Biofertilizers and Nanofertilizers

Science of the Total Environment 803 (2022) 149990
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Science of the Total Environment
journal homepage: www.elsevier.com/locate/scitotenv
Review
Biofertilizers and nanofertilizers for sustainable agriculture:

Phycoprospects and challenges
Durga Madhab Mahapatra a,b, Kanhu Charan Satapathy a,c, Bhabatarini Panda a,d,⁎
a
Center of Environment, Climate Change and Public Health, Utkal University, Vani Vihar, Bhubaneswar 751004, Odisha, India
b
Biological and Ecological Engineering Department, Oregon State University, Corvallis, OR, USA
c
Post Graduate Department of Anthropology, Utkal University, Bhubaneswar 751004, Odisha, India
d
Post Graduate Department of Botany, Utkal University, Bhubaneswar 751004, Odisha, 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
• Dwindling nutrients reserve as a serious

concern for future food security
• Synthetic fertilizers are pollution inten-
sive and environmentally unsustain-
able.
• Wastewater based green algal biomass
as low cost biofertilizers for climate
smart-agriculture
• Algal-nanofertilizers as game changers
for futuristic food production
a r t i c l e i n f o a b s t r a c t
Article history: Increased food demands and ceasing nutrient deposits have resulted in a great shortfall between the food supply
Received 14 June 2021 and demand and would be worse in the years to come. Higher inputs of synthetic fertilizers on lands have re-
Received in revised form 17 August 2021 sulted in environmental pollution, persistent changes in the soil ecology, and physicochemical conditions. This
Accepted 24 August 2021
has greatly decreased the natural soil fertility thereby hindering agricultural productivity, human health, and hy-
Available online 28 August 2021
giene. Bio-based resilient nutrient sources as wastewater-derived algae are promising as a complete nutrient for
Editor: Jan Vymazal agriculture and have the potential to be used in soilless cultivations. Innovations in nano-fortification and nano-
sizing of minerals and algae have the potential to facilitate nutrients bioavailability and efficacy for a multifold
increase in productivity. In this context, various options on minerals nanofertilizer application in agricultural
Keywords: food production besides efficient biofertilizer have been investigated. Algal biofertilizer with the nanoscale appli-
Algae cation has huge prospects for further agriculture productivities and fosters suitable development.
Nanofertilizer © 2021 Published by Elsevier B.V.
Biofertilizer
Agriculture
Wastewater
Algaponics
⁎ Corresponding author at: Center of Environment, Climate Change and Public Health, Utkal University, Vani Vihar, Bhubaneswar, 751004, Odisha, India; Post Graduate Department of
Botany, Utkal University, Bhubaneswar 751004, Odisha, India.
E-mail addresses: mahapatd@oregonstate.edu (D.M. Mahapatra), kanhu_c@yahoo.com (K.C. Satapathy), bhabatarini.bot@utkaluniversity.ac.in (B. Panda).
https://doi.org/10.1016/j.scitotenv.2021.149990
0048-9697/© 2021 Published by Elsevier B.V.
D.M. Mahapatra, K.C. Satapathy and B. Panda Science of the Total Environment 803 (2022) 149990
Contents
1. Sustainable agriculture: smart biofertilizer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

