UT-Battelle Department of Energy Exposure Monitoring Techniques for Nanomaterials American Chemical Society Meeting August 30, 2011 Joseph M. Pickel, Ph.D. CHO Center for Nanophase Materials Sciences Oak Ridge National Laboratory
May 15, 2015
UT-BattelleDepartment of Energy
Exposure MonitoringTechniques for Nanomaterials
American Chemical Society MeetingAugust 30, 2011
Joseph M. Pickel, Ph.D. CHO
Center for Nanophase Materials Sciences
Oak Ridge National Laboratory
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Acknowledgements
Scott Hollenbeck, CIH (ORNL-CNMS)
John Jankovich, CIH (ORNL- Ret)
Burt Ogle, Ph.D., CIH (Western Carolina)
Tracy Zontek, Ph.D., CIH (Western Carolina)
Randy Ogle, CIH (ORNL-Ret, RJLee Group)
Gary Casuccio (RJLee Group)
Michaela Hall, MPH (ORNL)
Samantha Connell (Alabama, Birmingham)
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Challenge and General Strategy for Nanomaterial Safety in the Laboratory
Review of Current Approaches
Discussion of New Developments
Outline
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Ensure that we are protecting workers– From materials that vary in size, shape, and
composition– Having unknown toxicity and reactivity– By measuring a number of properties (count, surface
area, mass)– Using tools, sometimes at or near their limits of
quantitation
Challenge
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Nanoscale Materials Properties
Relatively little mass– Mass of 1 billion 10 nm particles = mass of 10 µm particle
Large surface area Produced in large numbers Quantum effects
– Change their physical, chemical, and biological properties
Behave like gases– Stay suspended for weeks
Disperse quickly Tend to agglomerate quickly after production
– Good for health effects– Bad for science
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As in any hazardous exposure to chemicals, a good health and safety management approach should include these four elements:
1.Identify the hazard
2.Asses the risk
3.Prevent or control therisk
4.Evaluate the effectiveness of controlmeasures
Asses the risk
Evaluate the effectiveness
Identify the hazard
Prevent or control the risk
Control of Nanoparticles
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Starting Point: Identify/ Assess SituationLack of and/or uncertainty of data warrants that Nanomaterials must handled using the precautionary principle:
“toxic in the short run and chronically toxic in the long run”
Photos courtesy RJ LEE Group
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Prevent/Control Risk - Assumptions
- Traditional Controls Work- Engineering- Administrative- Personal Protection
- Material Releases Can be Measured
- Hazard and associated Risk are product of Toxicity and Exposure
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To check for releases (process control)– Leak checks on
containment – Effectiveness of
capturing system
To define ambient concentration– Establish need for
exposure control Exceedance of regulated
concentration Exceedance of operational
guidelines
Evaluate Effectiveness of ControlsSampling and Exposure Monitoring
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Ensure that we are protecting workers– From materials that vary in size, shape, and
composition (what are we looking for?)– Having unknown toxicity and reactivity (how much is
okay?)– By measuring a number of properties (count, surface
area, mass) (which is most important)– Using tools, sometimes at or near their limits of
quantitation (how many tools are enough?)
Challenge
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Current Guidance on Nanomaterial Safety
NIOSH: Approaches to Safe Nanotechnology
DOE Nanoscience Research Centers: Approach to Nanomaterial ES&H (Rev 3a, 5/08)
ISO/TR 12885:2008, Health and safety practices in occupational settings relevant to nanotechnologies
ASTM E2535 - 07 Standard Guide for Handling Unbound Engineered Nanoscale Particles in Occupational Settings
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Foundation of NSRC Approach…
Integrated Safety Management followed from inception
Designed to accommodate the planned R&D
ESH and projected R&D staff designed individual labs and controls
Used experience, benchmarking, and best available control technologies
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Sound Workplace Practice – SOGs/SOPs
Effective workplace controls: engineering, administrative, and PPE where appropriate (i.e. protect routes of entry, particularly inhalation and dermal exposures).
Safety and Health Training – disseminating appropriate hazard information
Safe procedures for handling and disposal of hazardous (and potentially hazardous) materials.
Nanotechnology Safety Approach
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Install similar engineering controls used to control gases and vapors:
EnclosuresLocal exhaust ventilationFume hoods
Use of HEPA Filtration
Limitation on number of workers and exclusion of others
Use of suitable personal protective equipment
Good Chemical Hygiene (Prohibition of eating and drinking in contaminated areas, Regular cleaning of walls and other surfaces)
Controls to limit exposure
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Tools for Evaluating Nanomaterial Exposures
Surface area – diffusion charger
Scanning Mobility Particle Sizer (SMPS)
Count– CPC(TSI), scanning mobility, GRIMM
Composition/Chemistry - GC-MS
Filter/Impinger/Impactor-TEM/SEM
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Sampling Strategy
Determine if nanomaterials are controlled at the source– Use of Condensation Particle Counter, TSI 3007
Range from 0.01 - >1 um with a concentration range of 0 to 100,000 particles/cc
– SMPS (Sequential Mobility Particle Sizer) Combination of electrostatic classifier and condensation particle
counter Determines particle sizes and distributions
– GRIMM Aerosol Spectrometer Particle sizes in 13 channels ranging from greater than 0.3 um
to greater than 10 um, with a count range from 1 to 2 million counts per liter
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Sampling Approach for CNMS Activities
TSI 3007 CPC, particle counts to 10nm
Nucleopore filter + SEM/TEM– size,– shape, – metallic composition
Baseline index of “clean” watch for other sources (air pollution, combustion)
Direct count, estimated mass, and surface area for each process
Passive monitoring (TEM/SEM Stub or grid)
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Working in fume hood
Grinding the barium fluoride inside the hood.
