
Exposure Assessment and Safety Considerations for Working with Engineered Nanoparticles
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Inhalt
Preface xiii
1 Introduction 1
1.1 Why A Book on Nanotechnology Health and Safety? 1
1.2 Some Scenarios 3
1.3 Organization of the Material 5
1.4 Our Approach to Nanoparticle Health and Safety 5
References 7
2 What is a Nanoparticle? 8
2.1 Nanotechnology, Nanomaterials, and Nanoparticles 9
2.1.1 Nanotechnology 9
2.1.2 Nanomaterial 9
2.1.3 Nanoparticle 9
2.2 Naturally Occurring Nanoparticles 10
2.3 Industrial Nanoparticles 12
2.4 Engineered Nanoparticles 14
2.4.1 Carbon Nanotubes 15
2.4.2 Fullerenes 17
2.4.3 Quantum Dots 17
2.5 Emerging Uses for Engineered Nanoparticles 19
2.6 Other Useful Definitions 20
2.6.1 Aerosol 20
2.6.2 Particle Inertia 21
2.6.3 Brownian Motion 22
2.6.4 Particle Diameter 23
2.6.5 Agglomerate versus Aggregate 24
2.7 Summary 25
References 26
3 Why are we Concerned? The Unique Properties of Nanoparticles 28
3.1 Surface?]to?]Volume Ratio 28
3.2 Particle Size 30
3.3 Particle Concentration 32
3.4 Dose Metrics: Particle Number, Surface Area, Morphology, and Surface Properties 33
3.5 Implications for the Occupational and Environmental Health Impacts of Nanoparticles 33
3.5.1 Respiratory Deposition 33
3.5.2 Skin Penetration 34
3.6 Implications for Physical Risks 35
3.6.1 Introduction 35
3.6.2 Current Status 35
3.6.3 Conclusions 36
3.7 Summary 37
References 37
4 Routes of Exposure for Engineered Nanoparticles 39
4.1 Introduction 39
4.2 Engineered Nanoparticle Exposure through Inhalation 40
4.2.1 Human Respiratory System 40
4.2.2 Particle Deposition in the Respiratory System 43
4.3 Engineered Nanoparticle Exposure Through Dermal Contact 46
4.4 Engineered Nanoparticle Exposure Through Ingestion 48
4.5 T ranslocation of Nanoparticles from the Lung 48
4.6 Summary 49
References 49
5 Current Knowledge on the Toxicity of Nanoparticles 51
5.1 Introduction 51
5.2 The Toxicity of Industrial Nanoparticles 52
5.3 Nanoparticle Toxicity: General Concepts 53
5.3.1 Routes of Exposure 53
5.3.2 In Vivo and In Vitro Testing 53
5.4 Carbon Nanotubes 54
5.5 Fullerenes 56
5.6 Quantum Dots 58
5.7 Metal?]Based Nanoparticles 58
5.8 Summary 59
References 60
6 Sources of Exposure 63
6.1 Overview of Occupational Exposures 63
6.2 Occupational Exposures in Research Facilities 64
6.3 Occupational Exposures in Manufacturing Facilities 65
6.4 Exposure Potential for ENPs in Different Physical States 66
6.4.1 Dry Powders 66
6.4.2 Liquid Suspensions 69
6.4.3 ENPs Bound to a Solid 72
6.5 Environmental Exposures to Engineered Nanoparticles 73
6.5.1 Environmental Releases 73
6.5.2 Exposures Through a Product's Life Cycle 74
References 76
7 Evaluation of Exposures to Engineered Nanoparticles 79
7.1 Current Knowledge Concerning Exposure to Engineered
Nanoparticles 79
7.2 Exposure to Engineered Nanoparticles by Inhalation 81
7.2.1 Mass Sampling 81
7.2.2 Surface Area Measurement 83
7.2.3 Number Concentration Measurement 84
7.2.4 Conversion between Number, Surface Area, and Mass Concentrations 98
7.2.5 Particle Characterization 99
7.3 Dermal Exposures to Engineered Nanoparticles 102
7.4 Evaluation of Exposures in Aquatic Environments 104
7.4.1 Introduction 104
7.4.2 Sample Collection 104
7.4.3 Measurement Methods 105
7.4.4 Exposure Characterization in Aquatic Environments 107
References 108
8 Exposure Characterization 112
8.1 Exposure Characterization Steps 113
8.1.1 Standard Occupational Hygiene Models 113
8.1.2 Exposure Characterization for Nanomaterials 113
8.2 Exposure Measurement Strategies 120
8.2.1 Single?]Location Measurement 120
8.2.2 Multiple?]Location Measurement 120
8.2.3 Near?]Field and Far?]Field Measurement 121
8.2.4 Dynamic Personal Sampling Measurement 122
8.3 Data Analysis and Interpretation 123
8.4 Statistical Analysis of Data 124
8.4.1 Pearson Correlation 124
8.4.2 T?]test 125
8.5 Practical Aspects of Aerosol Sampling and Microscopy Techniques 127
8.5.1 Aerosol Sampling Techniques 127
