Nanotechnology: Hazard Communication Issues Nanotechnology: Hazard Communication Issues 2006 NRT Worker Safety and Health Technical Conference May 31, 2006 This copy approved for distribution through the DOE IH/OS SIG Bruce Lippy, Ph.D., CIH, CSP Environmental Profiles, Inc. Baltimore, MD 21228,

A comment for the NEHI subcommittee Good work! An impressive example of the federal government being proactive and cooperative on H&S issues

Objectives At the end of this session, I would like you to be able to: 1. List several reasons that the standard MSDS format may prove inadequate for nanomaterials 2. Describe findings from the Hazcom literature that may prove useful in creating effective communication strategies for nanomaterials 3. Describe several findings from research on Technology Safety Data Sheets that may have implications for nanotechnologies.

Research efforts Bought “Nanotech for Dummies” Got 30% off

The promise is impressive, but let’s address the following: 1. Is it too soon to talk about Hazcom? 2. Who are the exposed worker populations? What do we know about their demographics? 3. Will the current approach to Hazcom be sufficient for nanomaterials?

Is it too soon to talk Hazcom? l Several at NEHI meetings felt that there was insufficient toxicological data l Over 200 consumer products listed on the Wilson Center for Scholars website l National Nanotechnology Initiative (NNI) is maintaining a list of about 600 commercial materials, many just for research. l Hazcom expert at OSHA suggested this is an area where they clearly have regulatory authority.

Is it too soon to talk about Hazcom? Nanotech Product Recalled in Germany Rick Weiss, Washington Post Thursday, April 6, 2006 CPSC recall of spray grout sealer

Courtesy Andrew Maynard Wilson Center for Scholars Around 200 consumer products:

Product categories

Health and Fitness Subcategories

Region of Origin

Major Materials

Review of Products in the Database Review of Products in the Database 1. Selected 10% of the 200 using a random number table 2. Searched their website for safety information, particularly MSDSs 3. Submitted written request for MSDSs through website or called. Found 1 MSDS out of 20 sites

My favorite nanoproduct: Anti-graffiti Paint Deletum My favorite nanoproduct: Anti-graffiti Paint Deletum 3000+

My Guess: used to remove nano-graffiti Image courtesy Justin Kumar, Ph.D., Indiana University

Example MSDS Received l Advanced Nanotechnology’s ZinClear (ZnO 58-62%) l Formulated for sunscreens, dispersed in carrier fluid l Uses ANSI Z400.1 format l Cites OSHA PEL for nuisance dust for ZnO –5 mg/m3 respirable –15 mg/m3 total dust

Another example: NanoWax

NanoWax MSDS Section 8: Exposure Controls/PPE WAX EMULSION: No exposure limits established (NLE) ALIPHATIC PETROLEUM DISTILLATES ( ): NLE ALUMINUM SILICATE ( ): NLE POLY(DIMETHYLSILOXANE) ( ): NLE ALKYL QUATERNARY AMMONIUM BENTONITE ( ) : NLE TETRAGLYCERYL MONOOLEATE ( ): NLE GLYCOL ( ) OSHA PEL 50 ppm - Ceiling ACGIH TLV 100 mg/m3 - Ceiling as an aerosol No indication which component is nano- sized. Is it important in this application?

MSDS for Multi-walled Carbon Nanotubes l Uses ANSI Z400.1 format l Eye irritation is primary warning l Available on web, undated, an OSHA violation l Written in all caps, against ANSI Z400 recommendations

MSDS for Multi-walled Carbon Nanotubes, Section 11 Toxicology “To the best of our knowledge the chemical, physical, and toxicological properties have not been thoroughly investigated.” Cambridge University, Department of Metallurgy

Toxicology on Carbon Nanotubes l Lam et al. (2004) Toxicological Sciences: “On an equal-weight basis, if carbon nanotubes reach the lungs they can be much more toxic than carbon black and more toxic than quartz.” l Oberdörster (2005) Environmental Health Perspectives: “Profound cytotoxicity seen for SWNT…” On a mass basis, toxicity: SWNT>MWNT>C60

Who is being exposed?

l Spokesperson for CBAN at Oct 2005 NEHI meeting unable to characterize the population l More educated population (Maynard, 3/06) l NNI spokesperson unaware of any study characterizing workforce (4/06) l Toured Georgia Tech Microelectronics Research Center Dec Are these average nanoworkers? Who is exposed? We don’t know

Who is exposed in England? Who is exposed in England? Aitken, Creely, & Tran, 2004, Inst. of Occupational Medicine, HSE, UK l Found no info on workers exposed in unv/research sector or in companies. l Est. 2,000 people currently employed in univ/research and private companies in UK. l 100,000 exposed to fine powders in industry, including pharmaceuticals l >1,000,000 may be exposed to nanoparticles via incidental production (welding and refining)

Will the current approach to Hazcom be sufficient for nanomaterials?

