Health and Environmental Safety of Nanomaterials

List of contributors xv

Preface xix

Part I General Introduction 1

1 Nanomaterials, nanofillers, and nanocomposites:

types and properties 3

James Njuguna, Farahnaz Ansari, Sophia Sachse,

Veronica Marchante Rodriguez, Shohel Siqqique

and Huijun Zhu

1.1 Introduction 3

1.2 Key terms and definitions 6

1.3 Common physical and chemical properties 7

1.3.1 Morphology and dimension 7

1.3.2 Composition 8

1.3.3 Agglomeration 8

1.3.4 Diffusion 8

1.3.5 Deposition 9

1.3.6 Surface coating and functionalization 10

1.3.7 Particle chemistry and crystalline structure 11

1.4 Types of nanofiller 11

1.4.1 Quantum dots 12

1.4.2 Nanotubes 12

1.4.3 Nanowires 13

1.4.4 Layered silicates 13

1.4.5 Polyhedral oligomeric silsesquioxanes 14

1.4.6 Dendrimers 16

1.4.7 Metal oxides 17

1.4.8 Graphene oxides 17

1.4.9 MXenes 19

1.5 Nanocomposites: selected examples 21

1.5.1 Nanocomposites filled with nanoplates 21

1.5.2 Nanocomposites filled with nanoparticles 25

1.5.3 Polyamide-6/clay nanocomposites 26

1.5.4 LDPE clay nanocomposites 28

1.5.5 Fiber surface modification and the deposition

of nanofiller on carbon fiber surface 29

1.5.6 Graphene/carbon fiber

1.6 Conclusion 32

Acknowledgment 33

References 33

2 Mechanisms of toxicity of engineered nanoparticles: adverse

outcome pathway for dietary silver nanoparticles in mussels 39

M.P. Cajaraville, N. Duroudier and E. Bilbao

2.1 Introduction 39

2.2 Factors affecting fate and toxicity of engineered nanoparticles

in aquatic environments 40

2.2.1 Intrinsic properties 42

2.2.2 Physicochemical processes 43

2.3 Uptake and toxicity of engineered nanoparticles in

aquatic organisms 43

2.4 Silver nanoparticles in the environment 45

2.4.1 Microalgae 48

2.4.2 Invertebrates 49

2.4.3 Fish 51

2.5 Bivalve mollusks as model species 52

2.5.1 Bivalves and eco-nanotoxicology 53

2.5.2 Biomarkers as suitable tools for assessing nanoparticles

toxicity in mussels 55

2.5.3 The omic’s approach: discovering new biomarkers

and adverse outcome pathways 57

2.5.4 Trophic transfer studies 58

2.6 Adverse outcome pathway for dietary silver nanoparticles

in mussels 59

2.7 Concluding remarks and future trends 67

Acknowledgments 68

References 68

3 Safety, regulation, and policy 83

Halshka Graczyk, Luca Fontana, Maged Younes and Ivo Iavicoli

3.1 Introduction: approaches to regulatory actions 83

3.2 Challenges for regulatory standards toward manufactured

nanomaterials 84

3.3 Existing standards covering international guidance 86

3.3.1 Definitions of nanomaterials 86

3.3.2 Risk assessment of nanomaterials 87

3.3.3 Occupational exposure limits 89

3.4 The way forward and conclusions 93

References 93

Part II Assessment of nanomaterials release and exposure 97

4 Measurement, testing, and characterization of airborne

nanoparticles released from machining of nanoreinforced composites 99

Kristof Starost, Sophia Sachse and James Njuguna

4.1 Introduction 99

4.2 Sampling and measurement techniques 105

4.3 Controlled environment for particle measurement 110

4.4 Guidelines, handbooks, and recommendations 118

4.5 Conclusion 120

References 122

Further reading 126

5 A study on the nanoparticle emissions into environment during

mechanical drilling of polyester, polypropylene, and epoxy

nanocomposite materials 129

Kristof Starost, Evelien Frijns, Jo Van Laer, Nadimul Faisal,

Ainhoa Egizabal, Cristina Elizetxea, M. Bla´zquez Sa´nchez, Inge Nelissen

and James Njuguna

5.1 Introduction 129

5.2 Method 131

5.2.1 Material fabrication 131

