1. Nanotechnology and Health
Todd Irick, MSc., CIH
Occupational Hygienist
Left – rigid ZnO nanowires on polymeric microspheres
 low-voltage and short-wavelength optoelectronics, photonics, actuators, and solar cells.
Right – very tiny droplet of indium (blue) with silicon nano-strands (green) growing around it.
Negative electrodes in lithium-ion batteries

2. silicon nano strands (green) from an indium droplet (blue)

3. Presentation Outline Nanomaterials Nanotechnology Nano Products
Nano Scale
Nano Health
Nano Controls
Nano Resources

4. Nanomaterials
Natural Volcanoes, forest fire, ocean spray, viruses and biomolecules
Incidental Combustion engines, incinerators, jet engines, welding fumes
Engineered Nano tubes, spheres and wires, metal oxides and polymers

5. Nanotechnology Nanotechnology: ‘molecular manufacturing’
Manipulation of matter at atomic, molecular and macromolecular scale to create new structures, materials and devices
1-100 nanometer (nm) scale length
Core: synthesis of engineered nanoparticles
‘Revolution’ in science
Discovery of nanoscale behaviour of elements and chemicals
Quantum size effect: “electronic properties of solids are altered with great reductions in particle size”
Trillion dollar industry
Introduction to Nanotechnology
So what exactly is nanotechnology?
Nanotechnology, often referred to as molecular manufacturing, involves the manipulation of matter at an atomic, molecular and macromolecular scale to create new structures, materials and devices (CRN, 2008; Castranova, 2011). The term itself remains loosely defined; however, it generally refers to engineered structures, materials, devices and systems with a scale length between nanometers (CDC, 2011). A nanometer is one billionth of a meter, roughly equivalent to the width of three of four atoms. For comparison, the average human hair is approximately 25,000 nanometers wide (CRN, 2008).
The fundamental basis of nanotechnology starts with the synthesis of engineered nanoparticles, particles with one dimension measuring less than 100 nanometer (Castranova, 2011). From there, nanomaterials of various shapes and sizes can be manufactured.
Ex: Nanofibers  nanotubes (hollow) / nanorods (solid)
Nanofibers, for example, can be engineered to form long hollow nanotubes or long solid nanorods (ACOEM, 2011).

6. The Nano Scale
Taken from:
One nanometer (nm) is one billionth (10-9), of a meter or one billion nanometers equals one meter
One million times smaller than the tennis ball
Nanotechnology has been considered a “revolution” in science because of the revolutionary discovery of the way elements and chemicals behave on the nanoscale compared to the traditional understanding of their properties on a larger scale.
Due to their small size, materials at the nanoscale begin to exhibit unique physical and chemical (physicochemical) properties that are distinctly different from those of fine-sized particles of identical chemical composition (CDC, 2011; Castranova, 2011). This phenomenon is known as the “quantum size effect”, where the “electronic properties of solids are altered with great reductions in particle size” (Rodgers, 2006). What does this mean?
Nanoparticles have much higher ratio of surface area (SA) to volume (V) (aspect ratio) that result in changes in mechanical, thermal and catalytic properties.
Gold and silver, for example, remain inert in daily life; BUT at nanoscale, gold becomes combustible while silver takes on anti-microbial properties (PMESEIC, 2005; Sudarenkob, 2010).
At a cellular level, changes in surface atoms also affect diffusion reactions such as ion transport, and catalytic interactions with biomaterials (Rodgers, 2006).
So thiis revolutionary discovery of nanoscale properties has opened a scientific gateway with a projected growth into a trillion dollar industry, transforming the development of a myriad of consumer products, medicine, as well as thousands of other industrial processes (Sudarenkov, 2010).