Current Approach l ANSI Z400.1 is universally used. Is it appropriate? Sufficiently flexible? l ANSI Section 16 holds promise l Regulatory exposure limits are required to be listed in MSDSs. Are they pertinent? l Given the importance of surface area over mass, what role should sampling play? l No specific OSHA Hazcom regulatory requirements for nano (Silk, 2006) l Strong movement in global harmonization

Is it enough to tweak current regulations? “New law may be required to manage potential risks of nanotechnology.” (Davies, Wilson Center Managing the Effects of Nanotechnology)

Sampling Issues, Courtesy Andrew Maynard, Wilson Center Sampling Issues, Courtesy Andrew Maynard, Wilson Center

ISO TC 229 Working Group on Health, Safety and the Environment Developing international standards for nanotechnology within three working groups: –terminology and nomenclature (convened by Canada) –metrology and characterization (Japan) –health, safety and the environment. (U.S.) Clayton Teague is leading

Review of Hazcom Literature (Sattler, Lippy & Jordan, 1997) l Conducted by the University of Maryland Medical School for OSHA l Looked at peer-reviewed literature on labels, warnings and MSDSs l Last major review of Hazcom literature (Silk, 4-06)

Key Finding: major lack of behavioral studies and appropriate test populations l Studying behavior is much better than asking people’s preferences, but more difficult to do l Preferential studies dominated behavioral studies l Populations tended to be those of convenience: students not workers! l Can we do better with nano?

These are students. Do they look like workers? My Son

Nano lesson: assumptions can be dangerous Studies of the ANSI Z protocol: standard ANSI slash not as effective as an "X" for warning consumers. Subject randomly chosen by computer

The most shocking finding! (Sattler, Lippy & Jordan, 1997) Women more likely than men to look for and comply with warnings.

Comparison of MSDS formats l Little research comparing formats of MSDSs l Where comparisons have been made, the International Chemical Safety Cards have been ranked more effective than the ANSI 400 format that is being promoted by industry and OSHA l ICSCs are on the NIOSH webpage

Critical Finding on Comprehensibility Critical Finding on Comprehensibility On average, literate workers only understood about 60% of the health and safety information on sample MSDSs in three comprehensibility studies (Kolp et al. 93; Phillips et al., 99; Printing Industries of America, 90). Readability is not comprehensibility

Potential lessons from Technology Safety Data Sheets

Health and Safety in DOE’s innovative technologies program l Several serious incidents l Small firms were the drivers l No hazard analysis and communication to workers Robotic CO2 blaster

Concept of Technology Safety Data Sheets l Conceived in 1994 as a tool for informing users of technologies about hazards l Patterned on Material Safety Data Sheets l Developed through 4 DOE and NIEHS National Technical Workshops l Cited by Dr. Sally Tinkle of NIEHS as an idea to explore with nanotechnologies

Aimed at workers, unlike MSDSs Available at:

Applicability to Nanotechnology Plasma Hearth Example There have been explosions at two separate facilities: one fatality, several injuries

Plasma operation for Nano PPG Industries, Lisa Morrison l PPG produces nanoparticles as colorants for glass in a plasma reactor in Allison Park, PA l They are commissioning a large pilot plant by conducting Hazard and Operability Study (HAZOP) of: –powder feeder system –plasma torch –reactor –bag filters l Not technically covered by OSHA PSM!

TSDS Phase Analysis l Risks vary during life cycle of a technology l Particularly appropriate for nanoproducts (Holman, 2006)

Risks: Maintenance Versus Operation Machinery fatalities 1997, Etherton, NIOSH Maintenanc e 48% Operations 45% Other 7%

Research Findings, Lippy, 2003 DOE Technology Developers l Survey through the Institute for Regulatory Science (62% return, 50/80) l 74% agreed or strongly agreed with statement: “This document format is quite valuable”

RESULTS Focus Group of State Environmental Regulators l Conducted through Southern States Energy Board in 2000 l Agreed that a TSDS as part of a permit application would significantly increase the likelihood of technology approval l “Will it run in the rain and will it kill the neighbors?”

RESULTS Survey of Workers l Heavy equipment operators l 935 mailings, 475 responded (50%) l 91% agreed with statement, “This document is quite valuable l 83% agreed that the similarity to MSDS increased ease of use

Questions? “If it weren’t for the people, the damned people always getting tangled up in the machinery. If it weren't for them, earth would be an engineer’s paradise.” Kurt Vonnegut, Player Piano