smart fertilizers with respect to environmental
protection.
5.1. Effect on soil quality
The anionic nanoclays i.e. LDHs with high negative surface charge are
able to retain different cationic and anionic nutrients, release rates of
which are more gradual than conventional fertilizers (Nunes et al., 2020).
Reports also have suggested that the application of LDH carries the poten-
tial to ameliorate acid soils (Choy et al., 2007). Thus, the application of
these materials can affect the heavy metal (e.g., As, Cd, Cu, Ni, Co, Mn,
etc.) contamination in soil.
Hydrogels used for the preparation of superabsorbent nanocomposites
are also important in storing soil moisture under dryland conditions
(Chirino et al., 2011). All the soil's physical, chemical, and biological activ-
ities are governed by an ample amount of soil moisture. The optimum soil
moisture varies from time, space, and type of crop to be grown. Hence, hy-
drogel becomes popular in sustainable crop production along with the
maintenance of soil health (Rizwan et al., 2021). Hydrogels, loaded with
nutrients, also serve a dual purpose in sustaining soil health,
i.e., conservation of soil moisture and controlled release of nutrients
R. Chakraborty et al.
(Rizwan et al., 2021). As the questions regarding the biodegradability of
acrylamide-based hydrogels lack rigorous explanations, new-generation
bio-polymers have come into this picture. The cellulose, chitin, and
chitosan-based matrix provide environmental safety due to its enhanced
bio-degradation potential, besides soil moisture conservation and smart nu-
trient delivery when loaded with plant nutrients (Guilherme et al., 2015).
Porous carbonaceous materials such as CNT-based nanomaterials have
been shown to promote growth in crops through the alteration of genes at
the molecular level (Safdar et al., 2022). Generally, these genes are in-
volved in leaf and root growth through moderating auxin levels. Enhanced
biomass can result in increased capturing of atmospheric CO2 through leaf
photosynthesis. These photosynthates can also be transferred to the soil via
root exudates, sequestering carbon in the soil thereby. Again, due to the
higher surface charge density of CNTs, adsorption of N from NH3 can take
place with the expense of NH3 volatilization and leaching of N as NO− 3 As acrylamide is potentially carcinogenic (Koszucka et al., 2020), it should
into groundwater, controlling the soil-N loss while increasing the nitrogen
use efficiency (Safdar et al., 2022). This enables the plant and microbes to
efficiently utilize available soil- N more efficiently. Nano-sized graphene
oxides, metal-oxide-biochars, and zeolites are proven to effectively remedi-
ate these heavy metals from soils through immobilization or adsorption
(Lehman and Larsen, 2014; Xiong et al., 2018; Baragaño et al., 2020;
Mandal et al., 2020; Zhao et al., 2021). Graphene oxides also have antimi-
crobial properties due to their sharp edges and free radical-generating ac-
tivities (Chung et al., 2015). Hence, graphene oxide nanoparticles can
effectively control targeted soil-borne pathogens. Nano-biochar can be ef-
fectively generated from major agro-wastes (straws and fiber wastes)
which takes waste management and carbon sequestration a step forward to-
wards carbon neutrality (Sivakumar and Mohan, 2020; Chaturvedi et al.,
2021; Sajjadi et al., 2021).
5.2. Effect on water quality
LDHs can intercalate nitrate and phosphate into their double-layered
structure, reducing their escape into the groundwater (Sharma et al.,
2021); as a result it has potential to stop eutrophication. Applications of
charged LDHs and nano-zeolites have shown anti-microbial activity in
water bodies, remediating microbiological pollution (Sharma et al.,
2021). The water-softening property of nano-zeolites through the ion-
exchange process enables these materials to be used as a solution for
water treatment (Lehman and Larsen, 2014). The CNFs, biochar, and
CNTs are also used as adsorbents for removal of organic and inorganic con-
taminants from water (Wang et al., 2022).
5.3. Effect on air quality
The CNTs can indirectly adsorb N from NH3, reducing its escape into the
atmosphere when incorporated in NCPFs (Safdar et al., 2022). Due to its
high surface area, nano-biochar is primarily applied in agricultural fields
for curtailing greenhouse gas emissions, i.e., N2O, CH4, and CO2
(Lehmann et al., 2006). Secondarily, biochar retards the CO2 emissions
from residue-burning, input materials for biochar production. Thus, the
nano-biochar based NCPFs may safeguard the air pollution and greenhouse
effect.
