Nanomaterials in Plants, Algae and Microorganisms: Concepts and Controversies: Volume 2

Nanomaterials in Plants, Algae, and Microorganisms

Concepts and Controversies: Volume 2

Editors

Durgesh Kumar Tripathi

Motilal Nehru National Institute of Technology Allahabad, Allahabad, Uttar Pradesh, India

Parvaiz Ahmad

King Saud University, Riyadh, Saudi Arabia

University of Kashmir, Srinagar

Shivesh Sharma

Motilal Nehru National Institute of Technology Allahabad, Allahabad, Uttar Pradesh, India

Devendra Kumar Chauhan

University of Allahabad, Allahabad, Uttar Pradesh, India

Nawal Kishore Dubey

Banaras Hindu University, Varanasi, India

Table of Contents

Cover image

Title page

Copyright

Dedication

List of Contributors

Chapter 1. Phytotoxic Properties of Zinc and Cobalt Oxide Nanoparticles in Algaes

1.1. Introduction

1.2. Production and Applications of ZnO and CoO Nanoparticles

1.3. Methods to Assess Toxicity of Metal Oxide Nanoparticles in Algae

1.4. Factors Influencing Phytotoxicity of ZnO and CoO Nanoparticles

1.5. Toxicity of Zinc and Cobalt Oxide Nanoparticles: Possible Mechanisms

1.6. Toxicity of CoO Nanoparticles

1.7. Future Research Directions

1.8. Conclusion

Chapter 2. Carbon Nanotubes as Plant Growth Regulators: Impacts on Growth, Reproductive System, and Soil Microbial Community

2.1. Introduction

2.2. Carbon Nanotubes: Uptake and Translocation

2.3. Release and Uptake of Carbon Nanotubes

2.4. Role of Carbon Nanotubes

2.5. Industrial Application of Carbon Nanotubes

2.6. Conclusion

Chapter 3. Zinc Oxide Nanoparticle-Induced Responses on Plants: A Physiological Perspective

3.1. Introduction

3.2. Properties of ZnO NPs

3.3. Synthesis of ZnO NPs

3.4. Positive Impacts of ZnO NPs on Plants

3.5. Negative Impacts of ZnO NPs on Plants

3.6. Conclusion

Chapter 4. Effects of Nanoparticles in Plants: Phytotoxicity and Genotoxicity Assessment

4.1. Introduction

4.2. Plant Uptake of NPs

4.3. Phytotoxicity and Genotoxicity Induction and Assessment

4.4. Phytotoxicity and Genotoxicity of the Most Widespread Nanoparticles

4.5. Conclusion

Chapter 5. Industrial Nanoparticles and Their Influence on Gene Expression in Plants

5.1. Introduction

5.2. Basic Principle Behind the Study

5.3. Conclusion and Future Perspective

Chapter 6. Role of Nanoparticles on Photosynthesis: Avenues and Applications

6.1. Introduction

6.2. Nanoparticles and Growth of Plants

6.3. Nanoparticles and Photosynthesis

6.4. Nanomaterials and Photosynthesis Under Abiotic Stresses

6.5. Nanoparticles and Yield of Plants

6.6. Conclusion and Future Prospects

Chapter 7. Nanoparticle-Induced Ecotoxicological Risks in Aquatic Environments: Concepts and Controversies

7.1. Introduction

7.2. Nanoparticle Toxicity Determination

7.3. Understanding the Mechanisms of Engineered Nanoparticle Toxicity

7.4. Engineered Nanoparticle Toxicity Across the Aquatic Food Web

7.5. Engineered Nanoparticles in the Ecological Cycle

7.6. Conclusion and Future Perspectives

Chapter 8. Phytotoxicity of Silver Nanoparticles to Aquatic Plants, Algae, and Microorganisms

8.1. Introduction

8.2. Environmental Concentration of Silver Nanoparticles

8.3. Silver Nanoparticles' Fate in Water

8.4. Importance of Shape and Size for Silver Nanoparticles' Toxicity in Photosynthetic Organisms

8.5. Aquatic Photosynthetic System

8.6. Effects of Silver Ions on the Aquatic Photosynthetic System

8.7. Mechanisms of Uptake into Aquatic Photosynthetic Organisms

8.8. Silver Nanoparticles' Effects on Aquatic Plants

8.9. Silver Nanoparticles' Effects on Algae

8.10. Silver Nanoparticles' Effects on Cyanobacteria

8.11. Silver Nanoparticles' Effects on Phytoplankton

8.12. Silver Nanoparticles' Bioaccumulation and Biomagnification

8.13. Biosynthesis of Silver Nanoparticles in Cyanobacteria and Microalgae

8.14. Discussion

8.15. Conclusion and Future Prospects

Chapter 9. Therapeutic Potential of Plant-Based Metal Nanoparticles: Present Status and Future Perspectives

9.1. Introduction

9.2. Synthesis of Nanomaterials

9.3. Biological Synthesis of Metal-Based Nanoparticles

9.4. Antifungal Activity of Nanoparticles

9.5. Mechanism Underlying the Antifungal Activity of Nanoparticles

9.6. Limitations in Practical Use of Nanoparticles for Antifungal Activity

9.7. Conclusion

Chapter 10. Antifungal Impact of Nanoparticles Against Different Plant Pathogenic Fungi