2. Biofertilizer: the way forward . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3. Nanofertilizer intervention: opportunity for modern-day agriculture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3.1. Nanofertilizer production and formulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3.2. Nanofertilizer variants and composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.2.1. Efficacy of inorganic nanofertilizer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.2.2. The usefulness of organic nanoparticles as nanofertilizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.3. Modes of nanofertilizer application: doses and responses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.3.1. Foliar-based applications/phyllosphere . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.3.2. Soil-based application/rhizosphere . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.4. Paradigm shift: nano aided revolution in precision farming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.5. Bibliometric analysis and scope for future work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
4. Nanofertilizer applications and its implications: risk assessments, regulations, and precautions . . . . . . . . . . . . . . . . . . . . . . . . . 11
5. People perceptions, awareness, ethical and market concerns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
6. Conclusion and recommendation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Declaration of author agreement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
1. Sustainable agriculture: smart biofertilizer content, the upstream processes for biofertilizers are cost-intensive
when transported for long distances and therefore necessitates mass
Agriculture is indispensable for human sustenance and elementary production indigenously (Chittora et al., 2020). These bio-based organic
development. To suffice the demand for food grains for 7.9 billion peo- fertilizers either could be from plant or animal sources or can be
ple (projected to be ~10 billion by 2050) 2–3 billion tons of grains (50% microbially derived (Lee et al., 2018). Live microbial biomass is a major in-
increase in annual production) is required. This can be achieved through gredient to these bio-based organic fertilizers. Such microbial agents have
a) innovative farming (Devaney et al., 2017) b) circular bio-economies a multitude of functions (Fig. 2) aiding soil amelioration, nutrient replen-
through Agri-technologies (Lokko et al., 2018) c) precision farming ishment, and conditioning (Bhardwaj et al., 2014), ultimately providing
(Wreford et al., 2019) and d) smart nano-interventions for sustainable the crops with optimal nutrients for higher yields and productivity
and climate-smart agriculture. Today, land degradation has affected (Table 1). They are generally applied as living/latent cells to the
the physicochemical and ecological integrity of the soil (Naveen et al., seeds, roots, and soil for uptake. They either inhabit the rhizosphere
2017), deteriorating its fertility dipping the grain yield, and increasing (as in Azotobacter, Azospirillum, Bacillus, Rhodobacter, etc.) or are
the gap between the supply and demand (Ramachandra et al., 2009; present inside the plant as endosymbionts (Anabaena, Rhizobium,
Ramachandra and Mahapatra, 2015). In addition, excessive use of syn- Mycorrhiza, etc.) and ensure the availability of translocated nutri-
thetic fertilizers (Mekonnen et al., 2014) has resulted in nutrients ents as well as other plant growth-promoting activities. Waste-
leaching, surface and groundwater contamination, eutrophication, derived biomass as algae with promising nutrient composition and
greenhouse gas emissions, toxicities, and ill effects on aquatic biodiver- crucial crop growth stimulators can be potential biofertilizers and
sity and human health (Chanakya et al., 2012, 2013; Li et al., 2017). In impart the dual benefit of environmental waste remediation and
this context, organic nutrient sources with a holistic nutrient composi- economic food grain production, where resilient agricultural nutri-
tion from non-edible and underutilized waste sources can be a potential ents are inadequate. Utilization of wastewater-derived algal bio-
option as a resilient nutrient source (El-Bassi et al., 2021). Nutrient-rich mass (Mahapatra et al., 2018) at micro/meso/nanolevels targeting
waste organics from various bioprocesses/environmental pollutants can crop fortification will aid in increasing the bioavailable mineral con-
therefore be nano-functionalized and used as nano-biofertilizers for fos- centration in the soil, together with the supply of plant growth-
tering global agronomy. Wastewaters derived algae possessing suitable promoting compounds and restricting pathogens (Shang et al.,
NPK (Haddad et al., 2017; Mahapatra and Murthy, 2021), biostimulants 2019). Several studies have shown the importance of algae from a
as plant growth-promoting compounds (Chew et al., 2019) and second- variety of sources as a potential biofertilizer besides other microor-
ary nutrients are the future of fertilizers (Mahapatra et al., 2018). A ganisms (Table 1).
schematic representation of the entire value chain encompassing
waste to nano mediated bio fertilization and its applications as in 3. Nanofertilizer intervention: opportunity for modern-day
algaponics is depicted in Fig. 1. Fertilizer applications at the nanoscale agriculture
are highly beneficial in terms of productivity (Box 1) and reduced appli-
cations of chemically synthesized fertilizers due to their excellent phys- 3.1. Nanofertilizer production and formulations
icochemical properties that enable them for an effective and controlled
nutrient release, transport, and plant assimilation. The overall fertilizer Nutritionally enriched bulk forms of fertilizers can be comminuted
use efficiency can be fast-tracked by a suitable amalgamation of or- into minuscule (nanoforms i.e. ideally 1–100 nm) units through various
ganics with nano-functionalized agro nutrients (Prasad et al., 2012; mechano-physical (top-down approach), chemical and biological
Pandey et al., 2019; Fraceto et al., 2016) for sustainable and climate- routes (bottom-up approaches), that eventually facilitates the nutrient
smart agriculture. uptake in crops and thereby reduces nutrient-related toxicity and
losses. The steps for the production of nanonutrient-based fertilizers fol-
2. Biofertilizer: the way forward lowing the aforementioned approaches are elucidated in Fig. 3. There
have been reports of both inorganic and organic, synthesis and formula-
There has been a gradual transition from synthetic fertilizer towards tions for components of chemical fertilizers like ammonium salts, potas-
various bio-based fertilization approaches (Ghosh, 2004). High moisture sium, phosphorus, urea, peat-moss, and substrates as lignin-based plant
2
Fig. 1. Schematic roadmap for integrated technology development and management platform for Algaponics.
wastes, etc. (Rajonee et al., 2017). The synthesis of plant biomass and oxysporum, etc. (Kitching et al., 2015; Panpatte et al., 2016). On the
microbially derived nanonutrient are eco-friendly and simple, compared other hand, higher plants Brassica juncea, Helianthus annuus, Medicago
to other approaches (Chaudhary et al., 2020). Already, many bacteria, sativa, and Sesbania spp. have been used for the superior formulation of
algae, fungi, and angiosperms have been used for nanonutrient synthesis. cobalt, copper, gold, nickel, silver, and zinc nanonutrients. Calcium cyana-
Bacteria as Clostridium thermoaceticum, Desulfovibrio desulfuricans, and mide is a carrier and over which urea is deposited as a new formulation,
Klebsiella aerogenes have been used for the synthesis of Zinc sulfide, which has shown encouraging results in the formation of nitrogenous
Gold, and metal sulfide nanonutrient. Cyanobacteria (e.g. Spirulina, nanofertilizer (Wan et al., 2010). Finely grained urea with a combinatory
Nostoc, Anabaena, Synechocystis, Phormidium, Lyngbya, Oscillatoria, etc.); in mixed compositions with various categories of biofertilizers for a con-
Green algae (e.g. Chlorella, Scenedesmus, Chlorococcum, Cosmarium, trolled release of N-rich fertilizers has been formulated by Wang et al.
Chlamydomonas, Botryococcus, etc.) have been used for the synthesis of (2013a). Components of humic and fulvic acids as ammonium humate
a variety of metallic nano-particles (Chaudhary et al., 2020; Guo et al., mixed with synthetic carrier and peat have been used as ingredients
2020). Metal and metal-sulfide nanonutrients have also been efficiently to nanoscale fertilizers. Such nano components are also stabilized as a
synthesized via a variety of fungus species as Aspergillus spp., Fusarium dispersion of particles of colloidal dimensions within an emulsion
Box 1
Advantages of nanofertilizers.
3
Fig. 2. Variants of biofertilizer used today with examples of model systems for each of these cases.
(Taiz et al., 2015) following varied methods of fertilizer encapsulation. 3.2.1. Efficacy of inorganic nanofertilizer
Nutrients of varied particle dimensions are ingrained with nano-
functionalized materials via a) thin layer of a nutrient coat on the sur- 3.2.1.1. Silver. Physico-chemical and biological ways are being adopted
face of functionalized materials b) nutrients encapsulated within the for silver nanoparticle synthesis. Antimicrobial properties of silver ions