6. Problems and limitations of NCPFs
The application of nanocomposite-based fertilizers may not always be
advantageous and encouraged as well due to the inherent drawback of
the materials used for the preparation of nanocomposites. For instance,
due to higher charged surface and free radical generation of nano-sized
graphene oxides, LDHs, and CNTs, the lipid layer of all bacterial (both ben-
eficial and pathogenic) membranes is prone to disruption at a faster rate as
compared to fungi in soil because strong chitin in the cell wall of fungi re-
sists the exposure of the membrane to the nano-particles than peptidogly-
can in the bacterial cell wall (Dwyer et al., 2012; Sharma et al., 2021). As
a result, profuse antimicrobial activity in the rhizosphere can be seen in
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the application of these material-based NCPFs. It may slow down the nutri-
ent conversion process in soil and beneficial activities of the soil
microbiome. The stability of LDH clay is completely pH dependent. Lu
et al. (2020) reported that the magnetic LDH composites were found to
be stable at alkaline pH, whereas the stability was greatly hampered at
pH 5.0 and 7.0. Therefore, the LDH-based NCPFs may not be suitable for ap-
plication to acidic and neutral soils. Green synthesis of nano-zeolites en-
ables high-temperature calcination of the inputs which in turn, generates
large amounts of air pollutants, i.e., NOx and CO2, capable of deteriorating
the air quality (Lehman and Larsen, 2014).
In superabsorbent polymers or superabsorbent nanocomposites interca-
lated with clay and/or reinforced with different fillers such as agri-residue,
biochar, nanocellulose, etc., where acrylamide or any of its derivatives have
been used for synthesis, there may be the chance of environmental threat.
be assessed that there should not be any kind of residual monomer i.e. ac-
rylamide in polyacrylate-based nanocomposites and also in their degrada-
tion products under field conditions. Biodegradability is another concern
for these polymeric nanocomposites.
In case of porous carbonaceous materials, particularly CNFs and CNTs,
shape, length, concentration, degree of aggregation, and surface modifica-
tion (Yan et al., 2019) are very crucial for application in the crop nutrition
sector as these materials have the chances to get transferred to animals, and
even to human through the food chain. Due to the higher tensile strength of
the reinforced nano‑carbon structures (CNFs and CNTs), biodegradation of
CNFs and CNTs in the natural environment is very slow (Frank et al., 2021).
Similarly, the thermal degradation of carbon-rich crop residues under
oxygen-limiting conditions for the production of nano-biochar consumes
a lot of energy, leaving behind an appreciable amount of CO2 emission
along with soot and smoke (Brown, 2012). Moreover, different porous car-
bons have been reported to exert mammalian toxicity (Malatjie et al.,
2022). Therefore, need-based safety assessment is paramount before the
utilization of these porous carbon-based nanoproducts as agri-inputs. For
utilization of nanocomposites to develop biofertilizers, toxicity study of
the immobilized microorganism alone and the developed biofertilizer prod-
uct on non-target organisms is mandatory for ecological safety, which is
lacking in the reported studies.
The limitations of nanocomposite-based fertilizers are very much com-
mon to other nano-enabled fertilizers. These may include a lack of globally
harmonized safety assessment guidelines towards different environmental
compartments as well as non-target organisms, information on registration
requirements, less number of field studies to assess their performance under
realistic conditions, lack of information on their environmental fate, etc.
Different toxicity parameters of metallic nano-sized nutrients have been re-
ported (Paunovic et al., 2020; Pohanka, 2019; Yao et al., 2019). However,
information on the toxicity assessment of nanocomposite-encapsulated
chemical fertilizers as well as bio-fertilizers is scarce. The shelf-life of the
nanocomposite-based biofertilizers should also be sufficient enough to
use them for a long time. The information as well as corresponding studies
are lacking in this regard in the reported literature so far. The analysis of
cost-effectiveness is a prerequisite for any agri-input before large-scale com-
mercialization. This economic aspect has also been ignored in the reported
studies of nanocomposite-based fertilizers. These limitations of NCPFs as
well as the constraints of the application of nanotechnology as a whole on
the crop nutrition sector have therefore been addressed in-detail under
Section 10.
