Nanomaterials and Nanocomposites Exposures to Plants: Response, Interaction, Phytotoxicity and Defense Mechanisms 9819924189, 9789819924189

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Smart Nanomaterials Technology

Azamal Husen Editor

Nanomaterials and Nanocomposites Exposures to Plants Response, Interaction, Phytotoxicity and Defense Mechanisms

Smart Nanomaterials Technology Series Editors Azamal Husen , Wolaita Sodo University, Wolaita, Ethiopia Mohammad Jawaid, Laboratory of Biocomposite Technology, Universiti Putra Malaysia, INTROP, Serdang, Selangor, Malaysia

Nanotechnology is a rapidly growing scientific field and has attracted a great interest over the last few years because of its abundant applications in different fields like biology, physics and chemistry. This science deals with the production of minute particles called nanomaterials having dimensions between 1 and 100 nm which may serve as building blocks for various physical and biological systems. On the other hand, there is the class of smart materials where the material that can stimuli by external factors and results a new kind of functional properties. The combination of these two classes forms a new class of smart nanomaterials, which produces unique functional material properties and a great opportunity to larger span of application. Smart nanomaterials have been employed by researchers to use it effectively in agricultural production, soil improvement, disease management, energy and environment, medical science, pharmaceuticals, engineering, food, animal husbandry and forestry sectors. This book series in Smart Nanomaterials Technology aims to comprehensively cover topics in the fabrication, synthesis and application of these materials for applications in the following fields: . Energy Systems—Renewable energy, energy storage (supercapacitors and electrochemical cells), hydrogen storage, photocatalytic water splitting for hydrogen production . Biomedical—controlled release of drugs, treatment of various diseases, biosensors, . Agricultural—agricultural production, soil improvement, disease management, animal feed, egg, milk and meat production/processing, . Forestry—wood preservation, protection, disease management . Environment—wastewater treatment, separation of hazardous contaminants from wastewater, indoor air filters.

Azamal Husen Editor

Nanomaterials and Nanocomposites Exposures to Plants Response, Interaction, Phytotoxicity and Defense Mechanisms

Editor Azamal Husen Wolaita Sodo University Wolaita, Ethiopia

Smart Nanomaterials Technology ISBN 978-981-99-2418-9 ISBN 978-981-99-2419-6 (eBook) https://doi.org/10.1007/978-981-99-2419-6 © The Editor(s) (if applicable) and The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 This work is subject to copyright. All rights are solely and exclusively licensed by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. The publisher, the authors, and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, expressed or implied, with respect to the material contained herein or for any errors or omissions that may have been made. The publisher remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. This Springer imprint is published by the registered company Springer Nature Singapore Pte Ltd. The registered company address is: 152 Beach Road, #21-01/04 Gateway East, Singapore 189721, Singapore

To my grandfather, Mohammad Hafizul Rahman

Preface

Rapid development of nanotechnology and subsequently the releases of nanomaterials and nanocomposites have drawn considerable attention. Because of their unique properties and novel features, they have been widely used in many sectors of science and technology. They are naturally present in the Earth and play a significant role in the dynamics of the overall Earth system, but these responses are not fully understood. It has been noticed that the large-scale anthropogenic production and unrestricted use of these materials has led researchers to consider the problems, challenges and consequences of their environmental impact. In this connection, as we know, plants are sessile and vital fundamental components of all ecosystems. Interaction between these nano sized particles and plants is an indispensable aspect of the risk assessment. Thus, the potential health and environmental effects of these particles need to be thoroughly evaluated before they are widely commercialized. When they enter the soil through agricultural application, atmospheric deposition, rain erosion, surface runoff or other pathways, the nanomaterials and or nanocomposites will accumulate in the soil as time goes because of their weak migration ability in soil. Exposure modeling have also showed that the concentrations of these particles in soil are higher than those in water or air, suggesting that soils might be the main source of nanomaterials and or nanocomposites released into the environment. Thus, plants serve as a potential pathway for the transportation of these particles. Through the food chain, these particles can be accumulated in high trophic-level consumers. All organisms in the ecosystem could suffer from oxidative stress induced by exposure of these materials. In recent years, research in this area has been focused on the interaction between plants and nano sized particles, and their effects ecology, the food chain and human health; thus, assessing the pros and cons of these materials requires interdisciplinary knowledge. Originally, this book focuses on nano sized particles phytotoxicity, which is an important precondition to promote the application of nanotechnology and to avoid the potential ecological risks. Both enhancive and inhibitive impacts of different nano sized particles on different plants have been reported. Moreover, under exposure, plant has shown numerous physiological changes, although significant variations in antioxidant enzyme activity and upregulation of heat shock protein have also been observed. Plants have evolved antioxidant defense mechanism which involves vii

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enzymatic as well as non-enzymatic components to prevent oxidative damage and enhance plant resistance to nanomaterials toxicity. The exact mechanism of plant defense against the toxicity of nanomaterials has not been fully explored. Further, the absorption and translocation of nano sized particles in different parts of the plant depend on their bioavailability, concentration, media composition, solubility, exposure time and so on. In this book, the influencing factors of nanotoxicity and the mechanisms of these toxic effects are also summarized. Subsequently, the defense mechanisms are presented as well. Moreover, the synergistic interactions between metal and metal-oxide nanoparticles and plant growth promoting rhizobacteria have examined. These interactions accelerated the functioning of microbial partner by improving the plant growth response and other significant traits. It has been suggested that the co-inoculation of nanoparticles with their microbial synergist can be utilized to increase the plant health and productivity during plant exposure to different stresses like salinity, heat, drought, heavy metal and so on. The plant-microbe interaction facilitated by nanoparticles activate the plant defense systems, increase the activity of antioxidant enzymes in plants, and trigger the accumulation of protective solutes that increase the plant health and productivity during stressful conditions. This book will provide some exciting and remarkable information on the above-mentioned topics to the scientist, researcher and student working field of plant biology, agricultural science, nanobiotechnology, plant biochemistry, plant physiology, plant biotechnology and many other interdisciplinary subjects. I extend my sincere thanks to all contributors for their timely response and excellent contributions. Finally, my special thanks go to Shagufta, Zaara, Mehwish, and Huzaifa for providing their time and overall extended support to put everything together. I shall be happy to receive comments and criticism, if any, from subject experts and general readers of this book. Wolaita, Ethiopia

Azamal Husen

Contents

Nanomaterials and Nanocomposites: Significant Uses in Plant Performance, Production, and Toxicity Response . . . . . . . . . . . . . . . . . . . . . Sharfa Naaz, Swati Sachdev, Ragib Husain, Vivek Pandey, and Mohammad Israil Ansari Nanomaterials and Nanocomposites Exposures to Plants: An Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Kazem Ghassemi-Golezani, Saeedeh Rahimzadeh, and Salar Farhangi-Abriz Phytotoxicity Response and Defense Mechanisms of Nanocomposites/Mixture of Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . Muhammad Ansar Farooq, Afsheen Fatima, Sana Rehman, Ayesha Batool, Iram Gul, Aamir Alaud Din, Hassan Anwer, and Muhammad Arshad Phytotoxicity Responses and Defence Mechanisms of Heavy Metal and Metal-Based Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Taruni Bajaj, Hina Alim, Ahmad Ali, and Nimisha Patel Synergistic Effect of Nanomaterials, Nanocomposites and Heavy Metals on Plant Growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Nazneen Akhtar, Sehresh Khan, Shafiq Ur Rehman, and Muhammad Jamil

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Effects of Nanomaterials/Nanocomposites on Trace Element Uptake and Phytotoxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127 Ana Cristina Ramírez Anguiano, Ana Paulina Velasco Ramírez, Adalberto Zamudio Ojeda, Humberto Daniel Jiménez Torres, Gilberto Velázquez Juárez, Jose Miguel Velázquez López, Milagros Melissa Flores Fonseca, and Sandra Fabiola Velasco Ramírez

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Toxicity Assessment of Silver Nanoparticles and Silver Ions on Plant Growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157 Mohammed Raffi Mokula and Azamal Husen Toxicity Assessment of Gold Ions and Gold Nanoparticles on Plant Growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175 Lipi Pradhan, Devyani Yenurkar, and Sudip Mukherjee Plant Response to Silicon Nanoparticles: Growth Performance and Defense Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191 Tina, Vedanshi Pal, Kritika Chauhan, Kumud Pant, Gaurav Pant, and Manu Pant Exploring the Effects of Iron Nanoparticles on Plants: Growth, Phytotoxicity, and Defense Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209 Noman Shakoor, Muhammad Adeel, Muhammad Nadeem, Muhammad Abdullah Aziz, Muhammad Zain, Muzammil Hussain, Imran Azeem, Ming Xu, Muhammad Arslan Ahmad, and Yukui Rui Iron Oxide Nanoparticles: Plant Response, Interaction, Phytotoxicity and Defense Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227 Sehresh Khan, Nazneen Akhtar, Shafiq Ur Rehman, and Muhammad Jamil Zinc Oxide Nanoparticles: Plant Response, Interaction, Phytotoxicity, and Defence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247 Salem S. Salem and Azamal Husen Titanium Oxide Nanoparticles: Plant Response, Interaction, Phytotoxicity, and Defence Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263 Atul Loyal, S. K. Pahuja, Naincy Rani, Pooja, Rakesh K. Srivastava, and Pankaj Sharma Aluminum Oxide Nanoparticles: Plant Response, Interaction, Phytotoxicity, and Defense Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285 Yusra Naaz Qidwai, Reena Vishvakarma, Alvina Farooqui, Poonam Sharma, Swati Sharma, and Archana Vimal Cerium Oxide Nanoparticle: Plant Response, Interaction, Phytotoxicity and Defense Mechanims . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301 Muhittin Kulak Elucidation of Synergistic Interaction Among Metal Oxide Nanoparticles and PGPR on the Plant Growth and Development . . . . . . . 311 Farwa Basit, Javaid Akhter Bhat, and Yajing Guan

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Interaction Between Metal Nanoparticles and PGPR on the Plant Growth and Development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327 Divya Kapoor, Sheetal Yadav, Mayur Mukut Murlidhar Sharma, and Pankaj Sharma Nanomaterials and Their Toxicity to Beneficial Soil Microbiota and Fungi Associated Plants Rhizosphere . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353 Mayur Mukut Murlidhar Sharma, Divya Kapoor, Rahul Rohilla, and Pankaj Sharma

About the Editor

Azamal Husen served as Professor & Head, Department of Biology, University of Gondar, Ethiopia and is a Foreign Delegate at Wolaita Sodo University, Wolaita, Ethiopia. Earlier, he was a Visiting Faculty of the Forest Research Institute, and the Doon College of Agriculture and Forest at Dehra Dun, India. His research and teaching experience of 20 years involves studies of biogenic nanomaterial fabrication and application, plant responses to environmental stresses and nanomaterials at the physiological, biochemical and molecular levels, herbal medicine, and clonal propagation for improvement of tree species. He has conducted several research projects sponsored by various funding agencies, including the World Bank (FREEP), the National Agricultural Technology Project (NATP), the Indian Council of Agriculture Research (ICAR), the Indian Council of Forest Research Education (ICFRE); and the Japan Bank for International Cooperation (JBIC). He received four fellowships from India and a recognition award from the University of Gondar, Ethiopia, for excellent teaching, research, and community service. Husen has been on the Editorial board and the panel of reviewers of several reputed journals published by Elsevier, Frontiers Media, Taylor & Francis, Springer Nature, RSC, Oxford University Press, Sciendo, The Royal Society, CSIRO, PLOS, MDPI, John Wiley & Sons and UPM Journals. He is on the advisory board of Cambridge Scholars Publishing, UK. He is a Fellow of the Plantae group of the American Society of Plant Biologists, and a Member of the International Society of Root Research, Asian Council of Science xiii

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Editors, and INPST. To his credit are over 200 publications; and he is Editor-in-Chief of the American Journal of Plant Physiology. He is also working as Series Editor of ‘Exploring Medicinal Plants’, published by Taylor & Francis Group, USA; ‘Plant Biology, Sustainability, and Climate Change’, published by Elsevier, USA; and ‘Smart Nanomaterials Technology’, published by Springer Nature Singapore Pte Ltd. Singapore.

Nanomaterials and Nanocomposites: Significant Uses in Plant Performance, Production, and Toxicity Response Sharfa Naaz, Swati Sachdev, Ragib Husain, Vivek Pandey, and Mohammad Israil Ansari

Abstract The discovery of nanomaterials is a great revolution in the field of science and technology. Owing to small size (less than 100 nm) and greater surface area than bulk material, nanomaterials exhibit extraordinary characters, which could help in solving diverse issues like food security. Nanomaterial is a term used to designate the materials having at least one dimension ranging between 1 and 100 nm size. Nanomaterials are characterized according to the size, morphology, source, physical characteristics, and chemical composition. Primarily, nanomaterials have been classified as carbon, inorganic, organic, and nanocomposites on the basis of their chemical compositions. These nanomaterials are used in agriculture as nanofertilizers, nanopesticides, and nanosensor to improve crop productivity. Application of nanomaterials in agriculture facilitate smart delivery of fertilizers and pesticides, which reduces the release of toxic chemicals into the environment. Moreover, it aids in detection of toxic pollutants as well as disease outbreak, thereby promoting food generation and sustainable agriculture. Despite the fact that nanomaterials exhibit tremendous potential to induce food security and are present in negligible quantities, their use may contaminate the agro-ecosystem, accumulate in living tissues and cause significant toxicological problems. It is therefore necessary to consider the risks associated with them, particularly in regard to their accumulation in plants and the toxicity that ensues at the base of the food chain. The phytotoxicity induced by nanomaterials affect plant at cellular as well as molecular level, transfiguring their physiological and metabolic processes. Thus, the emphasis of this chapter is on highlighting the revolutionary role of nanomaterials in field of agriculture. Further, S. Naaz · M. I. Ansari (B) Department of Botany, Lucknow University, Lucknow, India e-mail: [email protected] S. Naaz · R. Husain · V. Pandey Plant Ecology and Climate Change Science Division, CSIR-National Botanical Research Institute, Lucknow, India S. Sachdev Department of Liberal Education, Era University, Lucknow, India R. Husain Department of Botany, Bareilly College, Bareilly, India © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 A. Husen (ed.), Nanomaterials and Nanocomposites Exposures to Plants, Smart Nanomaterials Technology, https://doi.org/10.1007/978-981-99-2419-6_1

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it assesses the pros and cons of application of nanotechnology to fortify the food production. Keywords Nanofertilizers · Nanopesticides · Oxidative damage · Reactive oxygen species · Slow release fertilizers

1 Introduction Nanotechnology is the novel technology that deals with production and application of materials at nanoscale [1, 2]. This term was given by a Professor Norio Taniguichi in 1974 [3]. Nanotechnology focus on materials known as nanomaterials (NMs), which have size ranging from 1–100 nm (1 nm is one billionth part of the meter), at least in one dimension [4−6]. As per European Commission Recommendation, a “nanomaterial” is defined as a material created or developed accidently or spontaneously that comprises at least 50% particles that are between 1 and 100 nm in size [7]. Nanoparticles (NPs) differ from the bulk materials they are generated from in terms of their structure and chemical, electrical, magnetic, optical as well as mechanical properties [6, 8, 9]. NPs can be natural, incidental, or engineered depending on their origin [6]. Natural NPs such as soot are originated from the natural occurring activities including volcano eruption and incidental NPs are formed unintentionally from activities which are performed purposely. Engineered NPs are those which are produced intentionally by altering the existing characteristic of a material to perform a specified function [6]. The alteration in characteristics of existing material increases chemical and biological reactivity of NPs due to increase in surface area in relation to their volume [10]. NPs are produced by diverse chemical and biological processes that reduce the ionic form, but only biological processes are able to produce the final product without any hazardous chemical residues. Nanotechnology find applications in multiple dimensions due to unconventional properties and thus has a wide range of scientific perspectives [4, 11–14]. Nanotechnology is used in an array of industries, such as therapeutics, pharmaceuticals, energy, food, cosmetics, and others [1, 15–19]. Nanotechnology has the potential to completely transform the agricultural industry by finding solution to various agriculture-related challenges. Increasing agricultural output by preserving plant health and growth, and reducing input of toxic agrochemicals can be achieved by the use of nanofertilizers, nanopesticides, nanoremediation, and nanobiosensors that significantly revolutionize the agricultural sector [15, 16, 20–25] (Fig. 1). The use of nanotechnology i.e., nanoparticles/nanocomposites, which are designed to regulate nutrients/pesticides liberation through controlled-release of fertilizers/pesticides and show target-specific delivery, improves nutrients use efficiency, reduces nutrient loss, minimize dosage, and toxicity, and even facilitate water management [21, 26]. NPs that are used as sensors that helps to monitor the quality of the agro-environment [23, 27].

Fig. 1 Application of nanotechnology in agriculture sectors (adopted from [28])

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Certain NPs have been observed to show toxicity as their behavior is influenced by their size, composition, aggregation, surface corona, and dose of application [29]. Furthermore, NPs when exposed to the environmental conditions easily get altered, which affect their stability, transport, uptake, fate, and toxicity [29]. For instance, stability of silver NPs increases in soil containing humic and fulvic acids, which accelerate their mobility, enhancing ecological risk [30]. The toxicity of NPs not only depends on their physicochemical properties but also affected by the chemical characteristic of environment [29]. The direct application of NPs sometimes induces toxic implications on plants as well as on humans and can contaminate aquatic ecosystems [31]. Additionally, NPs with antimicrobial properties may show toxicity to beneficial microorganisms, threatening health of agro-ecosystem. Due to associated risk and wide spread use, it has become critical to assess the potential hazards of NPs used for agriculture on environment and living organisms. Thus, the present chapter makes an attempt to assess the growth stimulating attributes as well as toxic implications of different types of nanoparticles on plants, which helps to evaluate and weigh the ecological benefits of nanoparticles in agriculture sector.

2 Types of Nanomaterials According to the size, morphology, source, physical characteristics, and chemical composition, nanomaterials are classified [32]. The function of these nanomaterials is often determined by their classification. Nanomaterials, particularly, engineered NMs have been distinguished into four different categories on the basis of their composition: (1) inorganic-based nanomaterials, (2) carbon-based nanomaterials, (3) organic-based nanomaterials, and (4) composite-based nanomaterials [33].

2.1 Inorganic Nanomaterials Nanomaterials that made up of metals, metalloides and/or their oxides, phosphates, carbonates, and carbides are called inorganic NMs [32, 34]. Metal NMs can be made up of one (monometallic), two (bimetallic) or more than two (polymetallic) metals [34]. These NMs show localized surface plasmon resonance, which bestow them with unique electrical and optical properties [34]. Metal NMs such as gold, silver, copper, zinc, and iron have been extensively explored and found applications in multiple areas including agriculture, biomedical and even pharmaceutical sectors [34, 35]. In particular, silver nanoparticles (AgNPs) are frequently used as antimicrobial agent [35, 36]. The inorganic NMs also include semiconductor NMs, which are made up of materials having properties of a metalloid. Such types of NMs are used in optical, photocatalysis, and electronic devices [34]. NPs made up of oxides, carbide, carbonates, and/or phosphate of metal and metalloids are called ceramic NPs such as titanium dioxide, zinc oxide, iron oxide, cerium oxide, and copper oxide [34, 37].

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These NPs are found in several forms including amorphous, hollow, polycrystalline, and porous form [34]. Ceramic NPs can be used for photodegradation of dyes [37, 38] and therefore has potential for remediation of environmental matrices.

2.2 Organic-Based Nanomaterials The organic NMs are synthesized from organic materials like proteins, lipids, polymers, and carbohydrates [34]. Most common organic NMs include dendrimers, liposomes, micelle, cyclodextrin, and protein complexes like ferritin [33, 34]. Organic NMs are generally non-toxic and biodegradable materials, which are labile in nature, and show sensitivity toward both thermal and electromagnetic radiation [34]. Due to safe nature, organic NMs are often found application in field of biomedical and used for cancer therapy and targeted drug delivery [34].

2.3 Carbon-Based Nanomaterials Carbon nanoparticles are allotropes of carbon i.e., carbon containing organic NMs [32, 39]. Carbon nanomaterials are produced in shapes of hollow tubes, sheets, nanobuds, and sphere [40]. The functional carbon nanomaterials are grouped into four categories on the basis of dimensionality, which include 0-dimension (0D) such as quantum dots and fullerenes, 1-dimension (1D) (carbon nanotubes (CNT) including single-walled carbon nanotubes (SWCNT) and multi-walled carbon nanotubes (MWCNT)), 2-dimension (2D) NMs (graphene and graphene oxide), and 3-dimension (3D) (carbon sphere, graphene aerogels, carbon nanohorns, graphite, and carbon shell) [39−45]. Carbon NMs show distinctive physicochemical properties at nanoscale such as good electrical and thermal conductivity, high mechanical strength, electron affinity, and better sorption ability due to sp2 -hybridization of carbon [34, 43]. Moreover, certain carbon NMs like carbon nano onions exhibit low toxicity and biocompatibility. Owing to unique characteristics, carbon NMs have multifarious applications. These NMs are used for drug delivery, bioimaging, tissue engineering, and even facilitate monitoring of microbial ecology and can detect pathogenic microbes [34].

2.4 Composite-Based Nanomaterials Nanocomposites are hybrid materials formed by merging two or more dissimilar materials (having different physical and chemical properties) [46]. Moreover, in nanocomposites atleast one phase has one or more dimensions in nanometer size [46]. Nanocomposites are synthesized by amalgamating clays, metals, fullerence, or

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semiconductors with matrix materials to exhibit new as well as improved properties and structure, in particular, super hydrophobicity/hydrophilicity, electronic and ionic transport, and fouling resistance [47, 48]. The properties of nanocomposites are determined by the materials used, morphology, and the interfacial characteristics [47]. The matrix material which could be used include metallic, non-matellalic or polymeric substances [46]. According to the matrix structures, nanocomposites can be categorized into three groups: metal matrix nanocomposites like Co/Cr and FeMgO, polymer matrix nanocomposites such as polymer/TiO2 and polymer/CNT, and ceramic matrix nanocomposites including Al2 O3 /TiO2 and Al2 O3 /CNT [46, 49]. The multifunctional nanocomposites are widely used as catalyst and sensors [47]. The PVA/S-GQD (poly vinyl alcohol/fluorescent sulphur-doped graphene quantum dots) based fluorescent film used as a sensor to detect pesticides and reported to exhibit high selectivity toward carbamate pesticides with sensitivity at ppb level [50]. The application of nanocomposites in soil as a sensor of environmental pollutants thus could facilitate improved and sustainable agriculture.

3 Application of Nanoparticles in Agriculture Owing to the unique characteristics of the nanomaterials, the field of nanotechnology has been expanded rapidly and found application in various sectors including agriculture. In agriculture, nanomaterials facilitate plant growth, and regulate biotic stress with reduced application of toxic agro-chemicals. Treatment of plants with nanoparticles improves their growth and enhance resistivity toward stress by amplifying metabolites synthesis, photosynthetic efficiency, antioxidant activity, and water absorption ability [51]. Thus, use of nanofertilizer, nanopesticides and nonherbicides could aid in intensification of agriculture in a sustainable mode and escalate global food security (Fig. 2).

