Handling Pyrophoric and Other Highly Reactive Materials

Required: Before beginning a new project, get approval from your principal investigator (PI) to work with a pyrophoric or highly reactive chemical.

Required: The PI must provide appropriate, rigorous, and documented safety training.

• Instruct employees about the hazards and risks of handling pyrophoric materials and how to protect themselves. Ensure that:
  • A safety protocol is written into the research procedure.
  • Material Safety Data Sheets (MSDS), the manufacturer's handling instructions, and UCSD standard operating procedures are carefully read.
• Inform employees about possible health effects and routes of exposure (e.g., ingestion, inhalation, and skin contact). See:
  • Exposure response
• Provide and train employees in the correct use of:
  • Personal protective equipment (PPE)
  • Engineering controls
• Make sure everyone understands what to do in case of emergency by posting emergency procedures in the lab:
  • Emergency Guide
• Ensure fire extinguisher training is completed by employees who work with or near pyrophoric materials. See:
  • Staff Ed Fire Extinguisher Training
• Keep training records that include:
  • Topics covered
  • Materials distributed
  • Date
  • Employee names
  • Employee signatures

Evaluate the hazards before beginning work:

• Consult safety resources:
  • MSDS
  • Prudent Practices in the Laboratory: Handling and Disposal of Chemicals (1995), The National Academies Press:
    • Butyllithiums
    • Sodium (reactive metal)
    • Lithium aluminum hydride
  • Technical bulletins:
    • Handling Pyrophoric Reagents - Aldrich Chemical Company, Inc., Technical Bulletin AL-164 (PDF)
    • Handling Air-Sensitive Reagents, Sigma-Aldrich Co., Technical Bulletin AL-134 (PDF)
    • Safe Handling of Organolithium Compounds in the Laboratory (PDF), Chemical Health & Safety, May-June 2002
  • Safety alerts:
    • Laboratory Research Associate Dies of Burns from a Pyrophoric Chemical (PDF), California Department of Public Health, April 2009
    • Research Associate Dies from Burns Sustained While Working with a Pyrophoric Chemical, National Institute for Occupational Safety and Health, California FACE Report #09CA001
• Consider these hazards specific to pyrophoric materials:
  • High fire hazard
  • Special atmospheric conditions:
    • Some experiments may require dry or inert atmospheres.
  • Other common hazards:
    • Corrosivity
    • Teratogenicity
    • Water reactivity
    • Peroxide formation
    • Damage to the liver, kidneys, and central nervous system

• Know the locations and how to use the nearest:
  • Eyewash and safety shower
  • Emergency Guide
  • First aid kit
  • MSDS: Print and keep a copy with your emergency supplies.
  • Appropriate fire extinguisher: Avoid incompatible extinguishing agents:
    • Class A,B,C for pyrophoric liquids and supporting flammable solvents
    • Class D for reactive metals
      • Extinguishers containing water are not suitable for reactive metals.
      • Extinguishers containing or developing water, carbon dioxide or halons are not suitable for firefighting organolithium compounds as they react violently.
    • Contact EH&S Fire & Life Safety, (858) 822-7515, for questions regarding appropriate fire extinguishers.
• Prepare for spills. Clean up only very small quantities and only if you have been properly trained.
  • Read How to Handle Chemical Spills in Laboratories.
  • Keep a chemical spill kit easily accessible.
  • Use powdered limestone to completely smother and cover any organolithium reagent spill (sand is not suitable). Keep a container within arm’s length.
  • Dispose of spill containment materials as hazardous chemical waste. See:
    • Hazardous waste disposal

Class D fire extinguisher for reactive metals Image courtesy Lab Safety Supply

Required PPE: Anyone at risk must wear:

• Flame resistant lab coat at all times
  • Fully extend sleeves to the wrists.
  • Keep lab coat fully buttoned at all times.
• Full-length, non-synthetic pants
• Safety glasses or splash goggles (for higher volumes of reagents) with a face shield for work with liquids
• Appropriate gloves
  • Never re-use disposable gloves.
• Closed-toe shoes

Notes:

• Never wear synthetic materials as they may ignite causing severe burns (e.g., polyester or nylon).
• Leave all PPE in the lab when not in use.
• EH&S may be able to provide a a Nomex® lab coat and a high impact face shield (see images at left). Contact your EH&S Research Assistance Program specialist.

Flame resistant lab coat
(Click image to enlarge)
Flame resistant lab coat detail
Oberon Face Shield
Image courtesy Lab Safety Supply

Required:

• Use at least 1 of the following engineering controls:
  • Fume hood: Work inside a chemical fume hood at all times.
  • Glove box: When inert or dry atmospheres are required.
  • Portable explosion shield: May also be required to control the risk of explosion.
  • Gas cabinet: Contact an EH&S Research Assistance Program specialist to ensure your cylinders meet the gas policy. See the requirements of using pyrophoric gases:
    • UCSD's compressed gas policy
    • Caution: Changing cylinders is among the most dangerous aspects of working with pyrophoric gases. Do not change out a cylinder unless you have been trained to safely do so.
• Use less dangerous, more stable products when you can.
• Before conducting the actual procedure, always perform a dry run to identify and resolve possible safety hazards.
• Never work alone. Always work with a partner and inform colleagues in the area about the hazards of your project.
• Establish a designated, restricted access area:
  • Clear the area of unrelated and possibly incompatible hazards, especially flammable liquids.
  • Keep container sizes and quantities in the work area as small as possible.
  • Transport material in secondary containers and only in small quantities.

Treat any exposure seriously, no matter how slight it may seem at the moment.

• All exposures:
  • Be prepared to act quickly should clothing or skin catch fire.
  • Give first aid treatment, and then seek medical attention immediately as needed.
  • Call Campus Police at (858) 534-4357 (534-HELP) and request an ambulance, if transportation is necessary.
  • Call Poison Control, (800) 222-1222, if additional information is needed.
• Ingestion: Seek medical attention immediately.
• Skin exposure: Flush exposed skin with water for at least 15 minutes while removing any contaminated clothing.
• Eye exposure: Flush eyes with water for at least 15 minutes. Affected individuals may need help holding their eyes open under water. Seek medical attention immediately at an emergency room.

See Chemical Storage and Inventory Guidelines and follow these specifics:

• Meet safe storage requirements for each specific material, and store:
  • Group 1 metals under mineral oil
  • Under an atmosphere of inert gas, if required
  • Organolithium compounds at temperatures 25 C or below
• Avoid inadvertent incompatibles:
  • Heat/ flames, oxidizers, and water sources
  • CO² and fluorocarbons react exothermically with lithium alkyls
  • Protonactive substances (e.g., alcohols, amines, mercaptanes, and acids)
  • Halogenated compounds (e.g., solvents like tetrachloromethane, chloroform), as well as compounds with multiple bonds (e.g., ketones, nitriles) and oxidizing agents react vigorously with organolithium compounds
• Contact an EH&S Research Assistance Program specialist if you have questions about chemical and container compatibility.

Read these articles to help you identify and dispose of hazardous waste:

• Identify Hazardous Chemical Waste
• Store and Dispose of Chemical Waste
• Store and Dispose of Extremely Hazardous Chemical Waste
• Request a Hazardous Waste Collection

Note: Alert EH&S hazardous waste technicians when you request collection of pyrophoric materials.