7. Uptake of nano-nutrients by plants
Nano-nutrients enter the plants through highly porous root and leaf sur-
faces or via endocytosis or ion channels; they can also be absorbed by en-
couraging complexation with molecular transporters and root exudates
(Mastronardi et al., 2015). Nanoparticles (NPs) can go through roots in
one of two ways: either the apoplastic pathway or the symplastic method
(Deng et al., 2014). The non-living mode of uptake known as the apoplastic
route allows NPs to pass through cell walls and the gaps between cells. The
R. Chakraborty et al.
Fig. 4. Uptake of nano-nutrients by plants
(The symbol “ ” denotes nano-sized nutrients).
living channel, the symplastic route, uses plasmodesmata to move NPs from
cell to cell. The uptake mechanism of nano-nutrients by plants has been
schematically represented in Fig. 4. The size reduction of nanomaterials in-
creases the surface-to-mass ratio, which favors ions to get adsorbed or
desorbed gradually and steadily for a longer period (Subramanian et al.,
2015; Monreal et al., 2016). The particle size, chemical species, concentra-
tion, plant stage, external environmental conditions, duration of exposure
to the elements, etc. are some of the factors that directly affect nutrient up-
takes. Additionally, soil-dwelling microorganisms, notably mycorrhizal
Fig. 5. Environmental fate of nano-nutrients
(The symbol “ ” denotes nano-sized nutrients).
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fungi, control the uptake of nanofertilizers by plants. As a result of their
symbiotic relationship with plant roots, they offer a better environment
for plants to absorb nano-enabled fertilizers.
Another significant channel is the leaf. The NPs enter the plant cells dur-
ing foliar absorption through stomatal pores (Hong et al., 2014). However,
it has several drawbacks like nutrient mobility and leaf cuticle penetration.
The foliar pathway was used by Rios et al. (2019) to assess the utility of Zn
nanobiocarriers as a possible nanofertilizer in broccoli and pak choi plants
(Brassica rapa sub spp. Chinensis) grown hydroponically without zinc. In
R. Chakraborty et al.
comparison to the prior scenario, the combined use of the micronutrient
and the surfactant (PMP) significantly boosted its leaf concentration,
about three times.
There are alternative support systems, such as endocytosis, that allow
nanofertilizers to enter plants in addition to the primary root and leaf chan-
nels (Shinde et al., 2020). Through membrane-restricted vesicles, the endo-
cytosis process enables the movement of components from the extracellular
medium into the cell (Fan et al., 2015).
8. Environmental fate of nano-nutrients
The environmental fate of nano-nutrients has been represented in Fig. 5.
Various studies can be documented showing the size and concentration-
dependent toxicity of the nanoparticles (NPs), but these studies are limited
only to grow in artificial media or hydroponics. When the nano-nutrients
enter the biological environment, they may show completely different
properties. The environmental fate of these NPs depends upon their physi-
cochemical properties, which can undergo a variety of chemical and phys-
ical changes (Keller et al., 2017). The NPs can undergo various
transformations, including aggregation, adsorption to cell surfaces (micro-
bial and plant root), dissolution, and changes in surface chemistry. The dis-
solution of metal-oxide NPs may lead to the release of metals into the
environment, which may be toxic. After their release into the environment,
NPs may undergo either homoaggregation or heteroaggregation, depend-
ing upon whether they are interacting with other NPs or mineral and or-
ganic compounds (Batley et al., 2013). The impact of nanofertilizers
(NFs) on soil ecosystems is determined by their bioavailability, which is
the actual concentration of the NPs to which the organisms are exposed
(Karimi and Mohseni Fard, 2017).
Although the NFs are applied in low concentrations, they may accumu-
late over time, resulting in much higher concentrations, which may eventu-
ally lead to their toxic effects. Biomolecules present in the natural
environments also influence the transformation of the NFs. NPs may inter-
act with proteins, which are important constituents of any biological sub-
strate, and form a protein corona on their surface (Hu et al., 2016),
leading to surface changes in the NPs. Despite the involvement of proteins,
the presence of electrolytes influences the dissolution and aggregation of
NPs. The pH and the humic components of the soil are also known to affect
the association of NPs with the solid phase. Humic substances present in the
soil may act as stabilizers, but may also induce aggregation, depending
upon their concentration and other abiotic and biotic conditions. Therefore,
the type of soil and its conditions (i.e., moisture content, type and amount
of organic materials, presence of electrolytes, acidity/alkalinity of the
soil, mineral composition, and aeration level) are expected to determine
the stability and transformation of NPs (Grillo et al., 2021).