3.1 Plant Growth Management Plant require adequate amount of nutrients to grow and produce satisfactory quality of output. Low soil nutritional profile lead to the input of chemical fertilizers in agricultural soil. The large portion of fertilizers added to soil often remain in inaccessible form or lost in form of run off, leaching, and/or volatilization, which consequently result in increase in application frequency as well as dose quantity, and eventually degrade agro-ecosystem [17, 52, 53]. Increasing production of food is priority, but on the other hand maintaining health of the soil ecosystem is crucial. Thus, reducing the amount of fertilizers used to cultivate crops and improving nutrient use efficiency is crucial to produce food sustainably. Nanotechnology has been recognized to facilitate plant growth even under stress conditions, reduce nutrient loss,

Fig. 2 Use of nanomaterials in agriculture for sustainable development

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and regulate application dosage of chemical fertilizers by formulating nanofertilizers [51−53]. Nanofertilizers are either nutrients (micro- or macro-nutrient) in nanoscale or are nanosized materials that act as a carrier/additives for delivering nutrients/growth prompting compounds [55]. Nanofertilizers improves plant growth and productivity by improving seed germination, seedling growth, photosynthetic activity, nitrogen metabolism, and production of chlorophyll, proteins and carbohydrates [53]. Nanofertilizers use also shrink transportation expenditure and applied with ease due to smaller size [53]. Nanofertilizers are formulated to provide macro\micro-nutrients to the targeted site and at time when needed via mechanism of slow/controlled release of chemicals [52]. This mechanism aid in reduction of required dose quantity and improve nutrient use efficiency (NUE) [17, 51, 56, 57]. Slow/controlled release of nutrients/growth promoting substances involve surface coating of active ingredients (nutrients) with nanomaterials and are released in a controlled manner that they could be utilized by the plants when required [53, 54]. This improve nutrient use efficiency, prevent loss of mobile nutrients, and check conversion of nutrients into gaseous/chemical forms that cannot be absorbed by the plants [57]. Nanomaterials like nanoparticles/nanocomposites have demonstrated potential for slow- and controlled- release of nutrients. Nanocomposites containing clay material, which can bind with minerals and extend their retention time in soil, exhibit modified properties that support slow release of fertilizers and improve water holding capacity of soil [51, 58]. ZincAluminum layered double hydroxide nanocomposites aided controlled-release of plant growth promoting chemical compounds [59]. Treatment of soybean with phosphate nanofertilizer increased the growth rate and seed yield by 32 and 20%, respectively, compared to conventional fertilizer treated plants [60]. The application of mesoporous silica NPs at different concentrations improved the seed germination, plant biomass, chlorophyll and protein content, and photosynthetic activity of wheat and lupin plant [61]. Nanofertilizers can promote plant metabolism and nutrient uptake via nanometric pores with the aid of molecular transporters or nanostructure cuticle pores [62]. Nanomaterials present in vicinity of plants are absorbed through roots or leaf stomata, which depends on intrinsic characteristics such as their size, coating material, chemical composition of nanofertilizers as well as functional group present on their surface [17], and on extrinsic characteristics like soil organic matter, soil pH, site of nanofertilizer application, and exposure route [53]. After absorption, NMs are transported to various tissues, where they interact with cellular components and induce alteration at molecular level, eventually improving plant growth [17]. Fe NPs applied to Capsicum annum at low concentration was reported to be absorbed by the roots and then transported in a bioavailable form to the central cylinder, from where it was translocated to different plants and utilized, ultimately improving plant growth [63]. Chitosan NPs promoted seed germination and growth of Triticum aestivum by inducing expression of auxin-related genes, which resulted in elevated levels of indole-3-acetic acid (IAA) in plant [64]. The interaction of multi-walled carbon nanotubes (MWCNT) with tobacco cell culture increased the growth by 55–64% by triggering activation of genes involved in cell division, cell wall extension, and

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water transport [65]. MWCNT interaction increased the expression of aquaporin gene NtPIP1 as well as generation of protein NtPIP1. Application of NMs to crops in addition to plant growth helps to ameliorate the stress, particularly induced due to nutrient deficiency, drought, salinity, and temperature stress [53]. Satureja hortensis treated with AgNPs under salinity stress exhibited improved seed germination, plant growth, and resilience toward stress [66]. Silica is not an essential nutrient for plants but its deficiency makes plant weaker and susceptible to environmental stresses [17, 53, 67]. Thus, providing silica to plants can improve their growth and mediate stress tolerance. The foliar application of silicon oxide (SiO2 ) NPs on sugarcane reduced the effect of chilling stress by improving photosynthesis efficiency and photoprotection [68]. Treatment of plant with NPs induce tolerance to stress by ameliorating oxidative damage via generation of antioxidants. In a study, application of AgNPs were found to alleviate salinity stress on wheat by promoting the activities of major enzymatic antioxidants and abridging content of malondialdehyde and hydrogen peroxide (H2 O2 ) [69]. Nanofertilizers have immense potential to improve plant productivity by ameliorating nutrient deficiency and other environmental stress. However, before large scale field application, the economic viability and biosafety should be addressed to incur financial gain by farmers without compromising the health of living organisms.

3.2 Disease Management Plants are frequently affected by the biotic stress, which impedes their growth and productivity. To reduce the yield loss caused by biotic factors, chemical pesticides are regularly applied that consequentially contaminate the environment, kill non-target organisms, induce resistance in pests and pathogens, bioaccumulate via food chain, and impose health hazards to wild organisms and humans [55, 70]. To eliminate the risk associated with chemical pesticides, researches are undergoing all around the world to fabricate novel materials, which are efficient, and target-specific. As a resultant, smart nanopesticides have come into existence [70]. Nanopesticides include slow delivery system, which consists of encapsulated active ingredients (AI), used in agricultural practices [70]. Nanopesticides display multiple benefits over conventional pesticides, which include: better interaction with target, even at low application dose,generate less pesticide residue,improve water retention,as well as enhances water-solubility [70]. Nanopesticides exhibit good stability and improved efficacy, and thus are viable option for plant disease management. Several nanopesticdes have been formulated to manage plant diseases. For instance, sepiolite-based formulation of herbicide Mesotrione has been fabricated for slow release of active ingredient, which improved weed control efficiency and significantly reduced leaching of the active ingredients (mesotrione) compared to conventional formulation [71]. A nanoherbicide of biochar-based hydrogel microspheres for sustained delivery of 2, 4-dichloropheoxyacetic acid has been formulated to regulate release behaviour of hydrophilic pesticides, enhance its utilization efficiency,

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and abridge loss via leaching [72]. A controlled-release system for the insecticide spirotetramat was formulated using starch-chitosan-alginate encapsulation, which reduced its degradation rate, improved shelf-life of active ingredient (spirotetramat) and alleviated environmental contamination [73]. Application of nanotechnology to fabricate nanopesticides is of great relevance for improving crop productivity in a sustainable manner. It improve the efficiency of the pesticides, reduces application dose, and alleviated leaching of pesticides and environmental contamination.

4 Toxic Implications of Nanomaterials on Seed Germination, Plant Growth and Activity Nanomaterials are used in agriculture to improve plant productivity with minimum input of agrochemicals. Nanomaterials due to their unconventional properties have advantage over conventional agricultural activities but are also associated with the potential to contaminate the environment and harm the living organisms. Moreover, application of nanomaterials for plant production have been reported to induce toxicity in plants in several cases [55, 74]. The phytotoxic effect of nanomaterials depend on the size, dose, and nature of nanomaterials as well as on exposure time and conditions [55, 75]. Besides this, detoxification process recruited by particular plant determine the phytotoxic effect of NMs [76]. Active detoxification process increases resilience strength of plant against toxic effects of NMs. As different plants show dissimilar detoxification potential, thus, toxicity influence of a specific NMs differ from species to species [76]. NMs-induced phytotoxicity have been observed on physiological parameters like seed germination, plant biomass, root elongation and leaf numbers [55, 77]. NMs can negatively stimulate plant growth, resulting in reduced rate of seed germination and root elongation, slow down the plant growth, alter water uptake, alleviate phytohormone level, and abridge cellular metabolism [55]. At cellular and molecular level, NMs trigger generation of reactive oxygen species (ROS) that causes oxidative damage and eventually reduces photosynthesis, induces chromosomal abnormalities, and bring changes in the transcriptional profile of genes [55]. Interaction of NMs with plants, alter gene expression as well as molecular pathways, which ultimately abridge plant growth and development [55]. Carbon nanotubes (CNTs) are most commonly used carbon NMs that can easily enter plant cell walls and membranes. CNTs therefore have great promise for use in agriculture as targeted delivery systems for insecticides, fertilizer, and other chemicals. Numerous studies have demonstrated that the use of these CNTs can be beneficial for the growth and development of plants, however, CNT-induced phytotoxicity and inhibition has also been noted [78–81]. At high concentrations, they can shoot production of ROS, leading to redox imbalance. Although ROS generation under stress can have beneficial effects since they operate as signalling molecules, causing cellular responses to increase antioxidant production to scavenge ROS and allowing

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the plant to withstand stress [82–84]. Nevertheless, excess ROS affect biomolecules triggering oxidative stress in plants, which eventually result in damage [85–88]. Analogous to CNT, other carbon NMs have also been observed to induce phytotoxicity. According to [89] high dosage of carbon nanodots (1000 and 2000 mg L−1 ) resulted in decreased root and shoot biomass of maize plants because of H2 O2 buildup and intensified lipid peroxidation. In addition, antioxidant enzymes like CAT, APX, GPX, and SOD were activated by carbon nanodots exposure. It was observed that carbon nanodots were present in the root-cap cells, cortical cells, vascular bundle of roots, as well as the in the mesophyll tissue of the leaves. Moreover, secretion of carbon nanodots from leaf blades was noted. Growth of Arabidopsis seedlings grown in media containing water soluble fullerene malonic acid derivative (FMAD) were reported to be negatively stimulated [90]. FMAD hindered the elongation of the roots and hypocotyls in a concentration-dependent manner, but did not had an impact on germination capacity, probably due to the protective properties of seed coat. The interruption of cell division, improper microtubule organization, reduced auxin and intracellular ROS levels, and abridged mitochondrial activity in roots were reported. Graphene, a key carbon NM has been demonstrated to show toxic effects on living organisms and cater environmental toxicity [91]. Begum and Fugetsu ([92]) in a study found that the red spinach (Amaranthus tricolour and Amaranthus lividus), tomato (Lycopersicon esculentum), and cabbage (Brassica oleracea var. capitata) plants exposed to graphene showed decreased growth and biomass with an increase in ROS production and cell death, and moreover, the effects were concentration-dependent. Graphene significantly increased root elongation, but hindered the growth of root hair, which may be related to the oxidative stress that graphene-induced in the roots of wheat seedlings [93]. Sulfonated graphene NPs stimulated growth in maize seedlings (plant height, root and shoot biomass) at low concentrations (50 mg/L) but at high concentrations (500 mg/L), had a potent inhibitory effect that was accompanied by Ca2+ signalling, ROS production, and lipid peroxidation [94]. Exposure of wheat seedlings to graphene oxide induced toxicity at high concentration which was evident from severe damage to the morphology of seedlings, reduced growth parameters including biomass and increased electrolyte leaking from roots [95]. Besides carbon NMs, application of metal- and metalloid-based NMs have been documented to induce toxicity in plants and other living organisms [55]. ZnO NPs which is used as nanofertilizer have been reported to induce toxic effect on rice seedlings [96]. The exposure rice to ZnO inhibit growth of seedlings, reduced chlorophyll content by down-regulating genes related with photosynthetic pigments, and induced oxidative damage. Plants subjected to AgNPs have shown genotoxic effects as well as negative biochemical and physiological changes [97, 98]. This is a severe issue as AgNPs does not enter the soil environment as a result of their purposeful use as agrochemicals, but also indirectly through the use of consumer and industrial products. Similarly, TiO2 and CeO2 which are extensively used in paints, cosmetics, fuel additives, polished glass mirror, and other products are released into the environment [99, 100] and may induce oxidative stress, cytotoxicity and genotoxicity in plants [101, 102]. In a study conducted by Lopez-Moreno et al. [100, 103], genotoxicity in

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soybean and zucchini were reported to be induced on exposure to CeO2 and TiO2 NP. In many studies, the impact of NMs have been observed to be size and concentration dependent. For instance, CuO NPs with smaller size were reported to induce greater toxic effect on soybean than larger NPs [104]. Similarly, CeO2 NPs at higher concentration displayed phytotoxic effects on rice [105]. At highest concentration of CeO2 NPs (500 mg/L), membrane damage, lipid peroxidation, electrolyte leakage, altered enzymatic activity, and affected photosynthesis were reported in shoot of rice seedlings. Moreover, it has been found that CeO2 NPs can alter the nutritional profile of rice grain, affecting food quality [106]. Fe NPs at low concentration were reported to induce growth promoting effects on Capsicum annum by changing leaf organization, regulating development of vascular bundles, and elevating number of chloroplast as well as grana stacking, however, at high concentration, NPs negatively affected the plants [63]. Thus, it is imperative to assess the impact of NMs, particularly, their size and concentration on various plant species before their release to environmental matrix, particularly, to agricultural ecosystem.

5 Conclusion and Future Prospects Use of nanotechnology to develop new age smart delivery system for fertilizers and pesticides is an asset for achieving sustainable agriculture, boosting food security, and managing environmental pollution. Input of nanomaterials can transform the agriculture sector into more efficient and resilient system. Nanomaterials used as nanofertilizers, nanopesticides, and nanosensors could significantly improve crop productivity with reduced consumption of agro-chemicals by significantly reducing dose application, improving their shelf life, and abridging nutrient or active ingredient loss via leaching. Though nanomaterials application can notably promote sustainable agriculture in regime of climate change, but their use may also pose risk of environment contamination and toxicity in living organisms, owing to their small size and reactive nature. Thus, it is essential to gain deeper understanding on action mechanisms of different nanomaterials under different concentration and different environmental conditions. Although, at present the development of nano-based formulations for agriculture are in juvenile stage and require more in depth understanding, yet they exhibit immense potential to transform agricultural practices and therefore more efforts are needed to attain significant achievements. To promote the use of nanotechnology in agriculture at large scale, more research is required at national and international level. Moreover, collaboration between research institutes, universities, and industries is needed to transfer knowledge into product. Further, transparency in methodology and scientific output obtained is imperative to support policymakers and increase confidence in nanotechnology for commercial application.

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Nanomaterials and Nanocomposites Exposures to Plants: An Overview Kazem Ghassemi-Golezani, Saeedeh Rahimzadeh, and Salar Farhangi-Abriz

Abstract Application of nanomaterials with unique physicochemical properties and beneficiary effects is a novel technique that can enhance plant growth and productivity under a wide range of environmental conditions. Nanomaterials are cost-effective and eco-friendly products, which can replace conventional materials in agriculture. The special properties of nanomaterials such as high specific surface area, high surface energy, functional groups, and a high adsorption capacity play a major role in plant production. There are several types of nanomaterials, which are classified on the basis of their chemical properties, shape and size. Nanoparticles could be beneficial for plant production, if they are applied at a rate of less than toxic level. Application of nanoparticles and nanocomposites improves physicochemical properties of soils and physiological and biochemical processes of plants. These nanomaterials can also play a supportive role in enhancing stress tolerance of plants by invigorating plant defense system. Based on the important roles of nanoparticles and nanocomposites in nontoxic levels on plant growth and development, this chapter overviews the advantages and limitations of using nanomaterials as soil amender and plant growth stimulators. Keywords Metal nanoparticle · Nanocomposite · Application forms · Uptake · Plant production

1 Introduction Nanotechnology as an eco-friendly alternative in agriculture offers solutions for increasing sustainable production and lowering adverse environmental impacts on plants [1]. Rapid developments of nanotechnology introduced new ways of using nanomaterials in biotechnology and plant production. Nanomaterials can influence plant performance by improving the soil quality and nutrient supply (nano-fertilizers) [2–4]. These materials usually aim to reduce nutrient losses in fertilization and K. Ghassemi-Golezani (B) · S. Rahimzadeh · S. Farhangi-Abriz Faculty of Agriculture, Department of Plant Eco-Physiology, University of Tabriz, Tabriz, Iran e-mail: [email protected] © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 A. Husen (ed.), Nanomaterials and Nanocomposites Exposures to Plants, Smart Nanomaterials Technology, https://doi.org/10.1007/978-981-99-2419-6_2

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improve nutrient management and minimize the spread of chemicals [5]. Nanomaterials, especially nanoparticles (NPs) with differences in size, shape, surface area, and particle morphology, are produced to reduce application of fertilizers, while increasing plant production and quality [6–8]. Nanoparticles are defined as materials in the size range of 1–100 nm in diameter with unique physiochemical properties [6, 9, 10]. The size of the nanoparticle is an effective factor in their efficiency. The smaller nanoparticles can easily enter into the plant cells [4, 11, 12]. Nanomaterials are usually classified according to their chemical composition: inorganic-based nanomaterials (metal and metal oxide nanomaterials), carbonbased nanomaterials (graphene, fullerene, single-walled and multi-walled carbon nanotubes, carbon fiber, and activated carbon), and nanocomposites (combination of NPs with metal, metal oxide, chitosan, and carbon-based materials) [13]. Metal and metal oxide nanoparticles are produced by addition of reducing or oxidizing/precipitating agents during their synthesis, respectively. The nano-based fertilizers such as Fe, Mn, Zn, Cu, Mo NPs can promote plant growth and development at a small dose [14]. In the rhizosphere of plants, metal oxide nanoparticles are preferable to promote plant growth since they are easily released and absorbed as micronutrients [15]. Nanocomposites are materials with unique thermal and chemical properties that incorporate nanoparticles into a matrix of standard material [16]. The biochar-based metal oxide nanocomposites are the other new class of nanocomposites, which combine the benefits of biochar with nanomaterials. These materials can noticeably improve plant tolerance and physiological performance under stress conditions [17, 18]. Nanoparticles can enter the higher plants by the roots or by foliar spray of vegetative parts. Foliar NPs (water-based nanoparticles) are usually absorbed through the stomata and transported to different plant parts via apoplastic and symplastic pathways [19]. In soil application, nanoparticles depending on the type and size may diffuse into the seeds and change the water uptake. Moreover, nanoparticles can transmit to the roots and enter to the xylem and epidermal cells. After seedlings establishment, nanoparticles are transported from roots to the stem and then to the leaves [20]. Nano-priming (priming is defined as seed treatment by water or nutrient solutions to improve germination) is another method of nanoparticle application to prevent seed contamination by soil microorganisms, increase plant tolerance to abiotic stresses, and improve its productivity [21]. The physical and chemical characteristics of NPs and also the rate of their application may lead to beneficial or toxic effects on plants [22]. The positive effects of NPs in different forms and application methods have been reported on different physiological parameters, antioxidantdefense and photosynthesis efficiency, growth and development of plants [21, 23]. Additionally, plant species vary in the rate of absorption, transport, and accumulation of NPs [22]. The nanoparticles concentration in plants is usually related to the application rate and the growth medium including soil and solution [24]. Depending on the NPs and plant features, the general impact of NPs can be inhibitory, stimulatory, toxic, and neutral [25–27, 12]. The toxicity of NPs may be a combination result of various factors or conditions. In high concentrations, these nanoparticles can negatively impact the soil ecosystem and limit soil microorganisms and plant growth.

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Fig. 1 Classification of the most important nanomaterials used in plants production

This toxicity is related to size, shape, concentration, solubility, specific surface area, surface charge, and plant species [28–30]. This chapter emphasizes on the classification of nanomaterials (Fig. 1), properties and application forms, and the possible harmful and beneficial effects of these materials on plant growth and development.

2 Classification of Nanoparticles 2.1 Metal-Based Nanoparticles Nanomaterials have generally been used in agriculture in the form of nano-fertilizers with the aims of nutrients availability, soil amendment and protection of plants. Application of slow-release fertilizers for the management of nutrients, helps plants to receive available nutrients for a longer time. The nutrients such as K, Ca, Mg, Fe, Mn, Zn, Cu, and Mo are essential for the growth of plants. The Ni, Se, Si and Co can be also beneficial at low concentrations [31]. Metal-based nanoparticles (MNPs) are classified to metal NPs, metal oxide NPs and magnetic NPs. Metal NPs are flexible nanomaterials because of the ability to control their size, shape, composition, and structure during synthesis [32]. The metal ions used in the formation process, enhance the beneficial characteristics of NPs. These nanoparticles with different physicochemical properties and biological activities tend to induce more positive effects on plants in comparison to their bulk materials [14]. The metal-based NPs are produced from pure metals such as zinc, iron, copper, silicon, titanium, gold, silver, and other metallic NPs. Better physiochemical properties and high stability, reactivity, and surface area make these materials more capable for improving plant performance. The metal-oxides, such as TiO2 , Fe2 O3 ,

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Al2 O3 , ZnO, and SiO2 , are generally synthesized by sol–gel or hydrothermal reactions. Some of the important characteristics of these materials are suitable pore size, high specific surface area, proper crystallinity and porosity [33]. The nanoscale materials change the properties and behavior of bulk materials, thus high level of these materials may show toxic effects on plants and environment. The adverse effects of metal-based NPs on plants have been reported at physiological, morphological and cellular levels [34, 35]. It is, therefore, crucial to estimate the concentration range for different plant species. Moreover, the NPs phytotoxicity is related to the uptake, translocation and accumulation of NPs in plants [36]. The NPs could be applied as soil amendment or foliar spray on plants. It is important to understand the distribution and final destination of particles in plant tissues [35]. The intake of NPs by plants can be affected by aggregation, surface properties, and solubility. The plant uptake of metal-based nanoparticles could be influenced by some properties of these materials including hydrodynamic diameter, zeta potential, and ion release (Jampílek and Králová 2019). Furthermore, differences in plant species, growth conditions (such as soil, light, humidity, temperature) and duration of NPs availability can directly affect their uptake by plants. The foliar entry of metal NPs to plants occurs through stomatal and cuticular pathways [23]. In root exposure, the NPs may move through the symplastic or apoplastic pathways to penetrate to the epidermis of roots, translocate and finally distribute to stems and leaves via the xylem and phloem. Surface chemistry, distribution, solubility, and transformation of nanoparticles are affected by phyllospheric and rhizosphere processes, including root exudates and microorganisms [23, 37].

