Interaction of Engineered Nanoparticles with Agri-Environment

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Interaction of Engineered Nanoparticles with Agri-Environment Saheli Pradhan, and Damodhara Mailapalli J. Agric. Food Chem., Just Accepted Manuscript • DOI: 10.1021/acs.jafc.7b02528 • Publication Date (Web): 06 Sep 2017 Downloaded from http://pubs.acs.org on September 9, 2017

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Journal of Agricultural and Food Chemistry

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Interaction of Engineered Nanoparticles with Agri-Environment

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Saheli Pradhan*a, Damodhara Rao Mailapalli a

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a

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721302, India.

Agricultural and Food Engineering Department, IIT Kharagpur, Kharagpur, West Bengal-

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Corresponding author:

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Saheli Pradhan

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Agricultural and Food Engineering Department, IIT Kharagpur, Kharagpur, West Bengal

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721302, India.

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Email: [email protected]

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ACS Paragon Plus Environment


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ABSTRACT

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Nanoparticles with their unique surface properties can modulate the physiological,

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biochemical and physicochemical pathways like photosynthesis, respiration, nitrogen

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metabolism, solute transport. In this context, researchers have developed a wide range of

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engineered nanomaterials (ENMs) for the improvement of growth and productivity by

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modulating the metabolic pathways in plants. This class of tailor-made materials can

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potentially lead to the development of a new group of agrochemical nano fertilizer. However,

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there are reports that engineered nanomaterials could impart phytotoxicity to the edible as

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well as medicinal plants. On the contrary, there is a series of ENMs which might be

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detrimental, when applied directly and/or indirectly to the plants. These particles sometimes

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can readily aggregate and dissolute in the immediate vicinity; the free ions released from the

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nano-matrix can cause serious tissue injury and membrane dysfunction to the plant cell

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through oxidative stress. On that note, thorough studies on uptake, translocation,

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internalization and nutritional quality assessment must be carried out in order to understand

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ENMs- plant interaction. This review critically discusses the possible beneficial or adverse

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after-effect of nano fertilizers in immediate environment in order to interrelate the impacts of

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ENMs on the crop health and food security management.

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KEYWORDS

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Engineered nanomaterials, sustainable agriculture, plant nutrition, crop productivity,

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phytotoxicity

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INTRODUCTION

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Nanotechnology, the most emerging technology of twenty-first century, is growing to have

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approximately a trillion dollar market by 2020 in all over the world.1 Diverse applications of

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the fine-tuned nanomaterials starts from electronics, biomedical applications, imaging,

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biosensor-technology, drug formulations, and heavy material industry to consumer products

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like strain resistant clothing, cosmetics, sporting goods, and many more.2-4 Engineered

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nanomaterials (ENMs) have been utilized because of their unique properties and

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functionalities.5-7 In this present time of climate change and global warming; agriculture,

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which is the backbone of the modern civilization, demands much attention in the crop

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infrastructure, precision farming, and management practice so that both quality and quantity

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of the nutrients would not be compromised with increase in population throughout the world.

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The present rate of fertilizer addition in nutrient deficient and/or deprived agricultural soil is

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insufficient and expensive for stock up soil fertility and compensate for nutrient removal.

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Therefore, poor farmers are unable to apply sufficient fertilizer repeatedly to abide by with

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the recommended ratio.8 Besides many other distinct and overlapping factors, like

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immobilization, surface runoff, leaching, excessive application of resistant pesticides and

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herbicides, soil erosions, decline in soil fertility, moisture level, temperature affect the overall

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nutritional status.9-11 Appearance of genetically resistant insect, pests, weeds and plant

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disease can also lead to unpredictable changes in soil biota and ecosystem.12-15

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Macronutrients like nitrogen, phosphorus, and potassium along with other micronutrients are

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now becoming the constrains for the plants primary production in majority of the agricultural

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fields.16 Henceforth a new technology has to be evolved in order to provide an improved

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system, surpassing hazardous effects of environmental conditions and nutrient deficiencies.

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The new technology should be a bridge between basic science and applied technology, so that

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the functionality of the different crops and their associated biota would be improved for better



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use of nutrient efficiency, development of best value added products and an alternative for

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environmental remediation.17 In this context, nanotechnology can systematically transform

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the hindrance of various agricultural aspect like food security, low productivity in under

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nourished land as well as uncultivated areas, wastage and degradation of the shelf-life of

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cultivated products, technology, skill, processing and disease limitation of the agricultural

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practices.18,19

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Conventional fertilizers are usually applied to the field by either spraying or broadcasting.

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This limits the primary nutrient to reach to the targeted tissue of the growing crops, as

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majority of the active components are being lost due to leaching, degradation, hydrolysis and

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microbial degradation. Repeated application of conventional fertilizers, therefore, is

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recommended which again causes serious soil and water pollution.

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found to work like tiny shop comprising of billions of tinier factories. These can actively

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participate instantly to the potentially damaged area of concerns21 resulting in opsonization of

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nutrient release through nanofertilizer and improvising better protection through the delivery

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of nanopesticides and nanoherbicides.22

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The main focus of the current article is to study the impact of widely used ENMs and/or

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specialized nano-agrochemicals in plants and its immediately associated ecosystem. Although

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a large number of important reports, perspectives, critical reviews and articles have been

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published in the last 5 years; concluding remarks could not be made on the effect of any

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single nanoparticle (NP) in a plant system based on the available reports. It is because of the

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unique properties of the NP. Most of the properties of the NPs are size, shape or surface

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charge dependent.23-26 Hence it is important to enlist the activities of NPs in plant system

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prior to commercialization. However, little attention has been made on the fate and

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behavioural analogy of plants on physiological, biochemical and metabolic level after NP


10, 20

Nanoparticles are

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treatment. Most of the work has been restricted to the understanding of antioxidative

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pathways in NP-plant interaction.

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Meanwhile, this study includes detailed documentation of plant’s interaction with ENMs on

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physiological,

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bioaccumulation, and internalization in the treated plant model system are beneficiary for

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nutritional quality assessment in agriculturally important crop as well as medicinal plants. As

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the immediately surrounding ecosystem like soil, water-bodies, and micro-environment

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would likely to come in contact with NPs when they would be applied to the field. Therefore,

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it is mandatory to assess the potential influence of NPs on the agri-environment. In

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conclusion, we have also analyzed and offered suggestions to combat the possible unforeseen

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environmental hazards enforced by the nano-agrochemicals in the agro-ecosystem.

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Nanotechnology: What makes it unique in properties and applications?

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Nanoparticles because of its unique size (less than 100 nm in one of the dimensions), shape,

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compositions and atomic arrangements, interact with other ionic particulates, colloids, and

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biomolecules in complex manner.27 Apart from the uniqueness in size and shape, collective

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surface area of ENMs is very high which activates the reactions those occur at the surface

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like catalysis, detection reactions, and reactions associated with physical adsorption.28 Due to

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its size, electronic bands are gradually converted to molecular orbitals resulting in deviation

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from characteristics of any of the solid state physics and quantum chemistry. This, further,

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results in electromagnetic forces and wave-like nature to become the dominant part into their

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functions. High surface energy of ENMs triggers to have short diffusion paths and low

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stability of the interfacial region of the atoms, resulting in a decrease in the melting points.

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This provides them to come out with good semiconductor material with excellent optical

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properties and finite probability of having electron tunnelling properties compared to the bulk

biochemical,

cytological

and

metabolic


level.

The

NP

uptake,


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materials.29,30

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properties and characteristics to understand specialized optical, electrical and magnetic

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properties associated with it. For each of ENMs of different size and shape, the biochemical

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and biophysical properties would be different and material specific.31 Under these

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circumstances, it would be highly interesting to study the particulate behavior at atomic, sub-

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molecular and molecular level so that it could be tuneable for modulating its basic

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physicochemical properties.

