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Control Banding Approach to Safe Handling of NanoparticlesSamuel Paik, PhD, CIH
Email: [email protected]
Industrial Hygienist and Nanotechnology Safety SMELawrence Livermore National Laboratory
EH&S Challenges of the Nanotechnology Revolution
This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. LLNL-PRES
July 29, 2009
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Challenges in Traditional IH Approach
Control Banding Concept Development of CB Nanotool Application of CB Nanotool
Overview
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Personal air sampling Collect air samples from worker’s breathing zone
Compare concentration of particles of interest with exposure limits
Implement control measures to reduce concentrations below exposure limitsPersonal sampler
Personal sampling pump
Traditional IH Approach
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0%
20%
40%
60%
80%
100%
1 10 100
dae (μm)
Probability of penetration
Inhalable
Thoracic
Respirable
Sampled concentrations are representative of what the worker is breathing
Exposure index pertaining to health effects is known
Analytical methods are available to quantify exposure index
Exposure levels at which particles produce adverse health effects are known
inhalable thoracic respirable
Traditional IH Assumptions
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Sampled conc. are representative of what the worker is breathing Met by obtaining air sample from worker’s breathing zone. Due to their size, nanoparticles do not easily get separated from the sampled air.
Exposure index pertaining to health effects is known Not yet met. There is considerable debate on what the most appropriate exposure index is – Total surface area? Mass concentration? Number concentration?
Traditional IH vs Nanoparticles
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Analytical methods are available to quantify exposure index Some devices are available that measure nanoparticles, but most have significant biases and are not usually specific to the particle of interest (e.g., condensation particle counters, surface area monitors, etc.)
Exposure levels at which particles produce adverse health effects are known Not met. No established exposure limits for nanoparticles. Limited toxicological data.
Traditional IH vs Nanoparticles
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What can we do?
3 of the 4 assumptions are not met. A long way to go before traditional IH approach can be relied upon as effective risk assessment
Is there an alternative approach for risk assessment? Yes! Control Banding
CONTROL BANDING IS AN ALTERNATIVE APPROACH TO TRADITIONAL IH
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Overview Challenges in Traditional IH Approach
Control Banding Concept Development of CB Nanotool Application of CB Nanotool
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Definitions Control banding: A qualitative or semi-quantitative approach to risk assessment and risk management that groups occupational risk control strategies in bands based on their level of hazard.
CB Strategies: Overarching concept of the CB Model that is evolutionary and not a single toolkit.
Toolkit: Narrowly defined solutions approach to control worker exposures within toolkit’s parameters.
COSHH Essentials: A CB Toolkit Developed by UK HSE to Assist SMEs in Addressing the UK 2002 COSHH Regulations - Perform Risk Assessments for all Chemicals.
(definitions provided courtesy of David Zalk)
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* Maynard, AD. (2007) Nanotechnology: the next big thing, or much ado about nothing? AnnOccHyg 51(1);1-12.
Control Banding for Nano
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Factors that Favor Control Banding (CB) for Nano
Challenges with Traditional IHInsufficient toxicological information
Difficult to quantify exposure Efficacy of conventional controls
Applicability of four control bands
Product and Process Based Successful application in UK and pharmaceutical industry (e.g., COSHH Essentials)
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Overview Challenges in Traditional IH Approach
Control Banding Concept Development of CB Nanotool Application of CB Nanotool
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CB seems like a useful concept, but few comprehensive tools are available
Goal Explore feasibility of CB concept by developing pilot tool, utilizing existing knowledge on nanoparticle toxicology
Apply CB Nanotool to current R&D operations at LLNL
CB Nanotool Concept and Pilot
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Probability
Severity RL 1: General Ventilation RL 2: Fume hoods or local exhaust ventilation RL 3: Containment RL 4: Seek specialist advice
Extremely Unlikely
(0-25)
Less Likely (26-50)
Likely (51-75)
Probable (76-100)
Very High (76-100)
RL 3
RL 3
RL 4
RL 4
High (51-75)
RL 2
RL 2
RL 3
RL 4
Medium
(26 -50)
RL 1
RL 1
RL 2
RL 3
Low
(0-25)
RL 1
RL 1
RL 1
RL 2
CB Nanotool Risk Level Matrix
14 CB_Nano_DMZ_SYP.ppt
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For a given hazard category, should an “unknown” rating be given the same weight as a “high hazard” rating? Due to scarcity of data, most operations would require highest level of control
Decided to give an “unknown” rating 75% of the point value of “high” rating. This is higher than a “medium” rating.
