Nanotechnology: Hazard Nanotechnology: Hazard Communication IssuesCommunication Issues

2006 NRT Worker Safety and HealthTechnical Conference

May 31, 2006

This copy approved for distribution through the DOE IH/OS SIG

Nanotechnology: Hazard Nanotechnology: Hazard Communication IssuesCommunication Issues

2006 NRT Worker Safety and HealthTechnical Conference

May 31, 2006

This copy approved for distribution through the DOE IH/OS SIG

Bruce Lippy, Ph.D., CIH, CSPEnvironmental Profiles, Inc. Baltimore, MD

21228, 410.744.0700

A comment for the NEHI A comment for the NEHI subcommitteesubcommittee

Good work! An impressive example of the federal government being

proactive and cooperative on H&S issues

Objectives Objectives At the end of this session, I would At the end of this session, I would

like you to be able to: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 effortsResearch efforts

Bought “Nanotech for Dummies”

Bought “Nanotech for Dummies”Got 30% offGot 30% off

The promise is The promise is impressive, but let’s impressive, but let’s

address the following: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 Is it too soon to talk Hazcom?Hazcom?

Several at NEHI meetings felt that there was insufficient toxicological data

Over 200 consumer products listed on the Wilson Center for Scholars website

National Nanotechnology Initiative (NNI) is maintaining a list of about 600 commercial materials, many just for research.

Hazcom expert at OSHA suggested this is an area where they clearly have regulatory authority.

Is it too soon to talk Is it too soon to talk about Hazcom?about Hazcom?

Nanotech Product Recalled in Germany

Rick Weiss, Washington Post Thursday, April 6, 2006

CPSC recall

of spray

grout sealer

8-2005

Courtesy Andrew MaynardCourtesy Andrew MaynardWilson Center for ScholarsWilson Center for ScholarsAround 200 consumer products:Around 200 consumer products:

www.nanotechproject.org/consumerproducts

Product categories

Health and Fitness Subcategories

Region of Origin

Major Materials

Review of Products in the Review of Products in the DatabaseDatabase

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: My favorite nanoproduct: Anti-graffiti PaintAnti-graffiti PaintDeletum 3000+Deletum 3000+

My Guess: used to remove My Guess: used to remove nano-graffitinano-graffiti

Image courtesy Justin Kumar, Ph.D., Indiana UniversityImage courtesy Justin Kumar, Ph.D., Indiana University

Example Example MSDS MSDS

ReceivedReceived Advanced

Nanotechnology’sZinClear (ZnO 58-62%)

Formulated for sunscreens, dispersed in carrier fluid

Uses ANSI Z400.1 format Cites OSHA PEL for

nuisance dust for ZnO– 5 mg/m3 respirable– 15 mg/m3 total dust

Another example: Another example: NanoWaxNanoWax

NanoWax MSDSNanoWax MSDSSection 8: Exposure Section 8: Exposure

Controls/PPEControls/PPEWAX EMULSION: No exposure limits established (NLE)

ALIPHATIC PETROLEUM DISTILLATES (64741-66-8): NLE

ALUMINUM SILICATE (66402-68-4): NLE

POLY(DIMETHYLSILOXANE) (63148-62-9): NLE

ALKYL QUATERNARY AMMONIUM BENTONITE (68953-58-2) : NLE

TETRAGLYCERYL MONOOLEATE (9007-48-1): NLE

GLYCOL (107-21-1)

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-MSDS for Multi-walled Carbon walled Carbon

NanotubesNanotubes Uses ANSI Z400.1 format Eye irritation is primary

warning Available on web,

undated, an OSHA violation

Written in all caps, against ANSI Z400 recommendations

MSDS for Multi-walled Carbon MSDS for Multi-walled Carbon Nanotubes, Section 11 Nanotubes, Section 11

ToxicologyToxicology“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 NanotubesToxicology on Carbon Nanotubes

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.”

Oberdörster (2005) Environmental Health Perspectives: “Profound cytotoxicity seen for SWNT…” On a mass basis, toxicity:

SWNT>MWNT>C60

Who is being exposed?Who is being exposed?

Spokesperson for CBAN at Oct 2005 NEHI meeting unable to characterize the population

More educated population (Maynard, 3/06) NNI spokesperson unaware of any study

characterizing workforce (4/06) Toured Georgia Tech Microelectronics

Research Center Dec 2004. Are these average nanoworkers?

Who is exposed? Who is exposed? We don’t We don’t knowknow

Who is exposed in Who is exposed in England?England?

Aitken, Creely, & Tran, 2004, Inst. of Occupational Medicine, HSE,

UK Found no info on workers exposed in

unv/research sector or in companies. Est. 2,000 people currently employed in

univ/research and private companies in UK.

100,000 exposed to fine powders in industry, including pharmaceuticals

>1,000,000 may be exposed to nanoparticles via incidental production (welding and refining)

Will the current approach Will the current approach to Hazcom be sufficient to Hazcom be sufficient

for nanomaterials?for nanomaterials?