8.5.2 Microscopy Techniques 128
8.6 Practical Applications and Limitations 128
8.6.1 Particle Losses 128
8.6.2 Concentration Measurement versus Particle Samples 130
8.7 Typical Production Processes 130
8.7.1 Synthesis of Carbon Nanotubes 130
8.7.2 Composite Manufacture 131
8.8 Case Study: Manual Handling of Nanoparticles 133
8.8.1 Materials and Conditions 134
8.8.2 Particle Handling 134
8.8.3 Measurements 134
8.8.4 Aerosol Particle Characterization 136
8.8.5 Results 137
8.8.6 Discussion 144
8.8.7 The Challenge and Brainstorming 145
8.8.8 Study Questions 145
8.9 Case Study: Synthesis of Carbon Nanotubes 146
8.9.1 Materials and Synthesis 146
8.9.2 Measurement 147
8.9.3 Results 148
8.9.4 The Challenge and Brainstorming 155
8.9.5 Study Questions 156
8.10 Case Study: Exposure From Twin Screw Extrusion Compounding 156
8.10.1 Materials and Production Process 157
8.10.2 Measurements 158
8.10.3 Results 158
8.10.4 The Challenge and Brainstorming 162
8.10.5 Study Questions 163
References 164
9 Control of Occupational Exposures to Engineered Nanoparticles 166
9.1 Control of Airborne Exposures 166
9.1.1 General 166
9.1.2 Laboratory Fume Hoods 169
9.1.3 Alternatives to Conventional Fume Hoods 178
9.2 Control of Dermal Exposures 181
9.2.1 General 181
9.2.2 Clothing and Personal Protective Equipment 181
9.3 Administrative Controls and Good Work Practices 182
9.3.1 Housekeeping 183
9.3.2 Work Practices 183
9.3.3 Worker Training 183
9.4 Respiratory Protection 185
9.4.1 General Considerations 185
9.4.2 Respirator Designs 186
9.5 Case Study: Comparison of the Performance of Various Fume Hoods 195
9.5.1 Materials and Hoods 195
9.5.2 Measurements 198
9.5.3 Results 198
9.5.4 The Challenge and Brainstorming 206
9.5.5 Study Questions 206
9.6 Case Study: Performance of Nontraditional Fume Hoods 206
9.6.1 Materials and Hoods 207
9.6.2 Measurements 207
9.6.3 Results 207
9.6.4 The Challenge and Brainstorming 214
9.6.5 Study Questions 215
References 215
10 Control of Environmental Exposures 219
10.1 Control of Air Emissions 219
10.1.1 Factors Affecting Air Cleaner Performance 220
10.1.2 Categories of Air Cleaning Devices 220
10.2 Control of Water Emissions 228
10.3 Nanoparticles in Solid Waste 232
10.4 Control of Exposures Throughout a Product's Life Cycle 233
10.5 Uncertainties and Needed Research 234
10.6 Case Study-Filtration Control 234
10.6.1 Materials and Process 235
10.6.2 The Challenge and Brainstorming 246
10.6.3 Study Questions 246
References 247
11 The Regulatory Environment for Engineered Nanomaterials 249
11.1 Occupational Health Regulations 250
11.1.1 Occupational Health Regulations in the European Union 250
11.1.2 US Occupational Health Regulations 252
11.1.3 Summary: Occupational Exposure Regulations 256
11.2 Environmental Regulations 257
11.2.1 US Environmental Regulations 257
11.2.2 Environmental Regulations in the European Union 261
11.3 Comparison of Nanotechnology Regulation under TSCA and REACH 263
11.3.1 The Precautionary Principle and the Burden of Proof 263
11.3.2 Differences in Handling New and Existing Chemicals 264
11.3.3 Volume?]Based Thresholds and Exemptions 265
11.4 Private Law 265
11.5 Conclusions 266
References 266
12 Future Directions in Engineered Nanoparticle Health and Safety 269
12.1 Where we are Today 269
12.1.1 Research Efforts in the United States 269
12.1.2 Research Efforts in Europe 273
12.1.3 Progress toward Research Goals 273
12.2 Human Health Effects Studies 276
12.3 Exposure Assessment 276
12.3.1 Future Needs in Exposure Assessment Techniques 276
12.3.2 The Development of Occupational Exposure Limits 278
12.4 Optimal Approaches to Control Exposures 279
12.4.1 Engineering Control of Occupational Exposures 279
12.4.2 Control Banding 280
12.4.3 Respiratory Protection 280
12.4.4 Safe Work Practices 281
12.4.5 Air Pollution Control of Nanoparticles 281
12.4.6 Water Pollution Control of Nanoparticles 281
12.4.7 Nanoparticles in Waste Streams 282
12.5 The Future of Regulation 282
