Ames Procedural
Requirements

APR 1700.1

Last Revised: 09-21-2010

COMPLIANCE IS MANDATORY

Ames Health & Safety Procedural Requirements

Chapter 50 - Nanomaterials Safety and Health Guideline For Carbon-based nanomaterials

Table of Contents

50.1 Overview
50.2 Scope
50.3 Definitions and Background
50.4 Suspected Toxicity Concerns (For Handling Carbon-Based Nanomaterials, Lunar Dust, Terrestrial Reference Materials, and Quantum Dots)
50.5 Referenced Documents
50.6 Personnel Training and Certification
50.7 Required Lab Facility and Materials
50.8 Procedures for Handling Nanomaterials
50.9 General Safety Requirements
50.10 Hazard Exposure Assessment
50.11 Spill Response Forall Carbon-Based Nanomaterials
Appendix A: Ames Research Center Nanomaterials Hazard Exposure Assessment Form

50.1 Overview

This chapter provides the safety and health guidelines for the use of manufactured nanoparticles in research laboratories. These guidelines address recommended safety precautions applicable when these materials are used at Ames Research Center. Carbon nanostructured materials are most commonly used and produced in the research labs at Ames. These carbon nanostructured materials include single walled carbon nanotubes, multiwall carbon nanotubes, graphene sheets, fullerenes, and catalysts used to manufacture these materials. This document contains the most up-to-date safety procedures and shall be updated periodically as nanoparticle toxicological information becomes available. This document will be included as a part of the Ames Health and Safety Manual.

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50.2 Scope

This Chapter states the basic policy, requirements, and procedures for protection of employees from the hazards of occupational exposure to nanomaterials.

The safety procedures discussed in this document are applicable to any laboratory operations involving the handling of the manufactured nanoparticles, including carbon-based nonomaterials, lunar dust (including terrestrial reference materials), and quantum dot nonparticles.

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50.3 Definitions and Background

Nanometer – One billionth of a meter. Engineered Nanomaterials (manufactured nanoparticles) – Particles that have been purposefully manufactured or synthesized to have a size with at least one dimension in the range of about 1-100nm.

Carbon-based nanomaterials – Materials composed mostly of carbon, most commonly taking the form of a hollow sphere, ellipsoids or tubes. Spherical & ellipsoidal types of carbon materials are referred to as fullerenes. Cylindrical ones are called nanotubes.

Metal-based nanomaterials – These nanomaterials include nanocrystals, quantum dots, catalysts particles, thin-films, and nanowires.

Functionalized nanomaterials- Basic nanomaterials to which specific functional groups have been coupled, either by covalent bonding or Van der Waals associations.

HEPA filter – High efficiency particulate air filter. This type of air filter can remove at least 99.97% of airborne particles 0.3μm in diameter. These filters are composed of a mat of randomly arranged fibers. The particles become trapped in the filter by interception, impaction, and diffusion mechanisms.

Spill kit – Spray bottles containing water and disposable wipes, to be specifically used for cleaning surfaces contaminated with carbon-based nanomaterials.

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50.4 Suspected Toxicity Concerns (For handling carbon-based nanomaterials)

Nanomaterials often exhibit unique physical and chemical properties that impart specific characteristics essential in making engineered materials, but little is known about what effect these properties may have on human health. Research has shown that the physiochemical characteristics of particles can influence their effects in biological systems. These characteristics include: particle size, shape, surface area, aspect ratio, charge, chemical properties, solubility, and degree of agglomeration. Until the results from research studies can fully elucidate the characteristics of nanoparticles that may potentially pose a health risk, precautionary measures are warranted.

Taken from Version 1.1 Approaches to Safe Nanotechnology: An Information Exchange with NIOSH (ix).

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50.5 Referenced Documents

EPA 100/B-07/001 U.S. Environmental Protection Agency (EPA) Nanotechnology White Paper. Science Policy Council, February 2007.

SOP-009.63 Nanotube Handling SOP. Lyndon B. Johnson Space Center, August 2003.

Carbon Nanotube Safety and Handling. P. Nikolaev, W. Holmes, S. Arepalli. ERC Inc./ NASA Johnson Space Center.