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controlled into two and three-dimensional building blocks of molecular assemblages.

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Synthesis of nanoparticles:

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Nanoparticles can be synthesized in two approaches, viz., top down and bottom up under

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chemically controlled kinetics like nucleation, growth, shape, and composition of the starting

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material. Top down approach results in reduction of size to nano-scale well-organized

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assemblies from the bulk materials by isolating atoms from their primary coordinating

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matrices.32-35 Ball-milling, self-assembly, hard template synthesis of NPs, microfluidic

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particle formation, and nanolithography are some of those top down methods widely used

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nowadays. 32-35 Among them, ball-milling is the simplest technique of NP synthesis following

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the concept of attrition. Main limitation of this process is its least homogeneity and

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agglomeration.36 Meanwhile, in hard template synthetic process, porous template like

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anodized aluminium oxide and track etched polymer membrane, are filled with one or more

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materials to fabricate monodisperse NPs.37 By this process, segmented or multi-component

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NPs can be straightforwardly fabricated, but its scale depends only on large surface area,

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density and dissolution kinetics of the template. Microfluidic particle formation defines

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monodisperse nano-emulsion droplets (10-100 µM) by injecting proportionate amount of

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liquid into the micron-sized channel via cooling from the liquid to solid phase, solvent

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evaporation and thermal polymerization.38 Photolithography method is the best amongst

At nano scale thus more attention must be given to study the material

This is how these designed nanoparticles (NPs) could be


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those techniques which fabricates discrete colloidal particle; however this fabrication process

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is quite expensive.39

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Bottom up approaches begins at the atomic or molecular scale linked with chemical reactions,

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nucleation and growth processes to build up to the desired particle size in the form of

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structural composite material.40,41 It is chemically controlled synthetic process which is

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system dependent. Emulsion, co-precipitation methods, micelles formation, reverse-micelle

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formation are the few processes utilized to fabricate ENMs which mostly focuses on

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minimum coagulation or aggregation throughout the synthesis and assembly processes.

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Chemical, thermal and temporal stability can be thus attained which are main factors for

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scaling up relatively low-cost large scale production of ENMs by critically controlling size

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and the quality of interfaces between them. This approach can be effective for agricultural

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usages, as a homogeneous nano-formulation can be synthesized which is expected to be less

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hazardous yet target specific.

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After synthesis, ENMs need to be characterized thoroughly for future applications and

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particle biosafety analysis. Physicochemical characterization of these NPs is important to

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understand the material properties, characteristics and functionalities since these factors

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create functional characteristics like solubility, dispersibility, and stability of ENMs.29

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Microscopic techniques like transmission electron microscopy, scanning electron microscopy

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and atomic force microscopy are the most important techniques that have to be taken into

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consideration for the determination of size, shape topology of the synthesized ENMs. Apart

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from microscopic process, information regarding biophysical and mechanical character is

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very important to know the behavior pattern of ENMs. Fourier transform infra-red, RAMAN,

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X-ray photoelectron spectroscopic, energy dispersive X-ray spectroscopic, X-ray powder

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diffraction and thermo gravimetric-differential thermal analysis spectroscopic techniques

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provide basic information of ENMs like its chemical characteristics, surface functionalities,



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elemental compositions, thermal stability which are very useful to understand the particulate

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nature of the newly synthesized material. Before attempting to study their effect in the plant

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system, it is mandatory to understand well controlled physical and chemical properties of

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ENMs in order to avoid any unwanted environmental hazards beforehand.42 Compared to

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bulk counterpart, distinct physicochemical properties of these ENMs like size, surface

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composition and charge, shape, boiling point, melting point, pH, solubility, purity, stability,

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thermal and isoelectric properties define critically the physiological interactions and provides

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desired modification in cellular functioning in plant system.43 Nanoparticles possess greater

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surface area to volume ratio compared to its bulk counterpart this leads to greater active sites

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for biological activity. Moreover, due to the extremely small particle sizes compared to the

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bulk materials the energy gap between the valence band and conductance band is altered

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which leads to unique absorption and emission property. In a biological network such

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cumulative physicochemical properties could sometimes lead to unique response which is not

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possible for comparative bulk materials. However, detailed characterization of the newly

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synthesized nanomaterial is mandatory, so that mode of action of the material can be

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determined in terms of their biological applications.

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Nanotechnology in plant system

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Nanostructured materials, because of its potentiality to enzymatically activate membrane

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functionalities, motivate to control the functioning of plant cell wall, a gatekeeper for the

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entry of the nutrient of choice inside the cell and also act as a protector to the changing

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environment.44 It is the potential route of any particulate matter like ENMs for getting entry

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into the plant cell and modulating the biological network positively or negatively (as shown

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in Table 1). Considering these, ENMs can be used as either potent fertilizer or as a tool for

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bioremediation in the phyto-sphere. However, prior to commercialization, thorough


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phytological testing in both in vitro and in vivo set up must be carried out (Figure 1) in order

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to assure nutrient use efficiency with no or minimum material toxicity.

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Physiological and biochemical effect of NPs on plant

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Influence of ENMs on green plants depends on its size, shape, chemical properties and

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chemical milieu of subcellular sites to which it is accumulated. Depending upon the chemical

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and physical nature of the plant cell wall, ENMs act as catalyst or interactor or modulator in

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the course of cellular interaction. Physical interaction is mostly dependant on the cellular

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structure or mechanical clogging. Chemically it is influenced by the proximity to associate

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with cellular components like sulfhydryl and carbonyl group which has a potential to change

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cellular homeostasis imparting oxidative stress. Particle size and surface properties also

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influence the plant- ENMs interaction during the transport processes.45 Depending upon the

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size, shape, surface charge and quantum confinement,46 ENMs may act as a dual role in the

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plant system, either as nanofertilizer or phytotoxic agent. Solute dissolution, mechanical

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effect, catalytic activity on bioavailable surface, surface properties owing to the binding with

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proteins and changes in chemical environment play major part in determining the role of

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these chemically tuneable particles inside the plant. In order to assess current risk associated

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to ENMs US Environmental Protection Agency (EPA) has suggested to look into the

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following aspects prior to commercialization: (i) profiling of ENMs’ physicochemical

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properties, (ii) analysis of transformation and biodistribution, (iii) elucidation of

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environmental fate, (iv) potential effect on human health on exposure, (v) effect on

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ecosystem, and (vi) elucidation of shelf life and fate of the ENMs.47

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Carbon nanotube as potential fertilizer

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Different types of ENMs like multi-wall carbon nanotube (MWCNT), alumina, zinc and zinc

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oxide NPs were tested on six economically important crops (radish, rapeseed, rye-grass,



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lettuce, corn and cucumber) to understand seed germination and root growth phenomenon.

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These particles had very little influence in these physiological events except for 2000 mg/L

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doses of nano zinc on rye grass and same concentration of nano zinc oxide on corn. There

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were no interference in sprouting out of cotyledon from the seed coat and had no impact in

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the plant morphology.48 MWCNTs were tested on 15 days treated seven different crops (red

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spinach, lettuce, rice, cucumber, chilli, lady’s finger and soybean) at the concentration of 0,

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20, 100, 1000 and 2000 mg/L to study root and shoot growth, cell death and electrolyte

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leakage at seedling stage.49 At the higher concentration of 1000 and 2000 mg/kg, ENM was

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found to be toxic in red spinach and lettuce followed by rice and cucumber. Changes in

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stomatal structure lead to depletion and water loss inside the leaf resulting in such toxic

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response. However, there was no reported toxic effect on chili, lady’s finger and soybean.