The degradation of NMs is another phase of transformation. The soil or-
ganisms or the peroxidase enzymes can cause the degradation of the NPs,
which can either increase or decrease the toxicity of the by-products
(Lalwani et al., 2014; Vlasova et al., 2016). In biological environments,
the transformation of NPs is inevitable. The transformation of the NPs ex-
hibits remarkable changes in the properties of NMs, which need to be
assessed before their application.
9. Safety assessment strategies for nanocomposite-based smart
fertilizers
Nanomaterials used in agriculture have a number of toxicity issues that
have been observed to date, including genotoxicity, cytotoxicity, phytotox-
icity, mammalian toxicity, and toxicity to other non-target organisms
(Najahi-Missaoui et al., 2020). Moreover, the uptake of NCPFs by plant tis-
sues may cause a final transfer of these nanomaterials to humans. There-
fore, assessing different safety parameters are prerequisite for large-scale
application as well as adaptation of nanocomposite-based smart fertilizers.
Genotoxicity study is one of the most crucial parameters in this regard. NMs
have the capacity to alter genetic material, which could result in mutations
and ultimately different kinds of malignancies (Elespuru et al., 2018).
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Science of the Total Environment 863 (2023) 160859
Studies on the genotoxicity of NCPFs may be carried out using the existing
guidelines given by the Organisation for Economic Co-operation and Devel-
opment (OECD). Need-based Cytotoxicity tests, or toxicity to cells, should
also be carried out to assess the risks associated with these nano-products.
This type of study must be undertaken using different existing techniques
such as ATP Cell Titer-Glo, trypan blue, cell impedance, colony-forming ef-
ficiency, live/dead cell counts, etc. (Saifi et al., 2018). The different proto-
cols for testing the toxicity parameters of nanoparticles as suggested by the
EFSA Scientific Committee (2011) and guidelines for the evaluation of
nano-agri-input products by the Government of India (2020) have been en-
listed in Table 3. According to the regulations of the relevant regulatory
bodies, comparative efficacy studies of conventional versus NCPFs must
be conducted. It is also necessary to generate information on phytotoxicity,
and persistent behavior in various environmental compartments, particu-
larly in soil and water. Moreover, the impact of these nano-based input
products on natural enemies, soil microorganisms, and earthworms should
be assessed before their release for large-scale applications (Chakraborty
et al., 2021).
10. Present constraints of adoption of nanotechnology in crop nutri-
tion sector
Due to their greater effectiveness in releasing nutrients under controlled
conditions, nanocomposite-based fertilizers in agriculture have become
more popular than conventional fertilizers. The incorporation of nanoparti-
cles (NPs) in different matrices provides a better aspect for smart delivery
systems, good stability, controlled release, and uniform distribution.
These nanocomposites protect NPs from being lost or unaware dispersions.
However, several problems have been detected in the use of nanocompos-
ites which are stated below:
10.1. Lack of proper guidelines and legislative framework
The safety assessment guidelines and regulatory frameworks for
nanofertilizers are different in different countries (Subramanian and
Rajkishore, 2018). For instance, the Registration, Evaluation, Authorisation
and Restriction of Chemicals (REACH) evaluates the potential risk of any
nano-sized chemicals to the health of the workers and different environ-
mental compartments in European Union countries. To accomplish this,
all chemical manufacturers and importers should undertake the safety as-
sessment guidelines as mentioned in REACH Regulation (EC) No. 1907/
2006. However, in China, all nano-agri-input products including
nanofertilizers are regulated by Chinese Food Safety Law. In India, the
“Guidelines for Evaluation of Nano-Based Agri-Input and Food Products
Table 3
Toxicity assessment methods of NCPFs.
Test parameter OECD test method no.a
Dermal toxicity 427 (in vivo), 428 (in vitro)
Genotoxicity (in vitro) 476, 487
Genotoxicity (in vivo) 474, 488, 489
Eye irritation 437
Repeated-dose 90-day oral 408
toxicity (in vivo)
Inhalation exposure toxicity 403
Chronic toxicity 453
Development and reproduction 414, 415, 416
toxicity
Soils and sediments 222
Soil microbes 216, 217
Water 201, 202, 211
Other test methods
Cytotoxicity LDH release, XTT, MTT, Trypan blue, Alamar blue
Digestion studies (in vitro) Dynamic in-vitro human stomach, Dynamic
using digestion models gastrointestinal digestion system, Human Gastric
simulator
a
Information obtained from OECD website (OECD, 2022).