Version 1.1 Approaches to Safe Nanotechnology: An Information Exchange with NIOSH. Department of Health and Human Services, July 2006.

American Chemical Society http://membership.acs.org/c/ccs/nano.htm (Provided by and with permission of Dr. Peter Lichty of Lawrence Berkeley National Laboratory)

University of California http://labs.ucop.edu/internet/ES&H/draft_hs_guidelines.html

ICON (International Council on Nanotechnology) http://icon.rice.edu/

Chemwatch MSDS: http://coll.chemwatchna.com/

University of California, Davis SafetyNet#132

http://safetyservices.ucdavis.edu/environmenatal-health-safety/safetynets/master-list-1/nanotechnology-guidelines-for-safe-research-practices

Approaches to Safe Nanotechnology: Managing the Health and Safety Concerns Associated with Engineered Nanomaterials DHHS (NIOSH) Publication No. 2009-125

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50.6 Personnel Training and Certification

Before starting work in laboratories, safety training classes are required. Consult your supervisor or task requester for required and recommended safety training classes. This Nanomaterials Safety and Health Guideline is to supplement the safety training received in these classes. A copy of this Nanomaterials Safety and Health Guideline shall be made available to all researchers.

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50.7 Required Lab Facility and Materials

50.7.1 Lab Facility

1. Fume exhaust hood
2. Local exhaust ventilation associated with reactors
3. H2O or organic solvent spray bottles
4. Tacky mats covering floors at lab entrance and high use areas
5. Weekly lab bench, counter and floor wet mopping
6. Dedicated nanomaterial storage and labeling

50.7.2 Personal Protective Equipment (PPE)

1. Safety goggles
2. Nitrile gloves (or other impermeable gloves dependent on solvent or dispersing agent)
3. Disposable N95 or better masks (if fume hood is not available)
4. Lab coats (disposable preferred)
5. Open sandals, shorts, and skirts are prohibited

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50.8 Procedures for Handling Nanomaterials

50.8.1 Handling Carbon-Based Nanomaterials

1. Follow the general laboratory safety procedures as discussed in the Lab Safety Plan (LSP) and Standard Operating Procedures (SOP). Include specific procedures for handling nanomaterials in the Lab Safety Plan and SOP.
2. Conduct PPE assessment to ensure PPE selection is appropriate for the specific procedure.
3. Weighing dry, loose carbon nanoparticles must be done in a fume hood or a glove box.
4. Dry, loose carbon nanomaterials should be stored in sealed containers to avoid accidental dispersion of materials into the air and to avoid fire hazard. If more than 1g is required at a time, they should be stored in metal containers to avoid electrostatic discharge.
5. Manipulating quantities of dry, loose carbon nanomaterials greater than 1g require additional precautions, and shall be reviewed with management and the Nanomaterials Safety Committee before proceeding.
6. Routine handling of dry, loose carbon nanomaterials should be carried out in fume hoods or glove boxes until such time as the material is dissolved or suspended in liquid or become physically attached to a solid material.
7. If it is necessary to manipulate dry, loose carbon nanomaterials outside of the fume hood, a job hazardous analysis will be required, to include contained work area, use of respiratory protection, and clean up.
8. If the carbon-based nanomaterials are in solution or liquid suspension, then the quantity handled may exceed 1g. Use of the hood may be required by the safety requirements of the liquid.
9. Safety goggles, nitrile gloves and closed toe shoes are required in the laboratory. Lab coats are required when there is a risk of contaminating clothing. If there is a significant contamination of the lab coat or clothing, it should be disposed of as hazardous waste. Always rinse-off or change gloves once they are exposed to nanomaterials.
10. Avoid skin contact with nanoparticles or nanoparticle-containing solutions by using appropriate PPE.
11. Use fume hood exhaust to expel fumes from tube furnaces or chemical reaction vessels.
12. To prevent accumulation of nanomaterials on work area surfaces, routine cleaning is necessary. Bench surfaces and other work areas should be routinely damp-wiped. Frequency depends on laboratory usage, but at least weekly for active labs. If the work area surfaces are known to be contaminated, they should be cleaned immediately. Always have spray bottles and laboratory wipes handy.
13. Dispose of nanomaterials and cleaning materials (wipes) as hazardous waste.
14. Lab equipment and exhaust systems should be cleaned with water or other solvents prior to their removal, remodeling or repair.