The default control for operation for which everything is “unknown” is Containment (Risk Level 3). If even one rating is “high” with everything else “unknown”, resulting control would be Seek Specialist Advice (Risk Level 4). Provided incentive for responsible person to obtain health-related data for the activity
CB Nanotool: Treating Unknowns
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Nanomaterial: 70% of Severity Score Surface Chemistry (10 pts) Particle Shape (10 pts) Particle Diameter (10 pts) Solubility (10 pts) Carcinogenicity (6 pts) Reproductive Toxicity (6 pts) Mutagenicity (6 pts) Dermal Toxicity (6 pts) Asthmagen (6 pts)
Parent Material: 30% of Severity Score Occupational Exposure Limit (10 pts) Carcinogenicity (4 pts) Reproductive Toxicity (4 pts) Mutagenicity (4 pts) Dermal Toxicity (4 pts) Asthmagen (4 pts) (Maximum points indicated in
parentheses)
CB Nanotool (v2): Severity Factors
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Estimated amount of material used (25 pts)
Dustiness/mistiness (30 pts) Number of employees with similar exposure (15 pts)
Frequency of operation (15 pts) Duration of operation (15 pts)
CB Nanotool(v2): Probability Factors
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Particle surface free radical activity
Surface Chemistry (10 pts) Ability to generate reactive oxygen species,
oxidative stress responses Toxicological studies – Bronchoalveolar lavage
fluid collected from rodents: analyzed for markers of inflammation, lung tissue damage, antioxidant status, etc.
Auger spectroscopy
High: 10 pts Medium: 5 pts Low: 0 pts Unknown: 7.5 pts
Surface Chemistry (nanomaterial)
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Tubular/fibrous: high aspect ratio(e.g., carbon nanotubes)
Irregular shapes: generally more surface area than compact particles(e.g., iron powders)
Tubular/fibrous: 10 pts Anisotropic: 5 pts Compact/spherical: 0 pts
Unknown: 7.5 pts
Particle Shape (nanomaterial)
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ICRP (1994) model: adult, nose breathing, at rest. Courtesy of CDC-NIOSH.
Diameter (µm)
Dep
ositi
on P
roba
bilit
y
0.0001 0.001 0.01 0.1 1 10 100
Total
Tracheo- bronchial
Head airways Alveolar
1.0
0.8
0.6
0.4
0.2
0.0
1-10 nm
11-40 nm
>40 nm
Particle Diameter (nanomaterial)
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1-10 nm: 10 pts 11-40 nm: 5 pts >41 nm: 0 pts Unknown: 7.5 pts
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Insoluble particles Titanium dioxide, PTFE, BaSO4
Causes inflammatory response May penetrate skin, may translocate into brain
Soluble particles Potential systemic effects through absorption into blood
Insoluble: 10 pts Soluble: 5 pts Unknown: 7.5 pts
Solubility (nanomaterial)
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Carcinogenicity e.g., Titanium dioxide (IARC Group 2B potential carcinogen)
Yes: 6 pts No: 0 pts Unknown: 4.5 pts
Reproductive toxicity – mostly unknown Yes: 6 pts No: 0 pts Unknown: 4.5 pts
Mutagenicity – mostly unknown Yes: 6 pts No: 0 pts Unknown: 4.5 pts
Dermal toxicity – mostly unknown Either cutaneous or through skin absorption Yes: 6 pts No: 0 pts Unknown: 4.5 pts
MOST TOXICOLOGICAL DATA PERTAINING TO NANOSCALE IS UNKNOWN
Other Tox Effects (nanomaterial)
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Toxicological properties of parent material may provide insight into nanomaterial toxicity 30% of total severity score is based on parent material characteristics
Bulk hazard (Parent material) Is there an established occupational exposure limit?