12.6 Conclusions 282
References 283
Index 285
1
INTRODUCTION
1.1 WHY A BOOK ON NANOTECHNOLOGY HEALTH AND SAFETY?
Asbestos, once hailed as a "miracle" material for its insulating properties, has been an occupational and environmental health disaster. Many thousands of people, mostly workers but also members of the general population, have developed serious illnesses, including asbestosis, lung and colon cancer, and mesothelioma, and many have died as a result of their exposure. The reader may ask, "why start a book on nanoparticle health and safety with a discussion of asbestos, which most definitely is not a nanoparticle?" The answer leads us to our purpose in writing this book, at this time.
The authors have been to many nanoparticle health and safety meetings over the past several years. A constant theme at those meetings, both in the formal presentations and also in the informal discussions among the scientists in attendance, is "we have to prevent the next asbestos." Starting in the 1920s, exposure to asbestos from its mining, milling, and incorporation into products such as textiles was associated with severe lung disease that came to be called asbestosis; other hazards from asbestos exposure, such as lung cancer and mesothelioma, were not discovered until years later. In addition, the risks to workers using products containing asbestos and to individuals in the general population took some time to be appreciated.
Today, engineered nanoparticles represent a miracle new material (actually, a range of materials, as discussed later), just as asbestos was a miracle new material early in the last century. And, as with asbestos, there are early indications that there may be adverse health effects associated with at least some of these new materials; in fact, carbon nanotubes may have similar health effects as asbestos (see Section 5.4). The extent of the risk to workers and the general public is not known at this time. The answer to the question posed above leads to another question, that is, have we learned our lessons from asbestos and other similar occupational and environmental health disasters, so that we can develop the exciting new field of nanotechnology while protecting the health of workers and the general population, and prevent any adverse effects to the environment?
We believe that the answer to this question is "yes." The nanotechnology industry is still in its infancy, meaning that proactive steps can be taken to further its development in a safe, sustainable manner. Andrew Maynard and colleagues summarized the risks and opportunities in their 2006 Nature article as follows (Maynard et al., 2006):
The spectre of possible harm-whether real or imagined-is threatening to slow the development of nanotechnology unless sound, independent and authoritative information is developed on what the risks are, and how to avoid them. In what may be unprecedented pre-emptive action in the face of a new technology, governments, industries and research organizations around the world are beginning to address how the benefits of emerging nanotechnologies can be realized while minimizing potential risks.
This book has been written in an attempt to contribute to the minimizing of the potential risks of nanotechnology. In occupational and environmental health, we have a very simple model that guides our work, that is, exposure to a material or physical agent may lead to an adverse health effect in the exposed population. Although we have included a brief review of the current state of nanoparticle toxicology in Chapter 5, in order to put the need for exposure assessment and control in their proper context, this is a book about the exposure side of our model. In considering exposure, the two most important aspects are to evaluate the magnitude of the exposure and, in those cases where the exposure is judged to be excessive, take steps to control the exposure. These are the two major topics covered in this book.