2.2 Chitosan-Based Nanoparticles Chitosan as an amino-polysaccharide biopolymer and its derivatives are biodegradable, non-toxic and eco-friendly, which are used for plant growth stimulation [38]. Furthermore, chitosan has antibacterial and antifungal properties [39]. The chitooligosaccharides are obtained through physical, chemical and enzymatic degradation of the chitosan, which can act as molecular signals to regulate defense and growth processes of plants. They can also activate more genes related to metabolisms and plant defense [40]. The nanometer-sized chitosan nanoparticles are capable of entering plant cells to enhance plant bioactivities [41]. Various methods with various advantages and disadvantages are introduced for the production of chitosan nanoparticles. The most common and simple methods are ionotropic gelation and polyelectrolyte complexes [39]. Various active ingredients, such as nutrients, insecticides, and herbicides, can be combined and used with chitosan nanoparticles [42]. The controlled release of nutrients and agrochemicals by chitosan nanoparticles can improve plant production by reducing the effects of leaching, degradation and phytotoxicity [43]. In recent years, various synthetic strategies have been employed to couple different metals with chitosan nanoparticles. Because of its affinity for metals, the most

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common combinations of chitosan with metals are copper, silver, zinc, and iron, which produce non-toxic nanomaterials with better biological and physicochemical properties [44]. Characteristics of chitosan nanoparticles vary, depending on the biomaterials or active compounds in their combination form. For example, chitosanbased nanometals including iron, zinc, copper, silicon, silver, and zinc oxides with excellent antimicrobial properties can act directly on bacteria or fungi, or help as stimuli in the production of defense compounds by the plants [45]. According to the reports, chitosan-based NPs can potentially improve plant growth and yield by proper delivery of NPK and other nutrients, immobilization of metal ions and contaminants [41, 46, 47]. The chitosan-based NPs have identified as powerful stimulators of antioxidant enzymes that can enhance plant tolerance to abiotic stresses including salt, cold and heat [48, 49]. Plant response to chitosan-based nanoparticles are directly influenced by their physicochemical properties including particle size, surface charge (zeta-potential) and functional groups [38]. The high surface charge of chitosan-NPs provides higher binding with biological membranes. In agriculture, most researches focus on plant protection (against fungi, bacteria, and virus) and growth utilizing chitosan nanomaterials. The physico-chemical properties of these nano-structural materials accelerate their penetration through membranes [50].

2.3 Carbon-Based Nanomaterials Carbon-based nanomaterials with nanoscale sizes and unique properties influence growth and development by accumulating in plant tissues [51, 52]. Among these, the carbon nanotubes (CNTs, with a hollow structure containing linked carbon atoms in hexagonal structures) are more efficiently used in agriculture, because of their ability to enter seeds and plant cells in order to increase plant growth and development [51, 53, 54]. The CNTs are directly synthesized by chemical vapor deposition, which allow to control their sizes [55]. The CNTs are classified into two main single-walled and multi-walled types, depending on the structure. The singlewalled CNTs contain a single layer of a graphene sheet with diameters ranging from 0.4 to 2 nm. The multi-walled carbon nanotubes are made up multilayer graphene sheets with outer and inner diameters of 2–100 nm and 1–3 nm, respectively [53]. The CNTs can promote plant growth and reduce water pollution. The CNTs with high water conductivity are appropriate for plant water uptake, especially under stress conditions. The delivery of agrochemical materials to plants using CNTs can reduce chemical emissions into the environment and prevent damage to plant tissues [56]. Physiological and morphological features of CNTs treated plants can change under normal and stress conditions, depending on the size, concentration and type of CNTs, as well as plant species. Under saline conditions, the CNTs accumulate in plant cells at high concentration and enhance the transport of aquaporins (the most important membrane proteins and water channels), which can improve water uptake and transport across the cell membranes to reduce the adverse effects of salinity

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[52]. According to [57], multi-walled carbon nanotubes not only act as molecular channels, but also elevated the gene expression of aquaporin that positively affect the water uptake and transport, especially in stress conditions. Additionally, multiwalled carbon nanotubes have a positive effect on the activity of plasma membrane H+ -ATPase and balance of Na+ /K+ ratio in plant that limit Na entry into the plant cells [52]. According to the Vithanage et al. [54] and Safdar et al. [53], the CNTs can be applied as stimulants of seed germination and plant growth. Authors suggested that multi-walled carbon nanotubes by improving the uptake of water and nutrients act as a growth regulator, which improve the plants growth and tolerance against environmental stress conditions.

2.4 Nanocomposites Nanocomposites are combination of different materials to enhance the efficiency of the main matrix material by improving its efficiency (physical, chemical, and biological properties) [16]. Depending on the components, the nanocomposite can display a combination of mechanical, electrochemical, catalytic, and thermal characteristics [58]. These properties of nanocomposites are more beneficial than individual nanomaterials. Nanocomposites have a great potential to enhance nutrient availability for plants. Nutrients can be easily released from these nanocomposites in the form of soluble ions [16]. Nanocomposites can be classified according to their matrix such as chitosanbased, zeolite-based and biochar-based nanocomposites. Since chitosan contains free amine groups across its polymeric structure, it has a strong preference for metals and can be applied as a blended with other elements to produce nanocomposite [44]. Poly-catalytic properties of chitosan-based nanocomposites let them to have a controlled-release of agrochemicals to the plants [59]. Several studies have found that chitosan-metal nanocomposites are more beneficial than chitosan and metal in individual forms [60, 61]. Another group of nanocomposites are based on Zeolite. Zeolite as a microporous, crystalline aluminosilicate material can be applied to facilitate nutrients and water uptakes by plants. The slow decomposition rate of this material in soil leads to a prolonged use of nutrients by plants [62]. The synthesis of zeolite-based nanocomposites can enhance the ion exchange capacity and act as a continuous source of macro and micro-nutrients, which are necessary during of plant growth [63]. The biochar-based nanocomposites have been also studied for their specialized properties and applications. Biochar is a solid soil amendment, produced from agricultural wastes by pyrolysis processes, with a high potential in reducing the application of chemical fertilizers and increasing soil fertility and plant productivity [64, 65]. Production of biochar-based nanocomposites can create new complex materials with the benefits of biochar and nanomaterials. These nanocomposites are categorized in three types including oxide/hydroxide, magnetic and functional nanoparticlescoated biochar [66]. The oxide/hydroxide biochar nanocomposites are produced

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by pre-treatment of biomass or post-treatment of solid biochar by metal salt or oxide/hydroxide nano-metals [67]. Magnetic biochar nanocomposites are formed by pretreating biomass with iron ions or precipitating iron oxides on biochar matrix. The magnetic property of biochar improves its adsorption capacity and pollutant remediation [68]. In order to produce functional NPs-coated biochar, solid biochar is coated with functional NPS for instance chitosan and carbon nanotubes [66]. The composition process of a biochar-based nanocomposite creates an effective complex material with improved physical and chemical properties, which could be helpful in enhancing the growth and stress tolerance of plants [6, 17]. The increased surface area, cation exchange capacity, and porous structure of biochar in nanocomposite forms, promotes the adsorption process and mitigates detrimental effects of salinity. Compared with solid biochar, biochar-based nanocomposites of iron and zinc increased the sodium sorption capacity by about 72 and 131%, respectively [6]. The performance of nanocomposites by high adsorption capacity assists in balancing of nutrient uptake, especially under stress conditions [17]. A reduction in sodium content and an increase in biomass were found in dill and safflower plants after their exposure to biochar-based nanocomposites (Fig. 2).

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Fig. 2 Means of sodium content and biomass in dill (A, B) and safflower (C, D) plants affected by biochar-based nanocomposites under different levels of salinity. BNC-FeO: Biochar-based nanocomposite of iron, BNC-ZnO: biochar-based nanocomposite of zinc, BNC-MgO: Biocharbased nanocomposite of magnesium, BNC-MnO: Biochar-based nanocomposite of manganese, DW: Dry weight. Different letters indicate significant differences between treatments (p < 0.05) (F adopted from a [17, 69])

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3 Application of Nanomaterials and Their Beneficial Effects on Plants Due to their special physico-chemical properties, nanomaterials have a high ability to improve the growth and overall plant performance. These materials have a wide range of application methods for improving the growth and performance of plants under various growth conditions (Fig. 3). In this chapter, we will discuss these materials in three major sections: seed priming, foliar application, and addition to the rhizosphere.

3.1 Nano-Priming For rapid germination and uniform emergence, seed priming is a valuable technique to treat seed lots [70]. Seed germination and seedling establishment of numerous field and horticultural crops are enhanced by different priming methods [71]. Rapid and synchronized germination, higher nutrient uptake, relief from dormancy, germination a wider range of temperatures, improvement of water use efficiency, and synchronous crop maturity are some of the advantages of seed priming that have been reported [72]. Literally, “priming” refers to the activation of stress tolerance, especially to moderate and intermittent stress. The ability of plants to withstand biotic and abiotic challenges is increased by seed priming, which has long been recognized as a potential method

Fig. 3 Preparation, application methods, entry and effect of nanomaterials or nanocomposites to plant growth and performance (adopted from [4])

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of boosting crop production. It truly increases seed vigor, a complicated agronomic attribute influenced by a number of genetic and environmental factors, as well as germination [73]. Priming, in its simplest form, is a water-based approach that permits carefully regulated seed hydration to start pre-germinative metabolism but prevents the seed from moving toward full germination. Although seed priming is interesting for a very long time, its complete physiological underpinnings have not been well understood. However, a deeper knowledge of pregermination metabolism during priming and following germination will make it more effective, inexpensive, and yet distinctive approach. Based on the choice of priming ingredients, seed priming procedures are typically divided into various categories, including hydro-priming, osmo-priming, chemo-priming, hormonal priming, solid matrix-priming, bio-priming, nutritional priming, and thermo-priming [73, 74]. Application of nanomaterials as the main material for seed pretreatment has a long research background. Many reports are available on application of metal and carbon nanomaterials for seed pretreatment. According to the available reports, pretreatment of seeds by nanomaterials has beneficial effects on germination and establishment of seedlings in different environmental conditions. Many carbon and metal-based nanoparticles, such as carbon nanotubes are employed as seed priming agents to accelerate seed germination, and improve stress tolerance of seedlings [75]. Chickpea seed priming with Fe, Zn, and Ca nanoparticles increased seed weight and grain yield [75, 76]. Hussain et al. [77] found that priming of wheat seeds with different concentrations of nano silicon particles for 24 h can improve antioxidant activity, chlorophyll content, and plant growth under cadmium stress. Srivastava et al. [78] reported that plants from primed spinach seeds with iron pyrite nanoparticle (FeS2 + H2 O) have better carbohydrate metabolism during seedling growth and as a result, leading to higher biomass production and leaf expansion. According to An et al. [79] priming of cotton seeds with nano-cerium oxide particles increases the root and shoot growth under saline conditions. These researchers have stated that treating seeds with cerium oxide enhances the absorption of nutrients such as calcium and magnesium by plants grown in saline conditions. Anand et al. [80] have reported an increase in the seed germination percentage and seedling vigor of mung bean in response to seed priming with magnesium oxide nanoparticles. Kasote et al. [81] showed that watermelon seedlings’ antioxidant potential and defense-related hormones (jasmonates-linked defense) are increased by seed priming with iron oxide nanoparticles. Improvement of seed germination and physiological characteristics of plants by priming is not only achieved by metal nanoparticles, but also by nanoparticles based on carbon. In a field study, Joshi et al. [82] showed that seed priming with multiwall carbon nanotubes improves germination rate, absorption of phosphorus and potassium nutrients, plant growth and the size of xylem and phloem in wheat plants. Chen [14] studied the impact of multiwall carbon nanotubes on the growth and physiological efficiency of maize under cadmium stress and concluded that this treatment increases the growth and antioxidant activity of plants. [83] reported similar effects

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of multiwall carbon nanotubes on increasing maize growth under normal condition. Some of the effects of seed pretreatments with nano materials on growth and physiological efficiency of plants are shown in Table 1.

3.2 Foliar Application of Nanoparticles Foliar spraying of nutrients on plants can facilitate the absorption and transfer of nutrients from the rhizosphere to the leaves and improve the nutrients use efficiency. The use of nanomaterials for nutritional treatment on plants has advantages such as higher absorption rate and lower amount of consumption, compared to soil application. This encouraged researchers to conduct many studies to assess the possible effects of these materials on plant growth under various environmental conditions. Due to their small size, nano nutrients can pass through many biological layers and can directly enter the leaves of plants. In addition, plants have transfer genes that provide the ability of foliar absorption of elements. For example, Deshmukh et al. [91] showed that silicon transporter genes GmNIP2-1 and GmNIP2- 2 belonging to the NIP2 subfamily of aquaporins are active in soybean leaves and can absorb silicon from the leaf. Zhu et al. [92] studied the zinc absorption in nano-oxide form by plant leaves and concluded that nano-zinc oxide particles can easily pass-through plant stomata and enter the mesophyll of leaf cells. Muñoz-Márquez reported that the foliar application of nano molybdenum fertilizer has a better effect than molybdenum chelates and sodium molybdate fertilizers on rising green bean growth and nitrogen use efficiency (Fig. 4). Numerous studies have been conducted to evaluate the effect of foliar spray of nano nutrients on the growth and physiological efficiency of plants, which generally showed better effects of these materials compared to the normal form of the nutrients [94–97]. However, excess use of nano nutrients has caused toxicity in plant tissues [98]. Foliar spray of nano-nutrients in favorable and unfavorable environmental conditions has had positive effects on the growth and physiological characteristics of plants. In research conducted by [99], it was found that the application of nano zinc significantly increases the growth and physiological efficiency of plants. The use of nano iron particles in saline conditions decreased the oxidative stress in plant tissues and increased the synthesis of secondary metabolites and resistance of plants to salinity stress [100]. In another study by [101], foliar spray of plants with nano silicon has increased resistance to water stress through reducing lipid peroxidation and enhancing nutrient uptake by plants. Foliar application of nano zinc oxide particles on maize plants under cadmium stress has improved the stress resistance and growth of plants [102]. In addition to metallic nanomaterials, carbon and hydrogen nano-compounds have also been sprinkled on plants, which in most cases had positive effects on plant growth and efficiency. It has been reported that the negative effects of stress can be reduced and the growth of plants can be enhanced under water stress [103], salinity [104, 105] and heavy metals [41] in response to foliar spray of chitosan.

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Table 1 The effects of seed pretreatment with various nanomaterials on seedling performance of different plants Material

Plant

Result

Reference

Carbon nanotubes and silicon dioxide nanoparticles

Brassica juncea

Seed pretreatment with Dhingra et al. [84] nanomaterials caused improvements in agronomic potential of Brassica juncea

Multiwall carbon nanotubes

Zea mays

Plant growth was accelerated and cadmium toxicity in maize plants was reduced by seed treatment

Chen et al. [85]

Iron oxide nanoparticles

Citrullus lanatus

The nonenzymatic antioxidant capacity and prime or elicit jasmonates-linked defensive responses in watermelon seedlings were boosted

Kasote et al. (2020)

Multi-walled carbon nanotubes

Triticum aestivum

Grains per plant, Joshi et al. [82] biomass, stomatal density, xylem–phloem size, epidermal cells, and water uptake of plants were enhanced, without DNA damage

Iron oxide nanoparticles

Linum usitatissimum

The levels of Waqas Mazhar et al. malondialdehyde and [86] hydrogen peroxide were dropped by 66% and 71%, respectively. The activities of the antioxidant enzymes superoxide dismutase, peroxidase, and catalase were increased by 28%, 56%, and 39%, respectively

Graphene oxide nanoparticles

Cucumis melo

The germination percentage and seedling growth of Cucumis melo under salt stress were enhanced

Kaymak et al. [87]

(continued)

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Table 1 (continued) Material

Plant

Result

Reference

Magnesium oxide nanoparticles

Vigna radiata

Primed seeds of Vigna radiata showed a higher seed germination and seedling vigor, compared to conventional hydropriming method

Anand et al. [80]

Zinc oxide nanoparticles

Zea mays

Maize seed Salam et al. [88] pretreatment with zinc oxide nanoparticles noticeably protected stomatal and ultra-cellular structure of plant under cobalt stress and enhanced photosynthetic efficiency and biomass accumulation

Silver and titanium oxide nanoparticles

Solanum lycopersicum

Seed pretreatment improved seed germination, seedling growth, chlorophyll content and antioxidative activities of Solanum lycopersicum

Silicon nanoparticle

Melissa officinalis

Seed priming with Hatami et al. [90] silicon nanoparticles and seedling inoculation with pseudomonas strains had a significant role in increasing primary and secondary metabolites of Melissa officinalis

Sonawane et al. [89]

In most cases, this was achieved via reduction of lipid peroxidation and increment of antioxidant activities. Hajihashemi and Kazemi [106] found that foliar spray of nano-chitosan-encapsulated nano-silicon donor on plants under salt stress significantly improves osmotic adjustment via increasing proline, glycine betaine, and carbohydrates production in plant cells. Some of the effects of foliar spraying of plants with nanomaterials are summarized in Table 2.

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Fig. 4 The effects of molybdenum nano fertilizer, chelate and sodium molybdate on green been growth (adopted from [93])

3.3 Addition of Nanoparticles and Nanocomposites to the Soil Soil fertility is an important factor affecting the plant growth and development [114]. Supplying nutrients to the plants is one of the basic challenges in the agricultural sector, so using inorganic nano materials as soil amendments is one of the most interesting topics in terms of providing adequate nutrients for plants growth. Adding nanomaterials to the soil in most cases has far better effects than the usual form of nutrients in increasing plant yield. For example, the yield improvement due to nano fertilizers in rice was about 10% [115] and due to nano-encapsulated phosphorous treatment on wheat [116], soybean [117], and maize [116] was about 28%, 16% and 10%, respectively. The potassium nano fertilizers have increased the rice yield by 40%, compared to the usual potassium fertilizers [118]. Although addition of nanomaterials to the soil in most cases has positive effects on the growth and efficiency of plants, it has caused a decrease in soil health in some cases. For example, application of titanium dioxide has reduced soil carbonization and reduced its microbial population [119, 120]. Similar results have been reported in the reduction of soil microbial activity in response to copper and iron oxide nanoparticles [121]. Shalaby et al. [122] showed that the addition of nano-Se and nano-Cu in growth medium noticeably enhances banana seedlings (Musa spp) via increasing photosynthetic pigments and antioxidant activities in plant tissues (Fig. 5). The soil could be treated with pure or composite forms of nanomaterials, among which the biochar-based nanocomposites have received most attention in recent years. Due to the high cation exchange capacity of these materials and their high specific surface area, biochar-based nanocomposites have a high ability to inject elements into the rhizosphere and maintain its moisture. In the recent research conducted on the effects of magnesium, manganese, iron, and zinc nanocomposites

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Table 2 The effect of foliar application of nanoparticles on plant performance Material

Plant

Result

Magnesium oxide nanoparticles

Gossypium

Treatment with Kanjan [107] nanoparticles increased cotton seed production by 42.2, 39.9, and 24.8% in comparison to control. The MgO nanoparticles were superior than Mg fertilizers in the sulfate form in terms of cotton fiber quality including fiber length and strength. Foliar application of MgO nanoparticles also enhanced the concentration of some macronutrients such as nitrogen, phosphorus, potassium, and magnesium in cotton plants

Reference

Iron oxide nanoparticles

Oryza sativa

A potential treatment Rizwan et al. [108] for decreasing harmful effects of Cd toxicity in plants, as evidenced by increasing in biomass, and Fe concentrations in tissues, and decreasing Cd levels in plants

Zinc oxide nanoparticles

Solanum melongena

Foliar spray of zinc Semida et al. [109] oxide nanoparticles alleviated osmotic stress effects on eggplant cultivated in saline soil

Manganese nano-chelates

Glycine max

Foliar treatment Vaghar et al. [110] increased the soybean resistance against water stress

Chitosan nanoparticle

millet plants

This treatment Sathiyabama and increased finger millet’s Manikandan [111] yield and mineral nutrients content (continued)

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Table 2 (continued) Material

Plant

Result

Silicon nanoparticles

Oryza sativa

The nano-silicon Wang et al. [97] treatment reduced cadmium accumulation, cadmium partitioning in shoots, and oxidative stress, while boosted the amount of several mineral elements (Mg, Fe, and Zn) and antioxidative activities in rice, leading to a higher plant biomass

Silicon and titanium dioxide nanoparticles

Oryza sativa

Application of these nanoparticles on rice leaves improved photosynthesis and plant biomass through reducing cadmium accumulation and improving the antioxidant defense system

Rizwan et al. [112]

Treatment on leafy vegetables (5 mg L−1 Selenium) mitigated heavy metal toxicity in plants

Zhu et al. [113]

Selenium nanoparticles Brassica chinensis

Reference

Fig. 5 Banana seedlings growth in response to different application rates of nano-Cu and Nano-Se (adopted from [122])

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based on biochar, it has been found that these materials in the rhizosphere improve the water retention capacity of the soil and the growth of plants in normal and saline conditions. According to available reports, magnesium, manganese, iron, and zinc nanocomposites based on biochar reduce the availability and absorption of sodium by plants under salt stress, thereby reducing the harmful impacts of this stress on plants [17, 18, 69, 124, 123]. One of the up-to-date topics in the discussion of fertilizers based on nanoscience is the production of fertilizers based on nano chitosan with a greater stability in the rhizosphere [44, 47]. Fertilizers based on nano-chitosan can carry many nutrients such as nitrogen, potassium, and phosphorus. There are many reports of soil treatment by these nanomaterials [38, 125]. Production and application of chitosanbased nitrogen, phosphorus, and potash fertilizers by [46] significantly improved the growth and physiological efficiency of wheat. Addition of nano-chitosan containing potassium to the soil not only increased microbial activity in the soil and seed yield of corn, but also reduced the need for chemical fertilizers consumption [126]. Production and application of zinc fertilizer based on chitosan significantly increased the growth of plants [127].

4 Conclusions and Future Perspective Utilization of nanomaterials has led to important progress in improving the growth and development of plants. Most of the nanomaterial treatments are currently related to plant nutrition. In addition to increasing the growth and physiological efficiency of plants under normal conditions, application of nanomaterials is also successful in increasing the growth and productivity of plants under environmental stresses. Our current knowledge about the mechanisms of the nanomaterial’s actions on the growth and physiological cycles of plants is insufficient, and thus it is necessary to investigate the cellular and sub-cellular effects of different nanomaterials on plants.