<10 μg/m3: 10 pts 10-100 μg/m3 : 5 pts 101-1000 μg/m3 : 2.5 pts >1 mg/m3: 0 pts Unknown: 7.5 pts
Severity Factors of Parent Material
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Carcinogenicity Yes: 4 pts No: 0 pts Unknown: 3 pts
Reproductive toxicity Yes: 4 pts No: 0 pts Unknown: 3
pts
Mutagenicity Yes: 4 pts No: 0 pts Unknown: 3 pts
Dermal toxicity Either cutaneous or through skin absorption Yes: 4 pts No: 0 pts Unknown: 3 pts
Severity Factors of Parent Material
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Pertain to probability of exposure, irrespective of toxicological effects
Estimated amount of material used>100 mg: 25 pts 11-100 mg: 12.5 pts 0-10 mg: 6.25 pts
Unknown: 18.75 pts
Dustiness/mistinessHigh: 30 pts Medium: 15 pts Low: 7.5 pts None: 0 pts
Unknown: 22.5 pts
Number of employees with similar exposure>15: 15 pts 11-15: 10 pts 6-10: 5 pts 1-5: 0 pts
Unknown: 11.25 pts
Frequency of operationDaily: 15 pts Weekly: 10 pts Monthly: 5 pts Less than
monthly: 0 pts
Duration of operation>4 hrs: 15 pts 1-4 hrs: 10 pts 30-60: 5 pts <30 min: 0 pts
Unknown: 11.25 pts
Probability Factors
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Probability
Severity RL 1: General Ventilation RL 2: Fume hoods or local exhaust ventilation RL 3: Containment RL 4: Seek specialist advice
Extremely Unlikely
(0-25)
Less Likely (26-50)
Likely (51-75)
Probable (76-100)
Very High (76-100)
RL 3
RL 3
RL 4
RL 4
High (51-75)
RL 2
RL 2
RL 3
RL 4
Medium
(26 -50)
RL 1
RL 1
RL 2
RL 3
Low
(0-25)
RL 1
RL 1
RL 1
RL 2
CB Nanotool Risk Level Matrix
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Overview Challenges in Traditional IH Approach
Control Banding Concept Development of CB Nanotool Application of CB Nanotool
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Activities at LLNL (examples)
Weighing of dry nanopowders in glovebox Flame synthesis of garnet ceramic nanoparticles by liquid
injection Synthesis of carbon nanotubes and metal oxide nanowires onto
substrates within tube furnace Deposition of liquid-suspended nanoparticles onto surface
using low voltage electric fields Sample preparation of various nanomaterials by cutting,
slicing, grinding, polishing, etching, etc. Use of gold nanoparticles for testing carbon nanotube
filters Etching nanostructures onto semiconductors Addition of quantum dots onto porous glass Growth of palladium nanocatalysts Synthesis of aerogels Machining (e.g., turning, milling) of aerogels and nanofoams
for laser target assembly Sample preparation and characterization of CdSe nanodots and
carbon diamonoids
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CB Nanotool vs IH Judgment
Application to current operations 36 operations at LLNL
For 21 activities, CB Nanotool recommendation was equivalent to existing controls
For 9 activities, CB Nanotool recommended higher level of control than existing controls
For 6 activities, CB Nanotool recommended lower level of control than existing controls
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Overall (30 out of 36), CB Nanotool recommendation was equal to or more conservative than IH expert opinions
LLNL decided to make CB Nanotool recommendation a requirement
CB Nanotool is an essential part of LLNL’s Nanotechnology Safety Program
CB Nanotool as LLNL Policy
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International Acceptance of CB Nanotool Cited by IRSST as a “simple but effective tool [that] makes it possible to take into account all the available information (toxicity, exposure level) and to develop logical hypotheses on the missing information”Reference: IRSST (2009) Best practices guide to synthetic nanoparticle risk management. Report R-599, Institut de recherche Robert-Sauve en sante du travail (IRSST), Montreal, Quebec, Canada.
Positive response from over 15 institutions at AIHce ’09 (Toronto, Canada)
Invited author presentations in Germany, South Africa, Canada, and US
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Some notes for CB Nanotool Information on health effects from nanoparticle exposure is evolving – relative importance of factors may change
Ranges of values for a given factor correspond to ranges one would expect in small-scale R&D operations (e.g., amounts used, number of employees, etc.)
Score for a given rating within a factor can be set according to the level of risk acceptable to the institution
Some qualitative ratings can be bolstered or eventually replaced with quantitative ratings
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Publications
Paik, S.Y., Zalk, D.M., and Swuste, P. (2008) Application of a pilot control banding tool for risk level assessment and control of nanoparticle exposures. Annals of Occupational Hygiene, 52(6):419–428.
Zalk, D.M, Paik, S.Y., and Swuste, P. (2009) Evaluating the Control Banding Nanotool: a qualitative risk assessment method for controlling nanoparticle exposures. Journal of Nanoparticle Research, (advance access online: DOI 10.1007/s11051-009-9678-y).
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Acknowledgments
David Zalk, co-author, co-developer
Paul Swuste, co-author LLNL Hazards Control Department
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Questions?
Your attention is appreciated!
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