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50.8.2 Procedure for handling lunar dust and terrestrial reference materials

1. Follow the general laboratory safety procedures as discussed in the Lab Safety Plan (LSP) and Standard Operating Procedures (SOP). Include specific procedures for handling nanomaterials in the Lab Safety Plan and SOP.
2. Conduct job hazard analysis (JHA) and PPE assessment to ensure procedures and PPE selection are appropriate.
3. Dry lunar dust, lunar dust simulants and terrestrial reference materials should be stored in sealed containers to avoid accidental dispersion of material into the air.
4. Manipulating quantities of dry, lunar dust, lunar dust simulants and terrestrial materials, by methods such as grinding or milling should be done inside the fume hood or glove box.
5. Safety goggles, gloves and closed toe shoes are required in the laboratory. Lab coats are required when there is risk of contaminating clothing. If there is a significant contamination of the lab coat or clothing, it should be disposed of as hazardous waste. Always rinse-off or change gloves once they are exposed to nanomaterials.
6. Avoid skin contact with nanoparticles or nanoparticle-containing solutions by using appropriate PPE.
7. To prevent accumulation of mineral particles on work area surfaces, routine cleaning is necessary. Bench surfaces and other work areas should be routinely damp-wiped. Frequency depends on laboratory usage, but at least weekly for active labs. If the work area surfaces are known to be contaminated, they should be cleaned immediately. Always have spray bottles and laboratory wipes handy.
8. Dispose of mineral particles and cleaning materials (wipes) as hazardous waste.
9. Lab equipment and exhaust systems should be cleaned with water or other solvents prior to their removal, remodeling or repair.

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50.8.3 Procedure for handling zinc oxide

1. Follow the general laboratory safety procedures as discussed in the Lab Safety Plan (LSP) and Standard Operating Procedures (SOP). Include specific procedures for handling nanomaterials in the Lab Safety Plan and SOP.
2. Conduct job hazard analysis (JHA) and PPE assessment to ensure procedures and PPE selection are appropriate.
3. Manipulating any quantity of dry zinc oxide must occur inside the fume hood or glove box as to prevent harmful exposure of airborne particles and/or fumes.
4. Dry zinc oxide should be stored in sealed containers to avoid accidental dispersion of materials into the air.
5. Weighing dry zinc oxide particulates should always occur inside a fume hood or a glove box. A balance specificed for this purpose should be provided.
6. Assuming an 8 hour exposure, the threshold exposure limit for dry zinc oxide is set at 10mg/m3 (OSHA PEL). If the quantity used exceeds this limit, additional precautionary measures need to be taken and will need to be reviewed with management and the Nanomaterials Safety Committee before proceeding.
7. Safety goggles, impermeable gloves and closed toe shoes are required in the laboratory. Choice of gloves should be determined based upon the type of solvent or dispersing agent. Lab coats are required when there is a risk of contaminating clothing. Disposable lab coats should be considered if the risk of contamination is high. If there is a significant contamination of the lab coat or clothing, it should be disposed of as hazardous waste. Prior to disposal of gloves, rinse-off gloves to prevent accidental aerosolization of material and accidental skin exposure. Contaminated lab clothing and gloves should be bagged (placed in a plastic bag, then sealed) prior to disposal.
8. Avoid skin contact with nanoparticles or nanoparticle-containing solutions by using appropriate PPE.
9. To prevent accumulation of nanomaterials on work area surfaces, routine cleaning is necessary. Bench surfaces and other work areas should be routinely damp-wiped. Frequency depends on laboratory usage, but at least weekly for active labs. If the work area surfaces are known to be contaminated, they should be cleaned immediately. Always have spray bottles and laboratory wipes handy.
10. Nanomaterials and clean up materials (wipes) should be bagged prior to disposal and should be disposed of as hazardous waste.
11. Lab equipment and exhaust systems should be cleaned with water or other solvents prior to their removal, remodeling or repair.