R. Chakraborty et al.
in India” were released by the Government of India to ensure the safety and
quality of nano-enabled agricultural input products for larger acceptance by
beneficiaries (Guidelines for Evaluation of Nano-Based Agri-Input and Food
Products in India, 2020). Therefore, uniform guidelines for safety assess-
ment and legislative frameworks for use of nanocomposite-based
agrochemical products in agriculture are still lacking around the globe, con-
sidered as the major constraint in the rapid adoption of nanotechnology-
enabled fertilizer products in agriculture (Paul et al., 2020).
10.2. Phytotoxicity
Organic polymeric composites, containing inorganic NPs increased
further attention because of their hybrid compositions (Jeon and Baek,
2010). However, the increased water solubility of these organic polymers
can expose metallic NPs on crops over a shorter period, resulting in bio-
accumulation and phytotoxicity. The severity of these phytotoxicities var-
ied depending on factors like plant species, crop growth stage, greater sur-
face area, concentration, size of NPs, etc. (Navarro et al., 2008). NPs with
positive charges are more poisonous than those with negative charges
(Abdelmonem et al., 2015). During the seed incubation stage, oxidative
damage caused by nano-sized Zn, Cu, and Ti oxides has been demonstrated
to inhibit germination. (Lin and Xing, 2007; Shaw and Hossain, 2013;
Phogat et al., 2016). The toxic effects of CuO NPs decreased the rate of
seed germination and plant biomass in case of rice and root length as
well as the fresh weight in case of Arabidopsis thaliana seedlings (Shaw
and Hossain, 2013). Moreover, CuO nanoparticles (NPs) were found to re-
duce plant growth and change the structure of roots in wheat plants culti-
vated in a sand substrate (Dimkpa et al., 2012). In a study by Hossain
et al. (2016), the ZnO NPs strain adversely reduced root hardness, root
cell survival, and plant growth in soybean. Contrarily, in another study to
assess the potential of the ZnO and MgO nanoparticles as nano-fertilizers
to Citrus maxima at concentrations of 250, 500, and1000 mg L−1, ZnO
nanoparticles revealed low-level toxicity in plants (Xiao et al., 2019). Pho-
tosynthesis is one of the most important plant physiological processes that
is severely impacted by the application of nanoparticles. CuO nanoparticles
have been proven to reduce net photosynthesis rates in rice (Da Costa and
Sharma, 2016) and cucumber (Hong et al., 2016), as well as decreased
chlorophyll concentration in field mustard (Chung et al., 2019) and green
gram (Gopalakrishnan Nair et al., 2014).
Nanoparticles can have genotoxic effects on plants in addition to phys-
iological effects, either directly or indirectly. For instance, CuO nanoparti-
cles have been found to produce DNA damage in grasses and radish
plants, according to Atha et al. (2012). It is also unclear if metal salts or
metal oxide nanoparticles are hazardous to aquatic life or not
(Mukhopadhyay et al., 2022). The results of microarray analysis revealed
that there were no significant variations between the species' transcribed
gene segments when Daphnia magna was exposed to ZnO and CuO NPs
and their metallic salts. Furthermore, it was concluded that only hazardous
metal ions were responsible for the toxicity of ZnO and CuO NPs to
D. magna (Adam et al., 2015). At the cellular level, carbon nanotubes may
be detrimental to the bacteria. Even at low concentrations of single-
walled CNTs (10 μg mL−1), the materials with diverse functional groups
changed the gene and protein expressions of E. coli, causing cell disruption
(Le et al., 2019). Contrarily, by entrapping CNTs in polymeric gels such as
polyvinyl alcohol and alginate, the toxicity of CNTs to bacteria might be
completely reduced (Le et al., 2016).
10.3. Biodegradability
Matrices of nanocomposites have increased thermal stability, stiffness,
storage modulus, and tensile strength over other conventional polymers.
These properties make the nanocomposites very persistent in natural ecosys-
tems and decrease their biodegradability (Laughton et al., 2019). Starch ma-
trix reinforcement with multi-walled carbon nanotubes makes it stiffer and
there is a change in transition over high temperatures (Famá et al., 2012).
Organo-montmorillonite and carbon nanotubes were used to reinforce the
15
Science of the Total Environment 863 (2023) 160859
fillers of polybutylene succinate and polylactide-based nanocomposites
(Sivanjineyulu et al., 2018). Hydrogel-based nanocomposites are made bio-
degradable nowadays with the use of biopolymers such as guar gum, chitin,
chitosan, alginate, gelatin, etc. Previously used materials such as polyacryl-
amide and salts of acrylic acid, make small hydrogel fractions are very diffi-
cult to handle upon drying (Ahmed, 2015). However, currently used raw
materials like chitin and chitosan also have some drawbacks that show lim-
ited control over hydrogel pore sizes and mechanical resistance, while higher
degrees of de-acetylation could affect its biodegradability and regular micro-
pore size distributions in hydrogels (Batista et al., 2019).