CPC monitoring begins in room F263.
Crushed powder was shook from the filter paper into a glass holder.
At 10:09 a.m. to end of log, baseline of inside the hood.
Activity / Materials Range (p/cc) Mean (p/cc) SD Time (s)
Room background 970-1344 1214.19 50.58 426
Grinding in hood 1161-1929 1580.73 164.38 540Hood background 1481-1887 1665.16 78.83 145
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Worker and Environmental Assessment of Potential Unbound Engineered Nanoparticle Releases– Multiphase study (Assessment and Control Band
Development)– Conducted by LBNL and RJLEE group
Berkeley Study
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Protocol used to survey efficacy of control methods
Results motivated change to administrative protocols
Evaluation of Spray System at CNMS
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General Results of Sampling Protocol
CPC– Extremely effective to identify background levels and spikes– Background levels crucial to data interpretation– Not effective to collect employee exposure samples
GRIMM Aerosol Spectrometer– Provides particle size distribution– Did not measure particles less than 300 nm
Particle spikes found due to equipment:– HEPA vacuum– Heat exchanger on laser enclosure
Controls and work practices were effective overall:– Work in hoods (HEPA)– Wet methods– Closed systems / enclosures
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Discussion of Protocol
- Focus on research / laboratory environments (non-production)- Emphasis on CPC and Microscopy as convenient, universally
accessible tools- Combination approach allows confirmation of source
- Protocol measures particle count, distribution and composition- Forgo gravimetric measurements due to technical concerns- Forthcoming revision of protocol removes GRIMM
- Continuous Improvements to method via research– on new equipment and components– Sampling methods and assumptions
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Exposure limits for Nanomaterials
No current regulatory limits
ALARA in R&D (Prudent Practice)
Current guidance (and tox data) based on mass (e.g., LD50 mg/Kg)
Older standards based on particle counts
Not yet a foundation for a surface area based dose-response
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Other Considerations –Emerging Toxicity Information
Depends on chemistry, morphology, surface charges, etc.
Probably relates to particle surface area especially for insoluble/low soluble
Free radicals (in vitro) Increased inflammatory
response (in vivo) Translocation to target organs
(rodents) Allergic asthma like symptoms Aggravate symptoms of
pneumonia Cardiac effect-2 days later
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NIOSH on Titanium Dioxide
Exposure limit of 1.5 milligrams per cubic meter for fine TiO2 (particles greater than 0.1 micrometers in diameter)
0.1 mg/m3 for ultrafine particles as time-weighted averages for up to 10 hours per day during a 40-hour work week
Suggests that ultrafine TiO2 particles may be more potent than fine TiO2 particles at the same mass. This may be due to the fact that the ultrafine particles have a greater surface area than the fine particles at the same mass
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Surface area as dominant characteristic contributing to toxicity is plausible
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Nanoparticle Surface Area is Huge!
• 1/2 the size = 2x the surface area and 23 = 8x the number or particles
• Approaches 100% of atoms on the surface
•www.gly.uga.edu/railsback/1121WeatheringArea.jpeg
81
64 512
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Discussion on Exposure Guidelines
Current progress is towards mass based limits– NIOSH proposes mass based Recommended
Exposure Limit
Basis approximates limits of quantitation rather than toxicological considerations
Forthcoming article to propose 530 p/cc (53000p/cc for respirator) for non-doped carbon based aerosols– Extrapolated particle based guideline– Applicable to poorly soluble, low toxicity
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Summary and Conclusions All processes should be carefully evaluated and
prudent controls in place prior to start– Control banding
Air monitoring can evaluate release of nanoscale materials in workplace– Determine effectiveness of controls
Poor work practices can lead to potential contamination
Follow standard IH practices focusing on evaluation and control
Consider end results and future– Characterize materials– Ensure health and safety– Data for epidemiological studies
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Worker Health can be protected– Prudent practices– ALARA/ALARP Principles– Control Banding
Emerging information is solidifying technical basis for exposure assessment– Toxicological data– OELS– Sampling methodology,
techniques and tools…– But there is no “right answer” yet
Summary and ConclusionsAsbestos Fiber
Welding Fumes
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References and Resources Jankovic, J T; Hollenbeck, S M; “Ambient Air Sampling During Quantum-dot Spray
Deposition” International Journal of Occupational and Environmental Health 2010 ,16:4, 388-398.
Jankovic, J.T; Ogle, B.R.; Zontek, T.L.; Hollenbeck, S.M. “Characterizing Aerosolized Particulate As Part Of A Nanoprocess Exposure Assessment” International Journal of Occupational and Environmental Health 16:4, 451-457
Jankovic, J.T; Ogle, B.R.; Zontek, T.L.; Hall, M. A.; Hollenbeck, S.M. “Particle Loss in a Scanning Mobility Particle Analyzer Sampling Extension Tube” International Journal of Occupational and Environmental Health; 16:4, 429-433.
Zontek, T. L. ; Ogle, B.R.; Ogle, R.B “Evaluating an air monitoring technique” Professional Safety 2010 34 www.asse.org
Nanotechnology research resources– National Institute for Occupational Safety and Health (NIOSH)– National Nanotechnology Initiative (NNI)– Rice University's International Council on Nanotechnology
(ICON) – Nanoparticle Information Library (NIL)
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