8-Hour Training Course
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Transcript of 8-Hour Training Course
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MODULE 3: ASSESSING EXPOSURE TO NANOMATERIALS IN THE WORKPLACEINTRODUCTION TO NANOMATERIALS AND OCCUPATIONAL HEALTH
MODULE CREATED BY BRUCE LIPPY, PH.D., CIH, CSP
8-Hour Training Course
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This material was produced under grant number SH-21008-10-60-F-48 from the Occupational Safety and Health Administration, U.S. Department of Labor. It does not necessarily reflect the views or policies of the U.S. Department of Labor, nor does mention of trade names, commercial products, or organizations imply endorsement by the U.S. Government. 1-2
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Eight-Hour Training CourseModule 1
Introduction to Nanotechnology and Nanomaterials
Module 2
What Workers Need to Know about Nanomaterial Toxicology and Environmental Impacts
Module 3
Assessing Exposure to Nanomaterials in the Workplace
Module 4 Controlling Exposure to Nanomaterials
LUNCH (on your own)Module 5
Risk Management Approaches for Nanomaterial Workplaces
Module 6
Regulations and Standards Relevant to Nanomaterial Workplaces
Module 7 Tools and Resources for Further Study
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Lesson OverviewPurposeTo provide nanoworkers with a basic awareness of sampling and analytical approaches being used for nanoparticles, the limitations of the results and the viability of alternative hazard assessment methods.
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Lesson OverviewTopics
1. Methods currently being used to sample and analyze nanoparticles
2. Value of standard IH procedures and equipment for nanoparticle sampling
3. Use and limitation of sampling data4. Status of NIOSH, OSHA and
international occupational exposure limits
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Learning ObjectivesAt the end of this module you will be able to Compare and contrast standard IH sampling
and analytical methods with those used for nanoparticles
Describe the equipment used for nanoparticle sampling and analysis
Evaluate sampling results and compare them to recommended occupational exposure limits
Discuss the limitations of nanoparticle sampling and analysis
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Special thanks to NIOSH for their kind assistance and particularly to
Charles L. Geraci, Jr, Ph.D., CIHCoordinator,
Nanotechnology Research Center for the generous use of his slides
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“In the long term, nanotechnology will demand a revolutionary re-thinking of occupational health and safety.” John Howard, MD, NIOSH
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“It is likely that no single metric will completely characterize exposure.”
Linda Abbott and Andrew Maynard, Risk Analysis, 2010
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Let’s start with an exposure pathway model (Mulhausen and Damiano)
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Monitoring is classified as personal, area or biological
personal area biological
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Area monitoring determines concentration at a location over time
Photo courtesy NIOSH3-12
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Wipe sampling is another form of area monitoring
Photo courtesy NIOSH3-13
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Biological monitoring measures contaminants, metabolites or enzymes in the blood, urine or exhaled breath
What does NIOSH recommend for nanoworkers?
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Group exercise: What could we sample?
Typical nanostructure geometries. Illustration courtesy of the Opensource Handbook of Nanoscience and Nanotechnology 3-15
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What should we sample?
Metric QualificationMass Not always relevant
Surface area Better for low solubility particles
Surface chemistry Tox studies show effects
Particle number Within ranges Particle size Implicated in
particles translocating
Particle shape Fiber-like, spheres, mats 3-16
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Can we use standard industrial hygiene methods?
Respirable dust samplingPre-weighed cassettes for
gravimetric sampling
Yes!
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Active sampling uses pumps to pull contaminated air through appropriate media
Photo courtesy SKC3-18
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Personal pumps are hung on a worker’s belt with the media in the breathing zone
Photo courtesy Lawrence Berkeley National LaboratoryImage courtesy Wikimedia 3-19
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Most exposure limits are based on 8 hour time-weighted averages
hours1 2 3 4 5 6 7 8
exposurelimit
IncreasingExposures
This includes NIOSH’s recommendation for carbon nanotubes
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Pumps must be calibrated before and after sampling
Photo courtesy SKC, Inc. 3-21
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Particles are classified by their penetration. Where do nanoparticles fit?