5.3 Setup of mechanical drilling simulation process and

released particle sampling 134

5.4 Particle characterization 136

5.4.1 Mechanical testing 137

5.4.2 Statistical analysis 137

5.5 Results and discussion 137

5.5.1 Influence of nanofiller 137

5.5.2 PP-reinforced nanocomposites 140

5.5.3 PE-reinforced nanocomposites 142

5.5.4 EP-reinforced nanocomposites 143

5.5.5 EP/CF-reinforced nanocomposites 144

5.5.6 Influence of matrix 144

5.5.7 Influence on particle size and mass distributions 147

5.6 Conclusions 148

Acknowledgments 151

Conflicts of interest 151

References 151

6 Scenario simulation at laboratory scale for the assessment

of the release of engineered nanomaterials 157

M. Bla´zquez Sa´nchez and V. Marchante

6.1 Introduction 157

6.2 Approaches for release simulation: comparison of case

studies of nanocomposite drilling 158

6.3 Development of scenarios simulating different life cycle

stages of nanocomposites 164

6.3.1 Experimental setup 164

6.3.2 Avoidance of background particles in simulated scenarios

at laboratory scale 164

6.3.3 Different processes potentially leading to the release

of ENMs from nanocomposite samples 165

6.3.4 Online measurement of released (airborne) particles

from nanocomposite samples 166

6.3.5 Collection of released airborne particles from

nanocomposite samples for off-line analysis 166

6.4 Considerations for the (eco)toxicological assessment of

samples released from nanocomposites 167

6.4.1 Generation of samples released from nanocomposite

for (eco)toxicological assessment 167

6.4.2 Storage and labeling of samples released from

nanocomposites to be used in (eco)toxicological

assessment 168

6.4.3 Pretreatment of sample released from nanocomposites:

use of dispersing agents, sonication, stirring,

and mixing 168

6.5 Conclusions 169

Acknowledgments 169

References 169

7 A life cycle perspective of the exposure to airborne nanoparticles

released from nanotechnology enabled products and applications 173

M. Bla´zquez Sa´nchez, C. Fito-Lo´pez and M.P. Cajaraville

7.1 Introduction 173

7.2 Airborne ENMs released from NEPs and NEAs: exposure

at the workplace, household and environmental compartments 174

7.2.1 Workplace exposure 175

7.2.2 Consumer exposure 177

7.2.3 Environmental exposure 179

7.3 International guidance and standards and instrumentation for

airborne nanoparticle exposure assessment 180

7.3.1 International guidance 180

7.3.2 Standards 182

7.3.3 Instrumentation for exposure assessment to airborne

nanoparticles 183

7.4 Generic approach for the release assessment of airborne ENMs

from NEPs or NEAs from a risk assessment perspective 183

7.5 Conclusions 190

Acknowledgment 191

References 191

Part III Safety of particular type of nanomaterials 195

8 Nanomaterials at industrial workplace—an overview

on safety 197

Vinita Vishwakarma

8.1 Introduction 197

8.2 Medical and pharmaceutical industry 199

8.3 Food and agricultural industry 199

8.4 Textile industry 201

8.5 Cosmetic industry 201

8.6 Construction and paint industry 201

8.7 Automobile industry 202

8.8 Electronic industry 202

8.9 Sport industry 203

8.10 Petroleum industry 203

8.11 Water industries 203

8.12 Safe handling of nanomaterials 204

8.13 Conclusion 204

References 205

9 Clay minerals and solutions for green environment

and human health 211

Huijun Zhu, James Njuguna and Muhammad Adeel Irfan

9.1 Introduction 211

9.2 Characteristics of clay minerals 212

9.3 Effect of clay minerals on environment 214

9.4 Toxicity of nanoclays in humans 217