It is important to emphasize that this book pays relatively little attention to the judgment step just mentioned. In most cases, environmental health professionals make the decision as to whether a measured exposure is excessive by comparison to standards, such as published occupational exposure limits. These standards, in turn, are established based on results of toxicology and epidemiology studies that quantify the risk of exposure for a certain material. The difficulty with engineered nanomaterials, as discussed in Chapter 5, is that at this time there is insufficient information to set such standards. The consensus among occupational and environmental health scientists studying engineered nanoparticles is that until sufficient toxicology and epidemiology information is available for any given material, the precautionary approach must be followed in order to minimize the risk to workers, the general public, and the environment. This concept is further discussed in Section 1.4.
In the occupational environment, exposure assessment and control are the purview of industrial hygiene or, more widely used today, occupational hygiene; regarding the general environment, the equivalent field might be called "environmental hygiene," although this term is not widely used. In any case, the subject of this book is the current state of knowledge concerning the occupational and environmental hygiene aspects of nanotechnology. It is fair to say, however, that most of the focus in on occupational hygiene, and there are two reasons for this. First is the fact that the authors are occupational hygienists, so most of our experience and expertise, such as it is, falls within this field. The second reason is perhaps more important, which is that in a new and growing industry such as nanotechnology, most of the significant exposures will be to those workers who are doing research with and manufacturing nanomaterials. Consequently, most of the concerns and attention of the research community to date has been focused on nanotechnology workers, rather than the general public. As nanotechnology-enabled products become more widely used, we can expect more of the focus to shift to their environmental impact.
1.2 SOME SCENARIOS
Some scenarios may help to put the need for nanoparticle health and safety in its proper context. These scenarios are all fictional but based more or less on real situations now being encountered in the nanotechnology field.
- A small company specializes in the manufacture of relatively small quantities of high-quality powders in the micrometer size range for specialized niche markets. The company is too small to employ a person with health and safety training. The company president wishes to modify their production equipment to produce powders in the nanometer size range but has read of general concerns about the safety of nanoparticles. He asks his production manager to find out whether manufacturing nanopowders will present any new hazards to their workers.
- A university laboratory is conducting research on the use of carbon nanotubes (CNTs) as a new form of digital storage device. As part of this research, the laboratory technician must transfer small quantities of dry bulk CNTs from a 2 L jar to a beaker, weigh them on a balance, and disperse them in a solvent. These steps are now done on a laboratory bench, and the technician is concerned that she may be breathing in some CNTs that are being released from the powder.
- A plastics manufacturing company has recently begun pilot-scale testing of a new composite material, consisting of polyester reinforced with 2% by mass of alumina nanoparticles. The composite is produced in a twin-screw extruder. The polymer pellets are dumped into one hopper and the nanoalumina in another; they are fed by gravity into the throat of the extruder, where the pellets are melted by high temperature and pressure and mixed with the nanoalumina to form the nanocomposite. The extruder operator has noticed some of the alumina powder on various work surfaces around the hopper and is concerned that this may not be completely safe.
- A company uses the nanocomposite material produced above to make tennis racket frames. The pellets are fed into an injection molding machine which produces the tennis racket shape. However, extraneous material has to be cut off the frame with a saw and the frame must be sanded smooth. The plant occupational hygienist is concerned that these operations may release nanoparticles. In addition, the tennis racket manufacturer labels the product "contains nanomaterials for added strength" and is receiving anxious questions from consumers on their web site.
- An occupational hygienist working in the health and safety office at a large research university conducted a university-wide survey which found that more than 50 laboratories across the university claimed to be doing research with some type of nanoparticle. Many of the respondents stated that they did not know what practices should be followed when working with nanoparticles; the occupational hygienist decided that the university needed a policy on good work practices but he did not know how he would gather the information to develop such a policy.
- A research laboratory recently purchased a chemical vapor deposition furnace for making CNTs. While the furnace is a closed system during CNT production, at the end of a run, it must be opened and the CNT material must be scraped from the furnace walls into a drum. This process creates visible dust, which has caused the operator some anxiety.
- A research laboratory was...
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