Safe Handling of Engineered

Nanoparticles: Emerging

Consensus Standards

Rick Kelly, MS, CIH

Lawrence Berkeley National Laboratory

Center for Occupational and Environmental

Health & The Molecular Foundry

July 29, 2009
2004: How Do You Protect People When...

• You don’t understand the

toxicology

• You don’t know how well

PPE is going to work

• You don’t know what health

effects to expect

• You don’t really know which

routes of exposure are

important

• You don’t know how to

measure exposure

• You don’t know how to do

medical surveillance

• There are no regulations or

consensus standards

• The first NIOSH sponsored

Nano EH&S conference

hasn’t been held yet!
2004 University of California Guidelines

• University of California issues draft guidelines

on the safe handling of nanomaterials

—Use basic good laboratory practices

—Don’t forget hazards of precursors

—User respirators if handling nanopowders

outside of a hood

—Exhaust synthetic equipment to the outside

—Manage contaminated equipment

—Nothing on exposure assessment

—Nothing specific on waste

—No requirement to filter effluent
Department of Energy

Policy Statement 9/15/05

• Adopt, as appropriate, national consensus

standards as they emerge

• Use existing EH&S control systems

• Monitor research developments and react

accordingly

• DOE says it will support ongoing research

and policy making
NIOSH Publishes First Draft

Approach Document 10/1/05
NIOSH Publishes First Draft

Approach Document 10/1/05

• Raise Awareness of the issue

• Provide interim recommendations

• Facilitate information exchange

• Identify Information gaps

• Respond to the many inquiries they were receiving
NIOSH Publishes First Draft

Approach Document 10/1/05

• Air Monitoring–“...uncertain as to what measurement

technique should be used to monitor exposures in the

workplace.”

• Engineered Controls–“...control of airborne exposure to

nanoparticles...engineering control techniques similar to

those used in reducing exposures to aerosols.”

• Work Practices–“The incorporation of good work practices

...can help to minimize worker exposure...”

• Protective Clothing–“Currently, no guidelines are available

on the selection of clothing ...for the prevention of dermal

exposure...”

• Respirators–“Since nanoparticles are typically smaller than

100 nm they are theoretically collected more efficiently than

the 0.3 μm test aerosols.” (HEPA filtration and respirators)

• Spill Cleanup–“No specific guidance is currently available on

the cleaning up of nanomaterials spills.”
EPA Publishes First Draft

“White Paper” 1/2/05

• General review of the

issues, nothing that

can be used in the

field

• Required 25 months

to finalize
2005 DOE NSRC Approach Document
Purpose and Limitations

• Provide guidance to the five NSRCs for the

development of safety controls

—Not intended to be adopted verbatim

• Offer guidance for working with materials of

unknown hazard

• Promote consistency among the five nanocenters

• Does not preempt national, state or local regulations
Work Planning

• Review all work with nanomaterials for EH&S

concerns following an established safetyassessment process

—Develop a well defined description of the work

—Involve appropriate subject matter experts

• Industrial hygiene

• Fire protection (for reactive materials)

• Waste management

—Consider hazards of precursors and equipment

—Consider potential hazard of nanomaterials

captured on filters
Engineered Controls

• Work that could generate an aerosol should be

conducted in a enclosed, ventilated system such as

fume hood, glove box or glove bag

—Alternatively, use close capture system

—Filter/scrub exhaust air where nanoparticles may

be generated

—Do not recirculate exhaust air if possible

• Avoid HEPA filtered stand alone hoods or biosafety

cabinets if not exhausted to the outside

• NEVER use laminar flow hoods

(clean benches)

• Test and maintain these systems
Administrative Controls

• Develop and implement a chemical hygiene plan

specific to the scope of activities

• Housekeeping

—Clean surfaces after each shift if contaminated

• Consider reactivity of material when selecting method

• Dedicated HEPA Vacuum

• Wet wiping

• Work practices

—Keep materials in closed containers except

when inside ventilated systems

—Minimize potential for aerosol and skin contact

—Use PPE when engineered controls not used
Posting and Labeling

• Post signs at entrance to work

area warning of nanomaterials

• Label storage containers
Personal Protective Equipment

• Wear PPE when failure of a single control could entail

significant risk of exposure

— Alternately, equip engineered controls with performance

monitors

• Typical wet chemistry PPE when needed

— Closed toe, low permeability shoes

— Long pants without cuffs

— Gauntlet gloves or gloves with sleeve extenders

— Lab coats (consider notifying vendor)

— Eye protection

• Respirators should be half mask

P100 if used
Monitoring and Characterization

• Minimally, use direct reading

instrument to measure airborne

nanoparticle level

• Perform more sophisticated air

sampling

—Recommended method provided

in appendix A

• TSI 3007 Nanoparticle counter

• GRIMM particle sizer

• Filter collection with EM analysis

—Other alternatives

• Size selective nanoparticle counters

• Surface area counters

TSI 3007

TSI

surface area

meter

GRIMM Sizer
Worker Competency

• Identify people potentially exposed to nanoparticles

—Registry

• Provide appropriate nanosafety training

—Also training for chemicals, PPE, waste, etc

• Provide awareness-level training to guests (users)

• Provide written procedural requirements to guests
Medical Exams

• Provide workers with “baseline” medical evaluations

and nonspecific routine health monitoring program

—Worker

• works with nanoparticles & may inhale them or get them

on their skin, or

• spends significant time in area where dispersible

nanoparticle are handled, or

• works on potentially contaminated equipment

• Provide immediate exam for people

exposed in an “incident”