10.1. Introduction to Disease-Causing Plant Microbes

10.2. Various Technologies Used for Control of Plant Pathogens

10.3. Antimicrobial Activity of Nanoparticles

10.4. Nanoparticles Against Plant Pathogens

10.5. Oxide Nanoparticles

10.6. Other Nanoparticles Used for Plant Pathogens Control

10.7. Conclusion and Future Prospects

Chapter 11. Synthesis of Nanoparticles Utilizing Sources From the Mangrove Environment and Their Potential Applications: An Overview

11.1. Introduction

11.2. Synthesis of Nanoparticles from Various Sources in the Mangrove Environment

11.3. Applications of Nanoparticles Synthesized Using Mangrove Environment Sources

11.4. Future Prospects

11.5. Conclusion

Chapter 12. Recent Developments in Green Synthesis of Metal Nanoparticles Utilizing Cyanobacterial Cell Factories

12.1. Introduction

12.2. Bionanotechnology

12.3. Cyanobacterial Cell Factories and Bionanotechnology

12.4. Mechanism of Green Synthesis of Metal Nanoparticles

12.5. Recent Developments in Green Synthesis of Metallic Nanoparticles Utilizing Cyanobacteria

12.6. Applications of Nanotechnology

12.7. Conclusion and Future Prospects

Chapter 13. Chitosan and Its Nanocarriers: Applications and Opportunities

13.1. Introduction

13.2. Chitosan-Based Nanomaterials and Their Biological Activities

13.3. Carboxymethyl Chitosan: One of the Prominent Chitosan Derivatives

13.4. Nanovehicles for Delivery of Specific Drugs

13.8. Conclusion

Chapter 14. Biosensor Technology—Advanced Scientific Tools, With Special Reference to Nanobiosensors and Plant- and Food-Based Biosensors

14.1. Introduction

14.2. Types of Biosensor

14.3. Application of Biosensors

14.4. Conclusion and Future Perspectives

Chapter 15. Impact of Nanoparticles on Abiotic Stress Responses in Plants: An Overview

15.1. Introduction

15.2. Physiological Impacts of Nanoparticles on Plants

15.3. Impact of Nanoparticles on ROS and Antioxidant System

15.4. Nanoparticles and Metal Stress in Plants

15.5. Nanoparticles and Drought Stress in Plants

15.6. Nanoparticles and Salinity Stress

15.7. Nanoparticles and Other Abiotic Stresses

15.8. Conclusion and Perspectives

Chapter 16. Physicochemical Perturbation of Plants on Exposure to Metal Oxide Nanoparticle

16.1. Introduction

16.2. Sources of Metal Nanoparticles

16.3. Anthropological Interventions

16.4. Global Financial Status of Engineered Metal Nanoparticles

16.5. Fate of Engineered Nanoparticles

16.6. Physicochemical Stress in Plants: the Whys and the Wherefores

16.7. Major Metal Nanoparticles Affecting Plants

16.8. Amelioration of Nanoparticle-Induced Damage to Plants

16.9. Conclusion

Index

Copyright

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Dedication

Dedicated to

One of the eminent Botanist of India and our beloved teacher

Prof. P K Khare

Professor and Former Head

Department of Botany,

University of Allahabad, Allahabad, India

Dr. Durgesh Kumar Tripathi

Prof. Devendra Kumar Chauhan

List of Contributors

Vishnu Agarwal,     Department of Biotechnology, Motilal Nehru National Institute of Technology, Allahabad, India

Haseen Ahmed,     Laboratory of Photobiology and Molecular Microbiology, Centre of Advanced Study in Botany, Institute of Science, Banaras Hindu University, Varanasi, India

Simran Asawa,     Department of Biotechnology, National Institute of Technology Warangal, Warangal, India

Maumita Bandyopadhyay,     Plant Molecular Cytogenetics Laboratory, Centre of Advanced Study, Department of Botany, Ballygunge Science College, University of Calcutta, Kolkata, India

Aditya Banerjee,     Department of Biotechnology, St. Xavier's College (Autonomous), Kolkata, India

Marcella Bracale,     Department of Biotechnology and Life Sciences, University of Insubria, Varese, Italy

Marian Brestic,     Department of Plant Physiology, Slovak University of Agriculture, Nitra, Slovak Republic

Gitishree Das,     Research Institute of Biotechnology and Medical Converged Science, Dongguk University-Seoul, Gyeonggi-do, Republic of Korea

Guido Domingo,     Department of Biotechnology and Life Sciences, University of Insubria, Varese, Italy

Nawal Kishore Dubey,     Lab of Herbal Pesticides, Centre of Advanced Study in Botany, Institute of Science, Banaras Hindu University, Varanasi, India

Abhishek Kumar Dwivedy,     Lab of Herbal Pesticides, Centre of Advanced Study in Botany, Institute of Science, Banaras Hindu University, Varanasi, India

Rout George Kerry,     P. G. Department of Biotechnology, Utkal Univesity, Vani Vihar, Odisha, India

Lucia Giorgetti,     National Research Council (CNR) - Institute of Agricultural Biology and Biotechnology (IBBA), Pisa, Italy

Sushanto Gouda,     Amity Institute of Forestry and Wildlife, Amity University, Noida, Uttar Pradesh, India

Meeta Jain,     School of Biochemistry, Devi Ahilya University, Khandwa Road, Indore, India