7. Uses of Nanotechnology
Cosmetics
Recreation
Household
Engineering
Textile
Food & Beverages
Chemical industry
Auto industry
Construction
Pharmaceutical
Energy
Electronics

8. Applications of Nanotechnology
Use in wide variety of novel applications
Materials: Nano powders
Medical & Biological: smart drugs, imaging, disease detection and treatment
Energy & Electronics: computing ability; clean, efficient energy generation
Pollution: prevention and treatment processes, air and water quality
Nano membrane filtration systems
Applications of Nanotechnology
Impacts of Nanotechnology
Materials: Nano powders
Nano powders are the building blocks of nanomaterials, and the properties of Nano powders allow it to be effectively applied in the construction of new and improved materials. Plastics created using Nano powders can retain its transparency but behave like ceramics or metals by taking on properties such as conductivity, abrasion resistance or UV protection
Medical & Biological
Currently, “nanomedicine” proposes the potential of diagnosis and treatment at a molecular level, detecting and treating presymptomatic diseases, rebuilding neurons in neurodegenerative diseases (Alzheimer’s and Parkinson’s disease, for example) and bone regeneration
Pollution
New catalysts with improved chemical reactions can be designed using nanotechnology for environmental remediation, such as cleaning up car exhaust and removal of toxins from the environment (PMESEIC, 2005).
Nanotechnology has also been used in a wide variety of exciting, novel applications.
What does this mean for workers who handle these nanomaterials? Are some more likely to be exposed?

9. Nanoparticles: many shapes, many chemistries
Not all nanoparticles are the same!
Unique physicochemical properties of nanoparticles produce unique bioactivity
Understanding the relationship between nanoparticle properties & bioactivity is important for predicting relative pathogenicity
Physicochemical properties
Particle Size
Particle Shape
Oxidant Generation Capacity
Surface Functionalization
Rate of Dissolution
Nanoparticles: Biophysicochemical Properties
Engineered nanoparticles are created with specific sizes, shapes, surface features and chemistry. Their unique physicochemical properties are also likely to produce unique bioactivity (Rodgers, 2006). From a toxicological standpoint, understanding the relationship between nanoparticle properties and bioactivity serves as an essential tool for the prediction of relative pathogenicity of a given nanoparticle with specific properties. The following physicochemical properties are believed to be important determinants of biological response: particle size, particle shape, oxidant generation capacity and rate of dissolution.
Particle size: This appears to be a major factor in the biological response to nanoparticles
Particle shape: Nanoparticles with the high aspect ratio of long, thin nanotubes are significantly more toxic or induce a greater inflammatory response.
Both particle size and shape affect the ability of the particle to penetrate membranes and enter tissues
Oxidant generation capacity: Some nanoparticles have a greater ability to generate Reactive Oxygen Species (ROS) and cause oxidative stress on biological systems.
Surface functionalization: The biophysicochemical interaction of nanoparticle surfaces with biological systems differs among nanoparticles.
Rate of dissolution: The higher the rate of dissolution of a nanoparticle, the greater rate of translocation to systemic organs and clearance from the body (Castranova, 2011).
Aerosolization of nanoparticles during energetic processes, such as vortexing, weighing, sonication, mixing and blending, is extremely likely due to the small size and low density. Thus, worker exposure via inhalation is expected during production, use and/or disposal of nanoparticles (Castranova, 2011; Schulte et al, 2008).

10. Nanotube Carbon Nanotube (CNT)
Carbon nanotubes are tiny strips of graphite sheets rolled into tubes a few nanometers in diameter and up to hundreds of micrometers (microns) long.
considered to be the building blocks of future nanoscale electronic and mechanical devices.

11. Nano Tube Apps
Structural elements in bridges, buildings, towers, and cables
Open-ended straws for chemical probing and cellular injection
Nano electronics including batteries, capacitors, and diodes
Microelectronic heat-sinks and insulation due to high thermal conductivity
Nanoscale gears and mechanical components
Electron guns for flat-panel displays

12. Nano Health Concerns
Airborne nanoparticles can be inhaled and deposit in the respiratory tract
Inhaled nanoparticles may enter the bloodstream and translocated to other organs
Certain nanomaterials can cause rapid and persistent pulmonary fibrosis and cardiovascular dysfunction
Can migrate along the olfactory nerve into the brain

13. Nano Health Concerns
Multi-walled carbon nanotubes (MWCNT-7) and TiO2 nanoparticles classified by IARC (International Agency for Research on Cancer) as possibly carcinogenic to humans (2B)
Some studies have shown similar biological effects when compared with asbestos fibre exposures in the lungs of test animals.