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120. Perez-Hernandez H, Huerta-Lwanga E, Mendoza-Vega J, Alvarez-Solís JD, PampillonGonzalez L, Fernandez-Luqueno F (2021) Assessment of TiO2 nanoparticles on maize seedlings and terrestrial isopods under greenhouse conditions. J Soil Sci Plant Nutr 21:2214–2228 121. Petrova A, Plaksenkova I, Kokina I, Jerma¸lonoka M (2021) Effect of Fe3 O4 and CuO Nanoparticles on morphology, genotoxicity, and miRNA expression on different barley (Hordeum vulgare L.) genotypes. Sci World J 2021: 6644689 122. Shalaby TA, El-Bialy SM, El-Mahrouk ME, Omara AED, El-Beltagi HS, El-Ramady H (2022) Acclimatization of in vitro banana seedlings using root-applied bio-nanofertilizer of copper and selenium. Agronomy 12:539 123. Ghassemi-Golezani K, Farhangi-Abriz S (2021) Biochar-based metal oxide nanocomposites of magnesium and manganese improved root development and productivity of safflower (Carthamus tinctorius L.) under salt stress. Rhizosphere 19:100416 124. Ghassemi-Golezani K, Farhangi-Abriz S (2022) Improving plant available water holding capacity of soil by solid and chemically modified biochars. Rhizosphere 21:100469 125. Qu B, Luo Y (2020) Chitosan-based hydrogel beads: Preparations, modifications and applications in food and agriculture sectors-A review. Int J Biol Macromol 152:437–448 126. Kubavat D, Trivedi K, Vaghela P, Prasad K, Vijay Anand GK, Trivedi H, Patidar R, Chaudhari J, Andhariya B, Ghosh A (2020) Characterization of a chitosan-based sustained release nano fertilizer formulation used as a soil conditioner while simultaneously improving biomass production of Zea mays L. Land Degrad Dev 31:2734–2746 127. Yuvaraj M, Subramanian KS (2015) Controlled-release fertilizer of zinc encapsulated by a manganese hollow core shell. Soil Sci Plant Nutr 61:319–326 128. Husen A, Siddiqi KS (2014) Carbon and fullerene nanomaterials in plant system. J Nanobiotechnology 12(16):1–10 129. Shameem MM, Sasikanth SM, Annamalai R, Raman RG (2021) A brief review on polymer nanocomposites and its applications. Mater Today Proc 45:2536–2539

Phytotoxicity Response and Defense Mechanisms of Nanocomposites/Mixture of Nanoparticles Muhammad Ansar Farooq, Afsheen Fatima, Sana Rehman, Ayesha Batool, Iram Gul, Aamir Alaud Din, Hassan Anwer, and Muhammad Arshad

Abstract Nanocomposites (NCs) and mixture of nanomaterials (NMs) are used in different sectors including agricultural with the intention of increasing the crop productivity and protection. Depending on the particle type, concentration, and size, as well as the plant species, NCs application can have either beneficial or detrimental effects on plant growth. Plants species encounter NCs applied either directly in soil, through irrigation, or foliar application. To comprehend the transport and accumulation of NMs in plants, it is crucial to understand how plants interact with nanoparticles (NPs) and NCs as well as their defense mechanisms. There is a dearth of knowledge regarding the mechanisms of NMs translocation in plants and NMinduced activation of defense systems. This chapter covered the phytotoxic effects of NCs and/or mixture of NMs, the pathways involved in the capture and transport of NMs within plants, as well as the plants’ defense response. Keywords Nanotoxicology · Nanocomposite · Nanomaterials · ROS · Defense mechanism · Antioxidant enzymes

Abbreviations AgNPs AHA2 Al2 O3 APX/POX CaBPs CAT

Silver nanoparticles Autoinhibited H+ -ATPase Aluminum oxide Ascorbate peroxidase Calcium-binding proteins Catalase

M. A. Farooq · A. Fatima · S. Rehman · A. Batool · A. A. Din · H. Anwer · M. Arshad (B) Institute of Environmental Sciences and Engineering (IESE), School of Civil and Environmental Engineering (SCEE), National University of Sciences and Technology (NUST), Sector H-12, Islamabad 44000, Pakistan e-mail: [email protected] I. Gul Department of Earth and Environmental Sciences, Hazara University, Mansehra 21120, Pakistan © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 A. Husen (ed.), Nanomaterials and Nanocomposites Exposures to Plants, Smart Nanomaterials Technology, https://doi.org/10.1007/978-981-99-2419-6_3

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CeO2 CNPs Co3 O4 CuO DHAR DNA Fe2 O3 Fe3 O4 GPX GR H2 O2 MDA MnO2 NCs NMs NPs nZVI PUFAs ROS SOD TiO2 ZnO

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Cerium oxide Composite nanoparticles Cobalt oxide Copper (II) oxide Dehydroascorbatereductase Deoxyribonucleic acid Iron oxide Magnetite Guaiacol peroxidase Glutathione reductase Hydrogen peroxide Malondialdehyde Manganese oxide Nanocomposites Nanomaterials Nanoparticles Nano-zero-valent iron Polyunsaturated fatty acids Reactive oxygen species Superoxide dismutase Titanium dioxide Zinc oxide

1 Introduction Nanotechnology is transforming the world with groundbreaking discoveries that promise to improve human well-being and have the potential to play to improve the agriculture and food industries in the future. Nanotechnology is usually applied in the agro-industrial sector to produce goods including fertilizers, fungicides, herbicides, insecticides, and nanosensors [1–4]. These innovations could assist in meeting future agricultural requirements by improving crop quality and yield, protecting crops from multiple environmental stresses, and minimizing chemical pollution [5]. Numerous nanoparticles (NPs) including zinc oxide NPs, iron oxide NPs, and titanium dioxide NPs have been tested and results showed that these NPs help in increasing nutrients’ availability, reduce abiotic stress, and enhance plant growth [6–9]. After studying the impacts of NPs on individual plant parameters, researchers focused on identifying the impacts of nanocomposites on plant ecosystem. Regardless of the wide range of advantages of nanotechnology in agricultural sector, the uncontrolled application of NPs/nanocomposites (NCs) could lead to a lot of difficulties for animals, plants, and ultimately for humanity [10]. Recently, the researchers focused on nanotoxicology in which the harmful impacts of nanomaterials (NMs)/NCs and their associated interactions with plants have been

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evaluated. The phytotoxic impacts of the NMs on the plants have been studied but limited information is available on NCs’ impacts on plants. Even though the exact mechanisms of nanotoxicity are still unknown, it is implicit that the toxicity of NMs/NCs might be due to the chemical structure, characteristics, concentration, size, and surface area of NPs [11]. Depending on the use and application, several types of NMs/NCs are developed, including those that contain: (i) inorganic nonmetallic NPs, (ii) metallic NPs, (iii) organic polymeric components, and (iv) carbon-based NPs [12]. Unique characteristics of NMs enable unusual interactions with biological systems. Besides specific nano-size effects, plant species, NPs characteristics, and environmental conditions are the main determinants of how NMs will interact with plants [13]. NMs toxicity not only threaten living organisms but they are also leaving behind unknown byproducts in the environment. Autotrophs (plants) are the vital constituent of environment and have direct interactions with the water, soil, and atmosphere, each of which has the potential to be a pathway for the interaction and distribution of NMs [14]. Accordingly, the interaction of NMs with various plant species (such as the uptake and storage of NMs in plants) may impact the fate and transit of NMs in the environment [15]. Potential threat is that agriculture and human health, indirectly through the food chain, could be inimically affected by direct exposure of plants to various types of NMs [16]. Generally, the NMs interact with plants either through physical or chemical contact which leads to signaling in plants, and produces unidentified compounds like reactive oxygen species (ROS) that could affect plant growth and development [17]. The production of ROS which is generally triggered by extreme environmental factors, leads to the breakdown of membrane and macromolecules, reduces plant growth, and triggers cell toxicity. To reduce oxidative stress, the antioxidant mechanism of plants scavenges ROS through enzymatic and non-enzymatic processes to defend plant against varying environmental stresses [12]. The primary focus of this chapter is the current knowledge of the toxicological repercussions that NPs and NCs have in plants. Further, the production of ROS, its role in inducing oxidative stress, and the ability of plants’ antioxidative defense mechanisms to detoxify excessive ROS have all been thoroughly discussed.

2 Nanomaterials/Nanocomposites Characteristics Nanosized particles with nanoscale dimensions are incorporated into a matrix of conventional material to create NCs. The NMs included in NCs are nanoparticles, nanotubes, and nanofibers [18]. NCs are generally classified into three groups: (i) ceramic matrix NC, (ii) polymer matrix NC, and (iii) metal matrix NC. NMs or mixture of nanomaterials’ characteristics like particle size and shape, concentration, porosity, surface charge, and higher surface area to mass ratio, promote plant maturation and productivity while also protect them from a variety of abiotic challenges. In contrast, these same characteristics make them lethal, because NMs also cause

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oxidative stress, and genotoxic and cytotoxic reactions in plants, which affect physiological and biochemical activity, plant growth, and calorific value of plants [19]. In a study Allium cepa root hairs were exposed to gold (Au) NPs of three distinct sizes (15, 30, and 40 nm) at different concentrations of 0.1, 1, and 10 µg mL−1 , and the results showed that the plant system responded differently to each size and concentration. The malondialdehyde (MDA) content, an indication of oxidative stress and lipid peroxidation, increased significantly with the decreasing NPs size and increasing dose of AuNPs [20]. From the results, it is evident that NPs have different effects on plants depending on both the size of the NPs and the treatment dose that is applied to the plant. The toxicity of NPs and NCs primarily occurs in two ways: first, due to chemical toxicity induced by the chemical makeup of NMs, and second, due to stress impetus caused by the morphology of particles [15]. Considering that NPs have a greater ratio of surface area to volume and have the potential to be highly reactive, it is projected that they will be absorbed 15–20 times more than their corresponding parent material [21]. The effect of NMs on plants system can be assessed by the physicochemical properties of the NMs as they are considered as the primary cause of phytotoxicity in plant system. The type and NP morphology, crystal structure, concentration, size distribution, agglomeration, and surface charge are some of the parameters that, if they are individually modified, can relate to the poisonous level of NPs properties and can produce different effects in the same system [22]. Apart from the physicochemical characteristics of NMs, the toxicity also depends on some other factors including: (a) experimental design, (b) the phase in which NPs will come in contact with plants, (c) exposure time, (d) the entry routes and interplay of NPs, and (e) plant species [22].

3 NMs Uptake by Plants Plants have the ability to thrive in environments with naturally occurring concentrations of NMs or mixtures of NPs. However, the risk of plants’ exposure to NMs (single and/or composite) has increased to a greater extent, as NMs are synthesized and employed in a wide range of devices and products [23]. NMs could invade plants through different sources such as direct application of NMs, accidental release, uptake through polluted soil or sediments, or by atmospheric fallout. In several studies, application of NMs on plants showed both positive and negative impacts and these effects are due to the NM’s characteristics such as (i) particle size, (ii) concentration, (iii) chemical composition, (iv) surface activity, (v) modification, and (vi) aggregation [22]. Insight into the processes involved in the uptake and passage of NMs is crucial, regardless of the nature of their action. Uncertainty exists regarding the precise mechanisms underlying NPs’ absorption and translocation. However, based on the chemical composition, size, charge, and shape of NMs, studies have examined the three pathways by which NMs enter plant

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cells (Mehrian et al. 2016). Diffusion over the phospholipid bilayer is the initial step in the entry of NMs into plant cells. The second way NMs can invade is through endocytosis, which requires the plasma membrane to be involved. Aquaporins and ion channels make up the third mechanism mentioned in the literature. Once NMs have entered a plant cell, they can follow either the apoplastic or symplastic pathway as they make their way through the xylem. There is species-specific variation in NM absorption and translocation in plants. The features of NMs, such as size, shape, etc., also influence the NM’s mobility in plants [24]. There are active and passive processes at work in the entrance and translocation of NPs. The former, plant absorption from the growth medium, is regarded as an active occurrence, whereas the latter, plant entrance and translocation, are more or less passive processes [25]. The NPs’ ability to enter a plant does not guarantee their capacity to move anywhere within the plant. In addition to uptake and movement, NPs can also accumulate or agglomerate in distinct plant systems [26].

4 Phytotoxicity of Nanomaterials/Nanocomposites Several studies available on the plant–NMs interaction include the silica NPs, metallic NPs, and composite NPs (CNPs). In the literature, several studies explored the interactivity of metallic NPs with plants due to their absorption capacity and enhancing the essential nutrient availability for plants [27]. It is well noted that depending on the qualities of the NMs and plant types, after the NMs are assimilated by the plants, they may have both beneficial and harmful effects. Therefore, Fig. 1 summarizes the plant–NMs interaction as well as the effect of NMs on plant. To varying degrees, depending on the conditions under which they are grown, plants can take in both necessary and non-essential elements in amounts required for proper growth. It is possible that plant health will be jeopardized by the ingestion of excessive non-essential components [28]. It has been discerned that plant growth is stunted when toxic compounds build up in their tissues, and ultimately, the plants die from their inability to cope with the accumulated toxins [29]. Numerous experiments have been carried out to ascertain the deleterious impacts of NMs on some of the edible plants such as radish (Raphanus sativus), cucumber (Cucumis sativus), lettuce (Lactuca sativa), rapeseed (Brassica napus), and corn (Zea mays) [30–33]. Among different NMs, the effect of metallic NPs including titanium dioxide (TiO2 ), aluminum oxide (Al2 O3 ), iron oxide (Fe2 O3 ), and zinc oxide (ZnO) on plants have been studied. It has been stated that Hordeum sativum biomass, root, and shoot length were all decreased by the application of copper oxide (CuO) NPs. CuO NPs phytotoxic effects on the rate of transpiration, photosynthetic activity, and stomatal conductance were linked to this decline in plant growth [34]. In another study, 20% deduction in root length of Lactuca sativa was observed upon application of 50 mg/L Fe2 O3 NPs. Table 1 summarizes the effects of NPs on various plant species that are phytotoxic.

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Fig. 1 Interaction and effects of nanomaterials/nanocomposites on plants Table 1 Phytotoxic impacts of nanomaterials on different plant species Nanomaterial and size (nm)

Plant species

Effect on plants

Key references

CuO NPs (30–50 nm)

Hordeum sativum

Reduced root and shoot length Reduced transpiration rate

Rajput et al. [34]

TiO2 NPs

Lactuca sativa

Reduced nutritional quality [35]

Fe2 O3 NPs (60 nm)

Lactuca sativa

Decreased the root length by 20%

SiO2 NPs (35 nm)

Bt-transgenic cotton

Reduced plant height and biomass Affected micronutrient contents in roots

Le et al. [36]

CuO NPs (43 nm)

Rice

Reduced root length Abnormalities in ultrastructure

[37]

ZnO NPs (50 nm)

Pisum sativum

Reduced root elongation

TiO2 NPs (25 nm)

Tobacco

Inhibited germination rate, biomass, and root length

[38]

Cu NPs (40 nm)

Pisum sativum

Reduced biomass, root length

[39]

ZnO NPs (50 nm)

Cucumis sativus

Reduced seedling biomass

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5 Plant Response to Nanomaterials’ Toxicity NMs mainly enter plant system either through the leaves (floral application) or roots (directly added in soil or irrigation). After the entry of NMs into plants, they interact at cellular and subcellular levels that affect the physiology and morphology of the plants. A plant is said to be under “oxidative stress” when certain stressors, such as water deficiency, salinity, heavy metals’ baneful effects, and excessive NMs, are present. Reactive oxygen species (ROS) are produced by plants as a reactionary measure to the stress brought on by NMs through oxidative damage. These different ROS are a consequence of the detoxifying process of the plant. When plants are stressed, they produce more ROS, which leads to oxidative harm and cell death in several plant species. Direct appraisal of oxidative stress can be taken by tracking ROS production, lipid peroxidation, and electrolyte loss. Plants are broadly categorized into two groups in accordance with their reaction to NMs: (1) Physiological indicators and (2) Biochemical indicators (Fig. 2).

5.1 Physiological Indicators Numerous studies have shown the physiological indicators caused by toxicity of NMs such as biomass, leaf number, growth rate, germination percentage, and root

Fig. 2 Classification of plants based on their response to nanomaterials (NMs)

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elongation. Other significant plant physiological indicators of NMs harmful effects include decrease in seed germination, repression of plant length, and can even lead to plant mortality [40]. Previous studies have shown that the growth of plant species, for instance, soybean, wheat, ryegrass, and barley, were found to be inhibited by exposure to NMs and various attributes of plant growth were influenced including seed germination, shoot length, and plant biomass [41]. Several studies documented how NMs adversely influenced the physiology of a variety of plants. Lee and his coworkers [42] studied the application of ZnO NPs (44 nm mean size) and found that they reduced the sprouting percentage, primary root maturation, and leaves quantity in A. thaliana. Likewise, in another study application of silver NPs (AgNPs, size: 20 nm) reduced the growth of peanuts due to the inhibition of photosynthetic activity [43].

5.2 Biochemical Indicators The plants in which chlorophyll content and enzymatic activities (such as catalase and ascorbate peroxidase role) are affected due to the application of NMs are grouped as biochemical indicators. Furthermore, the NMs also cause changes in the metabolites and protein content, as well as affect the gene expression of these plants [44]. Different studies documented the detrimental impacts of NMs on plants including reduction in mineral intake, a drop in photosynthetic activity, disruptions in the microscopic structure ultrastructure of cellular organelles, oxidative strain, and DNA damage [45]. Zhao et al. [46] found a decline in photosynthesis key content, stomatal conductance, and net photosynthesis in corn upon application of nZnO (24 ± 3 nm) at 800 mg/kg. Furthermore, electron transport chain was blocked which hinder the photosynthetic pathway [46]. In another research study, the DNA damage and growth retardation of Raphanus sativus, Lolium perenne, and Lolium rigidum was found upon CuO NPs (size: 58 nm) application [47].

5.2.1

Reactive Oxygen Species (ROS) Generation

The consumption of oxygen (O2 ) generates ROS, which consists of a collection of free radicals, ions, and reactive molecules. According to studies, plants divert 1% of the oxygen they consume at several subcellular sites like chloroplasts, mitochondria, peroxisomes, plasma membranes, and endoplasmic reticulum to generate ROS [22]. By-products of numerous ongoing metabolic processes in different parts of the cell, or the impending electrons leakage into O2 from electron transport activities, which converts ground state oxygen (O2 ) into O singlets, superoxide anions (O2 − ), hydrogen peroxide (H2 O2 ), and hydroxyl radicals (OH+ ), are the two primary sources of ROS [48]. Hydroxyl radicals (OH+ ), which have one unpaired electron and cannot be detoxified by any known enzyme system, are the most hazardous and reactive of all ROS [49].

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Normally, in a typical plant, ROS are considered as signaling molecules created as a subsidiary product of aerobic metabolism. When conditions are strenuous, there is a disruption in the balance that exists between the production and degeneration of ROS. It is well known that, depending on their concentration, ROS can act either as harmful or beneficial species in plants. When ROS levels are low to moderate, they function as a second messenger in intracellular signaling cascades that regulate a variety of plant cells responses including stomatal exchange discontinuation, induction of apoptosis, seed germination, gravitropism, and tolerance development against varying stresses [50, 51]. However, at excess concentrations when ROS levels are high, they cause damage to biomolecules such as altering the intrinsic membrane properties by inducing protein oxidation, lipid peroxidation, DNA damage, electrolyte leakage, and membrane damage, ultimately leading cell towards expiration [26, 48, 49]. Lipid peroxidation: By producing lipid-derived radicals, which have the capacity to interact and harm proteins and DNA, lipid peroxidation amplifies cell damage. Particularly vulnerable to damage by ROS are the multiple bonded fatty acids (FA) found in membrane phospholipids. One of the byproducts of the oxidative damage of triglycerides in phospholipids is malondialdehyde (MDA) that causes the cell membrane mutilation [52]. Because the reactions taking place during this process are cyclic, even a single •OH can lead to the peroxidation of a large number of multiple bonded FAs [20]. Such as nCuO significantly increased the amount of ROS and MDA in rice, resulting in oxidative stress [53]. Protein oxidation: In general, ROS can cause protein oxidation, a covalent alteration of a protein. The locale-specific amino acids substitution, the disintegration of bonded amino acids or protein chains, the agglomeration of cross-linked reaction products, the alteration of electric charge, and accelerated proteins degradation can all be brought on by excessive ROS formation [48]. Carbonylated proteins, which are frequently utilized as a determinant of protein oxidation, are typically present in higher concentrations in tissues that have been damaged by oxidative stress. Hancock et al. [54] recognized that activated oxygen can absorb the hydrogen atom from cysteine residues and produce a thiyl radical as a result. The disulfide bridge will then be created by crosslinking this radical with another thiyl radical, which is produced when thiol undergoes one electron oxidation [54]. DNA damage: Deoxyribonucleic acid (DNA) in mitochondria, the cell’s nucleus, and chloroplasts can all be harmed by excessive ROS production through oxidative injury. DNA is attacked by oxidants, which cause deoxyribose oxidation, strand structural breakage, nucleotide loss, amendments to the organic bases of the nucleotides, and DNA–protein crosslinks. Additionally, modifications in one strand’s nucleotides may result in discrepancies with those in the other strand’s nucleotides, leading to mutations down the road. Single-strand breakage is triggered by ROS attacks on DNA sugars. Deoxyribose radical is formed when ROS removes an atom of hydrogen from its C4_ site and then it reacts further to cause DNA strand breakage. DNA protein crosslinks are generated when hydroxyl radical assaults either the proteins interacting with DNA or the DNA itself. If cloning or transcription antecedes repair, DNA protein crosslinks cannot be readily restored and may prove fatal [16, 55].

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6 Plants Defense Mechanism Plants are subjected to a wide range of environmental challenges, and in order to maintain their vitality under these conditions, they have evolved a variety of defense mechanisms. They could alter the biochemical, physiological, and molecular mechanisms that result in the emergence of a resistant response to environmental stimuli [56, 57]. Plants have chemical defense based on the manufacture and accumulation of naturally occurring bioactive molecules, such as alkaloids, terpenoids, phenolic compounds, and many polypeptides [58]. Moreover, as signaling molecules, the plant hormones salicylic acid, jasmonic acid, and ethylene can also play influential roles in defensive feedbacks [59]. Additionally, plants have several enzymatic and nonenzymatic stress-resistant mechanisms that can also be stimulated [60]. The gene networks are also activated during this first response, which results in a powerful defense that shields the plant from damage brought on by the stressors [61]. NPs have the potential to interfere with a plant’s ability to photosynthesize, which could result in an overabundance of ROS. As a result of the variation in ROS concentration, enzymatic content frequently varies, which activates plant natural defense mechanisms [57]. However, plant defense mechanisms that could mitigate nanotoxicity are not properly explored in the literature [62].

6.1 Antioxidative Defense Mechanism Plants have an antioxidant defense system that employs both enzymatic antioxidants like superoxide dismutase (SOD), ascorbate peroxidase (APX or POX), guaiacol peroxidase (GPX), dehydroascorbate reductase (DHAR), and glutathione reductase (GR), as well as nonenzymatic antioxidants like ascorbate, glutathione, thiols, and phenolics [60]. Around the world, plants have evolved an antioxidant mechanism that tends to stop the excessive production of ROS, such as H2 O2 , OH, and O2 free radicals. By removing ROS, these enzymes help protect plants from oxidative damage. SOD converts superoxide (O2 − ) into hydrogen peroxide (H2 O2 ), which is then broken down into water (H2 O) and oxygen (O2 ) by CAT. POX is involved in the breakdown of H2 O2 and other peroxides [62, 63]. Hence, an increase in antioxidative enzyme levels, such as those of SOD, CAT, and POX could help plant cells lessen the oxidative stress that could lead to optimum growth and yield of crop plants [57, 62]. According to Prasad et al. [62], among the most notable biochemical alterations after NP exposure is the emergence of oxidative pressure, which alters the equilibrium between cellular functions and plant defense mechanism. Multiple nanostructures can trigger biochemical changes that lead to free radical production, disruption of membrane transport systems, cellular membrane oxidative damage, and DNA degradation [62]. While some NMs can cause toxicity due to the oxidative stress by producing free radicals, some can function as antioxidants to neutralize these free radicals and support the preservation of a healthy metabolism [64]. The increased

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ROS level caused by NMs might be linked to the amplified stress signal, which may more effectively activate plant defense mechanisms. For example, the activation of antioxidant enzymes in response to NM administration has been examined in many studies. Different NMs can activate antioxidant enzymes, such as nCeO2 , nFe3 O4 , and nCo3 O4 for CAT, nCeO2 , nFe3 O4 , nCo3 O4 , nMnO2 , nCuO, and nAu (gold) for GPX, and nCeO2 , nPt (platinum), and fullerene for SOD [65, 66]. It has been observed in an experimental study that the application of TiO2 NPs on Moldavian dragonhead decreased the oxidative stress and reduced the membrane damage and production of H2 O2 [67]. However, NPs oxidant and antioxidant properties depend on a variety of elements, such as size, shape, or chemical composition [64]. Moreover, these effects can often be dose-dependent. For instance, according to Rizwan et al. [68], plant’s defense mechanism can effectively scavenge ROS by enzymes at lower concentrations of NPs. However, it could be hindered at higher concentrations.