nanofunctionalised materials and c) nutrients as nanoscale suspensions are well known, and thus silver nanoparticles have higher microbicide
dispersed in emulsions. (for fungi, rot, and various plant diseases) attributes compared to its
bulk forms owing to its enormous surface area (Saurabh et al., 2015;
3.2. Nanofertilizer variants and composition Duhan et al., 2017). Such properties will aid better plant disease man-
agement when fortified with biofertilizer. Here we envisage coating
Nanofertilizer's incredible utilization efficacy, absorption rate with biofertilizer with a thin film of silver nanoparticles that acts as a filter
minor nutrients loss can facilitate optimal nutrient uptake and assimila- to undesirable disease-causing pathogenic microbial communities in
tion in crops. Nanofortification through nano-coats over conventionally agriculture. There are studies on silver nanoparticle application as pesti-
used fertilizers can be used for augmenting the availability of the nutri- cides however, reports on the integrated biopesticides coupled with
ents to the assimilatory apparatus of the crop systems, which dramati- nanofertilizers are scant. Wilt pathogenicity control and regulation
cally increases the availability of the nutrients through a slow and in chickpea by Fusarium oxysporum was studied by applications of
sustained release of fertilizers that restricts nutrient loses through 50 nm spherical‑silver nanoparticles (Kaur, 2018). Silver nanoparti-
leaching and/or runoff (Janmohammadi et al., 2016). Such coats also cles biosynthesized from fungus have demonstrated high antifungal
avoid unnecessary interaction of the nutrients with microbes and assure and antibacterial properties acting upon Bacillus cereus, Enterobacter
its surface is protected. Several reports have suggested nanomaterial's aerogenes, Staphylococcus aureus, and Trichoderma sp. at high con-
beneficial role in restricting unwanted contamination and infections centrations (Fatima et al., 2018). In this experiment, the fungus
as in the case of nano-silica coated fertilizer that originates a binary was grown in MGYP (maltose, glucose, yeast potato) broth incubated
film over the surfaces thereby inhibits any contacts, attachments, and at 27 °C for 5 days and the fungal colonies were harvested through
future infections thereby helping the crops for better resistance to dis- sieving. AgNO3 was added to the harvested biomass and was
eases (Rastogi et al., 2019). Besides this silica has been a trusted bioma- incubated in dark for the production of Ag-nano-particles. Silver
terial in its nano form and has been reported to be beneficial in seed nanoparticles obtained were checked and verified through a UV–
nourishment and root development. In terms of adding the pedological Vis spectrophotometer (350–650 nm) then freeze-dried and stored
attributes, the nanoforms have been vital in boosting the hydraulic for further use. Direct application of silver nanoparticles to the
conductivity and moisture-retaining abilities of the soil. Earlier studies crops facilitates plant growth and has shown positive effects even
have clearly shown the advantages of mixing nanomaterials with at low concentrations, with better root and shoot elongation, high
biofertilizers as Bacillus spp. and Pseudomonas spp. that have shown in- leaf surface area, greater chlorophyll, and protein contents in the
creased growth and development of crops under in-vitro conditions case of P. vulgaris and Z. mays at the varied concentration compared
(Karunakaran et al., 2016) thus reestablishing the utility of nanoforms to negative controls (20–100 ppm; Salama, 2012). In terms of soil
as potential biofertilizer. Remarkable improvement in wheat's nutri- amelioration, oxidative dissolution of silver and polyvinylpyrrolidone-
tional contents i.e., high sugar contents have been observed by applying coated silver nanoparticles retarded the nitrification in the soil (Masrahi
nano chitosan-based nutrients as NPK fertilizer (Aziz et al., 2016). Ben- et al., 2014). Such interventions have also been shown to modify the mi-
eficial aspects on seed sprouting, seedling potency, early flowering, and crobes in the rhizosphere.
high pigment concentration as leaf chlorophyll content, faster shoot,
and root growth with higher pod yield were reported by Prasad et al. 3.2.1.2. Nickel. Nickel is an essential component of the plant enzyme ure-
(2012) upon treatment of peanuts with Zinc oxide nanoparticles en- ase that metabolizes urea nitrogen into usable ammonia within the
grained at 25 nm. Similar results were reported when treatment of plant. It regulates mineral absorption, enzymatic action, and many
wheat with silver nanoparticles showed better shoot and root elonga- other plant metabolic processes. Toxic levels of urea can accumulate
tion, pigment content, protein, and starch content (Salama, 2012). Sev- within the tissue in the absence of Ni forming necrotic regions on the
eral studies were conducted by using various nanoparticles viz. Iron, leaf tips. Nickel deficiency causes urea toxicity. Besides this Ni has
Silica, Silver, Titania with different plant systems viz. wheat (Iannone been known to be systemic fungicides used to control cereal nuts. In ad-
et al., 2016), maize (Suriyaprabha et al., 2012), soybean and spinach dition, at micronutrient levels, they assist in increasing crop yields.
(Hong et al., 2005; Yang et al., 2006) have shown an increased plant de- Biosynthesized nickel nanoparticle's antimicrobial activities were eval-
velopment, physiology and many of such studies are enumerated in uated and enumerated against a host of pathogenic microorganisms
Table 2. (Ameen et al., 2021) as
4
Table 1
A compilation of biofertilizer used and their impacts on respective crops.
Biofertilizer category Function in growth Crop systems Productivity/nutrient efficacy References
Cyanobacteria
Anabaena, Anabaenopsis, Aphanothece, Nitrogen fixation, Carbon fixation Supply of Oryza sp., Solanum 20–40 kg/ha Osman et al., 2010;
Aulosira, Calothrix, Camptylonema, nutrients in the submerged rice field, lycopersicum, Zea mays, 18–45 kgN/ha Zarezadeh et al., 2020;
Chlorogloea, Chlorogloeopsis, Produce growth-promoting substances Triticum, Gossypium, Pisum Vaishampayan, 1998; Singh,
Cylindrospermum, Fischerella, Gloeotrichia sativum, Matricaria 1961; Watanabe and
Hapalosiphon, Mastigocladus, Nostoc chamomilla L Cholitkul, 1979
muscorum, Nostoc sp., Nodularia,
Nostochopsis, Oscillatoria, Plectonema,
Rivularia, Scytonema, Stigonema,
Scytonema, Tolypothrix Westiella,
Westiellopsis and Wollea
Brown algae
Ascophyllum nodosum, Ecklonia maxima, Compositional Content - High NPK, Solanum melongena, Piper 12–32 kg/ha Norrie and Keathley, 2006;
Fucus vesiculosus, Laminaria digitata, Carbohydrates (improve aeration and soil nigrum, Vitis vinifera Sharma et al., 2014; Craigie,
Saccharina latissima, Stoechospermum structure under clay conditions that has 2011; Zodape, 2001; Crouch
marginatum better water retention); Plant growth and van Staden, 1993;
regulators, Improves growth and Blunden, 1991
development, Restricts desiccation and
other stress as (halo and drought
tolerance); microbicidal activities for the
virus, bacteria, and fungi, Augments
photosynthetic capacity.
Red algae
Phymatolithon calcareum, Source of carbohydrates and nutrients; McHugh, 2003; Smit, 2009
Lithothamnion corallioides availability of trace metals
Bacteria
Azospirillum N2 fixation, plant hormones synthesis, C4 plants having dicarboxylic 20–35 kg/ha Zeffa et al., 2019
(Alphaproteobacteria) enhanced root morphology pathway of photosynthesis
Azotobacter N2 fixation, plant hormones synthesis, Helianthus annuus, Oryza 15–25 kg/ha Mohamed et al., 2019.
(Gammaproteobacteria) phosphate solubilization sativa, Pennisetum glaucum,
Saccharum officinarum, Zea
mays with few vegetables
and plantation crops.
Bacillus Phosphate solubilizer, a biocontrol agent Abelmoschus esculentus, 30–140 kg/ha Yao et al., 2006; Win et al.,
(Bacilli) Gossypium sp., Oryza sativa, 2019; Bandopadhyay, 2020;
Triticum aestivum Dal Cortivo et al., 2020
Burkholderia Phosphate solubilizer Saccharum officinarum 25–40 kg/ha Paungfoo-Lonhienne et al.,
(Betaproteobacteria) 2014
Clostridium Potassium solubilizer Trifolium repens NA Zeiller et al., 2015
(Clostridia)
Pantoea agglomerans Solubilization of Zn, IAA and siderophore, Triticum aestivum – Kamran et al., 2017
(Enterobacterales) Plant growth-promoting activities
Thiobacillus Sulfur oxidation Oryza sativa, Camellia sinensis, Reddy et al., 2020
(Betaproteobacteria) Triticum aestivum with other
horticultural plants
Fungi
Aspergillus Phosphate solubilizer, potassium solubilizer Lagenaria siceraria, NA Din et al., 2019
(Ascomycetes) Abelmoschus esculentus
Trichoderma viride Phosphate solubilizer, Plant growth Camellia sinensis 53.46 kg/ha Xu et al., 2017
(Sordariomycetes) promotion ability
Mycorrhiza
Glomus, Gigaspora, Sclerocystis, Acaulospora, Solubilization of phosphate, plant hormones Carica papaya, Gossypium, 35–70 kg/ha Cely et al., 2016; Gao et al.,
Scutellospora production, Improves root morphology, Linum, Musa sp., Saccharum 2020
[Arbuscular Mycorrhizal Fungi (AMF)] officinarum, Solanum
lycopersicum, Solanum
tuberosum, etc.
Symbiotic-associations
Anabaena-Azolla association N fixing, PGP Activities, green manures Oryza sativa 40–80 kgN/ha Vaishampayan et al., 2001;
Moore, 1969
Processed and Treated Cyanobacteria and Algal Biomass