14. Nano Human Tissue Health Effects
increased oxidative stress, inflammation, DNA mutation, mitochondria and cell nucleus damage, & cell death
Non/slowly-degradable  accumulate in organs
Overload phagocytes
Move into lung tissues  chronic breathing problems
Interaction with biological processes
Production of reactive oxygen species (ROS), free radicals
Testing on human tissues and cell cultures has shown that certain nanomaterials are toxic. There was an increase in oxidative stress, and inflammatory cytokine production. Due to their small size they were taken up by cell mitochondria and nucleus. This allowed for structural damage, DNA mutation, and even resulting cell death. (3)
Nanoparticles have the ability to access any where in the body. An accumulation of particles in organs could have negative consequences. (10)
If someone received a large enough dose of nanoparticles, they could overload the body’s phagocytes (cells that ingest and destroy foreign matter). These cells would no longer be able to effectively protect against other pathogens, inflammation would occur, and one’s body’s defenses would weaken. (3)
Andrew Maynard says “certain nanoparticles move easily into sensitive lung tissues after inhalation, and cause damage that can lead to chronic breathing problems. (3)
Due to the large surface are of nanoparticles they will be absorbed onto the surface of macromolecules when exposed to tissue and fluids. Being attached on the outer layer of these cells can disrupt the cells communication mechanisms such as affecting the enzyme or protein receptors, gated ion channels, and much more. (10).
ROS and free radical production is one of the primary mechanisms of nanoparticle toxicity; it may result in oxidative stress, inflammation, and consequent damage to proteins, membranes and DNA (3)
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15. Nano Animal Health Effects
- Rats inhaling nanoparticles  found in brain & lungs
- Inflammation & stress response
- Induce skin aging (oxidative stress)
- Mice + Nano titanium dioxide = DNA & chromosome damage
- Mice inhaling silver nanofibers  capsular in lungs causing inflammation (precursor for cancer?)
- Brain & liver damage to fish from fullerenes - Water fleas killed from fullerenes - Soft-bodied organisms have high accumulation of nanoparticles – brain, liver, gills, testis, intestine, bloodstream
Animal
Rats that breathed in nanoparticles. Researchers discovered the particles settled into the brains and lungs of these rats, which caused significant increase in inflammation and stress responses. Another interesting finding is that these nanoparticles induced skin aging though oxidative stress. (13)
UCLA’s School of Public Health: lab mice consumed nanotitanium dioxide showed significantly higher rates of DNA and chromosomal damage. These rates were to a degree “linked to all the big killers of man, namely cancer, heart disease, neurological disease and aging”.
Toxicology Sciences: experiments with mice and nanofibers found that fibers >5nm were capsuled in mice lungs causing inflammation. The inflammatory response is a characteristic precursor for mesothelioma.
environmental
Nanoparticles are being released into the air and water during production, waste byproduct of production, disposal of products containing nanoparticles, and accumulate in soil, plants, and water. (10) So what happens once these nanoparticles accumulate in the environment?
Eva Oberdörster, Ph.D. (2004), found brain and liver damage in fish exposed to fullerenes for just 48hours at 0.5ppm. (Similar to the levels of other pollutants found in the bay).
In a similar test, fullerenes killed the majority of water fleas – part of the marine food chain (14).
((A fullerene is any molecule composed entirely of carbon, in the form of a hollow sphere, ellipsoid or tube. Carbon nanotubes, buckyballs, buckytubes)). Wikipedia – Fullerene.
National Institute of Environmental Studies (Japan): Researched the effects of nanoparticles on soft-bodied organisms. They found that soft-bodies organisms (medaka or Japanese rice fish) accumulated high concentrations and were found all throughout their bodies. Their eggs also had nanoparticles in the yolk. (15)
Has anyone
A nanoparticles used in socks to reduce foot odor are being released in the wash, a study reports. The silver nanoparticles used in socks are flushed into waste water. The nanoparticles have been found to be bacteriostatic – prevents the multiplying of bacteria without destroying them. These bacteria are found in natural ecosystems, farms, and waste treatment processes. (1)
Next time you’re at Wal-mart to pick up a pair of socks,
Conner
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16. Nano Exposures