Sunita Kataria,     School of Biochemistry, Devi Ahilya University, Khandwa Road, Indore, India

Zesmin Khan,     Department of Botany, Cotton University, Guwahati, India

Pradeep Kumar,     Department of Forestry, North Eastern Regional Institute of Science and Technology (Deemed University-MHRD), Nirjuli-, Arunachal Pradesh, India

Manoj Kumar,     Lab of Herbal Pesticides, Centre of Advanced Study in Botany, Institute of Science, Banaras Hindu University, Varanasi, India

Jayanta Kumar Patra,     Research Institute of Biotechnology and Medical Converged Science, Dongguk University-Seoul, Gyeonggi-do, Republic of Korea

Shiliang Liu

College of Landscape Architecture, Sichuan Agricultural University, Chengdu, China

School of Renewable Natural Resource, Louisiana State University Ag Center, Baton Rouge, LA, United States

Dipendra Kumar Mahato,     Department of Agriculture and Food Engineering, Indian Institute of Technology Kharagpur, Kharagpur, West Bengal, India

Indrani Manna,     Plant Molecular Cytogenetics Laboratory, Centre of Advanced Study, Department of Botany, Ballygunge Science College, University of Calcutta, Kolkata, India

Seema Nara,     Department of Biotechnology, Motilal Nehru National Institute of Technology, Allahabad, India

Abha Pandey,     Laboratory of Photobiology and Molecular Microbiology, Centre of Advanced Study in Botany, Institute of Science, Banaras Hindu University, Varanasi, India

Himanshu Pandey,     Faculty of Pharmaceutical Sciences, Sam Higginbottom Institute of Agriculture Technology and Sciences, Allahabad, India

Parul Parihar,     Ranjan Plant Physiology and Biochemistry Laboratory, Department of Botany, University of Allahabad, Allahabad, India

Anuradha Patel,     Ranjan Plant Physiology and Biochemistry Laboratory, Department of Botany, University of Allahabad, Allahabad, India

Jainendra Pathak,     Laboratory of Photobiology and Molecular Microbiology, Centre of Advanced Study in Botany, Institute of Science, Banaras Hindu University, Varanasi, India

Jayanta Kumar Patra,     Research Institute of Biotechnology & Medical Converged Science, Dongguk University-Seoul, Gyeonggi-do, Republic of Korea

Bhanu Prakash,     Lab of Herbal Pesticides, Centre of Advanced Study in Botany, Institute of Science, Banaras Hindu University, Varanasi, India

Sheo Mohan Prasad,     Ranjan Plant Physiology and Biochemistry Laboratory, Department of Botany, University of Allahabad, Allahabad, India

S. Rajeshkumar,     Department of Pharmacology, Saveetha Dental College and Hospitals, SIMATS, Chennai, TN, India

Rajneesh,     Laboratory of Photobiology and Molecular Microbiology, Centre of Advanced Study in Botany, Institute of Science, Banaras Hindu University, Varanasi, India

Radha Rani,     Department of Biotechnology, Motilal Nehru National Institute of Technology, Allahabad, India

Anshu Rastogi,     Department of Meteorology, Poznan University of Life Sciences, Poznan, Poland

Aryadeep Roychoudhury,     Department of Biotechnology, St. Xavier's College (Autonomous), Kolkata, India

Abhishek Sharan,     Department of Biotechnology, Motilal Nehru National Institute of Technology, Allahabad, India

Nandita Sharma,     Department of Biotechnology, Motilal Nehru National Institute of Technology, Allahabad, India

Deepmala Sharma,     Department of Mathematics, National Institute of Technology, Raipur, India

Devendra Singh,     Department of Biotechnology, Motilal Nehru National Institute of Technology, Allahabad, India

Deepak K. Singh,     Laboratory of Photobiology and Molecular Microbiology, Centre of Advanced Study in Botany, Institute of Science, Banaras Hindu University, Varanasi, India

Rachana Singh,     Ranjan Plant Physiology and Biochemistry Laboratory, Department of Botany, University of Allahabad, Allahabad, India

Shailendra P. Singh,     Laboratory of Photobiology and Molecular Microbiology, Centre of Advanced Study in Botany, Institute of Science, Banaras Hindu University, Varanasi, India

Rajeshwar P. Sinha,     Laboratory of Photobiology and Molecular Microbiology, Centre of Advanced Study in Botany, Institute of Science, Banaras Hindu University, Varanasi, India

Thounaojam Thorny Chanu,     Department of Botany, Cotton University, Guwahati, India

Sanjesh Tiwari,     Ranjan Plant Physiology and Biochemistry Laboratory, Department of Botany, University of Allahabad, Allahabad, India

Durgesh Kumar Tripathi,     Department of Biotechnology, Motilal Nehru National Institute of Technology, Allahabad, India

Neha Upadhyay,     Lab of Herbal Pesticides, Centre of Advanced Study in Botany, Institute of Science, Banaras Hindu University, Varanasi, India

Hrishikesh Upadhyaya,     Department of Botany, Cotton University, Guwahati, India

Candida Vannini,     Department of Biotechnology and Life Sciences, University of Insubria, Varese, Italy

Marek Živčák,     Department of Plant Physiology, Slovak University of Agriculture, Nitra, Slovak Republic