• Exempts non-resident people

—Guests, users
Waste Management

• If classified as hazardous per 40

CFR or state regulations,

dispose of waste using standard

hazardous waste procedures

• If not classified as hazardous,

send the waste to a RCRA

permitted TSDF anyway

—Include instruction on how to

dispose of material

• Do not permit nanomaterials to

be shipped to researchers home

institution for disposal
Spills

• Small spills cleaned up by lab personnel

• Large spills cleaned up by hazmat team

• Refer any people exposed in the incident for a

medical review

• Clean up spill using wet methods/HEPA vacuuming

• Treat all clean up equipment as “contaminated”

• Dispose of waste appropriately
More NIOSH Guidance 6/2007

• Use standard engineering

controls

— Enclose source

— Local exhaust

— HEPA filters

• Administrative controls

— Wet methods

— Cleaning

— Training

• PPE

— HEPA filtered

respirators work

• Summary of NIOSH

research activities,

partnerships, lit review
ASTM E 2535-07 (10/07)
Key Features

• Broad scope--R&D, manufacturing, other

• Applicable where there are no exposure

standards, no robust risk information

• Applies to unbound engineered nanoparticles or

their respirable agglomerates or aggregates

—Up to 10 μm aerodynamic size (unusual)

• The Control Principle: Minimize exposures to

“As Low As Reasonably Practicable”

—NSRCs judged that we were already doing this

but refused to refer to it as ALARP
Key Features

• Requires:

—Formal written management policy

• Materials characterization and safety data

• Documentation of exposure and risk assessments

• Engineering and other analyses

• Work rules, SOPs, response plans

• Training materials

• Feedback process

• Periodic review of program

—Program manager

—Training
ASTM–Key Features

• Air sampling if possible

—Exposure limits–Starting points

• ACGIH–Insoluble PNOS exposure <3

mg/m3 respirable

• EPA Ambient Air Quality Standards PM2.5

35 μg/m3

• NIOSH Nano TiO2 standard–0.1 mg/m3

• Carbon Nanotubes–TLV for quartz 25 μg/m3
ASTM–Exposure Control

• Engineering controls work

—Isolation

—Fixation--use non-dusty techniques

—Waste minimization

—Local exhaust

—Containment (within room)

—HEPA filters
ASTM–Exposure Control

• Administrative controls

—Housekeeping

—No compressed air, dry sweeping

—Wet Methods

—Decontaminatable surfaces

—Good hygiene

—Access controls

—Attention to process control,

equipment commissioning

—Training

—Process control
ASTM–Exposure Control

• Medical surveillance–think about it!

• Consider non-routine activities–Maintenance,

commissioning, decommissioning

• Control material transfer between containers

• Manage containers and storage

—Used containers

• Plan for waste handling

• Be prepared to responding to spills

• Use PPE as necessary

—Make sure it will work for your nanoparticles

• Communicate the hazard–Signs and labels

—Identify the hazards

—Specify work locations

—Indicate methods to protect oneselve’s

• MSDSs–get or prepare good ones!!
ISO Technical Report 12885 (10/2008)

• Health and safety practices in occupational

settings relevant to nanotechnologies

—Literature review

—Exposure assessment techniques

• Air sampling

• Dermal exposure assessment

—Risk assessment strategies

—Exposure control strategies

—Administrative controls

—Recordkeeping

—Waste management, fire and explosion control

—PPE
ISO Technical Report 12885 (10/2008)

• Health surveillance

—Consider whenever there is exposure and a

measurable biological indicator

—Establish individual baselines rather than

relying on population “reference values”

—“Basic worker health monitoring program” is

the minimum (lifted from NSRC guideline)

• Maybe pulmonary, renal,m liver and hematopoietic

system function testing, maybe not!
NIOSH Medical Surveillance Guide (2/2009)
NIOSH Medical Guide (2/2009)
NIOSH Medical Guide (2/2009)

• “No substantial link has been established

between occupational exposures to engineered

nanoparticles and adverse health effects.”

• “...toxicological research to date is insufficient

to recommend such (medical) monitoring, the

appropriate triggers for it and components of it.”

• Lack of information on sensitivity, specificity,

predictive values of tests
NIOSH Medical Guide (2/2009)

• “...insufficient information is now available to

make any recommendations beyond hazard

surveillance.”

• “NIOSH continues to recommend occupational

health surveillance as an important part of an

effective risk management program.”

• ”...continue using established approaches to

collect data that may be informative in the future

about whether there is an increase in the

frequency of adverse health events related to

exposure to engineered nanoparticles”.

• “Lack of evidence...should not stop employers

who want to take additional precautions,

including medical screening...”
Newest NIOSH Guide (3/2009)

• Update of prior

guidance

• Some good

information

• Doesn’t change a

whole lot
EPA CNT Rules (Pending)

• “May present unreasonable risk to human

health...”

• Requires full face respirators with N-100 filters

for “manufacturers” of carbon nanotubes!

• Requires protective clothing and gloves!

• Read more:

—http://hs.environmentalexpert.com/resultEachPressRelease.aspx?cid

=4280&codi=53524&lr=1
OSHA (Cal and Federal)
New DOE 456.1 Policy (January 2009)

• DOE rule relating to nano work at DOE labs

• Failed process, flawed product

—Ignore unless you are a DOE contractor

—To be revised in Winter 2009-10, hopefully

better product
Everybody is Working On This!
Questions?
More stuff to look at
Still More
NanoCEO Site/ICON

• Also ICON at

http://icon.rice.edu/