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There was another conflicting result which was showcased on the phytotoxic effect of the

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same ENMs on red spinach seedling after 15 days of exposure.50 The main reason for toxicity

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was detected due to the formation of reactive oxygen species (ROS) followed by cellular

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damage. When supplemented with ascorbic acid, the situation became just reversed which

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indicated the probable cause of system toxicity was due to oxidative stress. Notably, ROS is a

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toxic by-product, produced under various physiological stress conditions. It is plant’s primary

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defence mechanism where they can scavenge the toxic waste with the help of plant

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antioxidant and antioxidative enzymes.51 Role of ENMs on ROS formation and activity

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should therefore be closely examined for future biosafety of the crop as it could be a good

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indicator for evaluating potential threat of the materials on plant.

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Nano titanium oxide and iron oxide

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Zahra et al.52 have also studied the availability of rhizospheric inorganic phosphorus (Pi)

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upon the exposure of nano titanium oxide (TiO2) and nano iron oxide (Fe2O3) @ 0, 50,100,

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150, 200 and 250 mg/Kg dosages on Lactua sativa. SEM and EDAX analyses confirmed the


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uptake of Pi to the root followed by translocation to the shoot which was further confirmed by

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FTIR spectroscopic study. Fe2O3 NP could be easily translocated to the shoot compared to

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TiO2NP and control; even the availability of TiO2 NP in root tissue was found to be more

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compared to Fe2O3 NP and control. This study suggested that NPs might have strong affinity

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to absorb immobile phosphate ion from the soil which might be a good addition to the

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nutrient management system.

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Zero-valent iron NP (ZVI NP)

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Zero-valent iron nanoparticle (ZVI NP), an excellent phosphate ion absorbent was utilized in

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nutrient fortification program where phosphate-sorbed ZVI NP was applied to hydroponically

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grown spinach (Spinacia oleracea) and green algae (Selenastrum capricornutum). Algal and

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plant biomass was found to be increased by 6.7 and 2.2-4 fold, treated in all treatments. When

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phosphate was removed from the algal media, a sharp 3 fold decrease in algal biomass was

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noted. Even iron concentrations were increased significantly in root, leaves and stems of ZVI

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NP treated spinach as compared to the control.53 This signified the probable application of

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recycling and reuse of immobilized nutrients in practicing sustainable agricultural

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management.

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Micronutrient nanofertilizers

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It was reported that micronutrient nanofertilizers like manganese NP (MnNP) and copper

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nanoparticle (CuNP) had positive effects on legume plant, Vigna radiata as they could

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augment the light reaction of photosynthesis without damaging the photosystem. 54-56 Both of

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the NPs had shown promising results in C and N metabolism pathways and eventually no

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significant toxicity was observed within the cellular system.

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Nano cerium oxide and alumina



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Effect of uncoated cerium oxide (CeO2) NP was also tested on wheat and pumpkin in

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presence and/or absence of natural organic matter (NOM), fulvic acid (FA) and gum Arabic

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(GA), to understand the agglomeration, sedimentation, size distribution, surface charge of the

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NP during the plant-NP interaction. 57 More precisely uptake and translocation of those NPs

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into shoots were studied. TEM and SEM images confirmed the presence of NP in the root

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which were translocated to the shoot in pumpkin but not in wheat. However, uncoated NPs

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were more active compared to the NOM coated particles in both the treated plants. Like CeO2

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NP, nano aluminium had no significant effect on kidney bean and ryegrass plants. However,

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about 2.5 fold increase in aluminium concentration was observed in the leaves of rye grass

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while uptake of aluminium in treated kidney bean plants compared to control was not

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reported.58

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Graphene

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Activity of NP depends on the dose, exposure time of NP and plant species. When graphene

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was applied to the seedling stages of cabbage, tomato, red spinach and lettuce for 20 days; a

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steady decrease in root and shoot growth and biomass of the treated plants were observed

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with the increasing concentrations (500-2000 mg/L) of graphene treatments.59 It was due to

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accumulation of ROS which ultimately led to the cell death. Similar concentration dependent

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phytotoxic effect was reported when nanoceria was applied to rice seedling for 10 days at the

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concentration of 62.5, 125, 250 and 500 mg/ L.60

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Nano ceria

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Nanoceria at the concentration of 500 mg/L enhanced electrolytic leakage and lipid

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peroxidation in shoots of the treated seedling. Altered antioxidative enzyme activity and high

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level of ascorbate and free thiol had triggered membrane damage and photosynthetic stress in

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the treated plants. This observation was confirmed by other research group when they used


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the same concentration of nano ceria (0-500 mg/L) in rice seedling with medium amylase

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content for 10 days. There was no visual toxicity though enhanced lipid peroxidation.

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However, electrolyte leakage was observed at higher doses of nanoceria application. Lignin,

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fatty acid and hydrogen peroxide contents were decreased significantly at 500 mg/L treatment

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in rice seedling.61

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Nano copper oxide

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Similar phytotoxic effect was reported when nano copper oxide (CuO NP) was applied on the

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maize plants. However CuO NP had no effect on seed germination but the growth of the

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seedling was inhibited.62 CuO NP, because of its small size (20-40 nm) could be easily

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translocated to shoot from root. But interestingly, split-root experiment and TEM studies had

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reported the translocation of the NP from shoot, back to the root, which highlighted the

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potentiality of NP redistribution after translocation from root to shoot. CuO NP at the

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concentration of 20 and 50 mg/L was also found to inhibit seedling growth of Arabidopsis

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thaliana as well as pollen germination and harvested seeds.63 Cu content was significantly

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higher in root, flower, leave, harvested seeds as compared to bulk CuO and copper ions. CuO

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NP at 0, 20, 50, 100, 200, 400 and 500 mg/L concentration were applied to the Indian

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mustard plant grown in semi-solid half strength of Murashige and Skoog (MS) medium under

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controlled growth chamber for 14 days.64 Morphological changes like suppression of shoot

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growth, modification of root architecture and decline in total chlorophyll and carotenoids

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contents were recorded. CuO NP increased the hydrogen peroxide content leading to

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overexpression of POD, CuZnSOD activity and lignification in due courses. However,

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activities of CAT and APX remained unchanged after NP treatment. This report indicated the

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potential detrimental effect of CuO NP in the plant system.

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Silver NPs



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Silver nanoparticle (Ag NP), was another widely tested nanoparticles in the plants because of

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its prominent industrial usage. There was a high risk of particulate contamination in the

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surrounding environment leading to changes in the ecosystem. Ag NP at 0, 0.2, 0.5 and 1

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mg/L concentrations were tested on rice seedling for 7 days.65 It decreased root length, shoot

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length, fresh weight, total chlorophyll, carotenoids content and sugar content of the treated

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plants; whereas at higher concentrations of 0.5 and 1 mg/ L, it significantly promoted

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hydrogen peroxide formation and foliar proline accumulation. This led to more ROS

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generation, leading to potential damage to mitochondrial membrane potential and genetic

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modification in the expressions of oxidative tolerant in both root and shoot of treated rice

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seedling as observed from RT-PCR analysis. Similar morphological, genetic and proteomic

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changes were observed when 10 mg/L Ag NP was added to wheat seedling.66 It was due to

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the release of silver ions from Ag NP as observed in TEM study. Though at genetic level,

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amplified fragment length polymorphism study did not indicate any significant damage in

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DNA polymorphism; although major proteomic changes, especially to the enzymes related to

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energy metabolism, antioxidative activity as well as storage protein was documented. Down-

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regulation of HCF136 protein which had an integral role in photosystem biosynthesis and

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cytochromeb5 activity along with the up-regulation of eukaryotic translational initiation factor

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5A2 and 60S ribosomal protein indicated plant’s initial attempt to adapt to the changing

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environmental condition. Increased level of cysteine protease triticin γ, a storage protein

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expressed in seed germination and amino acid production signified plant’s response to

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develop primary defense mechanism in the post-Ag NP treatment. Meanwhile, in another

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experiment, different sized Ag NPs (20, 30-60, 70-120, 150 nm) were treated on jasmine rice

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at different concentrations of 0.1, 1, 10, 100 and 1000 mg/L to understand the effect of size of

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NPs on seed germination and seedling growth process.67 It was observed both physiological

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phenomena were influenced by the size-dependency of the NPs, i.e., NP’s activity was


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increased with small-sized NPs and vice-versa. Similar type of inhibitory activity of AgNPs

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was further documented when they were treated on Arabidopsis thaliana.68 Although, it did

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not have any inhibitory effect on seed germination, it had strong negative influence on root

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growth and activity of thylakoid membrane proteins resulting in suppression of growth and

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decrease in chlorophyll content. Altered expression in transcription of antioxidant and

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aquaporin gene hampered cellular homeostasis of water and antioxidative enzymes in post-

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AgNP treated plants.