Chapter 1

Phytotoxic Properties of Zinc and Cobalt Oxide Nanoparticles in Algaes

Abhishek Sharan, and Seema Nara     Department of Biotechnology, Motilal Nehru National Institute of Technology, Allahabad, India

Abstract

Excessive use of industrially important nanoparticles increases the chances of their release into the aquatic environment posing harmful effects to aquatic ecosystem. Many studies have suggested the toxic impact of metal oxide nanoparticles in aquatic plants such as microalgae. The present chapter describes the ecotoxicological properties of Zinc oxide and Cobalt oxide nanoparticles towards microalgae. On the basis of early studies and published data it can be suggested that stability of Zinc and Cobalt oxide nanoparticles in aquatic environment and their physicochemical properties such as size, shape, charge etc. greatly influence the toxicity of these nanoparticles. The primary mode of toxicity generation for Zinc oxide and Cobalt oxide nanoparticles across various tested species differ with each other. In case of Zinc Oxide nanoparticles, ionic dissolution and particle-induced generation of reactive oxygen species (ROS) are equally significant mode of action for toxicity while particle-induced generation of reactive oxygen species (ROS) and physical damage to cell membrane are associated toxic mechanism of partially soluble Cobalt oxide nanoparticles. Also, photocatalytic property of Zinc Oxide nanoparticles may be another important mechanism of toxicity. Finally, it has been concluded that current data available in this area of research is limited and more extensive studies are required to acquire proper understanding about the interaction of metal based nanoparticles with aquatic environment.

Keywords

Cobalt oxide; Ecotoxicity; Microalgae; Nanoparticles; Zinc oxide

1.1. Introduction

The application and utilization of nanomaterials has emerged as a rapidly growing multibillion-dollar commercial industry. Increased industrial production efficiency and recent advances in the research and development of nanomaterials have enormously increased the number of nanomaterial-based industrial, medical, and consumer products (Nanomaterials state of the market Q3 2008). By 2020 an increase from 1000 to 58,000  tons is expected in the total amount of nanomaterials produced globally (Nanoscience and nanotechnologies: Opportunities and uncertainties, 2004).

With the growing interest in and good future prospects for nanomaterials, metal-based and metal oxide nanoparticles in particular are likely to find applications in the areas of paint, fillers, medicine, food and food packaging, cosmetics, electronics, textiles, energy, and agriculture. Metal oxide nanoparticles are mostly used as components in numerous commercial products, and their industrial applications have led to serious concerns about their potential toxic impact on human health, plants, and the environment (Aschberger et al., 2011; Tripathi et al., 2017a–d; Singh et al., 2016; Singh et al., 2017). Most sewage and industrial wastewater is discharged into water bodies, including rivers, lakes, coastal waters, etc., inevitably causing the deposition of these nanoparticles in the aquatic environment (Daughton, 2004). Increasing use of metal oxide nanoparticles may eventually result in increased release of these nanoparticles into the aquatic system, adversely affecting the aquatic life. Thus the unexplored area of toxicity in the aquatic environment induced by metal oxide nanoparticles has been the subject of special interest recently (Blaise et al., 2008; Farré et al., 2009).

In the past decade, metal oxide nanoparticles such as zinc oxide (ZnO) and cobalt oxide (CoO) have been utilized in wide range of products. ZnO and CoO nanoparticles emerged as a prominent class of commercially important metal oxide nanoparticles because of their unique physicochemical properties. They are extensively used in industrial processes and consumer goods, including in pigments, catalytic processes, magnetism, sensor development, energy storage, and electrochemistry (Liu et al., 2005; Papis et al., 2009). As metal oxide nanoparticles are used in many products related to daily life activities, they are easily flushed out into the aquatic environment and affect the sustainability of the aquatic ecosystem. It is estimated that the annual production of skincare and cosmetic products containing ZnO nanoparticles is approximately 1000  tons worldwide, and around 25% of these products are washed off during bathing and swimming and discharged into the aquatic environment (Pikethly, 2004; Danovaro et al., 2008). ZnO nanoparticles are also deposited in high concentrations in surface waters and become toxic to the aquatic ecosystem (Gottschalk et al., 2009). Zn²+ is a well-established toxicant for aquatic life, and it is essential to study the toxic effects of nanosized ZnO particles to establish the risk to aquatic life. CoO nanoparticles have found applications in sensors, pigments, photocatalysts, energy storage, and biomedical applications (Asif et al., 2014). Toxicity of CoO nanoparticles has been studied with mammalian cells, but their toxic effects on aquatic life are underexplored. Because the environmental impact of these nanoparticles is not clearly understood, their phytotoxic effects of in aquatic ecosystem have attracted much greater concern. As less information related to phytotoxic effects of nanoparticles in the aquatic environment is available, the present scientific interest is to investigate the effects of nanoparticles on aquatic ecosystems, particularly on algae.

Phytoplankton and algae are major constituents of the aquatic food chain and play the key role of being primary producers in aquatic ecosystems. They are also responsible for the transfer of energy and nutrients to higher trophic levels. Many researchers have made efforts to understand the toxic impact of ZnO nanoparticles in marine and freshwater algal species. The toxic effects of ZnO nanoparticles are briefly summarized in Table 1.1. Microalgae show high levels of sensitivity toward water pollutants and present themselves as an excellent aquatic model to study the phytotoxic effects of nanoparticles in aquatic ecosystems (Chen et al., 2012c).