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50.8.4 Procedure for handling cadmium selenide

1. Follow the general laboratory safety procedures as discussed in the Lab Safety Plan (LSP) and Standard Operating Procedures (SOP). Include specific procedures for handling nanomaterials in the Lab Safety Plan and SOP.
2. Conduct job hazard analysis (JHA) and PPE assessment to ensure procedures and PPE selection are appropriate.
3. Manipulating any quantity of dry cadmium selenide must occur inside the fume hood. When working with dry cadmium selenide, it is especially important to work inside the fume hood, since harmful concentration of airborne particles can be reached quickly for cadmium selenide fume particles.
4. Dry cadmium selenide should be stored in sealed containers to avoid accidental dispersion of materials into the air.
5. Weighing cadmium selenide particulates should always occur inside a fume hood or a glove box. A balance specificed for this purpose should be provided.
6. For work procedures involving materials that have the potential to become aerosolized a respirator may be required. For evaluation for need for respirator consult QH (Health and Safety).
7. When handling quantum dot nanoparticles suspended in solution, always use chemical resistant gloves that are appropriate for the type of chemical exposure.
8. Assuming an 8 hour exposure, the threshold exposure limit for cadmium selenide is set for 0.2mg/m3 (Chemwatch). For nanoscale preparation, this exposure limit may not apply.
9. Safety goggles, impermeable gloves and closed toe shoes are required in the laboratory. Choice of gloves should be determined based upon the type of solvent or dispersing agent. Lab coats are required when there is a risk of contaminating clothing. Disposable lab coats should be considered if the risk of contamination is high. If there is a significant contamination of the lab coat or clothing, it should be disposed of as hazardous waste. Prior to disposal of gloves, rinse-off gloves to prevent accidental aerosolization of material and accidental skin exposure. Contaminated lab clothing and gloves should be bagged (placed in a plastic bag, then sealed) prior to disposal.
10. Avoid skin contact with nanoparticles or nanoparticle-containing solutions by using appropriate PPE.
11. To prevent accumulation of nanomaterials on work area surfaces, routine cleaning is necessary. Bench surfaces and other work areas should be routinely damp-wiped. Frequency depends on laboratory usage, but at least weekly for active labs. If the work area surfaces are known to be contaminated, they should be cleaned immediately. Always have spray bottles and laboratory wipes handy.
12. Nanomaterials and clean up materials (wipes) should be bagged prior to disposal and should be disposed of as hazardous waste.
13. Lab equipment and exhaust systems should be cleaned with water or other solvents prior to their removal, remodeling or repair.

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50.8.5. Procedure for handling gold nanoparticles

1. Follow the general laboratory safety procedures as discussed in the Lab Safety Plan (LSP) and Standard Operating Procedures (SOP). Include specific procedures for handling nanomaterials in the Lab Safety Plan and SOP.
2. Conduct job hazard analysis (JHA) and PPE assessment to ensure procedures and PPE selection are appropriate.
3. Manipulating any quantity of dry gold nanoparticles must occur inside the fume hood.
4. Dry gold nanoparticles should be stored in sealed containers to avoid accidental dispersion of materials into the air.
5. Weighing gold nanoparticulates should always occur inside a fume hood or a glove box.
6. If there are substantial metal impurities present, additional safety procedures may be required.
7. Safety goggles, impermeable gloves and closed toe shoes are required in the laboratory. Choice of gloves should be determined based upon the type of solvent or dispersing agent. Lab coats are required when there is a risk of contaminating clothing. Disposable lab coats should be considered if the risk of contamination is high. If there is a significant contamination of the lab coat or clothing, it should be disposed of as hazardous waste. Prior to disposal of gloves, rinse-off gloves to prevent accidental aerosolization of material and accidental skin exposure. Contaminated lab clothing and gloves should be bagged (placed in a plastic bag, then sealed) prior to disposal.
8. Avoid skin contact with nanoparticles or nanoparticle-containing solutions by using appropriate PPE.
9. To prevent accumulation of nanomaterials on work area surfaces, routine cleaning is necessary. Bench surfaces and other work areas should be routinely damp-wiped. Frequency depends on laboratory usage, but at least weekly for active labs. If the work area surfaces are known to be contaminated, they should be cleaned immediately. Always have spray bottles and laboratory wipes handy.
10. Nanomaterials and clean up materials (wipes) should be bagged prior to disposal and should be disposed of as hazardous waste.
11. Lab equipment and exhaust systems should be cleaned with water or other solvents prior to their removal, remodeling or repair.