Biofilm inoculants: 13–46% Fe and 15–41% enhancement of Fe Oryza sativa – Adak et al., 2016
Anabaena torulosa; Nostoc carneum; and Zn in rice grains compared to negative
Nostoc piscinale; Anabaena doliolum and controls.
Anabaena oscillaroides Improved activity of defense- and
[Cyanobacteria] pathogenesis- related enzymes and yield
parameters.
Municipal wastewater derived algae 35–51% in organic carbon content; 53% Triticum aestivum – Renuka et al., 2017
(as dry biomass): higher leaf chlorophyll; 37–48% increase in
Unicellular Alga consortia – Chlorella sp., grain yield with significantly higher
Scenedesmus sp., Chlorococcum sp., micronutrient (Zn, Fe, Cu and Mn) content
(continued on next page)
5
Table 1 (continued)
Biofertilizer category Function in growth Crop systems Productivity/nutrient efficacy References
Chroococcus sp. in grains, as compared to control with

Filamentous Alga consortia – Phormidium higher values of dehydrogenase activity
sp., Anabaena sp., Westiellopsis sp.,
Fischerella sp. and Spirogyra sp.
[Algal consortia: Cyanobacteria and green
algae]
Anabaena torulosa as novel biofilms- matrix Action against phyto-pathogenic fungi Triticum aestivum – Prasanna et al., 2013
with other microbes through enzyme action of β-1,3-glucanase
[Cyanobacteria and bacilli and/or fungus] and chitosanase activity
Dried cyanobacterial powder: High rice gain yield compared to inoculated Oryza sativa 1.5–2.0 kt/ha increment in Mishra and Pabbi, 2004
Anabaena sp., Nostoc sp., Aulosira sp. and controls productivity
Tolypothrix sp.
[Cyanobacteria]
Spirulina biofertilizer suspension Better germination, high seed viability, LAI Vigna radiata (L.) Wilczek 23–76 kg/ha Aung, 2011
[Cyanobacteria] and crop yield (20% high than negative (Total productivity)
controls)
Air dried algal biomass Faster germination growth of plants Oryza sativa 7–21% increased yields Dineshkumar et al., 2018
Chlorella vulgaris and Spirulina platensis through reduction in sulfate reducing
[Green alga + Cyanobacteria] mechanisms during germination
Catfish aquaponics pond High seed germination; increased root and Vigor: Arugula, Byam red, Pak – Wuang et al., 2016
Spirulina platensis shoot length and a 3-fold increase in choy growth.
[Cyanobacteria] seedling weight, as compared to negative Seed germination: Chinese
controls Cabbage, Kai Lan and White
Crown
Cellular extracts from dry biomass Foliar treatments: increased plant height Roma tomato (S. – Garcia-Gonzalez and
Acutodesmus dimorphus and greater numbers of flowers and lycopersicum var. Roma) Sommerfeld, 2016
[Green algae] branches per plant. Overall for all
treatments (biostimulant, foliar and as
biofertilizers) it showed faster germination,
enhance plant growth and floral production.
Processed marine alga (Laurencia obtusa + Jania rubens): 48.21% Maize (Zea mays L.) – Safinaz and Ragaa, 2013
Laurencia obtusa, Corallina elongata and increase in plant length, 61.84% increase in
Jania rubens K content and increase in leaves number.
[Red alga] (Laurencia obtusa + Corallina elongate):
90.86% increase in plant fresh weight.
All mix: 73.97% increase in phosphorus
content.
Jania rubens: 129.23% increase in the
plants nitrogen content compared with
control.
Dried algal powder Seed treatment: significantly increased fresh Lactuca sativa – Faheed and Fattah, 2008
Chlorella vulgaris and dry weight of seedlings as well as
[Green algae] pigments content
a) Bacteria: Bacillus subtilis, Escherichia coli, Klebsiella pneumonia, conditions. Investigations on titania nanoparticle treatment with ca-
Staphylococcus epidermidis, and Salmonella typhi (Gram −ve) nola seeds showed better seedling vigor and seed germination (@
b) Fungi: Aspergillus clavatus, Aspergillus fumigatus, Aspergillus niger, 2000 mg/L). At such high concentration enlargement of radical and
Candida albicans, and Candida tropicalis. plumule was seen (Mahmoodzadeh et al., 2015). Likewise, titania
application at various doses yielded increased seed germination in
There are many investigations where Ni-nanoparticles have been wheat and showed the detrimental effects of nanofertilizer at high
synthesized from bacteria, fungus, etc. Bacterial strains were grown in concentrations (Feizi et al., 2012). Titania nanoparticles (<4% by
LB broth and 1 mM NiSO4 was added to the cell-free supernatant, incu- concentration) facilitated nitrogen fixation and improved photosyn-
bated for 48 h, and subsequently centrifuged at 7500 rpm for 20 min at thesis with notable growth in spinach (Zheng et al., 2005). Size of
30 °C (Horeyalla et al., 2017). This resulted in Ni-nanoparticles synthesis nanoparticles being very central, titania nanoparticles (~30 nm)
based on the production of secondary metabolites and proteins, which when applied on Z. mays had hindered translocation due to the
could reduce the metal complexes to respective metals. Nickel ferrite higher size of nanoparticles compared to pore sizes of the roots
(NiFe2O4) applications as potential fungicides for plant fungus have (Asli and Neumann, 2009). In a similar study for titania nanoparticles
shown good results in terms of both protection and plant growth when applied in the wheat rhizosphere, there was variability in the
(Sharma et al., 2017). Such nanoparticles have been duly evaluated and translocation owing to selectivity based on sizes and affinity (Du
tested for fungicidal activity against F. oxysporum and C. gloeosporioides et al., 2011).
have been reported to inhibit the incidence of wilt caused by Fusarium
in tomato, capsicum, and lettuce and therefore plays an important role 3.2.1.4. Zinc. Zinc is a crucial micronutrient for crop systems acts as co-
in plant disease management boosting crop growth. factors, metal components, enzyme regulators and is of immense im-
portance for plant physiology. The crop systems acquire the divalent
3.2.1.3. Titania. Titania is one of the most crucial materials in catalysis forms (Zn2+) from aqueous solutions and are delivered in the form of
have shown significant improvements in the soil properties after appli- oxides (ZnO) and sulfates (ZnSO4). About 33% of the global population
cation in nanoforms that has resulted in ameliorating salinity in soil is Zn deficient, attributed to inadequacies of Zn in food mostly the
systems when explored in broad beans, and at 0.01% dose showed in- cereal grains (Guilbert, 2003). With rampant land degradation, there
creased root and shoot elongation, high leaf area index (LAI) with has been a consistent Zn deficiency in the soils; however, Zn as a
greater biomass densities compared to untreated soil with alkaline supplement has not been exclusively looked upon in the present NPK
6
Fig. 3. Steps of production of functionalized nano nutrients for biofertilizer applications.
centered fertilization schemes. If at all there are portions of Zn in chem-