17. Nano Exposure Assessment **Breathing Zone/Area/Background**
Nanomaterials with OELs (occupational exposure limits) NIOSH REL:
300 ug/m3 for nano TiO2
Sample for respirable dust by NIOSH 0600 (gravimetric)
Collect duplicate sample for electron microscopy
1 ug/m3 for CNT and CNF
Sample for respirable elemental carbon by NIOSH 5040 (diesel particulate)
Materials with no OEL:
NIOSH 7402 (TEM) and 7300 (Elements by ICP)
**Breathing Zone/Area/Background**

18. Nano Exposure Assessment
Direct Reading Instruments:
Condensation Particle Counter (CPC)
TSI CPC 3007 – 10 nm to 1000 nm (1 um)
Optical Particle Counter (OPC)
TSI OPS 3330 – 300 nm to 10,000 nm (10um)
TSI DustTrak DRX – 1,2.5, 4.0 and 10.0 um

19. Nano Exposure Assessment
Challenges:
Need for portability and cost effective evaluations
Variability of incidental background nanoparticles
No prescribed counting convention for microscopy (though many are offering suggestions
Wipe sampling may also be useful (followed by elemental analysis and microscopy (for nanoparticle and catalysts)

20. Working with Engineered Nanoparticles
Certain workplace tasks may increase risk of exposure:
Nanoparticles in liquid media w/o adequate PPE (skin)
Nanomaterials in liquid involving agitation (droplets)
Mechanical disruption of nanomaterials (aerosolization)
Handling nanostructured powders (aerosolization)
Nanoparticles generation in gaseous phase in non-enclosed systems (aerosolization)
Maintenance on equipment / processes; cleaning spills or waste materials
Cleaning dust collection systems (skin & inhalation)
Hazard Identification: Is there a reason to believe this could be harmful?
Exposure Assessment: Will there be exposure in real-world conditions?
Risk Characterization: Is substance hazardous and will there be exposure?
Risk Management: Develop procedures to minimize exposures.
List of certain workplace tasks may increase risk of exposure:
Nanoparticles in liquid media w/o adequate PPE ( increase risk of skin exposure)
Nanomaterials in liquid involving agitation (pour, mixing processes may increase likelihood forming respirable/inhalable droplets)
Following tasks increase likelihood of aerosol release and subsequent worker exposure in workplace:
Mechanical disruption of nanomaterials (machining, sanding, drilling)
Nanoparticles generation in gaseous phase in non-enclosed systems
Handling nanostructured powders
Maintenance on equipment / processes, cleaning up spills or waste materials
Cleaning dust collection systems used to capture nanoparticles can pose potential for both skin and inhalation exposure

21. Nano Control Measures
Engineering control (LEV, Class III Biological Safety Cabinet, HEPA filter with greater than 99.97% efficiency for most nano particles enclosures procedures
Elimination (for highly toxic substances)
Substitution (use of liquid instead of powders)
Administrative control (Worker Awareness, Purchasing Process, wet processes, sticky mats/gowning)
Personal Protective Equipment (PAPR with HEPA, coveralls for skin protection)
Control Banding

22. Nano Control Banding + = www.controlbanding.net
- Qualitative or semi-quantitative risk evaluation technique
- Used to provide easy to understand and practical approach to controlling exposures
- Consists of the following:
Health Hazards
(Risk Bands)
Exposure Potential
(Exposure Bands) + =
Control Band

23. Nanotechnology and Health Network (NHN)
Networking group that gathers and shares information and facilitates knowledge transfer on the topic of nanotechnology and health to workers and workplaces in Ontario 
Intent is to ensure sufficient knowledge is available to establish and maintain adequate controls for potential exposures where nanomaterials are present and handled/manipulated
The group is a mix of technical experts (e.g. CSA/ISO group members, researchers, regulators etc.) and also representatives that are be directly associated with the workplace operations (unions, health and safety representatives, facility management, etc.)