6.2 Gene Modification Molecular machinery is activated by a signaling network as the primary defense system activation mechanism, when dealing with a particular stress. Along with serving as a messenger, calcium (Ca) is crucial for signaling reactions to different stimuli. The cytosolic Ca ion (Ca2+ ) concentration [(Ca2 )cyt] increases in response to stress stimuli. Ca2+ -binding proteins (CaBPs) sense the elevated cytosolic Ca2+ concentration, and subsequently, CaBPs attach to the promoters of specific genes and either promote or downregulate their expression, allowing plants to hold out against stress [69]. The NPs can boost CaBPs’ expression and bind to them, which can subsequently result in downstream signaling, which in turn triggers the expression of stress-associated genes and the stimulation of the plant’s defensive mechanisms. According to research by Goyer [70] and Mirzajani et al. [71], Ag NPs or discharged ions interfere with cell metabolism through interactions with second Ca2 messenger receptors, ion channels, and Ca2 /Na (sodium) pumps. According to the study conducted by Miao et al. [72], the Ca2+ /calmodulin-dependent protein kinase II was found to be functionally modified as a result of interactions between watersuspended fullerene C60 nanocrystals. Similarly, Kim et al. [73] discovered that the administration of nano-ZVI (nZVI) improved drought tolerance by increasing the expression of AHA2 , a gene linked to the stomatal opening procedure in Arabidopsis. In addition, it appears that a crucial aspect of the reciprocity between NPs and plant responses to stress is the regulation of gene expression at the mRNA level by microRNA molecules. Several studies have also found that gene expression associated with cell division and cell elongation is increased following NMs treatment [74, 75]. Furthermore, plant responses to stress include epigenetic regulation of gene expression [76]. According to Berger [77], epigenetics regulates gene expression without changing the DNA sequence through altering histones or DNA methylation.

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However, just as the antioxidant property, this mitigating function of NMs is also dependent on NP size, shape, and dosage because some concentrations have been demonstrated to be hazardous for plants while lesser quantities have beneficial benefits. For example, according to Khan et al. [69], Tobacco plants exposed to nano-TiO2 and nano-Al2 O3 exhibit yellowing, wilting, smaller leaf diameters and quantity, stunted root growth, and a decline in biomass, and these NMs play a critical role in the plant response to metal stress [69]. Moreover, there are still many genes that need to be identified that take part in plant defense mechanisms before gene networks that are involved in stress reduction can be fully understood. Therefore, additional probing is required in order to acquire a rigorous insight into how genes are regulated when plants are subjected to varying concentrations of NPs [76].

7 Conclusions and Future Outlook Nanomaterials/nanocomposites are widely employed by the agricultural sector for the enhancement of crop yield. The phytotoxic effects, however, are a direct result of the unchecked and unregulated dissemination of these NMs/NCs. Understanding the mechanistic framework involved in the uptake of nanocomposites by plants is crucial for mitigating their potentially harmful effects on plants. But there is still limited and conflicting information available regarding conduiting pathways and operative mechanisms of nanomaterials/nanocomposites. Moreover, it has been difficult to draw definitive conclusions because of the complicated behavior of NMs. Therefore, the current research system must be expanded to include extensive field investigations in representative settings. Hence, it must be underlined that more research needs to be done on the propensities and effects of NCs/NMs resulting from their transmission and accumulation. Moreover, it is crucial to take into account the possibilities and consequences that NCs/NMs could build up in the food chain in the longer run, without compromising the pursuit of food security and crop protection.

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Phytotoxicity Responses and Defence Mechanisms of Heavy Metal and Metal-Based Nanoparticles Taruni Bajaj, Hina Alim, Ahmad Ali, and Nimisha Patel

Abstract Since the past several years, there has been a lot of focus on the soil-borne accumulation of heavy metals in plants. The agroecosystem has been found to be substantially impacted by the excess of dangerous heavy metals present in soil, such as Ni, Pb, Cd, Ag, Co, Cu, Zn, Mn and Cr, in a number of ways involving physical, morphological and biochemical aspects. By damaging the cellular structure of the plant, causing oxidative stress through the generation of ROS, manipulating the composition of biomolecules, altering the content and fluorescence of chlorophyll, reducing crop yields and depleting soil fertility, nanoparticles carrying heavy metals have contributed to the development of phytotoxicity in plants. However, it has been found that applying designed nanomaterials through solution, seed priming, spraying, etc., increases plants’ resilience to metal stress. Plants use a variety of defence mechanisms to defend themselves from Heavy Metal (HM) stress, including controlling metabolic responses (antioxidants and other enzymatic activities), altering gene expression, changing cellular composition, etc. To create plant varieties that can withstand nanotoxicity, various plants are genetically modified. Numerous PGPR (plant growth-promoting rhizobacteria) are useful in reducing the effects of phytotoxicity, which in turn improves crop production in metal-contaminated soil. They are also known to have high tolerance to heavy metals. Utilising a variety of plant species, detoxification programmes and phytoremediation techniques are used to deal with these heavy metal contaminants and preserve soil microbiota. Additional research is required to ascertain the threshold at which these heavy metals and/or nanoparticles alone can induce phytotoxicity and to take advantage of methodologies and plant regulatory mechanisms that can be used to remove these contaminants. Keywords Nanoparticles · Phytotoxicity · ROS · Antioxidants · HM stress

T. Bajaj · N. Patel (B) Department of Life Sciences, J. C Bose University of Science and Technology, YMCA, Faridabad 121006, Haryana, India e-mail: [email protected] H. Alim · A. Ali Department of Life Sciences, University of Mumbai, Mumbai 400098, Maharashtra, India © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 A. Husen (ed.), Nanomaterials and Nanocomposites Exposures to Plants, Smart Nanomaterials Technology, https://doi.org/10.1007/978-981-99-2419-6_4

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Abbreviations Ag AgNPs Al Al2 O3 AMF APX As ATP ATPase C3 C4 plants CAT Cd CdONPs CeO2 CeO2 NPs Chlorella vulgaris Co CO2 Cr Cu Cu(OH)2 Cu(OH)2 NPs CuNPs CuO DNA ENPs ETC Fe FeO4 GO GR GRSP GSH H2 O2 H3 BO3 Hg HM MDA Mn3 O4 MWCNTs NADPH dehydrogenase

Silver Silver nanoparticles Aluminium Aluminium oxide Arbuscular mycorrhizal fungi Ascorbate peroxidase Arsenic Adenosine 5’ triphosphate Adenosine triphosphatase Calvin cycle Plants undergoing Hatch and Slack cycle Catalase Cadmium Cadmium oxide nanoparticles Cerium (IV) oxide Cerium (IV) oxide nanoparticles Chlorella vulgaris Cobalt Carbon dioxide Chromium Copper Copper (II) hydroxide Copper (II) hydroxide nanoparticles Copper nanoparticles Copper oxide Deoxyribonucleic acid Engineered nanoparticles Electron transport cycle Iron Ferrate (IV) Graphene oxide Glutathione reductase Glomalin-related soil protein Glutathione Hydrogen peroxide Boric acid Mercury Heavy metal Malondialdehyde Trimanganese tetraoxide Multi-walled carbon nanotubes Nicotinamide adenine dinucleotide dehydrogenase

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Ni OS Pb PIP PPP PUFAs RG II RNA ROS Se SOD SWCNTs TCA cycle TiO2 TiO2 NPs U WS2 NPs Zn ZnO

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Nickel Oxidative stress Lead Plasma membrane intrinsic proteins Pentose phosphate pathway Polyunsaturated fatty acids Rhamnogalacturonan II Ribonucleic acid Reactive oxygen species Selenium Superoxide dismutase Single-walled carbon nanotubes Tricarboxylic acid cycle Titanium dioxide Titanium dioxide nanoparticles Uracil Tungsten disulfide nanoparticles Zinc Zinc oxide

1 Introduction Soil has been contaminated by the deposition of various heavy metals and metalloids with a density of more than 5 gcm−3 , which are the common natural habitat of millions of microbiota species. This has led to a fall in the amount of land that can be used for agriculture and has become the principal hazard to the environment and maintenance of the agroecosystem [1–5]. Due to the rising expansion of industries, the concentration of HM in the environment has increased [6–8], having dangerous consequences on the development and regular metabolic processes of flora [9]. HMs are created at a level that is deemed trace (less than 1000 mg kg−1 ), rarely dangerous, and can only be obtained in the soil ecosystem due to the pedogenetic processes of decomposing parent chemicals [10–13]. Other sources such as volcanoes, wastes containing metal dust and weathering of rocks, etc., leads to HM contamination in soil [14] as well as its addition to agricultural land through various anthropogenic activities for instance, industrialisation, mining, smelting [15, 16], release of HM wastes, paints and gasoline, use of fertilisers [17, 18], bio-wastes (compost, manure, domestic sewage waste) [19, 20], pesticides such as fungicidal chemicals containing copper (copper oxychloride and copper sulphate) [21], petrochemicals and atmospheric pollution [22, 23] and unprocessed water [24]. These anthropogenic metal contaminants can be recovered via chemical extraction methods since they are readily accessible and mobile in nature [25–28]. Its nature and mobility in soil are determined by a number of factors, including composition, speciation and metal content. The metals present in soil are

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classified as exchangeable metal, carbonate phase-bound metal, Fe and Mn oxideattached metal, organic matter-bound metal and residual metal on the basis of control of certain characteristics of metals such as (i) ion exchange, adsorbing and desorbing capacity, (ii) dissolution and precipitation, (iii) aqueous complexation, (iv) uptake by plants and (v) biological mobilisation and immobilisation [29, 30]. Microbes are able to bond strongly with metal ions present in soil mixtures because of the ionic charges present on their surface [31]. Growing plants under unfavourable conditions can lead to a variety of HMs stressors that reduce the translocation of important macro- and micronutrients, changing the metabolism of the plant and its growth in general [32–34]. The toxicity of HMs has a significant impact on a number of cellular systems and activities, including regulatory mechanisms, plant tissue growth, accumulation of ROS, nutrient uptake, etc. As a result, membrane lipid peroxidation and occasionally plant mortality occur [35–39]. Vascular plants have developed a variety of coping mechanisms, such as chelation, detoxification, sequestration and efflux, to lessen the harmful effects of toxic metals [40, 41]. When it comes to reducing the high concentration of HMs present in agro-ecosystems that adversely affect the food chain when transferred to those edible parts of plants present above ground region, the most appropriate and practical methods, such as phytoremediation and bioremediation, are frequently used [42–44]. The accumulation of HM in the food chain destroys not just plant growth but also human health, softening systemic bone, harming the neurological system, impairing reproductive function, and in extreme situations, even causing death [45, 46]. Due to numerous benefits like effective catalytic activity, distinctive magnetic and optical character, presence of numerous surface reaction sites and high surface activity, the usage of nanoparticles (NPs) in medical industry, agriculture, cosmetics and food technology has become increasingly important in recent years [47–61]. When used as nanopesticides and nanofertilisers [62–64], nanoparticles have been shown to have many benefits for vegetation [65–68], including improving seed germination, photosynthesis, OS (oxidative stress) resistance, rhizome growth and maturation and crop quality and yield [69–76]. Some nanoparticles, such as TiO2 , CeO2 and Mn3 O4 , are effective for enhancing the antioxidation capability of enzymes, which in turn is useful for improving crop yield and quality overall by minimising the creation of ROS (reactive oxygen species) in plants [77, 78]. Additionally, it has been found that applying nanoparticles to the leaves of plants can increase their ability to absorb and assimilate foliar fertilisers, lessen the damage caused by abiotic stress and thus increase their resistance to it, increase the antioxidative activity of enzymes and decrease the uptake of various HMs by plants, such as cadmium and lead [4, 79–82]. It has been reported that numerous detrimental effects in plants from the application of engineered nanoparticles (ENPs), particularly metal-based nanoparticles that cause phytotoxic effects including root pores blockage, inhibition of flow of nutrients and water and accumulation of ROS that in turn leads to cell membrane and cell wall structure alteration [83–86] as well as genotoxic effects including cell division impairment, cellular aberrations and cell disintegration [87–91].

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This chapter wraps up the current understanding of how HMs and metal-based nanoparticles negatively affect plants, their interactions with both plants and each other, and the protective measures taken by plants to counteract abiotic stress.

2 Toxicity Caused by Metals in Plants The appearance of metal in soil is governed by multiple soil characteristics, including pH of the soil, the cation exchange potential, the proportion of organic matter present and clay adsorption [92, 93]. Toxic heavy metal accumulation and absorption in the vegetal region of flora cause damage to plants by interfering with the functions of cell membranes, inhibiting the enzymatic action, inactivating photosystems and changing the metabolism of minerals [94–99]. Metal toxicity is largely responsible for OS, altering protein function and interfering with the function of pigment molecules [100]. Metal toxicity causes an overproduction of ROS, which damages several cellular components such as lipid and protein oxidation, genetic material damage, suppression of enzyme activity and even death [101, 102].

2.1 Seed Growth and Germination Process When germination conditions are favourable, seeds have a variety of sensing mechanisms that allow them to finish the advancement process. However, hazardous metals including Pb, Hg, Ag, Ni, Co, Cd, etc., have an unfavourable effect on seeds that are in the germination process [103–105]. Seed tolerance level for hazardous metals in soil is determined by their capacity to sprout in their presence [106]. For instance, the high concentration of Cr (VI) in wheat plants considerably inhibits seed germination and reduces root growth [107].

2.2 Inhibited Root Elongation The root region’s growth is very susceptible to the presence of HMs because they are absorbed by roots through mass and diffusion, which immediately inhibits root growth. As a result, the roots that are produced are shorter, ramified and irregular in shape [108–111]. Because of resistance to cellular division in the tip of the roots, metals like Cr and Pb, for example, inhibit the root growth and crop production of wheat plants [108, 112, 113]. Metals interfere with the apoplastic and symplastic pathways of metabolism after entering the tissues of roots and binding with the carboxylic group of the pectin component of cell walls, preventing root growth [114, 115]. A number of impacts of metal-induced inhibition can be seen in roots, including a reduction in the length

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of lateral roots and root hair, a change in colour, curvature, atrophy and thickening and broadening of roots [116]. The stiffness of the cell wall is impacted by longer exposure times and higher metal concentrations, which damages the rhizodermis and meristematic cortical layer and prevents root extension [117, 118].

2.3 Cell Membrane and Cell Wall A root’s cellular membrane experiences numerous physiological and structural changes as a result of exposure to metal ions, including the destruction of the plasma membrane by oxygen radicals produced freely under metal stress, which leads to ATPase inhibition and, in turn, a reduction in proton transport and overall transport activity (such as nutrient uptake). For instance, it has been noted that the build-up of Cr can disrupt a variety of mechanisms and metabolic processes in plants, such as changing the pigment molecules in chlorophyll, changing the pH and increasing the formation of biometabolites like glutathione and ascorbic acid [119–121]. Besides these, denaturation of proteins, lipid fluidity and cross-linking of thiol proteins are other effects of metal stress [122].

2.4 Effect on Photosynthesis Toxic metals like Cd and Zn have been found to stimulate a number of photosynthesisrelated components, including pigment molecules, light-capturing centres, electron transport, CO2 access, stomatal enzyme conductance, thylakoid membrane structure and C3 cycle enzymes [123, 124] (Fig.1). These components tend to slow down electron transport and more effectively inhibit photosystem II [125]. The symptoms such as leaf death (chlorosis), underdevelopment of the plant and a decrease in biomass production were noted as a result [99, 126–128]. In general, any changes to the concentration of plant pigment, whether they are quantitative or qualitative, can have a deleterious effect on the physiology of flora and its growth. Studies have shown that while Cr is known to have a stronger hazardous effect on plants when administered at low concentrations, HMs like Selenium and Ni, which are not necessary for growth, cause toxicity to plants like Brassica oleracea as their concentrations rise [129].

2.5 Oxidative Stress and Lipid Peroxidation According to studies, the toxicity of HMs causes an increase in OS [130–132]. ROS which has a serious impact on cells is produced when oxygen is excited to the singlet form of oxygen (1 O2 ), hydrogen peroxide (H2 O2 ), the superoxide radical or

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Fig. 1 Brief of the consequences of toxicity of HM on photosynthesis

the hydroxyl radical by transferring an electron to oxygen [133]. Particularly, free radical-containing ROS molecules exhibit an immediate and untargeted interaction with the lipids, proteins and nucleic acids of the cells. Therefore, plants produce a variety of antioxidative enzymes to deal with oxygen species (excessive accumulation of ROS) produced under stress, including catalase (CAT, dismutating H2 O2 ), glutathione reductase (GR), NADPH dehydrogenase, superoxide dismutase (SOD), ascorbate peroxidase (APX), the ascorbate– glutathione cycle, etc. Under typical circumstances, the production and neutralisation of ROS are well maintained. OS is caused by a build-up of ROS in cells and tissues of plants, which occurs when the balance of ROS production is disturbed under stress or unfavourable conditions [134]. By reacting with various proteins, lipids, pigment molecules involved in photosynthesis and other organelles, the production of ROS (for example, radical O2− ) and H2 O2 by various metal pollutants, such as Pb in plants, causes alterations in the membrane structural configuration and peroxidation of lipids present, which ultimately results in cell damage and death [135–140]. Malondialdehyde (MDA), the principal byproduct of lipid peroxidation, is formed in plants by the oxidation of PUFAs when plants experience significant OS in the absence of ROS, and it is primarily responsible for cell membrane rupture [141]. Additionally, [142], the increased peroxidation of cell lipid caused by the production of free radicals by HMs like Fe and Cu modifies membrane properties like permeability and flexibility as well as the activity of membrane-bound ATPase [143]. According to studies, metals like Cr can interfere with a variety of physiological processes, including lipid peroxidation, which produces many small hydrocarbon molecules like malondialdehyde from unsaturated fatty acids [144, 145], a reduction in plant growth and simulating OS and anti-oxidative defence in plants [94].

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2.6 Genotoxicity The term “mutagens” or “genotoxic agents” refers to molecules or substances that have the capacity to damage cells’ genomes (including nuclear and extra-nuclear genetic material). For instance, it has been discovered that Pb is a genotoxic substance that may cause cancer in humans [146]. The toxicity caused by Pb can be seen in plants as a variety of negative effects, including disruption of spindle formation [147], rupture of the cytoskeleton and nuclear damage [148], formation of micronuclei and DNA strand breaks [149, 150], chromosomal abnormalities, instable microsatellites [151] and depolymerisation of microtubules [152]. The normal functioning of genetic material (RNA and DNA is interrupted by damage or change to the sugar or base content in its structure as a result of the creation of ROS either directly or indirectly via Pb. This results in breaking in strands of DNA or RNA and fragmentation [153, 154]. In turn, this prevents DNA repair and replication [113]. Additionally, the presence of Pb in plant cells alters protein structure and/or suppresses protein synthesis at the transcriptional level, which in turn prevents nuclear proteins involved in DNA topoisomerase II, DNA repair and chromosomal segregation from functioning [146, 155]. Another example of resultant genotoxicity (possible impact on cell nucleus and other nuclear materials) and root extension suppression is the reduced cell division caused by high Al concentrations in plants including Cicer arietinum, Hordeum vulgare and Populus tomentosa [156–159]. However, the root cells of Populus tomentosa are not directly threatened by Al exposure,rather, this is because Al inhibits auxin transporters, which reduces cell division [159]. Additionally, excessive amounts of Al in plants have a negative impact on the DNA double helix, which slows both cell growth and DNA replication [4, 160].

3 Phytotoxicity Induced by Nanoparticles 3.1 Phytotoxic Effect of Nanoparticles on Soil It has been found that soil has a much higher concentration of ENPs than its composition in the air and water, indicating that soil is the main source of the nanoparticles present in the environment [161–171]. Nanoparticles have a wide range of unfavourable effects, including those on structural morphology, the microbiota, mineralisation and extracellular enzymes, with the most detrimental effects on soil microbes known to result from the leaking of nanoparticles among soil constituents [163, 172]. ENPs can possibly harm the soil microorganisms directly or indirectly. While the indirect effects are shown as a result of the interaction of nanoparticles with numerous naturally occurring organic chemicals found in soil, as shown in Fig. 2, the direct toxic effects are observed to have the proper mechanism of toxicity against bacteria.

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Fig. 2 Mode of nanoparticles to induce toxicity in soil microbiota

Despite this, higher plants help mitigate their effects by employing a variety of strategies, such as subsurface intentional release for nano remediation, application of nano-land of polluted bio-solids, use of nano-enabled products in leaching, surface runoff for waste polluted with nanomaterial effluent release and irrigation using nanoparticle-polluted water due to strong binding with these nanomaterials [173, 174].

3.2 Phytotoxic Effect of Nanoparticles on Plants According to studies [175–177], plants are subject to a variety of biotic and abiotic conditions, including salinity and drought, pathogen and drought and heat and salinity. These conditions are based on molecular, physiological, biochemical, morphological and anatomical principles [178, 179]. Due to their phytotoxicity and other damage, the use of nanoparticles at larger concentrations worsens the condition of plants. Plants experience OS, due to the toxic effects of nanoparticles [180–184]. The image below illustrates several possible methods via which nanoparticles can interact with plants (Fig. 3). However, it has also been found that nanoparticles can help plants cope better with both biotic and abiotic stresses like drought, cold, salinity, UV-B rays and floods [185–196]. For example, exposure to zinc and copper nanoparticles has a beneficial impact on plants by minimising the effects of drought stress by enhancing antioxidative enzyme activities, increasing the water content of foliage, maintaining

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Fig. 3 Different pathways of interaction between nanoparticles and plants

the pigment content and lowering the degree of lipid peroxidation [189]. Therefore, it is possible to see both beneficial and harmful effects of designed NPs in plants. As illustrated in Fig. 4, certain metals (such as Ag, Se, Co and Ni) and metal-based nanoparticles (such as CeO2 , Al2 O3 , FeO4 , TiO2 , CuO and ZnO) have been thought to have both negative and favourable effects on vegetation at different concentrations [197, 198]. The influence of nanomaterials can be seen in the physiological, biochemical, seed germination, biomass generation, photosynthetic process and other areas [194].

3.3 Regulation of Metabolic Pathways Due to ENPs Toxicity Typically, plants’ metabolites become disorganised in response to any unfavourable circumstance and/or as a result of the transport or ingestion of designed nanoparticles (ENPs). The metabolic pathways comprising lipid metabolism, glucose metabolism, amino acid metabolism, energy metabolism and secondary metabolism are frequently altered by ENPs.

3.3.1

Carbohydrate and Energy Metabolism

By weakening the activity of the photosynthetic process, which in turn results in declines in the amount of primary product decreased, nanoparticles like WS2 NPs and CdONPs are responsible for down-regulating the metabolism of carbohydrates.