ical fertilizers, they are not bioavailable to meet the zinc demands for oxide (Fe2O3) nanoparticles when applied for A. hypogaea as
the plants. In this context, zinc nanofertilizer can play an essential role nanofertilizer, showed shoot and root elongation, increased biomass,
to evade the prevailing Zn deficiencies in soil and fertilizers, as they phytohormones, antioxidants, and enzyme content (Rui et al., 2016).
are highly reactive in nanoscale compared to their bulk counterparts. Studies in C. maxima upon both γ-Fe2O3 nanoparticles and Fe3+
In terms of efficacy, heightened antimicrobial activity against bacterial treatment showed good growth with high iron accumulation as
and fungal species has been studied in ZnO nanoparticles (Jamdagni equated to controls and Fe (II)-EDTA treated plants (Hu et al., 2017).
et al., 2018), where lower the size, higher the antimicrobial activity In a study with translocated iron oxide, nanofertilizers hydroponically
(Siddique et al., 2013) and antibacterial activity in highly time- showed increased shoot and root growth wherein good growth and
dependent (Sirelkhatim et al., 2015) was reported. ZnO nanoparticles development was dose and time-dependent (Jeyasubramanian et al.,
at varying concentrations with chelated ZnSO4 (bulk grade) in 2016). Carbon-coated Fe-nanoparticles speckled on the leaves showed
suspensions and applied to peanut crops, showed augmented seed better translocation and Fe moved from leaves in all directions to
germination, seed vigor, early flowering, pigments as chlorophyll and other plant parts (Corredor et al., 2009). The magnetic properties and
carotenoids content, pod yield with an improved shoot and root large surface area of nanoscale iron oxide fertilizers have been proven
growth (Prasad et al., 2012). advantageous to the agricultural sector, wherein initial applications
were for remediating contaminated soil and groundwater. The amazing
3.2.1.5. Iron. Essential micronutrient as iron plays a very important role properties of nano zerovalent iron were the key where iron was oxi-
in phyto-metabolic processes as photosynthesis, respiration, DNA syn- dized to ferrous and ferric forms thereby reducing contaminated and
thesis, and repair. Iron is involved in the synthesis of chlorophyll, and undesirable organic matter into complex inorganic molecular com-
it is essential for the maintenance of chloroplast structure and function. pounds (Mukherjee et al., 2016). Nanocrystalline metals (Fe and Cu)
In addition, it serves as an ingredient to many vital enzymes such as cy- have been used to treat seeds of soybean plants, wherein the land appli-
tochromes of the electron transport chain and is indispensable. Nano- cations have shown an increased number of nodules, crop production,
scale iron as a nanofertilizer has the potential to substitute present- and chlorophyll index, (Ngo et al., 2014).
day iron-based chemical fertilizers. Studies have shown that iron
7
Table 2
Nanofertilizer variants with their applications on crops.
Applications/nanofertilizer Dose/concentrations Plants/crops studied Treatment time Plant responses References
Foliar applications
ZnO 15 mg/L Coffea arabica 40–45 days Superior net photosynthesis rate and vigor Rossi et al., 2019
ZnO 10 mg/L Cyamopsis tetragonoloba 4–6 weeks Good growth and physiology, improvement in Raliya and Tarafdar, 2013
biomass vigor and nutrient concentration
ZnO 10 mg/L Abelmoschus esculentus L. 60 days Increased photosynthetic apparatus (efficiency and Alabdallah and
Moench pigments concentration), the activity of CAT and SOD Alzahrani, 2020
activity, reduced proline, and total soluble sugar contents
ZnO + Si 50–150 mg/L (ZnO); Mangifera indica L. 140–150 days High plant growth, nutrients assimilation, and carbon Elsheery et al., 2020
150–300 mg/L (Si uptake
nanoparticles)
TiO2 and SiO2 20 and 30 mg/L Oryza sativa 55 days Improved growth/inhibition of Cd translocation Rizwan et al., 2019
Ag 30– 90 μg/mL Vigna unguiculata 4–7 days Inhibition of pathogenic bacteria like X. Axonopodis Vanti et al., 2019
Al2O3 400 mg/L Solanum lycopersicum 20 days Biocontrol agent against Fusarium Shenashen et al., 2017
Ag 50 mg/L Vigna sinensis 40 days Better root nodulation aiding high soil microbial diversity Pallavi et al., 2016
Ag 150 mg/L Solanum tuberosum 75 days Improved chlorophyll content and catalase activity Sidkey et al., 2016
CuO 150– 340 μg/mL Solanum Lycopersicum 11 days Effectively controlled disease Giannousi et al., 2013
TiO2 10–500 mg/L Linum usitatissimum 2 weeks Increased carotenoids and chlorophyll content, Aghdam et al., 2016
decreased MDA activity, and levels of H2O2
FeSO4 2 g/L Helianthus annuus L. 3 weeks High Leaf surface area, dry wt. of above-ground Torabian et al., 2017
biomass, leaf area, shoot dry weight, CO2 assimilation
rate, CO2 concentration just below stomata,
chlorophyll pigment content, Fv/Fm, and iron content
with reduced Na influx
Fe2O3 30–90 mg/L Dracocephalum Moldavica L 7 weeks Increased the LAI, secondary metabolites i.e. Moradbeygi et al., 2020
phenolics, flavonoids and pigments as anthocyanin
and the boost in the catalase, glutathione reductase,
ascorbate and guaiacol peroxidase, concentration
Se 10 mg/L Sorghum bicolor (L.) 10 days An improved antioxidant system, improved Djanaguiraman et al.,
Moench thylakoid membrane integrity, and composition 2018
Root applications
CuO 200 mg/kg Spinacia oleracea 60 days An enhanced physiological process like Wang et al., 2020
photosynthesis
Ag 50 mg/L and 75 mg/L Triticum aestivum Leaf generation Enhanced development and better heat stress Iqbal et al., 2019
stage tolerance
ZnO 20–25 mg/L Triticum aestivum Growth cycle Better harvest and biomass densities with consistent Du et al., 2019
yields
Fe/SiO2 15 mg/kg Arachis hypogaea, Zea mays 3 days Improved plants growth and biomass density Najafi Disfani et al., 2017
MgO 7– 10 μg/mL Solanum lycopersicum 5–7 days As a biocontrol through suppressing pathogen Imada et al., 2016
Ralstonia solanacearum
TiO2 2–10 mg/L Cicer arietinum 21 days Deceased electrolyte leakage index and MDA levels Mohammadi et al., 2013
SiO2 ≤100 mg/L Transgenic Cotton (bt) 3 weeks DNA delivery, and transport of proteins, and other Rui et al., 2014
biomolecules in plants with improved plant vigor,
shoot and root length, and biomasses density;
Supports the K influx in phyllosphere
TiO2 500–2000 mg/kg Triticum aestivum 12 weeks Enhanced seedling dry weight, relative water Faraji and Sepehri, 2020
content, antioxidative enzymes, increased total
chlorophyll and carotenoids, improved stomatal
activity, and rate of transpiration
Fe 25–100 mg/kg Triticum aestivum 45–80 days Good growth and physiology, enhanced Adrees et al., 2020
photosynthesis, Fe concentration, and reduced
cadmium concentration
Seed priming applications