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Nano zinc oxide

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Nano zinc oxide (ZnO NP) at very high concentration of 1000 mg/L was reported to exhibit

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root growth suppression in wetland plant, Schoenoplectus tabernaemontani as 8.6-43.5 % of

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zinc was accumulated in the treated root while for zinc ions, these were 1.66% to 17.44%.69

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However there was no report of translocation to the shoot which might be a reason for the

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ZnO NP induced root toxicity. This experiment was further validated by Bradfield et al.70

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who had reported the adverse effects of nano ZnO, nanoceria and nano CuO in sweet potato

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(Ipomoea batatas) at the concentration of 100, 500 and 1000 mg/Kg dry weight. However,

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nano ceria had no adverse effect on tuber biomass. Metals released from these three of the

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NPs were accumulated in both the peel and flesh of potato tuber, though cerium content was

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more (75-90%) in tuber and zinc content was more in the flesh (more than 70%). Nanoceria

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was aerially also applied to the hydroponically grown cucumber plant (Cucumis sativus) at

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the concentration of 20, 40, 80, 160 and 320 mg/L for 15 days. NP was taken up by plant

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leaves followed by translocation to the root as observed from ICP-OES and TEM analyses.71

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This result elucidated the uptake and translocation of atmospheric NPs which could be

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potential threat for environment and human health.



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However these ENM mostly impart toxicity at their higher concentrations and/ or their

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activity in plant is size, shape, surface activity specific. Many ENMs were fabricated to

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improve plant growth and productivity like magnetite NPs in soybean plant.72 It not only

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increased the chlorophyll content in sub-apical leaves but also modulated biochemical

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pathways in different stages of photosynthetic reactions. Interaction of NPs with plant is

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highly material specific, size- and shape dependent. Additionally majority of the research

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were restricted to laboratory set up. Hence, there is a huge gap between laboratory scale

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experiments and the same in field trial since environmental and other ecological parameters

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have significant impact in crop cultivation. More realistic approaches must be taken in this

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regards for improving both quality and quantity of crop in real time scenario.

370

Genotoxic and cytotoxic effect of NPs in plant

371

Several reports were documented in the light of genotoxicity and cytotoxicity induced by

372

ENMs on the plants. Several generic endpoints like structural and functional aberrations,

373

genetic abnormalities in various cytological processes like cell cycle, sister chromatid

374

exchange, sticky bridge formations, should be evaluated methodically during the evaluation

375

of cytotoxicity induced within the plants.73

376

Nanoceria and copper oxide nanoparticles

377

When soybean plants were exposed to nano ceria treatments, differential effects on plant

378

growth and elemental uptake were observed.74 Inhibitory effect was observed due to DNA

379

damage and mutation induced by ENMs as analyzed by Random Amplification of

380

Polymorphic DNA study. Similarly oxidatively modified mutagenic DNA lesions were

381

identified, which indicated suppression of plant growth when CuO NPs were applied in

382

agricultural and grassland plants such as radish, perennial ryegrass and annual ryegrass.75


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383

Nickel oxide nanoparticles

384

In depth cytotoxic analysis was reported when nano nickel oxide (NiO NPs) were applied in

385

tomato seedling at the concentration of 0.025- 2 mg/mL.76 2 mg/mL of NiO NP treatment

386

was found to be potentially toxic to the plant causing oxidative stress and mitochondrial

387

dysfunction, ultimately leading to apoptosis or necrosis. There was sharp increase in

388

intercellular ROS production due to over expression of antioxidative enzymes.

389

Approximately 125.4% increase in mitochondrial membrane potential led to increase in

390

number of apoptotic cell (21.8%) and necrotic cell (24%) as compared to apoptotic (7%) and

391

necrotic (9.6%) cell of the control one, found in Comet assay. Because of rapid dissolution of

392

nickel ion from NiO NP, it adversely affected peroxisomal activity and degeneration of

393

mitochondrial cristae leading to mitochondria dependent intrinsic apoptotic damage in the

394

plant.

395

Ag NPs

396

Studies were also conducted on genetic expression of Arabidopsis thaliana after PVP coated

397

Ag NP (20 nm; at the dose of 5 mg/L) treatment for 10 days by microarray technique to

398

identify the specific response to environmental contaminant including the activity of NPs.77

399

Approximately 286 genes were found to be up-regulated after NP treatment with respect to

400

control, and majority of genetic expressions were related to metal and oxidative stress.

401

Expression of 81 down-regulated genes were associated with pathogen and hormonal stimuli

402

like auxin regulated gene involved in organ size, ethylene signaling pathway, systemic

403

acquired resistance against fungus and bacteria. A significant overlap was also observed

404

between the genes differentially expressed in response to Ag NP and silver ion, indicating Ag

405

NP stress arises partly from silver toxicity and partly from NP-specific effects. In another

406

experiment, Ag NP was treated as anti-senescence when it was supplemented with silver ion



407

in 2, 4- dichlorophenoxyacetic acid (2,4-D) induced 8 day old mung bean seedling.78

408

Interestingly proportionate concentration of Ag NP was found to inhibit 2,4-D induced leaf

409

senescence. Activity of senescence associated 1-aminocyclopropane-1-carboxylic acid

410

synthase, lipid peroxidation, level of cytosolic hydrogen peroxide and glutathione reductase

411

were dramatically increased along with the decreased activity of CAT, POD, and SOD after

412

AgNP treatment. This could be used as potent nutrient inducer in the plant tissue culture

413

industry.

414

Specialized NPs

415

Researchers throughout the world are interested to design smart nanoparticle of choice so that

416

important physiological processes could be positively modulated. Photosystem II (PS II) core

417

complex was isolated from thermophilic cyanobacterium (Thermosynchococcus elongatus),

418

and histidine was conjugated to the C-terminus of CP47 subunit of the isolated protein so that

419

gold nanoparticle (Au NP) of 20 nm diameter size could be immobilized onto it.79 This new

420

PSII-Au NP complex was shown to increase oxygen uptake activity during photosynthesis as

421

comparable to that of free PSII. Nanoceria and nano indium oxide (In2O3) were applied for 25

422

days to A thaliana (0-2000 ppm) to understand the plant-NP interaction including overall

423

response, effects and accumulation of rare earth element oxide NPs’ and the underlying

424

biochemical and molecular mechanisms.80 In2O3 NP had little effect except in minor root

425

elongation; meanwhile, nanoceria increased the biomass at 250 ppm but at 500-2000 ppm

426

concentration, growth was seriously compromised even up to 85% in a dose-dependent

427

manner. In qPCR study, changes in gene expression like sulfur assimilation and activity of

428

enzymes related to glutathione biosynthesis pathway, genes related to metal detoxification

429

process were noted after nano ceria treatment. This report is found to be an important

430

documentation in NP toxicity. Use of NP rare earth oxide elements has dramatically

431

increased, yet knowledge of its fate and toxicity has lagged behind.