In this chapter industrially important and widely used metal oxide nanoparticles, namely ZnO and CoO, are explored as prominent contaminants of aquatic life with severe phytotoxic effects on algae. The factors responsible for influencing the fate and phytotoxic effect of these nanomaterials in aquatic systems and the plausible mechanism involved in toxicity generation are discussed later in this chapter.

1.2. Production and Applications of ZNO and COO Nanoparticles

The production and utilization of metal-oxide-based nanomaterials have increased remarkably and they are used in various industrial processes and products, such as catalysts, cosmetics, pigments, sunscreens, and food additives (Aitken et al., 2006; Shi et al., 2013). The worldwide annual production of ZnO nanoparticles lies in third position, with a volume of 550  tons, after SiO2 (5500  tons) and TiO2 nanoparticles (3000  tons) (Piccinno et al., 2012). CoO nanoparticles are considered as a low-volume product, and the minimum global production was estimated to be approximately 5  tons in 2014 (Nanomaterial: Future markets, 2015). ZnO nanoparticles market share is distributed across two important industries: cosmetics and paint. Cosmetics (including sunscreens) have in the largest market share at 70%, while the market share of the paint industry is about 30% (Piccinno et al., 2012). Apart from industrial applications, nanoparticles can also be utilized as nanofertilizers to provide macronutrients and micronutrients to the crops as ZnO nanoparticles (Zhao et al., 2013; Shweta et al., 2016; Tripathi et al., 2017b; Singh et al., 2017).

The unique physicochemical properties of ZnO nanoparticles have favored their utilization in widespread applications, such as the component protecting against ultraviolet (UV) radiation in cosmetics like beauty products, sunscreens, and toothpastes (Serpone et al., 2007). The photoactive nature of ZnO nanoparticles means they find applications in production of liquid crystal displays and solar cells. They are also widely used in paint and pigments, chemical fibers, textiles, and electronics (Heng et al., 2010; Song et al., 2010). And despite the very small global production, recent research has shown promising characteristics of CoO nanoparticles and they are therefore attracting huge interest in potential industrial applications such as pigments, catalytic processes, energy storage, sensor development, electrochemistry, magnetism (Liu et al., 2005; Papis et al., 2009; Li et al., 2011), development of nonenzymatic glucose sensors (Madhu et al., 2015), magnetic resonance imaging (Bouchard et al., 2009), etc.

Table 1.1

Chl a, chlorophyll a; EC, effective concentration; IC, inhibitory concentration; LOEC, lowest observed effect concentration.

Thus daily increasing use of metals containing nanoparticles in consumer products has raised serious concerns about their proliferation in aquatic ecosystems and subsequent toxicity in aquatic life forms. Many studies have suggested the induction of toxicity in aquatic plants such as microalgae when exposed to nanoparticles (Table 1.1).

1.3. Methods to Assess Toxicity of Metal Oxide Nanoparticles in Algae

There is wide variation in the toxic effects generated by metal oxide nanoparticles interacting with aquatic plants, especially microalgae. These variations can be the result of physicochemical properties of a particular nanoparticle, the surrounding environmental conditions, or behavior of nanoparticles in aquatic systems. Thus proper assessment of the toxicity produced in algal species in aquatic systems is of utmost importance. ZnO and CoO nanoparticles have been shown to differ from each other in their behavior in aquatic systems. For example, ZnO nanoparticles are highly soluble in water, so most of the toxicity produced is because of Zn²+ ions, while CoO nanoparticles are poorly soluble in water (Papis et al., 2009) and most of the toxicity observed is because of nanoparticle interaction with algal cell walls and subsequent internalization. There are various methods and techniques applied to assess these toxic effects, and some are discussed below.

1.3.1. Damage to Cell Wall Integrity

Nanoparticles in a particulate form can be adsorbed on to the cell wall of algae and compromise cell wall integrity by producing reactive oxygen species (ROS) in close proximity to the surface, increasing the pore size of rigid cell walls, and causing an increase in membrane permeability. Because of these effects, reduction in growth and cell lyses takes place, and even cell death. Many methods have been used to determine cell wall damage caused by nanoparticles and the resulting effects in algae. When the algal cell wall is exposed to ZnO or other metal oxide nanoparticles, the cell wall/membrane permeability is modified and cytoplasmic enzyme such as lactate dehydrogenase (LDH) is released outside the cell in the aqueous media. The intactness of the cell membrane is estimated by determining the amount of LDH in the media. LDH assay and acid phosphatase assay are the two important methods applied in evaluation of the toxicity of CoO and ZnO nanoparticles for microalgae (Rebello et al., 2010; Suman et al., 2015; Bhuvaneshwari et al., 2015).

The cell wall integrity of microalgae can also be examined by a fluorescent dye staining technique. Propidium iodide (PI) is a fluorescent dye mostly used in assessment of cell membrane integrity. PI can only pass through the cell wall/membrane when the membrane is damaged and permeability is increased; it binds with nucleic acid to produce red fluorescence, indicating compromised cell wall integrity. Flow cytometric analysis also uses PI-based fluorescent dye assay (Suman et al., 2015).