FeS2 80–100 μg/mL Brassica juncea; Cicer 12–14 h Improved germination and yield Das et al., 2016
arietinum; Daucus carota,
Sesamum indicum, and
Spinacia oleracea;
CNT 50–100 μg/mL Allium sativum, Arachis 24 h Superior seedling growth after germination and, Lahiani et al., 2013
hypogaea, Glycine max, better water intake with biomass density
Hordeum vulgare, Triticum
aestivum, Zea mays
TiO2 0.25% suspension Spinacia oleracea 48 h and 35 days Better biomass density, chlorophyll, N, and protein Yang et al., 2007
content.
Ag 0–10 mM Triticum aestivum 28 days Decreased antioxidative enzyme activity, increased Mohamed et al., 2017
POD activity, proline, sugar content
Ag 1 mg/L Triticum aestivum 2–10 days Wheat germination, growth, induce synthesis of IBA, Abou-Zeid and Ismail,
NAA, BAP contents, and reduced ABA 2018
CNT*/graphene 50–200 mg/L Gossypium hirsutum 7–15 days Higher fiber content, better root and shoot length for Pandey et al., 2019
new seedlings
CeO 500 mg/L Gossypium hirsutum L 24 h Decreased ROS levels, improved root growth An et al., 2020
parameters, better trigger to tolerance pathways
including ion homeostasis
CNT* (multi-walled) 10–200 mg/L Dodonaea Viscosa L. 2–5 days Improved seed germination, the average period of Yousefi et al., 2017
germination, root and shoot lengths, fresh and dry
weights of root and stem
8
Table 2 (continued)
Applications/nanofertilizer Dose/concentrations Plants/crops studied Treatment time Plant responses References
Aquaponics/soilless applications
ZnO 0.2 μM Nicotiana tabacum 10–15 days Enriched plant development, amplified metabolites Raliya and Tarafdar, 2013
production, high enzymatic activities, and physiology
of plants
Si 10 μM Triticum aestivum 15 days Enhanced antioxidants to protect against UV-B Tripathi et al., 2017
generated oxidative stress
Se 1–12 μM Lycopersicum esculentum 10 days Improved stem growth (fresh and dry wt. basis) Haghighi et al., 2014
diameter, root (fresh and dry weight), and greater
root volume
CNT*- Carbon Nanotubes.
3.2.1.6. Copper. Copper is vital as a micronutrient and is required for amino acids, humates, vitamins, natural biostimulants, micronutrients,
many enzymes and proteins; it also facilitates respiration and photosyn- and soil microbes. This adds to an incredible composition for boosting vi-
thesis and is therefore critical to plant metabolism of carbohydrates and tality of crop products, facilitating higher activities especially at the plant
proteins. The nanoscale copper has been used for catalysis, batteries, gas root zones. Whereas, Nanonat comprises vitamins and minerals to in-
sensors, electronics, heat sensor fluids, and antimicrobial agents, etc. duce chemical dressing in the case of crop products. The composition
(Kasana et al., 2017). Fungicidal and bactericidal properties of biologi- varies as 30–50% with the addition of biological nitrogen, phosphorus,
cally synthesized copper nanoparticles showed 3/4th growth inhibition potassium, calcium, magnesium, and other elements in it (Ekinci et al.,
of Phytophthora cinnamomi at 50 ppm concentration and with phenom- 2014). Investigations on organic nanofertilizer foliar application on the
enal inhibition on sporulation and formation of mycelia in case of growth of Cucumis sativus at doses 2 to 4 L/ha have shown higher yield
Alternaria alternata (Banik and Luque, 2017). Biosynthesis of metallic as compared to control. Moreover, an amalgamation of nanozeolite
nanoparticles as Cu can be accomplished by using directly plants and with NPK fertilizers aids in a regulated release of nutrients. The above
microbes or using enzymes, proteins, starch, amino acids, etc. Enzymatic findings suggest immaculate abilities of nanofertilizer or an organic
and non-enzymatic production of copper nanoparticles through an in- base to be used as slow-release fertilizers that regulate the release of nu-
teraction of copper salt with organic compounds are green (environ- trients especially nitrogen (Manikandan and Subramanian, 2016).
mentally friendly) and economic compared to energy-intensive and However, compared to the vast majority of studies on inorganic
expensive laser irradiation methods, spray tools, photochemical/ nanofertilizer, there are only a few studies on organic fertilizers and
electrochemical methods, and vapour-deposition techniques. A full list therefore there is a tremendous scope on algal biomass-based
of Cu-nanoparticle biosynthesis from various plants has been provided nanofertilizer synthesis, fortification, and application. It would be very
by Santhoshkumar et al. (2019). Biosynthesis can be carried out via interesting to note the utility and efficiencies of waste-derived algae-
both extracellular and intracellular matrices. In an intracellular ap- based nanofertilizer application for a) crop improvement b) soil amelio-
proach, the development of plants in metal-rich natural media or ration c) nutrient recycle and d) greenhouse gas abatement. Some of the
metal-rich augmentations for the integration of nanoparticles is per- examples of organic-based nanofertilizer blended with essential nutri-
formed (Biosynthesis of Cu-nanoparticles using copper-resistant ents are PPC Nano comprising of ~20% M protein (Sangeetha et al.,
Bacillus cereus, a soil isolate; Tiwari et al., 2016), whereas, an extracellu- 2019); NanoMax NPK comprising of a blend of organic acids chelated
lar approach involves the use of extracts from various cellular systems with major mineral ions, organic carbon supplements, amino acids, or-
for nanoparticle synthesis (ultrasound-assisted biosynthesis of CuO- ganic micronutrients/trace elements, probiotics and vitamins (Panda
nanoparticles using brown alga Cystoseira triodes; Gu et al., 2018). In et al., 2020); Nanogreen with extracts of corn, grain, soybeans, potatoes,
the case of plant growth stimulating activities, copper nanoparticles coconut, etc. (Sangeetha et al., 2019) and Biozar nanofertilizer being an
augmented seed germination and growth of many crops, with retarded amalgamation of micronutrients, organic materials, and macromolecules
growth at high nanoparticle concentrations (Kasana et al., 2017). Cop- (Kamiab and Zamanibahramabadi, 2016; Rathnayaka et al., 2018;
per oxide nanoparticles have found their use as nutrients, pesticides, Agrimonti et al., 2020). A compilation of yield improvements after the
herbicides plant growth regulators, and as extracts for soil amelioration application of nanofertilizer is shown in Fig. 4.
wherein the studies on its buildup in lettuce and cabbage (~250 mg/L)
have shown reduced water retention and enhanced vegetable growth 3.3. Modes of nanofertilizer application: doses and responses
(Xiong et al., 2017). Moreover, foliar spray application of copper nano-
particles from 50 to 500 ppm concentrations, showed increased yields One of the most important strategies in building novel formulations
with increased bioactive compound contents in fruits (ABA and antiox- is through nanoencapsulation that aids in the controlled release of nu-
idants) and imparted firmness in fruits (Lopez-Vargas et al., 2018). trients/minerals. This is necessary for bringing down the nutrient
doses, improving fertilizer efficiency and soil microflora. Such multipar-
3.2.2. The usefulness of organic nanoparticles as nanofertilizers tite interactions between the plant system, microorganisms, soil, and
Nanoparticles that are organic in origin are synthesized at molecular nanofertilizer require further in-depth investigations for a fundamental
and atomic levels through synthetic chemistry that creates a plethora of understanding. At the time of application and post-administration, it is
formulations as polymer conjugates, capsules, vesicles, liposomes, crucial and notable that during fertigation, the attributes of the
polymersomes, micelles, dendrimers, and polymeric nanoparticles. nanofertilizer viz., stability, persistence, reduced toxicities, solubility, as-
Presently there are a variety of products that are available to be used similatory efficiency, release properties normalized over time, etc. are
as NanoMax-NPK that comprise many protein-lacto-gluconates like or- not to be compromised. Therefore, the mode of delivery of nanofertilizer
ganic acids coupled with chelated nitrogen and phosphate, potassium, becomes of utmost importance and can be categorized as foliar and soil-
oxygen, organic and amino acids with vital organic nutrients, probiotics based applications.
that comprehensively provides a complete nanonutrient package for
crops. Organically devised liquid fertilizers as Ferbanat and Nanonat 3.3.1. Foliar-based applications/phyllosphere
can potentially produce novel nanobiostimulation to aid crop growth This involves delivering the nanofertilizers on the surface of the
(Ekinci et al., 2014). Ferbanat comprises an advanced bio stimulator leaves for the effective, targeted, and timely transfer of nanofertilizers
against stress besides adding soil microflora growth with ingredients as to plants. Many studies have been conducted to assess the efficacy of
9
Fig. 4. Nano-fertilizer applications and effects on crop productivity.