Page 18 of 59

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432

ZVI NPs

433

Various other ENMs like ZVI NP which is an outstanding source of groundwater

434

remediation, was applied on plant to understand its association with the plant. ZVI NP,

435

because of its unique particle size distribution and reactivity, activated plasma membrane

436

H+ATPase protein in A thaliana. This triggered a 5 fold increase in stomatal aperture by

437

decreasing apoplastic pH; even this phenomenon increased carbon assimilation into the

438

chloroplast under normal sensitivity.81 H+ATPase activity indirectly prompted the auxin-

439

transport from root to shoot in accordance with the chemiosmotic model of auxin. ZVI NP

440

could thermodynamically lower the solubility of iron via water decomposition following

441

electrochemical reaction into the rhizosphere. It facilitated ionic iron to be more available to

442

the rhizosphere which triggered activation of plasma membrane H+ATPase activity in plant.

443

This was one of best possible method generated for practicing sustainable agriculture to

444

remove atmospheric carbon dioxide, reported so far.

445

Metabolic profiling of plant under NP treatment

446

Metabolic profiling of treated plants is the potential biomarker for determining phytotoxicity

447

as it integrates the “-omics” data sets and system biology to understand the key regulatory

448

event in complex gene network.82 With the help of biomarker, it can open new arena which

449

only facilitate improvement of plant varieties but also provide a new tool for effective

450

biofortification and remediation for study activity of species specific agronomic interest and

451

their environmental impact.

452

Copper nanoparticles

453

1

454

Cu NP treatments changed the metabolic profiling of the treated leaves and root exudate of

H NMR and GC-MS based metabolic studies showed that 10 and 20 mg/L concentration of



455

hydroponically grown cucumber plants at their early developmental stages.83 Up-regulation

456

of amino acid during the root exudate sequestration was observed under Cu NP stressed

457

conditions. However, down-regulation of citric acid and upregulation of phenolic compound

458

associated with plant defense system provided a better platform to work against heavy metal

459

stress. This ultimately promoted an alternating detoxification mechanism in Cu NP treated

460

plants. In order to understand the reason behind seed germination of cucumber plant induced

461

by 200 and 400 ppm of CuO NP, SELDI-TOF/MS experiment was performed by the

462

researchers led by Moona et al.84 After NP exposure, 34 proteins were differentially

463

expressed in cucumber seeds, among which 9 expression patterns were significantly more

464

prominent in compared to control and bulk counterpart. Expression of biomarker 5977 m/z

465

protein after CuONP treatment might be reason for appearance of such phytotoxic response

466

in the germinating seeds.

467

Nano ceria

468

When nanoceria was applied to the kidney bean plant at the concentration of 62.5-500 mg/kg,

469

dose dependent increase in nanoceria was observed in organic matter enriched soil compared

470

to LAOM soil.85 Up-regulation of stress related proteins at 62.5 and 125 mg/kg

471

concentrations from quantitative proteome analysis was observed though it had no influence

472

in imparting phytotoxicity in treated kidney bean plants. However, down-regulation of

473

nutrient storage protein like phaseolin and proteins associated with carbohydrate metabolism

474

like lectin had significant effect in the productivity and qualitative nutrient assessment in

475

nano ceria treated plants. Therefore, study of metabolomics in order to understand the

476

complete biological picture inside the plant system after NP treatment has become a

477

fundamental approach for depicting the food-feed relationship in agro-ecosystem.

478

NP under abiotic stress condition


Page 20 of 59

Page 21 of 59


479

Plant is the prime source in ecosystem and uptakes heavy metals along with nutrients from

480

the soil and water by both active and passive transport process. That is why the most

481

vulnerable part of the plant is the root as it comes in direct contact with the heavy metals

482

present in the agricultural soil. 86-88 Plant’s primary response to such metal stress is tolerance

483

and distribution into different organs by sequestration. After getting entered into the cells,

484

heavy metal ions bind to the protein and are able to replace specific cation from the binding

485

sites, resulting in inactivation of enzymes and ROS, which is the prime source of oxidative

486

stress.89

487

Heat shock protein is one of these molecular chaperones that can potentially detoxify such

488

metal induced oxidative stress in the cell.90 Nanoparticles due to its small size and large

489

surface area have become an easy access for binding the heavy metal and thus reduced the

490

bioavailability and toxicity of the metals.91 When nano ceria at the doses of 400 and 800

491

mg/Kg were applied to 10-20 days treated corn plant; there was significant up-regulation of

492

HSP70 protein which ensured phyto-protection on the membrane prior to oxidative injury.92

493

Uptake, translocation of NP in the plants

494

Plant cell wall is a biological semipermeable barrier that regulates the entry of the ions and

495

water into the cell and thus develops a line of first defence mechanism under biotic and

496

abiotic stresses including NP mediated plant phytotoxicity.93 Theoretically ions can take up

497

by the plants via cell wall pore, apoplastic pathway and symplastic pathway as shown in

498

Scheme 1. However plant under normal condition, can absorb ENMs from the surfaces

499

through nano-/ micro-porous cell opening. It is passed through the protecting membrane of

500

the plant, i.e., cell wall, before coming to the plant cell protoplasm. However, pore of the cell

501

wall ranges from 3.5-3.8 nm (pore of the plant root hair) and 4.5- 5.2 nm (diameter of



502

stomatal aperture in palisade parenchyma) to 30 nm (inter-microfibrillar pore diameter) and

503

only small sized ENMs are permitted for their entry into the cell through the cell wall pores.

504

Larger sized ENMs can be taken up by the plants via apoplastic route (transport on the

505

surface between cell membrane and plasma membrane) or by the means of plasmodesmata,

506

called symplastic pathway.94 It was also observed, that ENMs triggered to form new pore on

507

cell wall and/ or enlarged the existing pore so that they could permit their entry inside the

508

plant cell.95 Therefore, in order to elucidate the reason behind the phytotoxicity, it is essential

509

to understand the uptake, translocation, and biodistribution of the ENMs inside the system

510

under normal as well as altered cell homeostasis.96

511

Quantum dots (QDs), nanosized zero-dimensional semiconductor having size-tunable optical

512

and electric properties can be used as potential biomarker for uptake and biodistribution

513

study. It's high fluorescence emission intensity, high photostability, a narrow emission

514

spectrum and broad excitation spectrum make them an excellent choice for the researchers to

515

use as tracking dye for NP-plant interaction studies.97 Cadmium selenide QDs (CdSe QDs) of

516

3.5 nm size was taken up by the cell wall of conifer, Picer omorika. QDs bind with the

517

hydroxyl group of cellulose and C-C, C=C bonds in lignin molecules in plant cell wall during

518

QD uptake.98 This interactive study provided a potential insight of the chemical modification

519

of cell wall component after NP treatments.

520

To understand the route of the NP uptake from the soil, nano ceria, a widely used in

521

semiconductor in manufacturing industry as fuel additive and polishing lenses,99 were FITC-

522

tagged and applied on corn kernel sown in a sandy loamy soil. A mixture of sandy loamy soil

523

and potting soil with high natural organic matter content at the doses of 400 and 800 mg/kg

524

were applied for this purpose.100 Presence of FITC-tagged CeO2 NP in plant cell wall, cortex,

525

and vascular bundle, indicated passive uptake of NPs from soil to the root. Possible reason


Page 22 of 59

Page 23 of 59


526

for finding NPs in the vascular bundle might be the attachment to the inner surface of

527

vascular tissue or the observation time was too short to allow NP to move to the leaf.101

528

Similar types of approaches had also been practiced by other research groups to understand

529

the probable route of the NPs uptake from the rhizosphere to the potentially active site of the

530

plant tissues.102-104 When CdSe/ZnS QDs was supplemented to A thaliana exposed Hoagland

531

solution for 1-7 days, not a single trace of QD was observed in the leaf; they remained

532

aggregated in the root as observed from ICP-OES and fluorescence microscopic

533

techniques.105

534

However, when carbon quantum dots (CQDs) at the concentration of 0.1- 1 mg/mL were

535

applied to the mung bean plants,106 shoot and root length of the treated plants increased in

536

dose-dependent manner. Meanwhile, CQDs followed apoplastic pathway where QDs were

537

transported to leaves from root by vascular system as observed from confocal microscopic

538

technique. This in vivo visualization of CQDs provided potential application in plant-nutrient

539

delivery system.