9.5 Life cycle assessment (LCA) of nanoclay-reinforced materials 218

9.6 Conclusion and future trends 219

References 219

Further reading 223

10 Ecotoxicology effects of carbon nanotubes 225

Bey Fen Leo, Isnazunita Ismail, Malarmugila Manimaran

and Rasel Das

10.1 Introduction 225

10.2 Test methods 227

10.2.1 Methods of identifying and quantifying carbon

nanotubes in environmental matrices 227

10.2.2 Environmental risk assessment of CNTs 233

10.3 Future development on risk assessment of NMs 244

10.4 Conclusion 246

References 247

11 Analysis and correlations of metal-organic frameworks:

applications and toxicity 253

Olivia L. Rose and Cerasela Zoica Dinu

11.1 What are metal-organic frameworks? 253

11.2 MOFs formation: a variety of synthesis conditions 254

11.2.1 Solvothermal and hydrothermal methods 254

11.2.2 Room temperature synthesis 257

11.2.3 Microwave synthesis 258

11.2.4 Mechanochemical synthesis 258

11.2.5 Electrochemical synthesis 259

11.2.6 Outlook on MOFs synthesis 260

11.3 MOFs applications 260

11.3.1 MOFs implementation in catalysis 262

11.3.2 Gas storage 265

11.4 MOFs applications in biomedical engineering 267

11.4.1 MOFs used in bioimaging as contrast agents 267

11.4.2 MOFs implementation as drug delivery agents 271

11.5 Toxicity: a comprehensive overview 275

11.5.1 In vitro toxicity evaluation of MOFs 277

11.5.2 In vivo toxicity evaluation 281

11.6 Outlook and future directions for MOFs implementation

and toxicity assessment 283

Acknowledgment 284

References 284

12 The safety assessment of food chemicals in the nanoscale 291

Reinhilde Schoonjans, Francesco Cubadda

and Maged Younes

12.1 Introduction 291

12.2 Identifying nanoparticles in products used in the

food/feed chain 292

12.3 Characterizing the physicochemical parameters 292

12.4 Testing the stability in the digestive tract 294

12.5 Testing the toxicokinetic behavior 294

12.6 Screening for biopersistence by testing in

lysosomal fluid 295

12.7 Testing (cyto)toxicity in vitro 296

12.8 Testing for potential genotoxicity 297

12.9 Testing toxicity in vivo 298

12.10 Assessing the level of exposure 299

12.11 Characterizing the risk 300

Disclaimer 301

References 301

Part IV Environmental risks of nanomaterials 305

13 Effects of nanomaterials on the benthic ecosystem: a case

study with the snail Lymnaea stagnalis 307

Valentina Ricottone and Teresa F. Fernandes

13.1 Introduction 307

13.2 Model test species: Lymnaea stagnalis 309

13.3 Ecotoxicology of nanomaterials to the great pond snail

Lymnaea stagnalis: a review 311

13.3.1 Silver nanomaterials 313

13.3.2 Copper oxide nanomaterials 319

13.3.3 Other metal nanomaterials 320

13.3.4 Carbon nanomaterials 322

13.4 Case study: Acute toxicity of nanomaterials on Lymnaea stagnalis 323

13.4.1 Test chemicals and NMs characterization 323

13.4.2 Experimental design 325

13.4.3 Data analyses 326

13.4.4 Results 326

13.4.5 Discussion 329

13.5 Summary and conclusions 334

References 335

14 Thermal degradation, flammability, and potential toxicity

of polymer nanocomposites 343

J.-M. Lopez-Cuesta, C. Longuet and C. Chivas-Joly

14.1 Introduction 343

14.2 Thermal degradation processes of polymers and nanocomposites 344

14.3 Thermal stability of nanoparticles 346

14.4 Instrumentation and techniques to investigate degradation

products of nanocomposites 350

14.4.1 Coupling of chemical analytic methods with thermal

analysis 350

14.4.2 Coupling of analytic physics methods with cone

calorimetry 351

14.5 Fire toxicity of degradation products of nanocomposites and its