(Sources: Mandeh et al., 2012; Manikandan and Subramanian, 2016; Mazumdar and Ahmed, 2011; Rathnayaka et al., 2018; Yang et al., 2009; Zebarth et al., 2009; Zhang et al., 2011; Zhao
et al., 2013; Zheng et al., 2005.)
nanofertilizer transport through this route in combination with NPK food grains. Although there has been towering production in food-
based molecules. Stomatal transfer of nutrients was observed when grains that had matched the food demand. However, at the same time,
Chitosan-based NPK nanofertilizers were foliar sprayed, and the the environment had been over-compromised, which has resulted in ir-
advanced microscopy results showed nanonutrients translocation revocable damage to the soil microflora, loss in organic content, soil
through the phloem. Nanofertilizer (Chitosan-based NPK) application humus, and inception of pathogen resistance, which is now a matter
on wheat, watermelon (nanocomposite) dramatically increased the of serious concern. In this context, necessary interventions are a requi-
crop productivity parameters as crop, harvest, and mobilization index site. Years of material research, breakthroughs in agricultural technolo-
(Wang et al., 2013b) and have been found to improve plasma mem- gies with a biorefinery approach together can be strategized to deal
brane permeability along with decreased cell morbidity. Crop experi- with such situations. The multifaceted abilities of nano-materials as a de-
ments with gold nanofertilizer revealed shoot elongation and plant livery mechanism, nutrient, sensor, and remediation agent can bring
girth increase with an increased number of branches, pods, and a re- about a revolution in today's modern-day farming. Lab on-chip devices
markable seed yield (Marzouk et al., 2019). In addition to this, for an ef- that can be remotely placed with sensors capable of monitoring the soil
ficient foliar mediated translocation, other key properties besides health, microbial status, and amelioration abilities can be devised with
particle size are the physicochemical environment and nano-climate immaculate accuracy and precision. Moreover, the fortified nanofertilizer
of the region that entails light, moisture, and partial pressure of the can themselves be the sensors that can capture field-based parameters
gases and gas composition; type of plant species (C3, C4 or CAM) and aid in better agricultural management through improved productivity
nanofertilizer application strategies (Birbaum et al., 2010; Aziz et al., and decision making (early detection of plant diseases). Nanoparticle
2016). mediated delivery system, charging the biofertilizers with surficial
neuroreceptors, interventions with nanochips (Duhan et al., 2017) at sev-
3.3.2. Soil-based application/rhizosphere eral agricultural practices would improve resource conservation, enhance
Application of nanofertilizers through the soils targeting plant nutrient recyclability and fulfill the food grain demand through a unique
systems has dual benefits i.e., soil amelioration as well as plant growth approach of nano-based precision farming. With improved methods for
and development. It has been reported that SiO2 based NPK nanofertilizer crop diagnostics, the nano-based sensors with viral detection kits can pro-
was found to be beneficial in saline soils (plant growth-limiting factor) vide early and timely warning of crop infestations that provides sufficient
having good productivity and compositional quality of Cucumis sativus time to the agricultural stakeholders and the farmers to take informed de-
(Yassen et al., 2017) with an enhanced NPK content and reduced Na con- cision and plausibly impart solutions on-site, which was not the case in
tent in the crop. In addition, the soil-based application of hydroxyapatite our as old agricultural practices. Investigations of crop status with nano-
nanorods improved germination rate as a plant growth fertilizer (Bala biosensors (Au, Ag, Cu) have shown remarkable accuracy in the detection
et al., 2014). Investigations on nutrient uptake and assimilation of N and (pathogens) and quantification of crop growth parameters elemental
P in-field moisture conditions with the help of an in-vitro incubation contents, fertilizer flux, moisture transitions, pH stability and has thus
study showed improved nutrient contents in plants. This study also evaded nutrient losses and ensured better crop production (Rai et al.,
showed better P and K release rates from the soil with investigations on 2012).
pH, moisture, and CEC capacities after nanofertilizer applications and Gold-based nanobiosensor is one of the most stable metal nanomaterial
therefore has great prospects for climate-smart farming defying regional biosensors featuring high surface area, surface functionalization abilities
and global constraints (Rajonee et al., 2017; Marzouk et al., 2019). and have been applied for heavy metal detection as well as nutrients appli-
cation in agriculture. In addition, the gold nanoparticle produced by phys-
3.4. Paradigm shift: nano aided revolution in precision farming ical adsorption of β-galactosidase on the surface of the transducer has
aided colorimetric detection of E. coli at a limit of 1 × 102 bacterial cells/
An evolutionary perspective of agriculture has witnessed times with mL (Miranda et al., 2011). Gold-based sensors have also been used for
adequate productivity with no chemical interventions during the pre- covalent immobilization of pyranose oxidase on the surface of trans-
green revolution period following by increased applications of chemical ducer that has been used for detection of glucose at the limit of 50 μM
fertilizers and pesticides for meeting the ever-growing demand for the (Ozdemir et al., 2010).
10
The nano silver biosensors can be in the form of biodegradable nano- etc. were ~0.12 million i.e. ~30% of articles manuscripts. Single keyword
hydrogels which can absorb and release water in a controlled fashion searches on nanotechnology, wastewater, sustainable agriculture, or-
ensuring optimal resource use and have been intended to be applied ganic farming, hydroponics, biofertilizer, and nanofertilizer yielded
in drought areas (Montesano et al., 2015; Pirzadah et al., 2019). Besides 80,112, 68,224, 25,830, 13,858, 3168, 938, and 108 articles respectively.
this, for ensuring pollutant-free waters and run-off nutrient concentra- Joint keyword searches involving numerous facets of agriculture with a
tions, fluorescent nanosensors made from silver nanoclusters have been research focus on specialized areas as fertilizers, organic farming, waste-
used for high precision nitrite detection (Chen et al., 2016). Such high- water, nanotechnology, nanofertilizers, nanoparticles showed 13,473,
sensitivity nanosensors having rich plasmonic properties are being 12,972, 9754, 2411, 154, 88. Wherein the wastewater with its various
used to measure environmental health and prevailing conditions. This uses in terms of algae, hydroponics, biofertilizer, nanofertilizer 1225,
can aid in monitoring, frequently reporting changes and thereby intelli- 173, 102, and 3 respectively. Multi keyword searches with agriculture,
gently controlling crops in/ex-situ. fertilizer, and wastewater; agriculture, nanofertilizer, and wastewater;
Copper nanobiosensor forms essential components for plasmonic nanonutrient, algae and hydroponics and wastewater, algae and hydro-
biosensing used for the quantitative determination of molecular ponics resulted in 1111, 35, 10, and 8 respectively. More notably, there
analytes and kinetic analysis of biochemical reactions. Although, plas- were very few studies on wastewater-derived nanofertilizer as poten-
monic biosensors interfaces are generally made from noble metals, i.e. tial bio-based fertilizers.
Au and Ag (unfeasible at industrial production scale), Cu-based biosen- Although the numbers provided might be indicative, but there is a
sor chips as CMOS (complementary metal-oxide-semiconductor) are great scope for research in the field of algal biofertilizer especially de-
simple, economic, and therefore more advantageous, where the struc- rived from wastewaters and its prospects through Nano-fortification
ture is protected from oxidation by SiO2 and Al2O3 dielectric film coats and consequent nanotisation, in the purview of increasing instances of
on the metallic surface (Stebunov et al., 2018). This enhances their nutrients scarcity in agricultural systems, decreasing soil organic
biosensing abilities due to better localization of the electromagnetic matter, climate change and associated global warming, nutrients, and
field above the biosensing surface apparent from experimental results their unsustainable extraction and industrial fixing of inorganic
where copper biosensors coated with thin films of Al2O3 and SiO2 nutrients as chemical fertilizers. In this context, this study envisions
have respectively shown 75% and 55% higher sensitivity to the prospects of wastewater-derived algae as potential candidates for
refractive index changes, compared to sensor chips made up of pure nanofertilizers through a unique algaponics approach. Environmental
gold metal that have been tested through surface plasmon resonance cleansing processes like wastewater treatment, nutrient recovery
measurements. As an advanced and compact nano biosensor, the through sustainable algal bioprocesses, and consequent nano fortifica-
copper-dielectric circuit is being coated with graphene oxide for organic tion with nanofertilizer production and its application in agricultural
molecule immobilization e.g. nucleotide hybridization (Li et al., 2020). fields will solely facilitate the biorefinery approach suitable for tropical
agrarian economies to accomplish a no waste and high precision agri-
3.5. Bibliometric analysis and scope for future work cultural society fostering sustainable development.
A detailed assessment of the total number of peer-reviewed and 4. Nanofertilizer applications and its implications: risk assessments,
published scientific articles during the last 10 years based on Pubmed regulations, and precautions
Indices on several aspects of agriculture has rendered ~0.38 million
publications as depicted in the bar chart (Fig. 5). In addition, the articles Nanofertilizer that can be prepared from a variety of nanoparticles
on various aspects of agriculture e.g. biotechnology, bioproducts, that has specific surface structures and reactivity in processes viz. reac-
bioresources, engineering, nanosciences, chemical biology, biophysics, tive oxygen species (ROS) generation, free radicals generation, redox
Fig. 5. Bibliometric analysis of research contributions from several aspects of agriculture and the way forward to algal biofertilizer, in the last 10 years.
11
reactions, and dissolutions (Joner et al., 2008; Siegrist et al., 2008). Such application of nanofertilizer in agriculture is in its infancy; however,
activities have resulted in ecological and/ toxicological impacts that are there is a great potential of these nano commodities to the entire value
absent with the bulk particles with similar composition. Nanotechno- chain of agriculture viz. processing, packaging, preservation, transporta-
logical interventions have not only improved the bioavailability of min- tion, storage, and final delivery. Many of the nano based products include
erals to crops for better crop yield but also aided in a decrease in nanofertilizers, nano based pesticides/weedicides, nanosensors, etc.
pathogens due to antimicrobial effects of nano-particles in crops. Fig. 6 (Rossi et al., 2014, 2019), might be consumed with food grains besides
explains the non-targeted cell death/apoptosis due to ROS formation, being in contact with human beings. Their ingress into the human circu-
nano particles undesirable involvement in the cell metabolism conse- latory system and interactions with the viscera requires smartly designed
quently causing premature cell death and might lead to implications toxicity assessments using both in vitro and in vivo methods that ensure
in the growth and the development of the crops. These are unintended safety to the health of humans and the environment.
effects from nano-particles (Dayem et al., 2017) that require further Risks associated with the utilities of nanotechnology products are
probing, with many sets of experiments conducted at various doses being judiciously evaluated and are a gradual process. However, in agricul-
and frequency of application and validation of results. Every technology ture there is a meager quantity of information on current risk assessment
has its pros and cons and therefore the concern is to optimally use the is inadequate for the realization of these products by industries. Due to
nano-nutrients as a precautionary measure that minimally hinders the this, the various stakeholders including the consumers fail to make crucial
growth and development of the crop systems. Such consequences are decisions or have informed choices to use the nano-based products against
likely to happen to crops when we are unaware of the dose–response other products. Lack of data invalidates the procedural utilities of such
and the lethality of nano-particles in the cellular systems. The ecotoxi- products and leads to uncertainties and chaos post-product use in connec-
cological implications upon contact, ingestion, or inhalation depend on tion with both human health and the environment. This affects the very
the architecture (shape, size, structure) and magnitude (quantity) of acceptability; belief in the consistency and reproducibility of the products
the nanoparticles (Aufan et al., 2009). Nanoparticles with diame- and would therefore have long-term constraints during commercializa-
ter ≤ 30 nm are of human and environmental health concern. Toxicity tion. Such triviality and uncertainities pose many questions
tests/assays can be conducted for evaluating possible antagonistic im-