Besides toxicities, poor loading capacity of nano-carriers (Demirci et al.,
2017), accidental non-reversible release patterns of nano-composites (Kah,
2015), costly synthesis (Verma et al., 2019), and difficulties in synthesis
processes (Khan et al., 2019) are some of the other nanocomposite related
questionable issues. Sometimes, the physical mixing of nanoparticles with
the polymer matrix may also create defects affecting the composite's me-
chanical properties (Chae and Kim, 2005).
11. Future prospects of nanocomposite-based smart fertilizers
(1) Interactions of nanocomposites with crops, animals, and human be-
ings including transfer of NPs in different trophic levels, co-contamination
with other soil pollutants, and toxicities towards different non-target organ-
isms had been poorly understood (Dimkpa and Bindraban, 2017). There-
fore, toxicity tests and risk assessments of nanocomposites must be
conducted before upscaling the NCPFs. Long-term experiments should be
conducted to validate food chain transfer followed by environment risk as-
sessments of released NPs (Wang et al., 2018).
(2) Generally, laboratory studies on the effect of NCPFs have been car-
ried out on target plants and organisms under controlled conditions, but
their applications cannot guarantee the effects on non-target plants or ani-
mals in an open environment. Therefore, experiments should be carried out
in open fields under natural conditions to extract realistic information. Fur-
ther experiments should also include the efficiency improvement of nano-
composites in arable crops without considerable losses and wastages.
(3) Nanocomposite-based fertilizers are considered as smart fertilizers
because of their engineered smart delivery of nutrients without significant
impact on their surrounding environments (Kottegoda et al., 2012; Solanki
et al., 2015). However, future studies should focus to evaluate the release
patterns and the environmental factors associated with their release
(Yuvaraj and Subramanian, 2015; Kottegoda et al., 2017; Guo et al.,
2018; Rop et al., 2018; Adhikary et al., 2020).
(4) Higher costs and risks are associated with nanocomposites synthesis
(Verma et al., 2019). Researchers must follow the cost-effective green syn-
thesis of nano-composite fertilizer products for agricultural applications
(Hussain et al., 2016). Utilization of inexpensive and naturally available
biochar, porous zeolites, clay minerals, etc. are important to bring down
the expensive nature of NFs.
(5) Due to improved effectiveness and capacity to precisely manage the
amounts and conditions of nutrient release, NCPFs result in a significant re-
duction in fertilizer volume and help to minimize environmental pollution
as well (Guha et al., 2020). The market for nano-enabled fertilizers is
expanding quickly on a global scale. The representative examples of com-
mercialized nanofertilizers from various nations have been enlisted in
Table 4. However, the major issues discussed above are still considered as
the bottleneck for the large-scale commercialization of NFs.
12. Conclusion
The use of fertilizers in agriculture is essential to meet the rising global
food demand. However, in the post-green revolution era, harmful environ-
mental and health issues have been discovered as a result of the improper
use of fertilizers, which has led to greenhouse gas emissions, eutrophica-
tion, groundwater contamination, etc. Due to the reduction of potential
economic losses and, in particular, environmental harm, nanotechnology-
based products, particularly nanocomposite materials, offer a feasible
R. Chakraborty et al. Science of the Total Environment 863 (2023) 160859

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and agglomeration dependent in vitro uptake and cytotoxicity of zinc oxide nanoparti-
Commercialized nanofertilizersa.
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Commercial product Nutrient(s) associated Industry Abd-Elrahman, S.H., Mostafa, M.A.M., 2015. Applications of nanotechnology in agriculture:
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NanoCS N, P, K, Zn LLC, USA Chahardehi, A.M., 2020. Clay-reinforced nanocomposites for the slow release of chemical
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NanoPhos P Acharjee, S., Giri, T.K., Behera, B.S., 2015. Studies on propagation through stem cuttings and
NanoK K effect of biofertilizers on growth of Ocimum kilimandscharicum G. in Odisha condition.
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TAG NANO (NPK PHOS, N,P, K, Ca, Zn Tropical Agrosystem India tured materials for energy and environmental remediation applications. Approaches in
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