assessment 355

14.6 Intrinsic toxicity of nanoparticles 358

14.7 Ultrafine particle production during combustion of nanocomposites 363

14.8 Conclusion and future trends 366

References 367

15 Nanoparticles as flame retardants in polymer materials:

mode of action, synergy effects, and health/environmental risks 375

Sławomir Michałowski and Krzysztof Pielichowski

15.1 Introduction 375

15.2 Polymer nanocomposites preparation methods 376

15.3 Nanostructured flame retardants 380

15.4 Combustion behavior of polymer nanocomposites 383

15.5 Synergies from combining classical and nanostructured

flame retardants 385

15.6 Health and environmental risks of conventional and

nanostructured flame retardants 401

15.6.1 Toxicological/environmental issues affecting

conventional flame retardants 401

15.6.2 Toxicological/environmental issues affecting

nanostructured flame retardants 402

15.6.3 Standardization and safety regulations 406

15.7 Conclusions and future trends 407

Acknowledgment 407

References 408

16 QSAR and machine learning modeling of toxicity of

nanomaterials: a risk assessment approach 417

Supratik Kar and Jerzy Leszczynski

16.1 Introduction 417

16.2 Types of nanomaterials and nanotoxicity 418

16.2.1 Metal nanoparticles (MNPs) 418

16.2.2 Metal oxide nanomaterials (MONMs) 419

16.2.3 Carbon nanomaterials 419

16.3 Why do the QSAR and machine learning approach require

for modeling of toxicity? 420

16.4 The concept and design of the major in silico approaches 420

16.4.1 Task 1: Experimental data generation 421

16.4.2 Task 2: Descriptors or features generation to correlate

experimental toxicity data 421

16.4.3 Task 3: The data analysis 421

16.4.4 Task 4: Model validation 422

16.4.5 Task 5: Model interpretation 422

16.4.6 Additional task: Docking studies to check

nanostructure and protein interactions 422

16.5 Application of QSAR and machine learning models in

toxicity prediction 423

16.6 Challenges and future directions 424

16.6.1 Study of biocorona 424

16.6.2 Interspecies nanotoxicity analysis 433

16.6.3 Mixture analysis 434

16.7 Overview and conclusion 435

Acknowledgment 435

Conflicts of interest 436

References 436

17 Life cycle assessment of engineered nanomaterials 443

Roland Hischier

17.1 Introduction 443

17.2 Life cycle assessment framework 443

17.3 LCA and nanotechnology 445

17.3.1 Inventory modeling of engineered nanomaterials 448

17.3.2 Prospective modeling 449

17.3.3 Life cycle impact assessment of releases of

engineered nanomaterials 451

17.4 Conclusion and outlook 452

References 455

18 Recycling of materials containing inorganic and

carbonaceous nanomaterials 459

L. Reijnders

18.1 Introduction 459

18.2 Recycling of engineered nanomaterials applied in reactors

or as recoverable analytes 463

18.3 Recycling of nanocomposites consisting of nanomaterials

and large-sized or macromaterials and of large assemblies

of nanomaterials 468

18.3.1 Extension of use and reuse 470

18.3.2 Remanufacturing 473

18.3.3 Materials recycling 473

18.3.4 Recovery of inorganic and carbonaceous

(nano)materials, where applicable combined

with processes such as depolymerization

and devulcanization 475

18.3.5 Pyrolysis and cracking 476

18.3.6 Combustion with energy recovery 477

18.3.7 Current resource cascading of nanocomposites 477

18.4 Nanomaterials and sacrificed nanomaterials present in wastes 478

18.5 Release of nanomaterials linked to recycling facilities 479

18.6 Conclusion 480

Acknowledgment 480

References 480

Index 497