Lipid peroxidation (malondialdehyde assay) can be used to evaluate indirectly the degree of cell membrane damage in microalgae. When nanoparticle-induced extracellular ROS attack membrane lipids, fatty acid radicals are generated, known as lipid hydroperoxides. Lipid hydroperoxides are further decomposed into water-soluble toxic by-products such as aldehydes, ketones, alkanes, glycols, lipid epoxides, alcohols, etc., which are highly toxic to cells and organelles (Gill and Tuteja, 2010). Malondialdehyde (MDA) is one of the by-products of lipid peroxidation, and is synthesized as a result of nanoparticle-induced peroxidation of membrane lipids. An elevated level of MDA is observed when algae are exposed to metal oxide nanoparticles (Wang et al., 2008; Chen et al., 2012a; Tang et al., 2015).

In general, morphological changes and cell growth can be determined by microscopic analysis and other cell-counting techniques. Surface modifications on algal cell walls can also be analyzed by scanning electron microscope or field emission scanning electron microscope (Ji et al., 2011; Chen et al., 2012b; Suman et al., 2015).

1.3.2. Oxidative Damage

Once internalized, metal oxide nanoparticles in either dissolved ionic form or particulate form can induce oxidative stress by generating ROS. Oxidative damage to the algal cells can be assessed by fluorescent/nonfluorescent probes, enzymatic and nonenzymatic antioxidant assay, inductively coupled plasma mass spectrometry (ICP–MS), etc.

The overall intracellular ROS produced can be estimated by applying widely used highly sensitive probes. One commonly used probe is H2DCF-DA (2′,7′-dichlorodihydrofluorescein diacetate), which is highly permeable through cell membranes and rapidly enters cells by passive diffusion. When inside the cell, it reacts with intracellular ROS and is converted to the DCF (2′,7′-dichlorofluorescein) fluorescent form. The extent of ROS generation is measured by measuring the fluorescent intensity of DCF (Foucaud et al., 2007; Tang et al., 2015).

Oxidative stress disturbs the antioxidant system in the cell. The measurement of enzymatic and nonenzymatic antioxidants in algal cells can be used to assess the oxidative damage caused by metal oxide nanoparticles. An increase in the activity of antioxidant enzymes such as superoxide dismutase (SOD) indicates nanoparticle exposure and subsequent ROS generation in algae. But overaccumulation of ROS will further reduce the activity of the SOD enzyme (Zhou et al., 2014; Suman et al., 2015). An assay using a nonenzymatic antioxidant such as glutathione (GSH) is performed to assess the oxidative stress when ROS level is below critical concentration (von Moos and Slaveykova, 2014). GSH assay is a good method to determine minute amounts of ROS generated in the cell. The reduction in GSH level in algae exposed to ZnO nanoparticles is indicative of the amount of ROS (Suman et al., 2015). To determine the amount of the intracellular ionic form of nanoparticles, such as ZnO nanoparticles, the ICP–MS technique is used. The detection of Zn²+ released from ZnO nanoparticles by ICP–MS, including intracellular zinc and zinc bound to the cell wall of C. vulgais, has also been reported (Zhou et al., 2014).

Apart from conventional methods of toxicity assessment, a high-content imaging technique has been used to detect toxicity to aquatic life. The toxic effects of metal oxide nanoparticles such as ZnO, CuO, NiO, and Co3O4 have been assessed in embryo and larvae of zebrafish by using bright-field and fluorescent-based high-content imaging. Bright-field imaging is used to visualize the phenotypic and developmental abnormalities (hatching in embryo), while high-content fluorescent-based imaging can be used to assess heat shock protein (Hsp70), which is overexpressed in interaction with a high dose of nanoparticles. Thus high-content imaging is a promising tool for in vivo hazard ranking and dose response relationship assessment for nanoparticles in aquatic ecosystems (Lin et al., 2011).

1.4. Factors Influencing Phytotoxicity of ZNO and COO Nanoparticles

Before assessing the commercial implications of nanomaterials, nanotoxicity and the action of metal oxide nanoparticles in aquatic environments must be studied as a priority. Many factors influence the toxicity of metal and metal-oxide-based nanoparticles for aquatic life, including physicochemical characteristics of nanomaterials (shape, size, charge, etc.), behavior of nanoparticles (aggregation, dissolution, etc.) in aquatic systems, concentration, and environmental parameters (temperature, pH, salinity, etc.). A general overview of ZnO nanoparticle interactions in marine ecosystems is illustrated in Fig. 1.1.

Figure 1.1  Overview of interaction of ZnO nanoparticles with marine biota, behavioral modifications, and transformation. 

Reprint with permission from Yung, M.M.N., Mouneyrac, C., Leung, K.M.Y., 2014. Ecotoxicity of zinc oxide nanoparticles in the marine environment. In: Bhushan B. (Ed.) Encyclopedia of Nanotechnology. Springer Netherlands, Dordrecht, pp. 1–17. https://doi.org/10.1007/978-94-007-6178-0_100970-1.