1. Are there standard protocols for the assessment of nano-contaminants
pacts and risks those nanoparticles pose to the health and wellbeing
in an agricultural environment?
of human beings. In vitro and in vivo studies conducted for this have
shown contradictory outcomes, with a similar type of Nanoparticle 2. Do the procedures for toxicity assessment provide information re-
and the organism due to a) noncompliance of a suggestive nanoparticles garding the persistence and delayed toxicity of the nanoproducts?
characterization requirement before toxicity evaluation and b) non- 3. Are there adequate and scientific regulatory frameworks that assure
availability of adequate risk assessment guidelines. Dose metrics are a risk-free nano-product-aided agricultural ecosystem?
one of the possible ways to reduce the dichotomy in the toxicity results. 4. Do we have adequate guidelines on
Dose metrics involve systematic screening of particle charge, concentra- a. Synthesis methods that are green and cost-effective
tion (number/mass), surface area, and net size as a yardstick to evaluate b. Fortification procedure
the nanoparticle toxicity. Such Dose metrics approach can benefit in c. Frequency, dose, and type of application on crops
a) ease of utilization of risk assessment data into the regulatory frame- d. Storage and preservation of nanofertilizer and
work and b) ease in drawing inference from comparative study results e. Risk assessment
that empowers the regulators to frame health-based threshold values 5. What impacts will nano products induce to the natural systems both
for respective metrics. Such exercises eventually aid the evaluators biotic and abiotic?
and decision-makers to compare, analyze and pool both the exposure, 6. Are there new mechanisms for nano-particle tolerance evolving with
hazard data, and finally infer upon the likelihood of health and occupa- the increased exposure of such nano-products into the agricultural
tional risks of nanoparticles. environment?
Ecotoxicological aspects and risks for health and hygiene for varied
nanoparticles viz. C-based, inorganic, and organic nanoparticles can be There could be many other queries that pose questions on uncer-
studied in post-nano-based biofertilizer formulations. Presently the tainties in the agricultural system. Potential risk assessment procedures
Fig. 6. Impact of exposure of fertilizer nanoparticles in plant systems.
12
would slowly evolve with time with an increase in studies related to the Gradually, it is being unveiled that nanotechnology advantages off-
interaction of nano-products with biotic and abiotic parameters. Espe- set the threats as compared with the majority on non-nano products.
cially in the case where the impacts are unforeseen with toxicity at However, the public perceptions towards the nanotechnologies are as
the delayed stage. This can be mapped with the help of dose-response per heuristics, media reporting, etc. (Dudo et al., 2011; Coles and
(relationship between the growth in crops (%) vis a vis the concentra- Frewer, 2013). Because of the present understanding and beliefs that in-
tion of the nanoproducts in the tissue on a dry wt. basis) for the crops fluence the level of awareness and perception towards nanotechnology
in an agricultural set-up (Ware et al., 2014). In the initial stages, the utilities in agriculture, certain ethical questions are pertinent.
growth of the crop is directly proportional to the building up of the nu-
trients in the tissue, up to a certain point (critical concentration) and 1. Eloquent on the fact that there are uncertainties in the implications
this is called as a deficiency phase. After which, with the increase in of Agro Nano-products, in the light of negative impacts on human
the tissue nutrients there is no further growth of the crop which con- health and the environment, should these Nano-products continue
tinues for a period (adequacy phase). Finally, after a certain point the to be commercialized?
nutrients in the tissue become harmful to the crop and are marked as 2. In terms of the use of nano-based biofertilizers that have ample
the toxic phase. Nanofertilizer bio-fortification takes place in the suffi- chances of being incorporated into the food grains, should there be
ciency/adequacy zone. Presently a set of conventional toxicity assess- a mandate to label the nanosized products that are in any way re-
ment assays are performed that focuses on lethality, morbidities, and lated to agricultural processes?
mortalities. For example, does-response at a sub-lethal level in terms 3. What should be the level of public awareness of the environmental
of oral, ocular, visceral, dermal toxicities. This also encompasses implications of the use of nanofertilizer in the entire agricultural
genotoxicity; immunotoxicity; procreative and developmental toxicity; value chains
teratogenic toxicity; growth, rummaging, behavioral changes that are 4. Is there a requirement of building a database that is publicly accessi-
highly expensive and time-intensive (Krewski et al., 2010). Sadly, the ble, wherein the results of the field trials and likely impacts of the
majority of these tests lag in an unswerving prognosis of the delayed farming practice are made accessible?
toxicity that identifies the effects on cells/organelles of an organism as 5. Should an uneducated user/framer opting for nanofertilizers be skill-
a whole, therefore seeking more studies on long-term expression pat- fully educated/trained before using the agri nanoproducts for farm-
terns through genomics and proteomics. Next-generation sequencers ing?
and high throughput metabolite profiling would be highly required for 6. Can suitable alternative methods as algaponics be devised to evade
better accuracy, precision, and timely realization of the impacts on cel- nanofertilizer dispersion/losses?
lular systems. Moreover, with hundreds of nano-compounds being syn- 7. Will a nano aided technological tool that provides choices for
thesized today, it becomes imperative to have these tools for rapid selecting the best nutrient combinations paving a path for intelligent
assessment and the efficient unraveling of the disruption pathways. nano-mediated agri practices be productive for all agriculture stake-
The expected increase in the synthesis and commercialization of holders in fostering agriculture sustainably?
Nanomaterials will eventually lead to environmental accumulation 8. Will the practices that encompass mapping and scrutinizing the im-
and associated effects upon exposure. However, in agriculture, the impacts, collating this information in the form of a database, and devis-
pact and deleterious effects of the proposed nanofertilizer have perhaps ing a tool that uses all this information to formulate and direct
not yet been expounded? A quick survey of the literature shows that sustainable agro practices become the futuristic decision-making
there has been an increase in studies related to the assessment and eval- tools for smart agriculture?
uation of toxic effects of nanoparticles. Studies have reported some toxic
effects from nanoparticles, albeit having many conflicts. Nanomaterial- 6. Conclusion and recommendation
associated toxicity comprises cell proliferation, membrane disruption,
necrosis, apoptosis, DNA damage, and oxidative stress. Similar mecha- Agricultural food grain production is very critical for human suste-
nisms are also reported from metal ions, pesticides, PCBs, and other nance and therefore requires techno-economically viable and environ-
chemicals (Klaine et al., 2008; Barata et al., 2005). mentally sustainable breakthroughs. Globally, there has been a surge
All these attributes as incremental impacts, additive nature, syner- in food grains due to the green revolution, simultaneously the dispro-
gistic roles, stimulation, and antagonistic impacts are crucial in studying portionate use of synthetic fertilizers has deteriorated the environment
the least possible concentrations of nanoparticles that trigger the initia- grossly and therefore seeks due attention. Screening and scrutinizing re-
tion of adversities in an environment where there might be other toxi- silient nutrient sources that are organic are safe and green for the agro-
cants as well. Such studies provide potential information and linkages environment. Fertilizers derived from biological origin have a plethora
that are advantageous for building a regulatory framework and policies of benefits over conventional chemical fertilizers and can be engineered
that safeguard the health of human beings in the context of nano for optimizing the crop spread, the release rate of release, and nutrient
interventions in agriculture. As there are health impacts from human use efficiency in the plants. Organically derived nutrient-rich biomass
exposure to industrial chemicals that are used in agriculture, the simul- as algal cells can provide nutrients, growth-promoting biomolecules
taneous effect of Nano products (nanofertilizer) becomes crucial along with other essential factors required for good growth and vigor
through direct consumption, respiration, and skin exposure. This new in plants. Nutrients profusely available in wastewaters can be suitably
class of compounds is yet to be vetted for their potential risks and there- routed to the crops through algae, compared to the rapidly infiltrating
fore have limitations for their use due to such uncertainties mostly and nutrient-rich runoff from applied chemical fertilizers. One of the
governed by their targeted application. key tasks is to enhance the assimilatory abilities of the nutrients and
control the release rates from fertilizers to avoid losses and evade envi-
5. People perceptions, awareness, ethical and market concerns ronmental pollution. In this context, green biomass as algae can be
transformed into nanoscale levels having suitable shape, size, and
Nanotechnologies have provided key breakthroughs for varied ap- structure with ideal surface properties to devise modern-day agro-
plications across disciplines, but large-scale commercial realization nanofertilizer that is more efficient and drastically reduce our depen-
will only be a reality, when there is a clear-cut understanding of the dencies on synthetic fertilizer. Nanofertilizer-based economies would
mode of action and its effects at varied platforms, scales, and utilities. produce ideal conditions for a spike in productivities, better resource
Therefore, there needs to be attended with ample precautionary mea- conservation, and a less polluted environment paving a path for a viva-
sures foreseeing its possible unintended effects as there are no records cious agro-economy. A due check on the impacts of these nanofertilizers
for this yet. in the environment is essential.
13
Declaration of author agreement Chanakya, H., Mahapatra, D.M., Ravi, S., Chauhan, V., Abitha, R., 2012. Sustainability of
large-scale algal biofuel production in India. J. Indian Inst. Sci. 92, 63–98.
Chanakya, H., Mahapatra, D.M., Sarada, R., Abitha, R., 2013. Algal biofuel production and
All the authors listed have approved the manuscript and agreed to mitigation potential in India. Mitig. Adapt. Strateg. Glob. Chang. 18, 113–136.
authorship and submission of the manuscript. Chaudhary, R., Nawaz, K., Khan, A.K., Hano, C., Abbasi, B.H., Anjum, S., 2020. An overview
of the algae-mediated biosynthesis of nanoparticles and their biomedical applica-
tions. Biomolecules 10 (11), 1498.
Declaration of competing interest Chen, C., Yuan, Z., Chang, H.T., Lu, F., Li, Z., Lu, C., 2016. Silver nanoclusters as fluorescent
nanosensors for selective and sensitive nitrite detection. Anal. Methods 8 (12),
The authors have declared no conflict of interest. 2628–2633.
Chew, K.W., Chia, S.R., Yen, H.W., Nomanbhay, S., Ho, Y.C., Show, P.L., 2019. Transforma-
tion of biomass waste into sustainable organic fertilizers. Sustainability 11, 2266.
Acknowledgment Chittora, D., Meena, M., Barupal, T., Swapnil, P., 2020. Cyanobacteria as a source of
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Coles, D., Frewer, L.J., 2013. Nanotechnology applied to European food production–a re-
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Climate Change and Public Health (ECCPH), Utkal University, Odisha, Marquina, C., Ibarra, M.R., de la Fuente, J.M., Rubiales, D., Pérez-de-Luque, A., Risueño,
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Biofertilizers and Nanofertilizers

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Science of the Total Environment 803 (2022) 149990

Contents lists available at ScienceDirect

Science of the Total Environment

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

Biofertilizers and nanofertilizers for sustainable agriculture:

• Dwindling nutrients reserve as a serious

1. Sustainable agriculture: smart biofertilizer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

Biofertilizer category Function in growth Crop systems Productivity/nutrient efﬁcacy References

Processed and Treated Cyanobacteria and Algal Biomass

(continued on next page)

Biofertilizer category Function in growth Crop systems Productivity/nutrient efﬁcacy References

Chroococcus sp. in grains, as compared to control with

Fig. 3. Steps of production of functionalized nano nutrients for biofertilizer applications.

centered fertilization schemes. If at all there are portions of Zn in chem-

Applications/nanofertilizer Dose/concentrations Plants/crops studied Treatment time Plant responses References

Seed priming applications

Applications/nanofertilizer Dose/concentrations Plants/crops studied Treatment time Plant responses References

CNT*- Carbon Nanotubes.

Fig. 4. Nano-fertilizer applications and effects on crop productivity.

Fig. 6. Impact of exposure of fertilizer nanoparticles in plant systems.

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