Fig. 4 The effect on plants when exposed to nanoparticles: left side represents the positive impact, whereas the right side of diagram represents the negative impact

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For instance, the generation of starch in Chlorella vulgaris and fructose, glucose and sucrose in barley [199, 200]. Contrarily, the resistance in the pathway of carbohydrate metabolism demonstrates that the rise in substance build-up by plant energy expenditure accounts for the decrease in biomass output [201]. Cu(OH)2 and CdONPs are nanopesticides that are concerned with downregulating energy metabolism by interfering with the TCA cycle in barley roots and lettuce leaves [199, 202]. This could be because nanoparticles are preventing citrate synthase and/or malate dehydrogenase from performing their functions [199]. Additionally, as a result of plants’ defence against metal ENPs, the TCA cycle pathway is hindered, which prevents the breakdown of metal iron [199, 203]. Despite this, if the TCA cycle regenerates the citric acid, ATP generation will be reduced and plant development will be constrained as a result of the initial disruption [199, 204] as shown in Fig. 5. Additionally, due to their antioxidant, osmo-protective and phospholipid roles in cell membranes, nanoparticles like Cu(OH)2 and hydrated graphene ribbon have been found to up-regulate the major products of photosynthesis by foliar spray and glucose metabolism [205]. TiO2 NPs, Cu(OH) and AgNPs are three further examples of nanoparticles that have been discovered to perform a substantial role in the upregulation of energy metabolism, which is based on the breakdown of sugar to

Fig. 5 Overview of the regulation of metabolic pathways (carbohydrate metabolism and energy metabolism) by the toxicity of nanoparticles in plants

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maintain their regular physiological and defensive functions [201, 202]. Increased PPP in algae cells caused by oxidised MWCNTs (multi-walled carbon nanotubes) causes an increase in pathway intermediates such as ribulose 5 phosphate. PPP serves as the starting material for the formation of nucleic acids, nucleotides and NADPH in access, all of which give protection against OS [204].

3.3.2

Amino Acid Metabolism

The bioprocessing of proteins requires amino acids, which also play a role in a number of signalling processes and the defence mechanisms used by plants when under stress [206]. According to studies, exposure to ENPs causes disturbances in the metabolism of amino acids. As a result of the accumulation and toxicity of nanoparticles, the plant either experiences upregulation or downregulation [207] in the pathway of amino acid metabolism. Numerous mechanisms exist for how nanoparticles promote amino acid metabolism. In Table 1, some of them are listed. AgNPs disrupt the inorganic nitrogen fixation pathway by lowering the concentration of amino acids like asparagine and glutamine, which also causes the senescence of leaves and inhibits photorespiratory activity by diminishing the glycine/serine ratio. The rise in ROS level caused by GO (graphene oxide), which inhibits plant development in C. vulgaris, can also diminish amino acid expression [211]. Additionally, nanocolloid toxicity in plants like rice and C. vulgaris has been linked to downregulation of the expression of amino acid metabolism (e.g., serine, alanine, glycine, glutamate, threonine and aspartate), which not only prevents cellular division but also causes cell membrane shrinkage due to decreased osmotic pressure in cytoplasm [212–214].

3.3.3

Lipid Metabolism

. Knowing that all cells’ structural membranes are primarily composed of fats, any alteration to fatty acids has an impact on the viability and sustainability of cells in adverse conditions [68]. Lipid metabolism is controlled by the following factors: . Cell membrane stability: Nanoparticles like TiO2 NPs, hydrated graphene ribbon and nanopesticides of Cu(OH)2 are involved in increasing the concentration of fatty acids (namely stearic acid, hexadecenoic acid, linolenic acid, linoleic acid, palmitic acid and octa-decadienoic acid) and the precursors for the synthesis of lipid present in membrane [68, 201, 205]. Contrarily, it has been shown that C60 fullerols inhibit fatty acid metabolism in cucumber plants, which affects the structural makeup of the cell membrane [215]. . Membrane fluidity: The fluidity of the membrane, which also depends on the amount of unsaturated fatty acids present, is related to the physiological functioning of the cell membrane and maintenance of the cellular metabolic pathway [68, 216]. For instance, C. vulgaris cells exposed to nanoparticles SWCNTs (single-walled carbon nanotubes) and GO have fewer unsaturated fatty acids,

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Table 1 Different defence mechanisms against stress are displayed by plants as a result of amino acid upregulation brought on by nanoparticle exposure Type of nanoparticle

Amino acid upregulated

Pathway of stress defence Key reference

Metal ENPs like CdONPs, CuNPs, Cu(OH)2

Proline, asparagine, Amino acid reduces the [199, 202, 203] glycine, histidine, aspartic bioavailability of acid, tryptophan nanoparticles by acting as metal ion chelators

CuNPs

Beta-alanine, leucine, alanine, glycine, proline, phenylalanine, lysine, valine, threonine, serine

Translocation of copper is [203] hindered across the cell membrane of roots by providing site for its binding

Proline

Stress-induced acidification of cell, thereby dropping down the release of metal ions

[201]

HMs

Glutamine, glycine, proline

Promoting the synthesis of antioxidants like superoxide dismutase (SOD) and glutathione (GSH) which is vital for maintenance of redox state and reduce ROS

[201–203, 208]

Cu(OH)2 and CuNPs

Valine, alanine, leucine

Source of oxidative phosphorylation energy act as adaptation process against stress

[68, 208, 209]

CdONPs

Tryptophan, phenylalanine, tyrosine

Act as precursor for the biosynthesis of protective secondary metabolites like phenolics, anthocyanins, plastoquinone, flavonoids

[199, 210]

CdONPs

Tryptophan

Increase tolerance against [199] Cd by reducing lipid peroxidation

CdONPs

Tryptophan and phenylalanine

Protection of cell membrane and increase tolerance against Cd

[199]

which induces osmotic stress and causes the fluid property of the cell membrane to disintegrate, which in turn inhibits the movement of NPs towards the cytosol [199, 217]. Unlike SWCNTs, oxidised MWCNTs have been found to increase the amount of unsaturated fatty acids in Chlorella pyrenoidosa, hence enhancing membrane fluidity.

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Therefore, the destabilisation and disruption of cell structure as well as cell plasmolysis are linked to an increase in the fluidity of cellular membrane [204].

3.4 Impact on Human Health via Food Chain Nanoparticles like AgNPs, CeO2 NPs [218], La2 O3 NPs [219] and AuNPs [220] pose a serious risk to human health by entering the food chain and subsequently entering the human body. This is because they are transferred to the terrestrial trophic level in the food chain via primary producer, i.e. plants [221–223]. According to studies, transferring hazardous nanoparticles like AgNPs into mammalian cells has serious effects on the body. In rats, for example, it produces inflammatory lesions and reduces the function of the lungs [224]. AgNP levels rise in the rat brain and olfactory bulbs as a result [225]. AgNP exposure also increases OS, cellular damage, immune response, inflammation and other adverse effects in human cells [226–228]. Therefore, to lessen the effect on human health, it is necessary to access and minimise the bioaccumulation of nanoparticles in the trophic food chain and their subsequent transfer into the human body.

4 Foliar Application of Nanomaterials Plants often absorb NPs through their stomata, ion channels, endocytosis, pores or fissures, protein transporters and trichomes [129, 229–232]. The primary mechanisms by which metals are absorbed by leaves are through the epidermis and stomata permeation [233], which are subsequently translocated via symplastic or apoplastic routes [232, 234]. Numerous variables, including the type of flora [235], microorganisms in the foliage and rhizosphere [236], the dosage of nanoparticles (NPs used [237, 238], the particle shape, size and charge [4, 239, 240], pH and matrix of soil [241], impact NPs’ entry into the leaves and their effect are impacted by changes to their surface, such as encapsulation or coating, which alters their attributes like lipophilicity and adhesion [231]. Humic acid, citrate, polyvinylpyrrolidone, iron, aminopropyl triethoxysilane, polyethylene glycol, fluorescein isothiocyanate and natural organic matter are frequently used to modify the surface of NPs in order to increase their capacity for absorption [242–246]. The charge, porosity, redox potential, catalytic activity, crystallinity and aggregation capability of NPs all affect how well they penetrate foliage [247]. The many stages of plant development and life cycle determine the concentration of NPs absorbed, stored and transported into the plants [242, 248]. It has been pointed out that applying a sufficient amount of macroor micronutrients to leaves can lessen the harm caused by root application techniques [230]. But depending on the size of the particle, the shape of the epidermis, the leaf area and the stage of plant growth, cuticular wax and leaf hair prevent the absorption of NPs by leaves [249, 250].

74 Table 2 The advantages and disadvantages of foliar spray

T. Bajaj et al. Adverse effects

Beneficial effects

Stoma closure and blockage Enhance germination of seeds of pores Reduction in photosynthetic activity

Increment in shelf life of plant

Young leaf dysplasia, chlorosis, foliar burns

Increased tolerance to unfavourable condition

Cytotoxicity and genotoxicity

Enhance fruit quality

Increase in OS and plant necrosis

Increased photosynthetic as well as enzymatic activity

Reduced enzymatic activity Increase resistance to pathogens Electrolytic leakage

Provide sufficient nutrients

Reduced biomass production

Increase crop yield

4.1 Outcomes of Application of Foliar NPs on Flora According to reports, nanoparticles can have a beneficial or negative effect on plants. When applied to plants in sufficient amounts, nanoparticles increase crop yield, reduce OS, improve the quality of the crop and increase its resistance to disease [245, 251, 252], whereas high concentration has a negative impact on the plant’s overall development [253]. ZnNPs, for instance, can be applied topically to plants to encourage fertilisation. However, excessive Zn spraying prevents seed development [254]. Additionally, when plants experience a Zn deficit, it slows down their growth [255]. Table 2 provides a summary of the many positive and negative consequences of foliar spraying nanoparticles on plants.

5 Plant Defensive Mechanism to Mitigate HM Stress 5.1 Phytoremediation of Heavy Metals It is well recognised that plants perform a significant part in mediating the transit and uptake of numerous harmful compounds, including both inorganic and organic pollutants, in order to lessen environmental pollution and enhance environmental quality. Using plants to clean up the environment is a method called phytoremediaion. For the phytoremediation of both organic and inorganic contaminants, various techniques are developed. Rhizofilteration, which involves the uptake of pollutants

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like Pb by plant roots from polluted soil or other aquatic environments [256], phytovolatilisation, which removes volatile substances like mercury [257], phytoextraction, which removes contaminants by harvesting inorganic substances accumulated in plant shoots and other aerial parts [258] and phytostabilisation are some other techniques [259]. However, adopting phytoremediation solutions has a number of drawbacks, including dependence on the climate, soil quality and processing times. As a result, little attention is paid to these techniques. Additionally, the process of phytoremediation is impacted by the physiology and age of the plant. The process is also limited by other elements like surface area, depth and root volume.

5.2 Effect of AMF and Regulation of ENMs Toxicity on Plants The microbiota that exists in the rhizosphere of plants controls the process of phytoabsorption of ENMs [260, 261]. Arbuscular mycorrhizal fungi (AMF), the most prevalent microbial population, develop mutually beneficial symbiotic associations with 80% of vascular plants and play a role in root architecture and ETC (electron transport cycle) functions [262, 263]. The symbiotic relationship between AMF and host plants is made possible by the fast-growing hyphae’s ability to proliferate under unfavourable stress conditions like metal poisoning [264, 265]. Due to AMF’s symbiotic relationship with plants, study is currently concentrated on the effect of AMF as well as the bioaccumulation of ENMs and the method by which they are introduced into plants. Through the immobilisation of metals by the glomalin-related soil protein (GRSP and the production of the appropriate transporter, the AMF can control the mass consumption of ENMs in plants and their transportation throughout the host [266, 267]. However, enhanced antioxidant activity and nutrient uptake by plant roots also support the development of plant resistance to ENMs [268–270]. Furthermore, by stimulating and restricting other soil microbes through the species-specific effects of AMF on them, the rhizosphere soil’s enzymatic activity can be improved and the transformation of nutrients and plant growth processes can be expedited [5].

5.3 ENMs Immobilisation in Soil by AMF Hyphae Secretion The immobilisation of GRSP, an obligatory glycoprotein with metal ions produced by AM hyphae, on ENMs inhibits the bioavailability of ENMs. This glycoprotein is highly effective in binding HMs, which serves to decrease metal bioavailability and prevents excessive metal accumulation in the host [271, 272]. The host plant Trigonella foenum-gracum (fenugreek) showed a decrease in the Zn content in ZnONPs as a result of an increase in the amount of GRSP produced by Rhizophagus

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intraradices. Wherein the complexation and fixing of ZnO nanoparticles and Zn ions existing in it by chelation of metals due to weak ionic contact and strong chemical bonding reduces the transport of ZnONPs from the soil to the host plant (fenugreek) [260, 273]. Researchers have discovered that the mycelial secretion of glomamycin can improve the immobilisation of metal in soil. For instance, one of the researches indicated that the low concentration of FeONPs stimulated Glomus caledonium’s secretion process. However, when the amount of FeONPs increases, the amount of GRSP drops, increasing the likelihood that GRSP will get metal complexed. Because there are more active sites and adsorption sites on the surface at both high and low FeONP concentrations, the detectable amount of glomalin falls with high mass concentrations of FeONPs [267] As shown in Fig. 6, the plants utilize a variety of mechanisms to combat the stress caused by HMs and metal-based nanoparticles.

5.4 Membrane Transport Genes Inhibition by AMF Many additional HMs are still present in soil with permeable ability, ensuring their passage into the plant through passive or active pathways despite the hyphae secretions that stop some nanoparticles from entering the host plant [234]. By suppressing the expression of membrane transporter genes, AM colonisation aids in blocking the passage of HM into the plant cell. Additionally, this controls the expression of aquaporins, which aids in preserving the equilibrium of cellular osmotic pressure [274– 277]. Scientists have discovered that, in contrast to non-mycorrhizal tissues, tomato mycorrhizal tissues play a role in the downregulation of potassium channel genes and PIP genes (plasma membrane intrinsic proteins), as well as the decrease of Ag concentration in hosts [268]. It was proposed that the transport of Ag into the shoot is mediated by the downregulation of intrinsic protein genes and potassium channel genes. Additionally, the OS brought on by AgNPs affects aquaporin expression and function, which in turn affects how plants respond to osmotic stress [268].

5.5 Effect of AMF on Oxidative Stress Caused by ENMs Due to their build-up and toxicity in cells, ENMs are known to induce ROS in plants. Numerous antioxidants (such as POD, CAT, and SOD) are improved by AMF, which lowers the OS caused by nanoparticles and HM toxicity and stabilises the cellular redox balance [269]. For instance, it has been discovered that corn’s exposure to Fe3 O4 NPs inhibits the action of antioxidative enzymes. In contrast, when maize plants are inoculated with AMF, the Glomus in the AMF increases CAT activity, boosting the breakdown of H2 O2 and preserving the oxidation-reduction balance in cells [278].

Fig. 6 The toxicity induced by various HMs and metal-based nanoparticles and the defensive strategies used by plants for their removal

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5.6 Promotion of Enzymatic Activity in Soil and Enhancement of Nutrient Transformation by Rhizosphere AMF is renowned for giving the host plant nutrients. AMFs are known to work with other microbial communities in soil that are beneficial for nutrient consumption because they are unable to directly absorb organic nutrients due to a lack of the enzymes needed for the mineralisation of organic compounds [279, 280]. The growth of AMF and their attraction to these microbes are influenced by the carbon-rich chemicals generated as a result of the recruitment of soil-dwelling microorganisms [279, 281]. AMF changes the composition of the soil, i.e., the species diversity and richness of microbes present at low soil phosphorus content, in order to gain more nutrients for the host plant, such as maize [282]. Although species-specific AMF affects the absorption of nutrients from particular microbial communities in soil to a large degree [283]. In plants where AM is inoculated, as opposed to non-inoculated plants, it has been reported that the relative abundance of bacteria such as Bacilli that participates in Phosphorus mineralisation and Anaerolineae that are involved in the decomposition process of carbon and amino acid metabolic pathway is enhanced and the population of Nitrospira that contributes to nitrite-oxidising process is reduced [284]. AMF competes with Nitrospira and other nitrogen-converting bacteria for inorganic nitrogen uptake because it is also known to help the host plant absorb nitrogen [285, 286]. AMF are also in charge of enhancing the enzymatic activity in soil by altering the species population and variety of the soil microbiota, which is also involved in stimulating the nutrition cycle between plants and microorganisms that takes place in the rhizosphere of the host plant. Additionally, this improves and stabilises the microbial community’s homeostasis in the soil environment. Nevertheless, research is currently being done to determine the phytotoxic effects and AMF’s modes of action on nanoparticles [287].

5.7 Improvement in Biomass Production in Mycorrhizal Plants The HMs’ detoxification method is determined by their chemical makeup, supply and diffusion following absorption in the tissues of the host plant. Numerous plant species’ tolerance mechanisms have been discovered to be caused by the compartmentalisation and detoxification of HMs in plants [282, 288]. For instance, when mycorrhizal fungi like Glomus intraradices colonise the alfalfa roots, the biomass output of shoots improves and the distribution of Cd is improved in the cell walls of shoots and roots [289]. AMF induces plant tolerance to HM stress and increases biomass output. AMF mediates HM remediation by changing the chemical form and compartmentalisation of HM in the host plant’s numerous cellular organelles [290].

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5.8 Exogenous Supply of Chemical Compounds for Reducing Toxicity Heavy metal toxicity can be reduced by altering the rhizospheric region by adding various chemical compounds, metals or elements, as well as metal-containing nanoparticles exogenously. The use of various elements and their contribution to plant growth and the reduction of HMs are listed in Table 3.

6 Conclusion and Future Perspectives Due to the phytotoxicity it causes, the widespread use of HM and metal-based nanoparticles has garnered a lot of attention. Studies have shown that increased mass accumulation of toxic metals in soil and consequently in plants are to blame for the rapid decline in crop development and yield output on both a small and large scale. After entering the plant through the roots and moving into the shoot and other aerial parts of the host, toxic metals and nanoparticles such as Al, Cu, Cr, Pb, Ag, Cd, CuONPs, ZnONPs, TiO2 NPs, etc., disrupt the cell and other organelles as well as the redox balance, change the integrity of the cell membrane, alter the activity of various enzymes and hormones, damage DNA and inhibit protein synthesis and induce OS by On the development and maturation of plants, numerous harmful impacts can be seen at both the cellular and molecular levels. The build-up of different HM affects the creation of ATP, photosynthesis, respiration and other metabolic biochemical pathways, as well as the formation of intermediate and end products. The concentration of the metals and the level of plant tolerance to it determine how strongly the metals cause toxicity. Despite this, plants employ a variety of defence mechanisms and tolerance techniques to lessen the toxicity of HMs. To lessen the harm they cause, various detoxification techniques are applied, such as phytoremediation and AMF-assisted bioremediation of heavy metal-polluted soil. Future studies and research are necessary to ascertain and utilise the defence mechanisms employed in order to remove the poisonous HMs present, preserve the environment and identify various flora species and their mechanisms of action in regulating the harmful effect.

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Table 3 The numerous factors’ contributions to enhance plant development Element supplement

Function

Key reference

Boron (H3 BO3 , boric acid)

Progression of plant Formation of primary cell wall by the complex formation of borate-RG II between the network of RG II (rhamnogalacturonan II) and boric acid

[291, 292]

Reduces the pectin methyl esterification and formation of a negative layer for immobilisation of metal (e.g., Al) in pectin present in cell wall

[293]

Sulfur (GSH, cysteine, hydrogen sulfide)

Alleviate OS [291] Mitigate HM stress (e.g., Al) in Triticum aestivum, Hordeum vulgare and Brassica napus by enhancing antioxidant activity and reducing ROS and oxidised/peroxidised products of proteins and lipids Reduction in metal uptake and upgraded [294] absorption of nutrients such as Mg, P and Ca along with citrate secretion from roots

Magnesium

Replace toxic metals in the binding sites due to its similarity in sizes

[295]

Increase in citrate efflux induced by Mg accumulation to upregulate membrane H + ATPase in plants like Populus tomentosa

[159]

Mg transporters when expressed in [296] excess resist the metal accumulation (Al) in Nicotiana benthamiana Phosphorus

Helps in precipitating Al on the surface [295, 297] of roots or apoplastic pathway which inhibits the entry of metal via symplastic pathway also. Although, the accumulation of Al reduces the availability of P present in acidic environment of soil to the plants

Fluoride

Highly phytotoxic, available for plants in [298] acidic environment. Alters the uptake of nutrients by manipulating the type or quantity of soil containing F or Al which both when present quickly react to form AlF3. This complex, in turn, helps in F uptake by plants (Phaseolus vulgaris) (continued)

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Table 3 (continued) Element supplement

Function

Key reference

Silicon

Helps in alleviation of toxic metals like Mn, Fe, Al, Zn, Pb, Cd, As and Cr

[299]

Resistance towards metal stress by [300, 301] increasing pH of solution, producing the complex like hydroxyaluminosilicate or aluminosilicate complex in plant, enhancing the chlorophyll and carotenoid content in leaves and synthesising phenolic and organic acid Enhance antioxidative defence mechanism to alleviate Al-induced toxicity

[299]

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Synergistic Effect of Nanomaterials, Nanocomposites and Heavy Metals on Plant Growth Nazneen Akhtar, Sehresh Khan, Shafiq Ur Rehman, and Muhammad Jamil

Abstract Soil and water quality is deteriorating because of the alarming growth in population and rapid industrialization. Heavy metal sludge is widely dumped in soil and water resources is the principal source of contamination. Different techniques have been used to remove these heavy metals. With the development of nanotechnology recently, the usage of nanoparticles in remediation processes has significantly been increased. Previous studies have displayed that metal oxide nanoparticles have been found to be effective at lower concentration for plant growth and metabolism under heavy metal stress. Higher concentrations of nanoparticles cause oxidative stress in plants and increase their toxicity. This chapter examine the synergistic effect of nanoparticles especially zinc, iron, silver oxides, titanium dioxide, and heavy metal on plant growth. Moreover, this chapter also highlights current advances regarding heavy metal stress and the possible mechanism of interaction between nanoparticles and heavy metal in plant growth. Keywords Nanoparticles · Heavy metals · Interaction · Plant growth

1 Introduction Rapid increases in industrialization and anthropogenic activity have damaged our environment due to heavy metal contamination. They contain toxic matters that enter and disturb the physicochemical property of water [1]. The use of nano-materials (NMs) and the advancement of nanotechnology have both greatly increased during the past few decades [2, 3]. Nanoparticles can penetrate plant cell walls and seed coats, depending on their size, concentration, and solubility [4–7]. The metabolic processes of plants may change as a result of this penetration and change the plant biomass N. Akhtar · S. Khan · M. Jamil (B) Department of Biotechnology and Genetic Engineering, Kohat University of Science & Technology (KUST), Kohat 26000, Pakistan e-mail: [email protected] S. U. Rehman Department of Biology, University of Haripur, Haripur, Pakistan © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 A. Husen (ed.), Nanomaterials and Nanocomposites Exposures to Plants, Smart Nanomaterials Technology, https://doi.org/10.1007/978-981-99-2419-6_5

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and grain/fruit yield. However, certain plant species have demonstrated the toxicity of combining treatments of HMs and nanoparticles. In general, plants’ reactions to metal oxide nanoparticles (NPs) in terms of their physiological, biochemical, and developmental processes can be both favorable and unfavorable. NPs and heavy metals have the capacity to enter the tissues of living plants and spread throughout the plant system [8]. They move through the soil matrix’s or aqueous medium’s symplastic or apoplastic region to enter the roots’ epidermis, cortex, the xylem and phloem to the stem and leaves. When NPs were applied to some plant species, it changed the expression of heat-shock protein and antioxidant enzyme activity dramatically. However, these defensive mechanisms have not yet been sufficiently studied and understood. Some plant species have developed antioxidant defense mechanisms to decrease oxidative damage and increase plant tolerance to toxicity induced by the metal or metal oxide NMs [9]. The bioavailability, concentration, solubility, and exposure period of the NMs determine their absorption and transport in various regions of the plant. Despite having practical uses, NMs have the potential to be hazardous to both terrestrial and aquatic ecosystems. Biodiversity is likely to be impacted since the increased production, use, and discarding NMs will inevitably result in an increase in their ecosystem release. Consequently, the results of their interactions with living things, whether direct or through the food chain (plants, animals, and humans), must be thoroughly researched and understood [10]. Nanoparticles have high reactivity, photolytic properties and affinity to different chemical groups. Metal-based NPs are becoming more popular for use in agricultural sciences and might help to reduce nutrient loss and increase crop production [11]. However, nanoparticles may prove to be poisonous for plants at larger concentrations and prevent it from being used as a nano-fertilizer, while at lower concentrations it may prove beneficial for plants depending on their growing environment and species. Nanoparticles have a variety of cellular functions, including the production of chlorophyll, photosynthesis, the development of chloroplasts, and dark respiration. They can combine more molecules to form complexes, increasing the availability of nutrients for plant organs [12]. Some plant species experience substantial changes in their morphological, physiological, and biochemical characteristics as a result of exposure to nanoparticles [13]. According to reports, nanoparticles boosted the activity of antioxidant and rubisco enzymes, the rate of photosynthetic carbon dioxide fixation and chlorophyll synthesis, all of which led to an increase in crop output. Nanoparticles have been shown to positively broad bean plants grown in salty soil in terms of plant growth, antioxidant enzyme activity, soluble sugars, amino acids, and proline content as well as lower levels of H2 O2 and MDA. Reactive Oxygen species (ROS) primarily increased in the presence of high nanoparticles concentrations, followed by chlorophyll breakdown and cellular toxicity. Additionally, NP interacts with a variety of cellular processes and damages cell walls and plasma membranes [14]. This chapter summarizes the findings of numerous researchers that looked at the combined effect of nanoparticles (zinc oxides, iron oxides, silver oxides, titanium dioxide) and heavy metals on plant growth. Furthermore, this chapter also highlights the current knowledge about the recent development in the field of nanoparticles and heavy metal stress and the possible mechanism of interaction during plant growth.