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50.9 General Safety Requirements

1. No eating or drinking in any of the labs
2. If needed, the Ames Procedural Requirements (APR 1700) for laboratory safety can be reviewed at the following websites: http://server-mpo.arc.nasa.gov/Services/CDMSDocs/Centers/ARC/Home.tml
3. Chemical Hygiene: Ch 13 @ q.arc.nasa.gov/safetymanual
4. Personal Protective Equipment: Ch 33 @ q.arc.nasa.gov/safetymanual
5. Compressed Gas Cylinder Safety: Ch 44 @ q.arc.nasa.gov/safetymanual
6. Lab Safety Plan (LSP), Standard Operating Procedures (SOP), and MSDS are required documentations to be read by everyone and kept in the labs at all times. Job Hazard Analysis Worksheet (JHA) may be required for some lab procedures.
7. When setting up new equipment for an experiment, contact the Occupational Safety Health and Medical Services Division to obtain advice on hazard control measures.
8. When setting up new equipment, contact the Environmental Services Division to obtain advice on requirements for air permits and hazardous waste disposal requirements.

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50.10 Hazard Exposure Assessment

1. Hazards Assessments shall be conducted prior to beginning work with manufactured nanomaterials by a qualified industrial hygienist to identify appropriate work procedures, controls , and personal protective equipment to ensure worker safety. The assessment shall evaluate several factors, including, but not limited to, the physical and chemical properties of the nanomaterial, the process by which the material will be generated and /or used, and existing engineering controls (e.g.,fume hood, glove box.).
2. All exposures to manufactured nanomaterials shall be kept to a minimum by utilizing the basic hierarchy of controls described below:

3. Assessments of exposure of lab workers to carbon-based nanomaterials shall be documented in the lab safety plan. The form in Appendix A may be used for this purpose.
4. The Ames Health Unit shall inquire about working with engineered carbon nanomaterials as part of the recorded information in medical histories and maintain this information as part of the employee’s medical record.

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50.11 Spill Response Forall Carbon-Based Nanomaterials, lunar dust, terrestrial reference material, quantum dot nanoparticles, and gold nanoparticles

1. Laboratories working with nanomaterials shall maintain a spill kit suitable for decontamination of spills of the materials they are using.
2. Except for very small spills that can easily be cleaned in less than 5 minutes, laboratory employees shall leave the area or don a respirator and disposable protective clothing and comply with requirements for emergency response by hazardous materials users specified in APR 8800 Chapter 15
3. . Suspensions of carbon nanoparticles may be absorbed with Kimwipes or cleaning cloths. Clean up promptly before the surface dries. If the surface begins to dry, re-wet the area immediately.
4. For dust or powders of carbon nanoparticles, damp cleaning methods are preferred. Contaminated surfaces should be sprayed with a water mist, then wiped clean. Electrostatic microfiber cleaning cloths may be used to wipe instrument surfaces that water may damage.
5. Contaminated cleaning cloths and disposable protective clothing shall be bagged in plastic bags and disposed as hazardous waste in accordance with APR 2800 Chapter 4. Lab coats should be laundered when practical.
6. Drying and reuse of cleaning cloths is prohibited, as this practice can result in re-dispersion of particles.
7. Energetic cleaning methods such as dry sweeping, vacuuming, or the use of compressed air shall be prohibited unless precautions are taken to ensure that particles suspended by cleaning action are trapped by HEPA filters.
8. If a spill is beyond the capability of laboratory personnel to handle, their only required action is to call 911 and prevent personnel other than designated hazardous material emergency response team members from entering the affected area.

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Appendix A

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