540

Adverse effect of cadmium selenide quantum dot (CdSe QD) and CuONP were reported

541

when they were treated for 21 days to wetland plant, Schoenoplectus tabernaemontani, grown

542

in hydroponic mesocosms.107 Reduction of the plant biomass and internalization of QDs in

543

root cortical and epidermal tissues were observed after application of 5-50 mg/kg CdSe QD

544

to the plant. Alternatively, MWCNT when applied to the wheat and rapeseed plants, they

545

were translocated to the leaves from the root and mostly accumulated to meristematic zone,

546

like, the peripheral areas and in newly developed leaves, not in the active sites of the plants.

547

However, the transfer factor of MWCNT never exceeded beyond 0.005% indicating classical

548

mechanism of plant tolerance to the external compounds.



549

Similar report on root-shoot translocation of TiO2 NP (14-655 nm) in wheat plant was

550

observed.108 Smallest particle was readily taken up by the root and distributed through the

551

plant tissue without any dissolution or crystal phase modifications. However, there had been

552

a threshold point of 140 nm, above which plant restricted its entry to the root and particles of

553

size of diameter 36 nm or below of it would be accumulated only in root parenchyma tissue

554

in wheat. In order to get entry to the cell, ENMs must enter to the cell following symplastic

555

pathway or by dissolving the pectin matrix of the cell wall or xyloglucan matrix of cellulose

556

and thus creating a larger pore-size in the cell wall. In order to understand the fate and

557

bioavailability of nano ceria in aged soil, it was applied to radish plant grown in the 7 month

558

aged silty loam soil.109 However, ENMs treated aged soil did not interrupt the soil texture and

559

characteristics, though ionic concentration was increased in the processed soil compared to

560

the normal soil. This physiological phenomenon did not hamper the nutritional status or

561

radish growth behavior after the ENMs treatment indicating nano ceria had neutral effect on

562

aged soil. It is noteworthy to mention that, uptake and biodistribution of ENMs by plant cell

563

is itself another very interesting subject and separate critical review must be documented.

564

Effect of NP on plant reserve materials and nutrient quality assessment

565

Plant stores reserve nutrients like α-amylase, protease, starch etc in the germinating seeds for

566

future usage.110 ENMs can modulate functionalities of these enzymes. However, little

567

attention is paid in nutrient quality assessment of food crops. Saharan et al111 have shown,

568

copper-chitosan NP complex when applied to maize seed, significant amount of seed

569

germination vigor along with shoot root length, rootlet no, fresh and dry weight was

570

increased with respect to its bulk counterpart. In due course, both α-amylase and protease was

571

increased though starch and protein content was decreased in germinating seeds after


Page 24 of 59

Page 25 of 59


572

treatment. Such enhancement in seedling growth was due to the mobilization of reserve

573

materials like starch through the higher activity of α-amylase and protease.

574

Research group led by Rico et al., 112 applied nano ceria at 0-500 mg/kg concentration to the

575

agricultural soil to examine biodistribution, nutrient content, antioxidant property and

576

nutritional quality of three different varieties (high, medium and low amylase) of rice grains.

577

Nanoceria significantly altered the metabolic profiling of the fatty acid, starch and

578

antioxidant values except the flavonoids in treated rice grains. In terms of bioaccumulation,

579

more Ce were accumulated in low and medium varieties of rice grain compared to the higher

580

one, indicating nano ceria might compromise the nutritional value of the rice grains.

581

However, when nanoceria was considered to evaluate the physiological and biochemical

582

consequences of three generations of Brassica rapa over a range of 0-1000 mg/L,

583

insignificant inhibitory effect was detected in the first generation of crop plants.113 Plants in

584

second and third generations had reduced growth and biomass compared to the filial and first

585

generations. Seed yield and quality were also compromised in both second and third

586

generation plants due to oxidative stress. The reason for such adverse effect developed in

587

consecutive two generations might be the accumulation of aggregated nanoceria in the cell

588

wall as well as within the intercellular space which could block the water transport pathway

589

during the process of seed development.

590

NP in trophic transfer process

591

Plants are the baseline of the nutrient cycling and terrestrial food webs. Recent studies have

592

carried out to study trophical transfer from the primary producer to the consumer in order to

593

account the potential threat to food chain.114,115

594

Trophical transfer of ENM to the next level depends on ENM stability and surface properties.

595

To understand its mode of action, anionic surfactant, poly (acrylic acid-ethylene glycol)



596

cationic surfactant, polyethylenimine and neutral surfactant, poly(maleic anhydride- alt-1-

597

octadecene)-poly (ethylene-glycol) coated CdSe/ CdZnS QDs were applied to Arabidopsis

598

thaliana116 grown in hydroponic medium. Among them, PAA-EG coated QDs were easily

599

taken up by the root and leaf petiole showing no aggregation or dissolution as observed in

600

PEI and PMAO-PEG coated ones. Direct metal uptake was accounted in the leaf petiole due

601

to ionic dissolution of ENMs inside the cell. Trichoplusia ni, an insect herbivore which was

602

fed with QD treated Arabidopsis sp. leaves, showed reduced biological activities. QD

603

fluorescence was also detected in Ti ni bodies which ensured trophic transfer of surface

604

modified QDs from plant to insects.

605

Further in-depth work was published when rare element oxide ENMs like nano lanthanum

606

oxide (La2O3) amended soil was used for lettuce cultivation along with its bulk counterpart.

607

Leaf tissues were fed to primary consumer, Acheta damesticus, which was again fed to

608

mantises, a predatory consumer.117 After 48 h of depuration, trophical transfer was observed,

609

though biomagnification did not occur and the ENMs concentration in each level was more or

610

less equivalent or less than the bulk material.

611

Similar NP mediated producer-consumer relationship of terrestrial food chain was studied

612

when kidney bean plants were grown in nano and bulk cerium oxide supplemented soil.118

613

Treated plants were fed to primary consumer; Mexican bean beetles (Epilachna varivestis)

614

which were consumed by spined soldier bug (Podisus maculiventris). After 36 days of

615

exposure, no aggregation of NP was observed owing to its limited chemical transformation

616

outside or inside the plant tissue.

617

consumer since 98% of Ce was excreted in bulk material. Ce content in tissues was

618

biomagnified by the factor of 5.3 from the plants to adult beetles and further to bugs. In the

619

same context, when gold nanoparticles (Au NP) were biomagnified in soil-producer-

620

consumer system, there was little transfer from primary consumer, earthworm to predator,

119-122

Low level of Ce concentration was found in primary


Page 26 of 59

Page 27 of 59


621

bull frog in ENMs treated soil.123 The effect of trophic transfer to the aquatic micro-organism

622

to invertebrates has not yet been studied extensively though it has major impact to the

623

ecotoxicological analysis and future human health risk assessment.124-126

624

Effect of NP in agri-environment

625

NPs are predominantly present in environment in the form of aerosol as well as in soil and

626

water surface. These particles either intentionally or unintentionally is mixed up in the

627

surrounding atmosphere which might be ecotoxicologically hazardous for the system as

628

shown in Figure 3.127,

629

eventually, all would come to mix into the water, soil and atmosphere via sewage treatment,

630

waste handling, and aerial deposition.129 Considering such complexity of ENMs, ecological

631

assessment in the agricultural field and its immediate associated microenvironment (soil,

632

aquatic bodies, and waste water treatment) has to be taken into account.