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2 Heavy Metals (HMs) HMs is the radioactive substance whose density is five times greater than that of water. These metals come within the following three basic categories: precious, toxic, and radioactive [14, 15]. In contrast to non-bioavailable HMs, soluble, mobile, non-precipitated are extremely toxic metals (form that is stationary, suspended, and composite). The United States Environmental Protection Agency (USEPA) reported mercury, cadmium, arsenic, chromium, copper, and lead as toxic metals [16, 17].

2.1 Effect of Heavy Metals on Plant HMs come from different sources, including agrochemical, anthropogenic, and environmental ones. Land erosion, volcanic exposures, mineral weathering, and fossil fuel combustion are the natural sources of HMs [18, 19]. Oil, paint, battery, leather, and industrial processes like refining, smelting, and electrolysis are a few examples of anthropogenic sources [14]. Water pollution is also caused by agricultural sources such as agrochemicals, chemicals, sewage, and groundwater drainage. Improper disposal of industrial wastes and pesticides in agricultural practices has a negative impact on water safety [20]. Figure 1 demonstrated that heavy metals from a wide range of sources enter into the soil and water resources and caused significant problems in food crops. [21] reported that the largest concentration of HMs in vegetables was found in crops irrigation water with waste water, in contrast to vegetables without leaves. As a result, these metals impede cellular photosynthesis, which influences plant growth, enzymatic activity, and mediated denaturation in proteins and nucleic acids [22]. Basically, HMs (Pb, Cd, Cr and Cu) alter various processes like water, nutrient, and oxygen intake as well as severely disrupt the pathway involved in chlorophyll production to affect the biological processes of plant growth (Fig. 2). HMs (Pb, Cd, Cr and Cu) increases seed production while harming the seeds, sugar particle surface increases the mitochondria, nucleus, and thicknesses of cell membranes [23]. Toxic metals impair plant microcirculation throughout production by raising osmolality, decrease energy potential, altering plant height and evaporation level, and generating ROS by lipid bilayer, protein, and cause the oxidative DNA rupture [21, 11]. Changes in metabolism and anti-oxidation that occur throughout growth are strongly connected with seedling survival and have an impact on the quality and production of plants [23]. Various heavy metals have different impact on growth through a variety of mechanisms, including decreased water availability, a change in the metabolism and antioxidant activities, as well as an imbalance in growth hormones [24]. Lead (Pb) released toxic ions in plants and caused the DNA disruption, enzyme degradation, and structure immersed in a membrane [25]. HMs cause oxidation and damage the lipids, lipo-membranes, and various enzyme (lipid peroxidation, superoxide anion or reactive oxygen species, per oxidation) cause the severe

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Fig. 1 Different sources of heavy metal caused soil and water pollution ultimately reduced plant growth

Fig. 2 Direct and indirect impact of different heavy metals such as Pb, Cd, Cu and Cr on crops

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damage to cell organelles [26]. Cadmium severely damages biological processes by decreasing plant growth, photosynthesis, nutrient absorption, the circulatory tract, causing oxidative stress, chlorosis, and necrosis in plants [27]. Cadmium (Cd) has an impact on plant growth by damaging cytoplasmic enzymes, inducing oxidative damage to moisture cell organelles, and altering critical cations [28]. Cadmium (Cd) cause oxidation of lipids, lipo membranes, and various enzyme (lipid peroxidation, superoxide anion or reactive oxygen species, per oxidation) lead to damage the cell organelles [29], secrete the organic ions with apoplasts and help in root development, metal-binding legends such as metallothioneins and phytochelatins act as anti-oxidative enzymes [30]. Different organic matter such as organic manures, compost, ash, phosphate, lime, and biosolids, plants boosted the comprehensive rooting system and sensitivity towards cadmium (Cd) [11]. Chromium (Cr) severely damages biological processes by decreasing plant growth, photosynthesis, nutrient absorption, the circulatory tract, causing oxidative stress, chlorosis, and necrosis in plants [27]. By damaging cytoplasmic enzymes, inducing oxidative damage to moisture cell organelles and altering critical cations and has an impact on plant growth [31]. Chromium (Cr) cause oxidation of lipids, lipo membranes, and various enzyme (lipid peroxidation, superoxide anion, or reactive oxygen species, per oxidation) lead to damage the cell organelles [29], secrete the organic ions with apoplasts and help in root development, metal-binding legends such as metallothioneins and phytochelatins act as anti-oxidative enzymes [32]. Different organic matter such as organic manures, compost, ash, phosphate, lime, and biosolids, plants boosted the comprehensive rooting system and sensitivity towards chromium [11]. A decrease in antioxidant defenses based on hydrogen peroxide accumulation and related oxidative damage could inhibit plant growth [33]. Copper (Cu) changes a variety of biological plant processes, such as how plants absorb water, nutrients, and oxygen, and obstruct the route that produces chlorophyll [34]. Copper (Cu) metals degraded the plant cells’ mitochondria, nuclear envelopes, and cell wall thickness along with the shape and number area of seeds, sugar grain size, and subcellular structures [27]. Copper (Cu) affect osmoregulation in plants by raising osmolality, lowering water potential, during the growth process by causing an oxidative burst in lipid membranes, proteins, and DNA as well as by increasing leaf area and transpiration level [35].

3 Nanoparticles/Nanomaterials Nanoparticles (NPs) are extremely small entities with high reaction rates, fast suspension, and water uptake rates [1]. They can have a single component (graphene, thin films, or surface coatings), two dimensions (nanowire and nanotube), or three components (nanomaterials in crystals, dendrimers, fullerenes, colloid, or small particles of certain semiconductors (quantum dots) [28]. NPs also form strong bonds (ionic and covalent lattice bonds) with others and reduce their size. These NPs significantly remove the HMs from contaminated areas. NPs (nanoparticles) penetrate in contamination areas where no microbes can enter, and (ii) they make water redox and serve as

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a foundation for water purification [36]. Many non-biodegradable inorganic metals (Cr, Hg, Cd, and Pb) can be harmful to microbes. NPs with a specific quantum effect and surface plasmon ability having less time to extract HMs from water. They will pass through >20 m of groundwater and continue to be active in the water and soil for roughly 8 weeks. Various nano-sized metal oxides such as Al2 O3 , Fe2 O3 , MnO, TiO2 , MnO, CeO, MgO, and ZnO NPs are used for removing HMs from wastewater [12].

3.1 Effect of Nanoparticles on Plant Growth Nanoparticles from a wide range of sources enter the soil and water resources and caused significant problems in food crops. As a result, these nanoparticles impede cellular photosynthesis, which influences plant growth, enzymatic activity, and mediated denaturation in proteins and nucleic acids [22]. Basically, higher concentration of nanoparticles alters various processes like water, nutrient, and oxygen intake as well as severely disrupt the pathway involved in chlorophyll production to affect the biological processes of plant growth [9]. Toxic particles harming the seeds, surface, increases the mitochondria, nucleus, and thicknesses of cell membranes [23], impair plant microcirculation throughout production by raising osmolality, decrease energy potential, altering plant height and evaporation level, and generating ROS by lipid bilayer, protein, and cause the oxidative DNA rupture [20]. Nanoparticles at higher concentration released toxic particles in plants and caused the DNA disruption, enzyme degradation, and structure immersed in a membrane [25]. Nanoparticles cause oxidation and damage the lipids, lipo-membranes, and various enzymes (lipid peroxidation, superoxide anion, or reactive oxygen species, per oxidation) in plant and cause the severe damage to cell organelles [26]. Nanoparticles severely damages biological processes by decreasing plant growth, photosynthesis, and nutrient absorption, the circulatory tract, causing oxidative stress, chlorosis, and necrosis in plants [27]. Different organic matter such as organic manures, compost, ash, phosphate, lime, and bio-solids, plants boosted the comprehensive rooting system and sensitivity towards nanoparticles [37]. Higher concentration of toxic particles severely damages biological processes by decreasing plant growth, photosynthesis, and nutrient absorption, the circulatory tract, causing oxidative stress, chlorosis, and necrosis in plants [27]. A decrease in antioxidant based on hydrogen peroxide accumulation and related oxidative damage could inhibit plant growth [33]. Nanoparticles change a variety of biological plant processes, such as how plants absorb water, nutrients, and oxygen, and obstructs the route that produces chlorophyll [38]. Nanoparticles degraded the plant cells’ mitochondria, nuclear envelopes, and cell wall thickness along with the shape and number, grain size, and sub-cellular structures [27]. Nanoparticles affect osmoregulation in plants by raising osmolality, lowering water potential, during the growth process by causing an oxidative burst in lipid membranes, proteins, and DNA as well as by increasing leaf area and transpiration level [39]. There are different nanoparticles which have different impact on plant growth such as Zinc

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oxide nanoparticles, silver nanoparticles, iron oxide nanoparticles, and titanium oxide nanoparticles.

3.2 Effect of Zinc Oxide Nanoparticles on Plant Growth ZnO NPs are important due to optical devices, solar cells, and storage systems. ZnO NPs have porous nano semiconductors and longer life cycles [2]. ZnO NPs wire forms determine their contact with the plant cell. NPs easily enter the cell wall as compared to rod-shaped bacteria. The quantity of ZnO NPs also affects their interaction with plants and boosts the scavenging enzyme by generating Zn+2 ions and improves the toleration of plant cells [13]. Low concentrations of ZnO NPs encourage plant development and increase HMs’ ability to withstand stress, however higher quantities of NPs have no positive effects on plants. ZnO NPs function as an essential nutrient for plant growth, a component of enzymes, a regulator of hormones and the manufacture of chlorophyll, and a stimulant of cell defense. Lower zinc ion concentrations boosted the biomass and development of peanut seeds, and other species to promote plumule development in capitata in the presence of heavy metals [40]. The chlorophyll and carotenoids in the cauliflower, tomato, and cabbage plants were boosted by ZnO NPs (9.0 M). ZnO NPs enhanced ryegrass, corn, radish, rapeseed, lettuce, and cucumber germination and roots [41] at 2000 ppm, soybean crop production at 4000 ppm, mung bean seedlings at 20 ppm and grams seedlings at 1 ppm under stress. Small concentrations of ZnO NPs were shown to boost the protein and nitrogen levels in cabbage (brassica, oleracea, capitata), chickpea, peanut, onion, cyamopsis tetragonoloba, and cicer arietinum under heavy metal stress [2]. ZnO NPs (20 and 30 g/ml) also enhanced sesame (sesamum umindicum L) seedling growth and cucumber (cucumis sativus) and kabuli chickpea growth. Many enzymes in plants are known to be activated by Zn+2 ions [34]. Endocytosis enables ZnO NPs to penetrate plant cells, wherein particles form pores, disrupt cell membrane, and reach the cytoplasm. Transporters (aquaporins) are proteins found on the surface that transport NPs throughout plant cells [42]. Additionally, NPs move to the central cylinder and other upper regions of the root through the xylem [13]. Furthermore, NPs are transferred in plant cells by two routes: one lipophilic (cuticular wax diffusion) and one includes hydrophilic (travel through the cuticle and stomata’s polar aqueous pores) [22]. It has been noted that nano-ZnO has a considerable impact on rice roots at the early seedling stage while having no negative effects on the percentage of seeds that germinate [11, 43]. Cotton (Gossypium hirsutum L.) seeds coated with ZnO nanoparticles gives plants a growth boost by increasing their uptake of zinc and phosphorus and releasing zinc ions slowly and sustainably into their cells without causing phyto-toxicity [44, 45].

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3.3 Effect of Iron Oxide Nano-Particles (Fe2 O3 ) on Plant Growth Iron oxide nanoparticles at low pH levels remove heavy metals by shifting the surface charge to a negative charge while at higher pH levels, repelling other metals with a negative charge [46]. This result showed that a significant amount of unoccupied surface sites was present at the beginning of the process at minute 80 but after that the contact and occupancy became problematic due to repulsion between the adsorbate and adsorbent at 110 min [22]. As a result of decreasing boundary layer resistance, the results demonstrated that adsorption efficiency increased at higher concentration. Arsenic content was dramatically reduced when iron oxide nanoparticle concentrations were lower. Furthermore, it was found that the surface chemistry and characteristics of nanoparticles limit the mobility of arsenic in plants. In response to arsenic stress, lipid per-oxidation activity increased; however, iron oxide nanoparticles reduced arsenic flow in water and plants and balanced ROS production. As a results maximum exchangeable sites are available for heavy metals adsorption. However, when the all metal adsorption sites have been used up, further increasing the adsorption dose does not effect on the presence of heavy metals [36]. According to reports in the literature, iron oxide nanoparticles interact with heavy metals in contaminated media and prevent their migration in plants because of their high surface-to-volume ratio. Iron oxide nanoparticles function as a nutrient to promote plant germination. It was revealed from the study that higher content of heavy metals was observed in plants [47]. It was observed that bioaccumulation factors decrease in the plant after treatment with Bacillus subtilus synthesized Fe2 O3 NPS under metalscontaminated water [22]. According to studies, iron oxide nanoparticles improve plant physiological and germination characteristics [48]. After treatment with Fe2 O3 NPs synthesiszed from Bacillus subtilus, plants cultivated in arsenic-contaminated water showed an improvement in their tolerance index. But the tolerance index decreases in arsenic-treated plants, when iron oxide nanoparticles remove arsenic from water and stop down its mobility in the plant and increase germination [31].

3.4 Effect of Silver Nanoparticles (Ags NPs) on Plant Growth Silver is the metal that aquatic creatures perceive to be the most dangerous as compared with mercury. AgNPs are bio-accumulative and incredibly deadly to the living organisms. The safety and environmental toxicity of AgNPs introduced into ecosystems are therefore raised serious questions. Taking into account that plants are the first trophic level in ecosystems and an essential link in the food chain, assessing the toxicity of AgNPs requires a thorough understanding of their effects on plants [49]. Enzymatic antioxidant activities are increased in plant cells after exposure to AgNPs to shield the cells from the oxidative stress of nanoparticles and heavy metals. For example, Wolffia globosa plants treated with 10 mg/L of

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AgNPs showed clear signs of oxidative damage. Increased SOD activity was seen in tomatoes when exposed to AgNPs (Lycopersicon esculentum). Bacopa monnieri (Linn.) treated with AgNPs showed increased peroxidase and catalase activities while Spirodela polyrhiza cells have considerably higher catalase activity. Additionally, after exposure to AgNPs, the antioxidant glutathione level and SOD and peroxidase activity both increased with increasing dose. Similarly increased antioxidantive activities was observed in potato (Solanum tuberosum L.) plant treated with AgNP [50]. In antioxidant defense systems, non-enzymatic antioxidants such thiols, ascorbate, glutathione, and anthocyanins can also be beneficial after AgNP treatment. Anthocyanin accumulation in spherical AgNP-treated Arabidopsis seedlings was shown to be significantly and dose-dependently elevated. Like how anthocyanin accumulation was greatly boosted in turnip after exposure to greater AgNPs concentrations, other antioxidants like ascorbic acid, carotenoids, and proline are also thought to play a role in plants’ antioxidant defense reactions to AgNPs. To potentially lessen the damaging effects of ROS, carotenoids can stimulate antioxidant activity. After exposure to AgNPs, rice showed a large increase in the amount of carotenoid in its shoots, demonstrating carotenoid is utilized by plants to reduce the impact of ROS generated by AgNPs. Asparagus officinalis showed a rise in ascorbic acid concentration after application of AgNPs [12].

3.5 Effect of Titanium Dioxide (TiO2 ) Nanoparticles on Plant Growth Titanium oxide (TiO2 ) nanoparticles have been discovered to enhance plant development by enhancing the intake of vital metal nutrients. Titanium dioxide nanoparticles with concentrations of 0.01 and 0.03%, improved the levels of chlorophyll (a and b), carotenoids, and anthocyanins [51]. Similar studies with beneficial benefits of titanium dioxide nanoparticles were reported in canola (Brassica napus), Solanum lycopersicum (L.), and Vigna radiata (L.). While a study revealed that titanium dioxide nanoparticles are dangerous to Oryza sativa, as evidenced by a decline in seedling development, metabolic processes and photosynthetic activity (1000 ppm). It was also observed that phytotoxic effects caused by industrial nanoparticles on physiological, biochemical, genetic, and molecular aspects in a variety of plants [52].

4 Synergistic Effect of Nanoparticle and Heavy Metals on Plant Growth The synergistic effect of heavy metals and nanoparticles on plant growth depends on the size of the particles and other pertinent environmental parameters like point

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of zero charges and redox potentials. Due to their large surface area and high rate of dissolution, small nanoparticles can easily pass-through plant membranes and interact with plants and improve its growth (Fig. 3). The atomic structure and dissolving speeds of NPs vary due to their variances in form and aggregation property [13]. NPs in the agglomeration or aggregate form exhibit lower internal activity and interaction with plants as compared to disperse NPs [53]. Different functional groups are present on the surfaces of nanoparticles, which causes oxidative stress under heavy metals [16]. Plants release specific proteins that aggregate NPs and heavy metals in media, changing their physicochemical state [54]. According to, [55] NPs become less crystalline and more amorphous under heavy metals because of their contact with plants. It was observed by [56] that plants released specific proteins that broke down the NPs and heavy metals inside the cells. Ions are required for the catalytic, structural, and regulatory activities of plant enzymes, while NPs at lower concentrations serve as micronutrients for plant growth (dehydrogenase, thiol peroxidase, glutathione reductase and protein domains) [23]. It was reported by [57] that the organic form of trace elements (including iron, zinc, magnesium, and selenium) was more available to plants than inorganic versions due to analysis of the adsorption process of plants. There are certain ionizable groups in plant cell walls (amino, carboxyl, phosphate, and hydroxyl groups (OH) that have the capacity to take up metals and NPs ions [43]. In plant cells, NPs ions play a specialized role in cellular respiration, intracellular signaling, DNA replication, and RNA synthesis. The plant addressed its nutrient needs by employing ions as a cofactor in its metabolic activity [54]. NPs ions form a chemical connection with the plant’s carboxyl group and dissolves the zinc ions within the cell wall [56]. By reinforcing the plasma membrane, cell wall, or capsule of microbial cells, lower concentration of NPs ions enhanced the amount of plant resistance against HMs [58]. Most nanoparticles are dangerous to plants in high quantities. It is hypothesized that plants must take up nanoparticles and toxic metals and transmit them to various tissues for them to cause harm. Moreover, depending on their reactivity, mobility, and other properties, the nanoparticles and heavy metals combine to interact with numerous metabolic processes to affect plants [59]. Higher quantities of the nanoparticles-heavy metals are seen to penetrate the plant’s cell wall and plasma membrane, causing harm, and interact with many processes (Fig. 4). Plant tissue can be contaminated by toxic particles through the root or through above-ground areas like wounds and root junctions [43]. Nanoparticles-heavy metals pass through a variety of chemical and physiological barriers in order to be absorbed and transported. The first barrier that toxic particles must pass when interacting with a plant is the cell wall. Smaller toxic particles can pass through this layer rather easily in comparison to larger nanoparticles because plant cell walls are made of cellulose, a structure that allows the passage of small particles while restricting the larger ones. The plant cell wall’s size exclusion ranges from 5 to 20 nm [22]. According to some reports, some nanoparticles cause the cell wall to develop larger pores, which makes it easier for big nanoparticles and heavy metals to enter. The nanoparticles may exit the cell wall by endocytosis and then proceed to different plant tissues via

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Fig. 3 Synergistic effect of lower concentrations of nanoparticles and heavy metals (HMs) improved plant growth by enhancing different processes

symplastic transport. A mathematical model suggests that a lipid exchange mechanism for nanoparticle transport into plant cells was recently put forth. According to the study, zeta potentials, size, and magnitude of nanoparticles play a significant role in transportation inside a plant [50]. Nanoparticles combined with heavy metals may disrupt plant metabolism by supplying micronutrients, regulation of genes, or by interacting with various plant oxidative mechanisms, causing an oxidative burst [54]. It is clear from the earlier portion of this review that different toxic particles can cause oxidative disruption when they are present in excess amounts and produce ROS [50]. The introduced toxic particles and heavy metals may disrupt the mitochondrial and chloroplast electron transport chains, which could lead to an oxidative burst that is indicated by an increase in the quantity of ROS. It has been noted that under the impact of various stressors, the rate of carbon fixation is restricted, increasing photo inhibition and perhaps causing the photo system to overproduce superoxide anion radicals and water [34]. It is understood that once the ROS is generated because of nanoparticle interaction, it interacts with practically all biological components, causing DNA damage, protein changes, and lipid peroxidation. Numerous studies have demonstrated that plants and nanoparticle contact cause increased lipid peroxidation and DNA damage; it demonstrates that plant-nanoparticle interaction causes lipid peroxidation which causes the death of plant cells. ROS are recognized to play a signaling role in a range of cellular activities, including the tolerance to environmental stimuli, despite their destructive