24. NHN Representation Labour
Unifor, Public Service Alliance of Canada, Canadian Union of Public Servants, Canadian Association of University Teachers, Canadian Labour Congress, District Labour Councils
Research/Regulatory
Health Canada, National Research Council, Natural Resources Canada, Occupational Cancer Research Centre, Canadian Centre for Occupational Health and Safety
Prevention
Workplace Safety and Prevention Services, Infrastructure Health and Safety Association, Public Service Health and Safety Association, Workplace Safety North, OHCOW

25. NHN Priorities
Identify methods for identification of specific industries, organizations and operations that produce/use/manipulate nanomaterials
Strategy for prioritizing identified groups (who are most vulnerable?)
Strategy for communicating prioritized groups to discuss/evaluate current practices and control measures
Establishing a process for evaluation and reporting on findings

26. Identification of Facilities/Operations Involved with Nanotechnology
– list of organizations involved with the research, development and manufacture of nanomaterials (subset of Canadian facilities available)
Health Canada Survey
The Nanotechnology Products Database (NPD) lists 6934 products that meet the ISO definitions of nanotechnology and nanotechnology products, from 1361 companies in 52 countries (
The Consumer Products Inventory (Nanotechproject.org, PEN) lists 1,800+ manufacturer-identified nanotechnology-based consumer products introduced into the market(
The Danish Nano database lists 3025 products (

27. Development of On-Line Awareness Tools
CCOHS 20-minute on-line awareness course (free to participants); infographic/podcasts
Outline:
What is nanotechnology?
What are nanomaterials and how are they made?
Are nanomaterials a health hazard?
What are areas or activities where exposure can occur?
What should be done to control or eliminate worker exposure to nanomaterials?
What is the role of the health and safety committee?

28. February 2018 NIOSH Nano Publications

29. NIOSH Poster a Worker Guide to Prevent Nano Exposures

30. CSA Z
Nanotechnologies — Exposure control program for engineered nanomaterials in occupational settings
1 Scope
2 Reference publications
3 Definitions and abbreviations
4 Establishment of a nanomaterial exposure prevention and control program
Annexes
A (informative) — Nanomaterials: Description and manufacturing processes
B (informative) — Nanomaterials: Characterization and identification of hazards
C (informative) — Nanomaterials: Framework for exposure assessment to nanomaterials
D(informative) — Nanomaterials: Hazard and risk assessment methodologies
E (informative) — Nanomaterials: Preventive and protective measures
Figures
1 — Overview of an occupational health and safety management system
2 — Process flow chart

31. Employee Services and Development Canada (ESDC
ENGINEERED NANOPARTICLES
Health and Safety Considerations
1. Introduction
2. Definitions
3. Routes of Entry and Health Effects
3.1 Inhalation Exposure to Engineered Nanoparticles
3.2 Dermal and Eye Exposure to Engineered Nanoparticles
4. Existing Occupational Exposure Limits (OELs)
5. Potential for Employee Exposure in Federally Regulated Workplaces
6. Methods of Exposure Evaluation
6.1 Risk Assessment and Risk Management
6.2 Challenges in the Sampling Methodology for Nanoparticles
6.3 Inhalation Exposure Assessment
6.4 Dermal Exposure Assessment
7. Control Measures
7.1 Control Banding
8. Summary and Future Directions

32. Summary Identification and awareness in workplaces is required
Although health effects are not fully known, enough to support the precautionary principle
Ensure products and processes are identified, awareness and training in place
Information on recommended control measures is established (wide variety of resources available) based on exposure assessment and control banding
Conner

33. Resources http://www.ccohs.ca/oshanswers/chemicals/nanotechnology.html