Current ApproachCurrent Approach ANSI Z400.1 is universally used. Is it

appropriate? Sufficiently flexible? ANSI Section 16 holds promise Regulatory exposure limits are required to be

listed in MSDSs. Are they pertinent? Given the importance of surface area over

mass, what role should sampling play? No specific OSHA Hazcom regulatory

requirements for nano (Silk, 2006) Strong movement in global harmonization

Is it enough to tweak Is it enough to tweak current regulations?current regulations?

“New law may be required to manage potential risks of nanotechnology.” (Davies, Wilson Center

Managing the Effects of

Nanotechnology)

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

CenterCenter

ISO TC 229 Working ISO TC 229 Working Group on Health, Safety Group on Health, Safety

and the Environmentand the EnvironmentDeveloping 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 Review of Hazcom Literature Literature (Sattler, Lippy & (Sattler, Lippy &

Jordan, 1997)Jordan, 1997) Conducted by the University of

Maryland Medical School for OSHA Looked at peer-reviewed literature on

labels, warnings and MSDSs Last major review of Hazcom

literature (Silk, 4-06)

Key Finding: major lack of Key Finding: major lack of behavioral studies and behavioral studies and

appropriate test appropriate test populationspopulations

Studying behavior is much better than asking people’s preferences, but more difficult to do

Preferential studies dominated behavioral studies

Populations tended to be those of convenience: students not workers!

Can we do better with nano?

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

My Son

Nano lesson: assumptions Nano lesson: assumptions can be dangerouscan be dangerous

Studies of the ANSI Z535.3-1991 protocol: standard ANSI slash not as effective as an "X" for warning consumers.

Subject randomly chosen by computer

Subject randomly chosen by computer

The most shocking The most shocking finding! finding! (Sattler, Lippy & Jordan, (Sattler, Lippy & Jordan,

1997)1997)

Women more likely than men to look for and comply with warnings.

Comparison of MSDS Comparison of MSDS formatsformats

Little research comparing formats of MSDSs

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

ICSCs are on the NIOSH webpage

Critical Finding on Critical Finding on ComprehensibilityComprehensibility

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 Potential lessons from Technology Safety Data Technology Safety Data

SheetsSheets

Health and Safety in DOE’s Health and Safety in DOE’s innovative technologies innovative technologies

programprogram

Several serious incidents Small firms were the

drivers No hazard analysis and

communication to workers

Robotic CO2 blasterRobotic CO2 blaster

Concept of Technology Concept of Technology Safety Data SheetsSafety Data Sheets

Conceived in 1994 as a tool for informing users of technologies about hazards

Patterned on Material Safety Data Sheets Developed through 4 DOE and NIEHS

National Technical Workshops Cited by Dr. Sally Tinkle of NIEHS as an

idea to explore with nanotechnologies

Aimed at

workers, unlike

MSDSs

Available at:

www.wetp.org

Applicability to Applicability to NanotechnologyNanotechnology

Plasma Hearth ExamplePlasma Hearth Example

There have been explosions at two separate facilities: one

fatality, several injuries

Plasma operation for Plasma operation for NanoNano

PPG Industries, Lisa PPG Industries, Lisa MorrisonMorrison PPG produces nanoparticles as colorants for

glass in a plasma reactor in Allison Park, PA They are commissioning a large pilot plant by

conducting Hazard and Operability Study (HAZOP) of:– powder feeder system– plasma torch– reactor– bag filters

Not technically covered by OSHA PSM!

TSDS Phase AnalysisTSDS Phase Analysis Risks vary during life cycle of a

technology Particularly appropriate for

nanoproducts (Holman, 2006)

Risks: Maintenance Versus Risks: Maintenance Versus OperationOperation

Machinery fatalities 1997, Etherton, Machinery fatalities 1997, Etherton, NIOSHNIOSH

Maintenance

48%

Operations

45%

Other

7%

Research Findings, Research Findings, Lippy, Lippy, 2003 2003

DOE Technology DOE Technology DevelopersDevelopers Survey through the Institute for Regulatory

Science (62% return, 50/80) 74% agreed or strongly agreed with

statement: “This document format is quite valuable”

RESULTSRESULTSFocus Group of State Focus Group of State

Environmental RegulatorsEnvironmental Regulators Conducted through Southern States

Energy Board in 2000 Agreed that a TSDS as part of a

permit application would significantly increase the likelihood of technology approval

“Will it run in the rain and will it kill the neighbors?”

RESULTSRESULTSSurvey of WorkersSurvey of Workers

Heavy equipment operators 935 mailings, 475 responded (50%) 91% agreed with statement,

“This document is quite valuable

83% agreed that the similarity to MSDS increased ease of use

Questions?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

Blippy@episervices.com

Blippy@episervices.com