633

Soil is the ultimate sink for the ENMs that come into it through precipitation, irrigation, and

634

sludge disposal. The deposition rate of ENMs is size, shape, surface charge and soil mineral

635

type dependent. This might be the probable reason for electrostatic interaction of negatively

636

charged cerium oxide NP to the clay edges.130 Some clay minerals on the coarse surface of

637

the grains provide binding sites for positively charged ENMs. In case of ENMs absorption

638

from the soil solution to the root surface, pH, ionic strength, zeta potential and particle size

639

distribution of soil plays dominating role into it.131 Reduction in ionic strength increases the

640

magnitude of the repulsive electrostatic double layer forces between the equally charged

641

colloids and mineral grains, leading to the release of ENMs. However, ENMs has emerged as

642

an excellent biomarker for soil remediation as it might work on the most challenging issues

643

like unwanted leaching and surface runoff, irrigation and wastewater effluent discharge.132

644

While NPs pass through the porous medium like soil, either physical filtration (particle size >

128

Whether they were released intentionally or accidentally;



Page 28 of 59

645

pore) or true filtration where ENMs remove from the solution by interception, diffusion, and

646

sedimentation.133 However, depending upon the chemical or physical conditions like change

647

in pH, ionic strength, flow rate, the filtrate can also be resuspended into the system.134

648

Zinc oxide nanoparticle (ZnO NP) in clay minerals soil column exhibited low mobility at

649

various ionic concentrations. The main reason behind this phenomenon was the

650

agglomeration and ionic dissolution of ZnO NP in presence of soil colloids.135 ZnO NP

651

absorbed soil had potentiality to release in the presence of chemical perturbation as observed

652

from Elusion curve. This was due to the surface charge properties, size distribution and

653

interconnectivity of pores among the soil associated with it. Because of this, irregular shaped,

654

large aspect ratio of single walled carbon nanotube had been restricted its mobility in natural

655

soil medium.136

656

As

657

commercialization, it is inescapable that ENMs and their by-products will enter the aquatic

658

ecosystem. Consequently, many questions would arise related to the route of entry, fate in

659

interaction of larger sediments and natural aquatic colloidal particulates and implication of

660

ENMs’ exposure for organism health and ecosystem integrity.137 Since suspended sediment

661

particles would sequester and transport the contaminant ENMs over a significant distance,

662

hydrodynamics and particle size distribution of ENMs and morphology of aquatic bodies

663

would play pivotal role in aquatic ecosystem. In marine and estuarine, sea-surface micro

664

layer with its biomolecular components would modulate the behavioural pattern of ENMs

665

associated with it.138 However, when released into the aquatic environment, activity of NPs

666

mostly depend on particle specific property like size, shape, chemical composition, surface

667

charge and coating; particulate state, surrounding solution chemistry like water pH, ionic

668

strength, ionic composition and NOM content and hydrodynamic properties of ENMs.139 A

669

major concern arises when widely commercialized metal based ENMs come into contact with

the

nanotechnology

industry

is

growing

with

large


scale

production

and

Page 29 of 59


670

the aquatic ecosystem. Their mechanisms of ion dissolution and release kinetics into the

671

water bodies are highly unpredictable and different from bulk materials as they do not always

672

obey the theoretical assumption related to it. For example, high temperature and low pH

673

increase the rate of dissolution from metal and metal oxide ENMs in aquatic ecosystem.140

674

Metal composition will also hamper the active binding site of the organism; form a surface

675

coating on ENMs themselves, hence imparting toxic effect to the system.

676

In order to address these issues related to the active concentration released in the aquatic

677

system and potential harmful impact of it, most widely used Ag NP was tested in 19 wetland

678

mesocosms, along with its bulk counterpart.141 Though Ag NPs were expected to dispose in

679

wastewater stream only, 10% of its concentratin of released effluent would eventually come

680

into contact with aquatic water bodies. Ag NP was found to be toxic leading to significant

681

release of dissolved oxygen content and chloride following the exposure. Dissolved methane

682

concentration was also increased 40 times relative to control which caused serious risk in the

683

aquatic ecosystem. ENMs also cause a range of lethal and sublethal effect in aquatic

684

organism including respiratory toxicity, disturbances to trace elements in tissues, inhibition of

685

Na+K+-ATPase and oxidative stress.142 Only the water system, aquatic organisms were

686

reported to be affected by ENM either positively or negatively.143-155 Hence this field of

687

research should be critically analyzed as it would directly connected to the human food chain.

688

Production of “nano waste”

689

Given the proliferation of ENMs and their unforeseen potential for significant impacts to the

690

aquatic environment, efficient removal of ENMs from the waste water stream is mandatory.

691

The use of constructed wetlands (cell wall) for waste water remediation can be developed

692

because this facility is less expensive, simple in operation and environment and wildlife

693

friendly.156 However ENMs do not produce the same way as normal waste and a standard



694

guideline should be formed for predicting the fate of ENMs deposited in landfills.

695

Unfortunately, more focus has been given in the development of 3rd and 4th generation of

696

nano products without even releasing the fate of nano-waste that would be produced along

697

with it. A strong and effective regulatory system has to be implemented emphasizing the

698

properties of material physical, chemical and physicochemical properties. Besides basic

699

information regarding the nature of ENMs produced and emitted from the manufacturing

700

companies, must be collected. The expected lifetime of the products containing ENMs along

701

with the release rate of ion from the nano waste under the influence of waterland moisture has

702

to be taken into consideration prior to commercialization. In this context, thorough

703

ecotoxicological studies of the desired material must be carried out in the laboratory set up

704

for avoiding uncontrolled and unforeseeable risks associated with it.

705

Future research

706

The concept of clean energy and sustainable agricultural management practice has become

707

more significant for minimizing nutrient deficiency and optimizing crop productivity and

708

yield. Several factors, like loss of active nutrients from the soil through surface runoff,

709

leaching, evaporation, photolysis, and degradation of microorganisms, influence the

710

efficiency of plant productivity. ENMs with their high surface area, increased hardness,

711

ductility, magnetic coupling, catalytic enhancement, selective absorption behavior have been

712

promised to be a potent nanofertilizer for site-specific delivery in plant. However, prior to

713

commercialization, the physiochemical determinant, route of exposure, biodistribution,

714

molecular determinant, genotoxic and regulatory aspects of these ENMs have to be taken into

715

account. These materials in the due course of fertilization, ends up to the waste water stream

716

through irrigation or biosolid disposal and might create an imbalance to the immediate

717

ecosystem consisting of soil, water and atmosphere. Since ENMs can readily dissolute and


Page 30 of 59

Page 31 of 59


718

aggregate in many of the cases, the released ions can be potentially harmful to the living

719

system, starting from single cell green algae to multicellular organisms. In US, the utilization

720

and potential release of ENMs are regulated through the Environmental Protection Agency

721

(EPA) and toxic substance control act. However it appears that there is currently no

722

regulatory body to decide the laws related to the utilization of maximum acceptable levels of

723

ENMs in the environment. Henceforth thorough studies on plants’ physiological, biochemical

724

and anatomical traits should be closely evaluated after ENMs treatment in laboratory

725

condition prior to field testing. Metabolic pathways in treated plants must be checked in order

726

to have a complete understanding of fate and behaviour of the nano-agrochemicals in vitro.

727

All these products would have an exposure to the immediate environment; ecological

728

parameters should be evaluated carefully with the focus on the rhizospheric soil and water

729

bodies where all these products would be eventually deposited during crop cultivation.