1.4.1. Physicochemical Characteristics of Nanomaterials

The unique physicochemical characteristics of each nanoparticle govern its industrial applications in commercial products; they include size, shape, surface charge, reactivity, dispersivity, etc. Since metal oxide nanoparticles are widely used engineered nanomaterials, changes or variations in their physicochemical characters drastically influence their toxicity. A brief description of toxic effects due to physicochemical properties of ZnO nanoparticles is summarized in Table 1.2. With decreasing size of nanoparticles, their surface area increases, thereby enhancing their surface characteristics in terms of charge. It is observed in many studies based on size-dependent toxicity of nanoparticles that those with a smaller size range are more toxic compared to their larger size counterparts. With decrease in size their ability to penetrate into plant tissue increases. It is suggested that the primary particle size of the dispersed nanoparticles affects the overall toxicity (Manzo et al., 2013). When green algae D. subspicatus is exposed to TiO2 nanoparticles of particle size range 25–100  nm, it was observed that the smaller ones inhibited growth to a larger extent (Hund-Rinke and Simon, 2006). Beyond the size of metal oxide nanomaterials, morphology also influences the toxicity of the nanoparticles toward aquatic life forms, including microalgae. In a study it was observed that the toxicity of rod-shaped ZnO nanoparticles to marine algae P. tricornutum was greater than that of sphere-shaped nanoparticles (Peng et al., 2011). Thus it is necessary to characterize the shape of metal oxide nanoparticles exactly to evaluate their shape-dependent toxicity. Surface charges are also found to be important in establishing contact between the nanomaterials and cell walls of microalgae. Algal cell walls have a negative charge and therefore may attract positively charged nanoparticles or their ionic forms, such as Zn²+ ions, and enable strong chemical interactions between nanoparticles and algal cell walls (Wong et al., 2010). As the size decreases, nanoparticles become more reactive. This unusual reactivity makes them more toxic, and the corresponding charge of nanoparticles makes them more reactive toward cells and proteins compared to their natural bulk counterparts (Stark, 2011; Deng et al., 2013).

1.4.2. Processes Affecting Stability of Nanoparticles and Toxicity

Mobility and dispersal of nanoparticles in water bodies play a significant role in toxicity generation. Different processes like adsorption, aggregation, dissolution, and concentration have significant effects on the fate of nanoparticles in aquatic environments. The processes of adsorption and aggregation during ZnO nanoparticle interaction with Chlorella sp. have resulted in deformed algal cell morphology, reduced viability, and compromised membrane integrity. These effects are due to dissolution of ZnO nanoparticles into zinc ions, causing mechanical damage to cell walls (Chen et al., 2012b). The increased rate of dissolution of Zn²+ ions can reduce cell growth and chlorophyll concentration in marine phytoplankton T. pseudonana when exposed to ZnO nanoparticles. Freshwater algae may suffer similar effects when exposed to ZnO nanoparticles (Ma et al., 2013; Miao et al., 2010; Franklin et al., 2007). On the other hand, aggregations of nanoparticles lead to formation of larger particles and removal from the water column in the form of sediments. In marine environments it has been found that aggregates of nanoparticles are formed and settle in the form of sediments (Bian et al., 2011). Although the aggregates of nanoparticles are sedimented in aquatic systems, they can be taken up by benthic organisms and filter feeders; this results in bioaccumulation or biomagnification in food chains, generating possible toxicity. Concentration of metal oxide nanoparticles in both dissolved ionic form and as nanoparticles in an aqueous system may affect algal growth severely, even at low levels. A cytotoxic effect on C. vulgaris at low concentrations of 50  mg/L ZnO nanoparticles is observed. The viability of C. vulgaris decreased by 90.49  ±  0.3% at 24  h at 50  mg/L ZnO nanoparticles, whereas at 300  mg/L the viability of C. vulgaris significantly reduced to 23.69  ±  1.8%. A complete suppression of growth of three marine diatoms is observed at 10  mg/L of nanoZnO (Suman et al., 2015; Peng et al., 2011). In another study, different concentrations of CoO nanoparticles are applied to Navicula and Chetoceros spp. and it is observed that exposure to 0.2  mg/mL CoO nanoparticles for 5  days resulted in decreased cell densities in both microalgae (Rebello et al., 2010). It is also reported that ZnO nanoparticles at low concentration (0.081  mg/L) are toxic to freshwater algal species, but in marine species they are not toxic (Aravantinou et al., 2015).

Table 1.2

1.4.3. Environmental Factors

Metal oxide nanoparticles can exhibit different toxicities to aquatic organisms under different environmental conditions. Ionic strength, pH, and temperature play very important roles in the degree of dissolution and aggregation and the related toxicity in the aquatic environment. Due to its high ionic strength, rapid aggregation of nanoparticles tends to take place in seawater compared to freshwater. Experimental evidence suggests that aggregate size of ZnO nanoparticles significantly increases with increasing salinity, and therefore toxic effects of ZnO nanoparticles toward the marine diatom T. pseudonana are reduced in terms of growth inhibition and photosynthetic performance with increased salinities (Yung et al., 2015). The pH of water bodies keeps changing, which can also bring changes in aggregation and ionic dissolution of nanoparticles. An elevated toxicity of ZnO nanoparticles in marine diatom T. pseudonana is observed at low pH and at the same time an increase in ionic dissolution from ZnO nanoparticles is observed in the exposure medium (Miao et al., 2010). Temperature is another important environmental factor governing the algal physiology and growth in aquatic systems. The effect of temperature was evaluated on the marine diatom S. costatum when exposed to ZnO nanoparticles. Growth inhibition is observed beyond the thermal tolerance limits of microalgae based on IC10 (inhibitory concentration at which growth is reduced to 10%) value for 96  h of exposure (Wong and Leung, 2014). The reactivity of metal oxide nanoparticles can also be increased at higher temperature. Elevated temperature can increase the rate of dissolution of metal oxide nanoparticles and thereby increase their toxicity. Apart from high temperature, low pH and minimum particle size also enhance the rate of dissolution of nanoparticles (Bian et al., 2011; Zhang et al., 2010; Liu and Hurt, 2010).