• 100 μm diameter
Inhalable
• 10 μm diameterThoracic
• 4 μm diameter
Respirable
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Nanoparticles Have Almost No Mass
Edge of a single 10 micron particle
Relative size of 10 nanometer particles for comparison
A 10 mm particle weighs the same as one billion 10 nm particles
Courtesy Larry Gibbs3-23
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Standard 37-mm filter cassette
Large particles bias mass measurements
If you’re carrying a grocery bag full of cantaloupes, you’re not going to notice a handful of grapes
Courtesy L. Gibbs3-24
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Examples of Potential Exposures
Photos courtesy of M. Methner, NIOSH 3-25
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NIOSH recommends a graded approach to measurement
Step 4: use less portable equipmentMore sensitive aerosol sizing equipment
Step 3: collect personal samplesFilter-based samples for EM and elemental analysis
Step 2: collect samples at sourceFilter based samples for EM and elemental analysis
Step 1: screen area and processParticle counters and simple size analyzers
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NIOSH’s Nanoparticle Emission Assessment Technique (NEAT)*
Initial assessment is semi-quantitative comparing particle numbers at sources to background
* Nifty government acronym
Extended investigation using less portable, more expensive analyzers
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Focused on determining leakage from operations, not personal exposures
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NEAT correlates simple and complex measurements
Starting Point
TEM and Elemental AnalysisParticle Counters and
Size Analyzers3-28
More complex
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The NEAT protocol has some difficultiesTEM sample can be overloaded (as
we learned at WTC)Nominally collect at 7 lpm for
duration of task (15-30 minutes)
MWCNTs
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NEAT instrumentationCondensation Particle Counter (10 -1000nm range, p/cc)
Optical Particle Counter (300-10,000nm, p/l)Reports 3 particle
sizesTSI Aerotrak 9303
TSI 3700 CPC
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Kanomax Model 3800 Condensation Particle Counter
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Condensation particle counter operation
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Laser Detector
Condenser
Heatedsaturator
Alcohol-soaked felt
Pump
What
difference
does this
make?
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Scanning mobility particle sizers provide more data, but are more difficult to use in the field
2.5 - to 1,000 nm particles
167 size channels
TSI Series 3936
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NIOSH recommends Method 5040 to quantify exposure to airborne carbon nanotubes*
37-mm quartz-fiber filter Flow rate of 2 to 4 liters per
minuteSize selective samplers may
be neededReported as elemental carbon
* NIOSH Draft Current Intelligence Bulletin, 2010 37-mm
quartz-fiber filter3-33
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NIOSH chose mass-based REL over counting with electron microscopyAnimal toxicology
studies are mass-basedCounting protocols
haven’t been developed, although ASTM has a committee working on it
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But mesotheliomas have been produced in mice with MWCNTs that are fibers with long aspect ratios (Takagi 2008, Poland 2008)
Multi-walled carbon nanotube penetrating the pleura of the lung. Courtesy of Robert Mercer, and Diane Schwegler- Berry, NIOSH
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NIOSH says 10,000 carbon nanotube combinations are possible
≠
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The counting protocols will be similar to asbestos TEM methods now in place
EPA AHERA Method Appendix A to Subpart E of Part 763
1 structure (fiber)
2 structures (fibers)
3 structures (fibers)
1 structure (bundle)
1 structure (cluster)
1 structure (matrix)
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Your turn! Categorize and count the following structures
1.__________________ 2.__________________
3.__________________ 4.__________________3-38
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Electron microscopy is the gold standard. It allows:
Characterization of bulk material for comparison to airborne particles
Indication of the presence of specific engineered nanomaterial (ENM)
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Transmission electron microscopy methods resemble asbestos analysis
Grid with sample
Grid inserted into holder
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TEM allows several measurements
Morphology EDS (EDXA) for
chemical composition
Particle count Particle length and
diameter
NIOSH image of MWCNT
EDS
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Elemental analysis for metals allows better characterization
• NIOSH recommends sampling high emission areas: both breathing zone and area
• Conduct elemental analysis (NIOSH 7300, metals with ICP)
• Characterize and verify by TEM
Raw single walled nanotubes, photo courtesy NIOSH
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NIOSH analysis of metal reactor cleanout provides good example of EM capabilities
Air sampleBulk product sample
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Harvesting SWCNTs from a Carbon Arc Reactor
Task-based BZ air sample analyzed via
TEM w/EDS
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There are no OSHA PELs, but there are several recommended OELs
Nanomaterial OEL Ref. YearTitanium dioxide 0.3 mg/m3
ultrafine2.4 mg/m3 fine
NIOSH 2011
Photocopier toner 0.06 mg/m3 BAuA 2009CNTs 0.01 f/cm3 IFA 2009Fibrous (3:1 aspect ratio, length 75,000 nm)
0.01 f/cm3 BSI 2007
MWCNTs 0.05 mg/m3 Bayer only
2010
MWCNTs 0.0025 mg/m3 Nanocyl only
2009
CNTs and nanofibers
0.007 mg/m3 NIOSH Draft REL
2010Adapted and updated from Schulte et al. J Nanopart Res (2010) v.12
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Possible Group Exercise: Review sampling reports and answer the following questions:1. What kind of samples were
collected?2. What media did they use?3. What method did they use to
analyze them?4. What types of structures did they
find?5. Is there anything in the report that
you don’t understand?3-46
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Learning ObjectivesAt the end of this module you will be able to Compare and contrast standard IH sampling
and analytical methods with those used for nanoparticles
Describe the equipment used for nanoparticle sampling and analysis
Evaluate sampling results and compare them to recommended occupational exposure limits
Discuss the limitations of nanoparticle sampling and analysis
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Learning ObjectivesAt the end of this module you will be able to Compare and contrast standard IH sampling
and analytical methods with those used for nanoparticles
Describe the equipment used for nanoparticle sampling and analysis
Evaluate sampling results and compare them to recommended occupational exposure limits
Discuss the limitations of nanoparticle sampling and analysis
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QUESTIONS OR COMMENTS?