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Fig. 4 Synergistic effect of higher concentrations of nanoparticles and heavy metals (HM) reduced plant growth by affecting different processes

activity [60]. Whether ROS functions destructively or as a signal depends on the balance between ROS creation and scavenging. The creation of enzymatic (superoxide dismutase, catalase, and guaiacol peroxidase) and non-enzymatic (ascorbate, glutathione, carotenoids, tocopherols, and phenolics) molecules is a component of the antioxidant mechanism. Plants enhance the synthesis of antioxidant compounds to deal with stress. According to numerous research, plants exposed to toxic particles produce more of the anti-oxidant chemical that the antioxidant system is regulated in response to the interaction of toxic particles with plants [61]. If the generated antioxidants fail to regulate the ROS, the cell dies by apoptosis or necrosis after the ROS oxidizes the macromolecules in the cell, this ultimately results in the plant’s demise. Additionally, recent research has shown that phytohormones are essential for indicating the plant stress response. It is believed that a complex network of antagonistic and synergistic interactions between numerous hormones results in the hormonal control of plant development and stress adaptation [62]. The ROS are intricately connected to hormone signaling as well and have an impact on one another’s activities. It is known that many hormonal pathways are either activated or deactivated in response to various types of stresses. Another factor regarded as a reliable indicator of a plant’s general performance is photosynthesis [15]. Since it is the only source of energy for plants, it has an effect on every part of their physiology and metabolism. Numerous studies have demonstrated that toxic particles have an impact on plants’ photosynthetic pigment content and activity. The photosynthesis process may be substantially hampered by an extremely high toxic particles concentration,

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which could stunt or kill plant growth. According to several investigations, exposure to toxic particles causes a noticeable decline in plant development. In some plants, the root is the main organ for taking up toxic particles from soil/water and is more negatively impacted than the shoot [43]. By increasing nitrate reductase activity, these NPs improved soil fertility, crop yield, nutrient absorption, and sustainable agriculture production [63]. These findings supported the results showing that nano-TiO2 lengthens spinach crop life by enhancing photosynthesis and nitrogen fixation. The results showed that onion, cucumber, tomato, and Glycine max plants’ seedling growth and photosynthesis were enhanced by lower concentration of toxic metals and particles [64]. HMs have a far lesser propensity to translocation to the higher parts of the plant than toxic metals and particles do, and they are much more likely to be absorbed in the roots. Toxic particles bind to roots to penetrate plant cells and then move apoplectically to the cortex and epidermis. It was also reported through the vascular bundle, AgNPs reach the plant’s roots and are transported to xylem vessels via transpiration. Toxic particles penetrate the plant by building compounds with binding protein and organic residues [36]. Plants transport toxic particles by three different pathways. The first route is based on NP size, with small NPs (5–20 nm) getting taken up by auxin-filled holes in the core epidermis cell wall and then dispersed into the endodermis by osmotic and capillary activity. The single statute pathway, the second approach, involves the root system, cell walls, an ion channel, and a protein known as aquaporins interacting to allow the passage of toxic particles via polysaccharide fiber. The third pathway uses stomata pores, which capture toxic particles and carry them to the lower parts of the plant [2]. Small NPs are absorbed in root plant cells and transported by root parenchyma cells to various areas of the plant. Crystalline nanoparticles reach the top of cells, whereas anatase particles remain in the roots. Plants respond differently to toxic particles with cationic and anionic positive and negative charges. Since electrostatic forces bind with negative charge root cells, in wood plants, toxic particles with cation move quicker than anione. Since electrostatic interactions connect with negatively charged root cells, ion NPs move quicker in hardwood plants than anione-containing NPs [63]. TiO2 nanoparticles remediate lead (Pb) in rice (Oryza sativa L.) plant by bioaccumulation at high exposure levels. TiO2 nanoparticles restrain the growth of duckweed and prevent photosynthesis, protein synthesis, and nitrogen fixation [51]. Magnetic nanoparticles (Fe3 O4 ) successfully absorbed heavy metal ions by mitigate Cd-induced root inhibitory effect and oxidative stress in cucumber and wheat seedlings [47]. The highest Cd accumulation with TiO2 nanoparticles was reported by other scientist [10]. A recent study reported that adding nZVI particles enhanced the stability of arsenic in the rhizosphere of sunflowers. It has been demonstrated that nZVI particles made arsenic in the rhizosphere of sunflower plants more stable. nZVI can restore the stability of Cr by reductively transforming Cr (VI) into a more stable and benign state [21]. Co Fe2 O4 nanoparticles might not pass through the seed coat or root system at the start of germination. There is no discernible difference in the tomato plant (Solanum lycopersicum L.) when they are present. According to the

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experimental findings, adding nZVI particles caused a 16, 29.5, and 31.7% increase in Cd accumulation in the roots, stems, and leaves [63]. The impact of nano-hydroxyapatite on the capacity of rye grass to extract lead as well as the efficacy of the remediation at 1, 1.5, 2, 3, and 12 months. It was stated that employing salicylic acid nanoparticles could enhance the plant’s ability to remove arsenic. Cd and Pb remediation using nano-chlorapatite and metal-phosphate complexes immobilized by precipitation [40]. As the new metal phosphates were being removed by nano-hydroxyapatite, Cu and Zn that were involved in ion exchange, surface complication, and precipitation stabilized them. Al2 O3 nanoparticles caused harm to the epidermal and cortex cells in the wheat plant (Triticum aestivum L.) by vacuolization and shrinking, and the toxic effect prevented plant growth [49]. By causing hydroxyl radical-induced cell wall loosening, nZVI particles in Cress Heynh (Arabidopsis thaliana (L.)) increased plant growth and root elongation. Other nano-hydroxyapatite inhibits plant growth in the Phaseolus radiatus L. (mung bean) plant by causing cell death and localized high intracellular concentration caused by hydroxyapatite nanoparticles. Plants that produce mung beans (Phaseolus radiatus L.) improved the underlying process [64]. Plants can reduce the toxicity of Cd and Pb in fava beans (Vicia faba L.) and enrich Cd and Pb in the leaves by using utilized carbon nanotubes and carboxylate multiwall carbon nanotubes [2]. CeO2 in soybean (Glycine max (L.) Merr nanoparticles considerably reduces (70%) the movement of Cd from roots to shoots, which lessens its toxicity. The ability of plants to remove Cd, Cu, and Pb from rice (Oryza sativa L.) depends on the kind of metal ions present, the amounts of those metal ions in the soil, and the accumulation of C60 fullerenes in rice panicles [47]. Plants use many ways to [44] immobilize/mobilize HMs ions in polluted areas [62]. In order to attract rhizo sphere bacteria, plant roots exude organic acids (exudates), which have an impact on the soil’s HM mobility, solubility, and adsorption [50]. These exudates contain anti-oxidants and play a key role in the interactions of bacteria with particles. Active efflux pumps are produced by plants, which also convert metals into less toxic or non-toxic forms [22]. By establishing a relationship with plants and NPs, microbes release exo-polysaccharides and other volatile chemicals. The findings are further supported by Akhter et al. [43], and they reported that metals get adsorbed as a product of microbes and high NP levels. Microbes stimulate crop growth by creating phyto hormones, chelating, exo-polysaccharides, and ethylene [16].

4.1 Synergistic Effect of ZnO Nanoparticles (ZnO NPs) and Heavy Metals on Plant Growth Higher concentration of ZnO NPs and heavy metals caused nitrate reductase activity, metabolic processes, and the development of a plant under oxidative stress. Additionally, it had an impact on the size of the rape plant root ends, the epidermis, the pericycle cell, the quantity of chloroplasts [44]. They triggered phyto toxicity

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by changing the central metal atom (Mg2+ ) in chlorophyll to produce zinc+2 ions. Higher doses of ZnO NPs inhibited the cauliflower germination, lowered the alfalfa and soybean seedling growth (by 80 and 25%) and reduced cucumber growth (75 and 35%) under metal stress [65]. ZnO NPs at 300 mg/L altered leaf stomata, increased carbon monoxide levels, decreased (chlorophyll a and b) levels, and boosted food uptake in Arabidopsis plants under abiotic stress. According to reports, ZnO NPs reduced the growth of chinese cabbage, wheat, soybeans, species roots, and soy (brassica pekinensis L.) and Cucumber in the garden (lepidium sativum L.) [53]. ZnO NPs at 300 mg/L altered leaf stomata, increased carbon monoxide levels, decreased (chlorophyll a and b) levels, and boosted food uptake in Arabidopsis plants. Cowpea plants were shown to be poisonous and reduced the shoots’ and roots’ size [51]. The NPs changed plant nutrition in terms of minerals, photosynthesis, and stress from free radicals and genotoxicity. Antioxidant enzyme activity increased in crops at low levels of NPs toxicity while decreasing at higher ones. Due to exposure of crop plants to NPs, the concentration of NPs increased in different plant parts including fruits and grains which could transfer to the food chain and pose a threat to human health. Regarding plant species, development phases, growth conditions, method, dose, and duration of NPs exposure, among other things, the effects of NPs on crop plants vary substantially. Effect of different concentrations of ZnO NPs on physiological processes of plant (Table 1). Along with the direct toxicity of NPs to crops, which is likely another contributing factor, changes in the indirect growth circumstances may also have an impact on crop growth. NPs may alter the bacterial populations in soils in comparison to bare soils, which may have an impact on crop development and productivity. It is well known that ENPs affected the types and activities of soil microorganisms, which in turn affected crop growth and biomass [67], [68]. Pesticides, paints, and direct releases from industry are all ways that NPs can get into soil [61]. Considering that they are immobile, interact with the soil and the air, and are released into the environment, plants are vulnerable to NPs. However, multiple studies found that major crops like wheat (Triticum aestivum L.), rice (Oryza sativa L.), maize (Zea mays L.), and soybean had negative effects from metal NPs on their growth and physiology [22]. According to several studies, NPs changed the expression of genes involved in root growth, lowered the mitotic index, impeded cell division stages, and affected the tips of many plants’ roots. Although nanoparticles may not directly harm plants, they can harm them indirectly by changing the growth medium, harming the roots, changing the bacterial communities in the soil, and leading plants to take in co-contaminants. Thus, NPs have the potential to affect crop development, productivity, and potential for food chain entry [43].

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Table 1 Effect of different concentrations of ZnO NPs on plant physiological process Experimental plant

Physiological process

ZnO–NPs concentration

Size

Key references

Lupinus termis

Zn Boosts plant growth

20, 40, and 60 mg/L

21.3 nm crystal

[63]

Peanut

1000 ppm ZnO NPs encourages the growth of seeds and plants

1000 and 2000 ppm

25 nm

[65]

Gossypium hirsutum L

Growth 25, 50, 75, 100, accelerates as the and 200 mg/L ZnO NPs dose is increased

2–54 nm spherical and rod

[64]

Cyamopsis tetragonoloba L

Promotes plant growth

10 mg/L

3.8 nm spherical

[40]

Lupinus termis

Improves the lupine plant’s tolerance to salt by lowering the Na level and raising the Zn concentration

60 mg/L

Rod shaped 21.3 nm

[47]

Zea mays L

No discernible 400 mg/kg impact on macronutrients All decreases, Zn are mostly collected in cucumber seeds

NA

[63]

Lupinus termis

ZnO NPs Increases photosynthetic pigments, which improves photosynthesis

21.3 nm crystal

[49]

Hydrilla verticillata and Phragmites Australis

Chlorophyll 0.01, 0.1, 1, 10, content decreases 100, and at high 1000 mg/L concentration of ZnO NPs

Cyamopsis tetragonoloba L

Increases photosynthetic chlorophyll pigment

20, 40, and 60 mg/L

10 mg/L

[2]

3.8 nm spherical

[12]

(continued)

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Table 1 (continued) Experimental plant

Physiological process

ZnO–NPs concentration

Size

Key references

Maize

Increases chlorophyll content

10 mg/L

15–25 nm

[66]

Gossypium hirsutum L

Photosynthetic pigment content increases

25, 50, 75, 100, and 200 mg/L

2–54 nm Spherical [65] and rod

Wheat

Total chlorophyll 100 and 200 mM 5–20 nm spherical content increased ZnO NPs

[21]

4.2 Synergistic Effect of Iron Oxide Nano-Particles (Fe2 O3 ) and Heavy Metals on Plant Growth Fe2 O3 NPs in the environment are a threat to plants. Even though plants require iron oxides for survival, iron oxide nanoparticles (NPs) can be harmful to living things. It has been reported that Chlorella pyrenoidosa algae growth was decreased by iron oxide nanoparticles. Similarly when Elodea Canadensis came into contact with Fe2 O3 NPs in the presence of light, major physiological changes occurred, and the plant’s leaves quickly became yellow because the pigment concentration decreased. Effect of different concentrations of Fe2 O3 NPs on different plant activities is given in Table 2. Chlorophyll is necessary for important plant processes, and iron oxide NPs can disrupt its production. Maghemite nanoparticles reduced the overall chlorophyll content of Helianthus annuus L. in the plant roots, hindering the plant’s ability to absorb micronutrients like Mg, a nutrient linked to chlorophyll synthesis [55]. It has been stated that corn (Zea mays L.) at lower concentration increased total chlorophyll as compared to the control sample. Fe2 O3 NP reduced the chlorophyll content by 11.6, 39.9, and 19.6% at doses of 20, 50, and 100 mg respectively. With iron oxide nanoparticles, oxidative stress is a problem since it generates reactive oxygen species (ROS), which can seriously harm cells [57]. The majority of other ROS are derived from superoxide (O2− ). It results from the breakdown of molecular oxygen (O2 ). Additionally, NPs cause OH· production, and oxidative stress may be brought on the elevated level of ROS in cells. Lipid peroxidation, or the destruction of cell membrane lipids result in ROS generation. These negative effects are explained by the creation of ROS and connected it to protein, lipid, and DNA damage [58].

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Table 2 Effect of higher concentrations of Iron oxide nanoparticles (Fe2 O3 ) on different plant chractreistics Experimental plant

Effect of Iron oxide nanoparticles (Fe2 O3 )

Concentrations

Key references

Solanum lycopersicum

When used under salt stress, MDA concentration reduce and SOD, CAT, POD, and APX activities increases

15 and 30 mg/L

[16]

Solanum lycopersicum

By controlling Na concentration 15 mg/L and manipulating antioxidant enzymes like SOD and guaiacol peroxidase in tomato callus, 15 mg/L of Iron oxide nanoparticles (Fe2 O3 ) reduces the negative effects of NaCl

[2]

Lupinus termis

MDA, SOD, CAT, POD, and APX activities increases under salinity stress

20–60 mg/ L

[15]

Triticum aestivum

Increases the activity of antioxidant enzymes (SOD and CAT)to improve drought resistance

15 and 30 mg/L

[45]

Oryza sativa

Improvements in plant height, 1000 mg/L chlorophyll content, biomass, tiller number, and yield are seen in plants treated with Iron oxide nanoparticles (Fe2 O3 )

[42]

Glycine max

Iron oxide nanoparticles (Fe2 O3 ) boost soybean seed germination and rate during drought stress

0.5–1 mg/L

[47]

Lupinus termis

Iron oxide nanoparticles 20–60 mg/L (Fe2 O3 ) primed seeds primarily encourage development in stressed plants and raise levels of photosynthetic pigments, organic solutes, total phenols, ascorbic acid

[55]

T. aestivum

By boosting the production of lateral roots, Iron oxide nanoparticles (Fe2 O3 ) cause root morphology modification in wheat

[60]

20–60 mg/L

(continued)

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Table 2 (continued) Experimental plant

Effect of Iron oxide nanoparticles (Fe2 O3 )

Concentrations

T. aestivum

Iron oxide nanoparticles 20–60 mg/L (Fe2 O3 ) increase the production of lateral roots in wheat, which results in alteration of the root morphology

[65]

Leucaena leucocephala

By reducing the activity of antioxidant enzymes like SOD, CAT, and POX and lowering lipid peroxidation

[57]

20–60 mg/L

Key references

4.3 Synergistic Effect of Silver Nanoparticles (AgsNPs) and Heavy Metals on Plant Growth AgNPs can also change the permeability and fluidity of the membrane; this may affect how well nutrients and water are absorbed. According to a research [46] radish (Raphanus sativus) sprout exposure to AgNPs resulted in a substantial loss in nutritional content and a dose-dependent decrease in water content (Ca, Mg, B, Cu, Mn, and Zn), showing that changes in both water and nutrient content may be how AgNPs affect plant growth [63]. AgNPs have an impact on plant hormones as well as Arabidopsis seedlings’ root gravitropism decreased in a dose-dependent way. Additional research revealed that AgNPs inhibited auxin synthesis, and auxin receptorrelated genes were shown to be down-regulated in response to AgNP exposure. Ultra-high performance liquid chromatography electrospray for hormonal analysis, total cytokinin levels were shown to significantly increased, when AgNP building occurred in pepper tissue. It was found that exposure to Ag2 S-NPs may impair the growth of wheat and cucumber. After exposure to Ag2 S-NPs, expression of six ethylene signaling pathway genes was found to be considerably increased in cucumber, indicating that Ag2 S-NPs may affect plant growth through interacting with this route [63]. AgNPs can potentially be harmful at the cellular and molecular levels in plants (Table 3). Numerous investigations revealed that changes to cell structure and cell division occur along with the restriction of plant growth, when exposed to AgNPs. It was observed that AgNPs may cause a reduction in cell size, turgidity, and vacuole size (Brassica oleracea var. capitata L.) in cabbage (Brassica oleracea L.) and maize (Zea mays L.). Similarly it was observed that the vacuoles and the integrity of the cell wall were damaged when AgNPs entered the cell of Brassica campestris, and other organelles may also have been impacted [26]. Furthermore, AgNP treatment in Allium cepa greatly reduced cell division and the mitotic index was decreased. AgNP treatment dramatically decreased the mitotic index (MI), increased chromosomal abnormalities, and micronuclei in broad bean (Vicia faba L.) root tip cells, showing that AgNPs interfered with the cell cycle and mitosis in these cells. According to a

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recent study, the AgNPs may be easily internalized by the wheat root tip cells. After internalization of AgNPs, the root tip cells displayed chromosomal abnormalities including chromosome breakage, spindle failure, fragmentation, uneven separation, and dispersed and lagging chromosomes. These abnormalities greatly impeded cell activity, uptake, movement, and severe phyto-toxicity of AgNPs in plants [46].

4.4 Synergistic Effect of Titanium Dioxide (TiO2 ) Nanoparticles and Heavy Metals on Plant Growth Numerous studies have shown that applying titanium dioxide to chickpeas enhanced their resistance to cold stress (Cicer arietinum L.), heat stress in tomato, drought in wheat and flax (Linumusitatissium L.), cadmium toxicity in green algae (Chlamydomonas reinhardtii P. A. Dang) and soybean and tomato Xanthomonas per forans bacterial spot illness. The chlorophyll content of tomato and oilseeds was raised by foliar spraying with titanium dioxide nanoparticles, improved Rubisco (Ribulose1,5-bisphosphate carboxylase/oxygenase) activity and facilitated net photosynthesis in Arabidopsis, spinach, tomato and basil (Ocimum basilicum L.). Titanium dioxide nanoparticle treatments significantly increased the biomass or crop yield of wheat, mung bean (Vigna radiata L.), snail clover (Medicago scutellata Mil), tomato, and wheat [45]. The photocatalyzed property of nano-anatase TiO2 enhances light absorption, the conversion of under long-term lighting, the conversion of electricity and chemical energy from light, carbon dioxide absorption, as well as preventing chloroplast ageing. The nano-anatase titanium dioxide nanoparticle improves the absorption of photosynthetic carbon due to the activation of Rubisco, a compound made up of Rubisco and Rubisco activase, which may accelerate Rubisco carboxylation. According to the molecular mechanism of the carbon reaction, nano-anatase induces the Rubisco activase (RCA) marker gene, and higher protein concentrations as a result improved Rubisco activase activities Rubisco carboxylation and a rapid photosynthetic carbon reaction [47]. Plant transpiration and water conductance and net photosynthetic rate are improved by exogenous application of titanium dioxide nanoparticles, while effect of higher concentrations of titanium dioxide nanoparticles (TiO2 ) reduces different plant activities (Table 4).

5 Conclusion Heavy metals have negative impact on plant growth. Various strategies are used for the remediation of heavy metals, in which nano-remediation plays significant roles. Nanoparticles, which are considered to be a “bio safe” material, have the power to promote plant growth and seed germination. Additionally, nanoparticles affect

12 µg/mL

Mitotic index decrease, increase of 40 µg/mL chromosomal abnormalities, decrease of seed germination (at higher concentrations)

Callus cells of Triticum aestivum Peroxidation of membrane lipids, (wheat) deactivation of antioxidant systems

Seeds of Allium cepa (onion bulbs)

100 µg/mL

Silver oxide nanoparticles (Ags NPs) 10 µg/mL cause cell membrane instability and growth suppression

Green algae (Pseudo kirchneriellasubcapitata)

Root cells of Allium cepa (onion Mitotic index decrease, micronuclei bulbs) index and chromosome aberration index increase

MiRNAs Down-regulated processes include those involved in photosynthesis, hormone signalling, ROS homeostasis, heavy metal transport, and growth and development

Zea mays L. (maize)

800 µg/mL

Root growth is being hindered 20 µg/mL because of a cell-wide buildup of silver oxide nanoparticles (AgsNPs) negative effects on chromosomes and cells

Allium Cepa (onion bulbs)

Max concentration

Effect of silver oxide nanoparticles (AgsNPs)

Experimental plants

Table 3 Effect of higher concentrations of Silver oxide nanoparticles (Ags NPs) on different plant activities

< 100 nm and 500

Iron deficiency↑, chlorosis↑

[28]

Herbaceous cattail

>200

NZVI-treated plants↓, blank-treated plants↑

[29]

nZVI

Reference

Fe3 O4

25

Eruca sativa

4

Plant chlorophyll fluorescence↓, Genomic template stability↓

[30]

Fe3 O4

12

Arabidopsis thaliana

25

Reduced seedlings↓, root length↓

[31]

Fe3 O4

13

Barley

1000

H2 O2 ↓ content in plant leaves and roots

[32]

Fe3 O4

9

Chinese Mung 20 Bean

Plant CAT enzyme activity↓

[33]

Fe3 O4

18

Chinese Mung 10 Bean

Plant CAT enzyme activity↓

Fe3 O4

18

Chinese Mung 20 Bean

POD enzyme activity in plant↓

Fe3 O4

18

Chinese Mung 20 Bean

SOD enzyme activity in plant↓ (continued)

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Table 1 (continued) NPs type

Size (nm)

Crop

Concentration (mg L−1 and mg kg−1 )

Impact

Reference

Fe3 O4

30

Maize

500

Maize root fresh weight↓, roots MDA↓ and polyphenol content↓

[34]

Fe3 O4

21.2

Muskmelon

400

Plant chlorophyll↓ [35] and soluble protein content↓ after 4 weeks of application

nZVI