1.5. Toxicity of Zinc and Cobalt Oxide Nanoparticles: Possible Mechanisms

As discussed above, the toxic impacts of metal oxide nanoparticles in aqueous environments may be influenced by many physicochemical and environmental factors, but their mechanism of toxic action is not clearly understood. Views proposed by different groups on toxicity mechanisms of a particular nanoparticle are dissimilar. ZnO and CoO nanoparticles show different solubility behavior in aqueous media. ZnO nanoparticles have a very good rate of solubility and therefore most ZnO nanoparticles are dissociated into ionic form in aqueous media. In contrast, CoO nanoparticles are partially soluble in water and most of their nanoforms are retained in aqueous media. Both of these nanoparticles show different reactivity with the surrounding environment; thus their mechanisms of toxicity in aqueous media can be explained by dissolution, aggregation, and adsorption. Most of the literature available to date focuses on the first mechanism of toxicity, but aggregation and adsorption also affect the toxicological impact of these nanoparticles in aquatic food chains.

1.5.1. Dissolution

Many metal oxide nanoparticles tend to dissociate into ions in aqueous media. The extent of dissolution depends upon the solubility characteristics of nanoparticles. As mentioned, ZnO nanoparticles are more easily soluble in water than CoO nanoparticles; most of the information available to date concerns the dissolution-based toxicity of ZnO and much less work has been done on CoO nanoparticles. In most of the research it has been observed that ionic zinc dissociated from ZnO nanoparticles is significantly responsible for the toxicity in aquatic environments. Toxicity in marine algae has been found to be closely related to the concentration of released Zn²+. The rate of dissolution is affected by various physicochemical factors, such as particle size, surface area, roughness, morphology, etc. (Farré et al., 2009). Miao et al. (2010) systemically examined the kinetics of Zn²+ release under different conditions and found that it is mainly influenced by pH and specific surface area of the ZnO nanoparticles. Moreover, the extent of nanoparticle solubility depends upon their size. Yang and Xie (2006) find faster release of ionic zinc from ZnO nanoparticles than from its microsize particles. In addition to size and surface area, other physicochemical factors like roughness and curvature may influence the dissolution of metal oxide nanoparticles in aquatic environments (Borm et al., 2006). Solubility behavior of nanoparticles is different in different water systems. ZnO nanoparticles show higher solubility than their bulk counterpart in saltwater than freshwater (Wong et al., 2010). Dissolved Zn²+ ions reduce cell growth and chlorophyll concentration in marine phytoplankton T. pseudonana when exposed to ZnO nanoparticles. Freshwater algae may suffer similar effects when exposed to ZnO nanoparticles (Ma et al., 2013; Miao et al., 2010; Franklin et al., 2007). In another study, Ates et al. (2016) found that cobalt oxide nanoparticles are more soluble in seawater than nickel oxide nanoparticles, resulting in a higher level of ionic dissolution. Though there is a wide acceptance of the idea that toxicity is induced by dissolved Zn²+ in aquatic environments, it is still not clearly understood to what extent ionic zinc contributes to the toxicity of ZnO nanoparticles. Some researchers have proposed that ZnO nanoparticles also produce toxicity in algae and other aquatic organisms in particulate form (Nair et al., 2009; Wong et al., 2010). According to a recent study, ZnO nanoparticle toxicity through dissolved Zn²+ and nanoparticle-dependant effects are observed to express distinct genes in D. manga. Three distinct biomarker genes, multicystatin, ferritin, and C1q, are identified to express differentially under ZnO nanoparticle exposure. Thus environmental exposure to ZnO nanoparticles in aquatic organisms can be identified by using different biomarker genes (Poynton et al., 2010). The ion-induced and particle-dependent toxicity of ZnO nanoparticles can be determined by applying this biomarker gene expression method in a precise way. In the case of partially soluble nanoparticles, such as CoO nanoparticles, it seems more acceptable.

1.5.2. Aggregation

It has been demonstrated that the stability of nanoparticles in aqueous media is inversely proportional to their tendency to aggregate (Mackay et al., 2006). Once nanoparticles enter a water system, the strength of repulsive forces acting between charged surfaces of nanoparticles determines the formation of aggregates of nanoparticles. For example, a ZnO nanoparticle is surrounded by adjacent particles in a liquid medium and carries an equal positive charge, causing development of electrostatic repulsion between two adjacent particles. The ZnO nanoparticles remain separate and stabilized in the liquid suspension only if the electrostatic repulsion is higher than force of attraction (van der Waals attraction force). However, in marine environments high ionic strength reduces the interparticle electrostatic repulsion forces, resulting in the formation of nanoparticle aggregates which settle as sediments (Bian et al., 2011). Aggregation limits the rate of dissolution and the resulting ionic toxicity. The size and shape of nanoparticles influence the character of toxicity in aquatic systems. Small-size nanoparticles possess larger surface area and reactivity. When aggregation occurs between spherical particles, only a very small contact point is occupied, resulting in increased