730

However, little focus has been given on this issue irrespective of knowing the facts that these

731

could potentially harm the surrounding biota. More rigid policies should be formed since

732

nanoparticles do not behave in the similar way like their bulk counterpart. Prior to that,

733

detailed physicochemical characterization and their potential behaviour in plant and its

734

surrounding vicinity should be documented so that efficient plant sustainable agricultural

735

system with well-defined regulatory body could be proposed for enhanced nutrient use

736

efficiency without any environmental damage.

737

ACKNOWLEDGEMENT

738

This work was generously supported by major grant from the Food security-MHRD,

739

Government of India (Grant No: 4-25/2013-TS-1) for providing financial support.

740

741



742

REFERENCES

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1203


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1204

FIGURE CAPTIONS

1205

Figure 1. Schematic diagram showing phytotoxicity assessments to be followed in ENM

1206

treated plant model system prior to commercialization.

1207

Figure 2. Schematic representation of nanoparticle uptake and translocation in the plant.

1208

Nanoparticles are taken up by the plant root from the rhizosphere and transported to leaf via

1209

apoplastic (blue in colour) and symplastic (red in colour) pathway. They can be stored at

1210

different places inside the plant (leaves, root, bark) depending upon nature of the particle

1211

properties and plant species.

1212

Figure 3. Effect of nanoparticles in agriculture and its associated environment (soil, waste

1213

water system and surrounding micro-climate)

1214

1215

1216

1217

1218

1219

1220

1221

1222

1223



1224

Page 52 of 59

Table 1: Effect of ENMs on plant system Nanoparticles

Size (nm)

Plant

Exposure

Effect

Multi-wall carbon nanotube (MWCNT), alumina, zinc and zinc oxide NPs

MWCNT: 10-20 nm; alumina: 60 nm; zinc 35 nm; ZnO: 20nm

Radish, rapeseed, rye-grass, lettuce, corn and cucumber

0-2000 mg/L

No significant impact on seed germination and root morphology

MWCNT

_

Red spinach

15days

Nano titanium oxide (TiO2) and nano iron oxide (Fe2O3)

15 nm

Lactua sativa

0, 50,100, 150, 200 and 250 mg/Kg

Uptake of NP from root to shoot

Spinach (Spinacia oleracea) and green algae (Selenastrum capricornutum)

Hydroponically grown

Increase in biomass

Zero-valent nanoparticle

iron 20 nm

Toxic due generation

to

ROS

Zerovalent iron oxide 54 nm NP

Arabidopsis thaliana

-

Activated plasma + membrane H ATPase protein; enhanced stomatal function

Cerium oxide (CeO2) 17-100 nm NP

Wheat, pumpkin

-

No toxic effect, translocation of NP from root to shoot

Nano aluminium

8 nm

kidney bean and ryegrass plants

-

had no significant effect; 2.5 fold increases in aluminium concentration was observed in the leaves of rye grass while there was no report of uptake of aluminium in treated kidney bean plants compared to control

Graphene NP

8 nm

Seedling stages of cabbage, tomato, red spinach and

20days

Decrease in root and shoot growth and biomass of the treated plants with increasing concentrations


Page 53 of 59


lettuce

Nanoceria

8nm

Rice

Nanoceria

20 nm

Kidney bean

FITC-tagged CeO2NP

8 nm

Nanoceria

of NP treatments

10 days, 62.5, 125, 250 and 500 mg/L

Toxic at high concentration. Altered antioxidative enzyme activity and high level of ascorbate and free thiol trigger membrane damage and photosynthetic stress in the treated plants.

62.5-500 mg/Kg

No influence in phytotoxicity in treated kidney bean plants.

Corn

400 and 800 mg/Kg

Translocation from root to shoot

8 nm

Rice

0-500 mg/Kg

NP accumulation in plant

Nanoceria

20 nm

Brassica rapa

0-1000 mg/Kg

No significant effect in first generation; reduction in biomass in second and third generation

Manganese nanoparticle

20 nm

Mung bean

15days treatment, pot culture

Increase in growth, modulatory effect in photosynthesis and nitrogen metabolism

Copper nanoparticle

20 nm

Mung bean

15days treatment, pot culture

Increase in growth, modulatory effect in photosynthesis and nitrogen metabolism

Nano copper oxide

20 nm

Maize

-

No effect on seed germination but the growth of the seedling was inhibited

Copper nanoparticle

20-40 nm

Cucumber

10 and 20 mg/ L, hydroponically grown

Modulation in metabolic pathways at the early developmental stages

Nano copper oxide

40 nm


20 and 50 mg/ L

Inhibit the growth of seedling, pollen germination and harvested



Page 54 of 59

seeds Nano copper oxide

40 nm

Indian plant

Copper-chitosan NP

40 nm

Maize

mustard

Cadmium selenide 30- 80 nm quantum dot (CdSe QD) and CuONP

Schoenoplectus tabernaemontani,

Cadmium QDs

Picer omorika

selenite 3.5 nm

0.20, 50, 100, 200, 400 and 500 mg/ L concentration; in semi-solid half strength of Murashige and Skoog (MS) medium for 14 days

-

Morphological changes like suppression of shoot growth, modification of root architecture and decline in total chlorophyll and carotenoids contents were recorded. CuONP increased the hydrogen peroxide content leading to overexpression of POD, CuZnSOD activity and lignification in due courses. However activities of CAT and APX remained unchanged after NP treatment. Increased in biomass

5-50 mg/Kg, 21days

Reduction in biomass and NP internalization

-

Plant uptake through cell wall

0.1- 1 mg/mL

Shoot and root length of the treated plants increased in dose-dependent manner

5 mg/ L, 10 days

Changes in genetic expression after microarray analysis

Carbon quantum dots (CQDs)

Mung bean plants

PVP coated AgNP

20 nm


Silver NP

20 nm

Rice

0, 0.2, 0.5 and 1 mg/ L, 7days

Decreased root length, shoot length, fresh weight, total chlorophyll, carotenoids content and sugar content at higher conc.

Silver NP

20 nm

Rice

0.1, 1, 10, 100 and 1000 mg/ L

No effect in seed germination; decrease in plant biomass and chlorophyll content


Page 55 of 59


Silver NP

20 nm, 30- Arabidopsis 60 nm, 70- thaliana 120 nm, 150 nm

Graphene NP

-

Gold nanoparticle + 20 nm Photosystem II (PS II) core complex was isolated from thermophilic cyanobacterium (Thermosynchococcus elongatus) Nano nickel (NiO NPs)

oxide 23.34 nm

-

Cabbage, tomato, red spinach and lettuce

20days

Chloroplast of cyanobacterium

-

Tomato

0.025- 2 mg/mL

No inhibitory effect on seed germination; had strong negative influence on root growth and activity of thylakoid membrane proteins resulting in suppression of growth and decrease in chlorophyll content Decrease in biomass

Enhanced photosynthesis

Toxicity at the concentration

higher

Nano zinc oxide

-

Schoenoplectus tabernaemontani

-

Root growth suppression at high concentration

Nano ZnO, nanoceria and nano CuO

-

Sweet potato (Ipomoea batatas)

100, 500 and 1000 mg/ Kg dry weight

No adverse effect on tuber biomass in nanoceria

1225 1226 1227 1228 1229 1230



1231 1232

Figure 1

1233 1234 1235 1236 1237 1238 1239 1240 1241 1242 1243 1244 1245


Page 56 of 59

Page 57 of 59


1246

1247

Figure 2

1248 1249 1250 1251 1252 1253 1254 1255 1256 1257 1258 1259 1260 1261 1262



1263 1264

Figure 3

1265 1266 1267 1268 1269 1270 1271 1272 1273 1274 1275 1276 1277 1278 1279 1280 1281


Page 58 of 59

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1282


TOC Graphical abstract

1283 1284 1285


Interaction of Engineered Nanoparticles with Agri-Environment

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