Identification and Management of Shock Sensitive

1
Identification and Management of Shock Sensitive
Reactive Chemicals

• Lydia Boada-Clista
• U.S. Department of Energy
• Ohio Field Office

2
Identification and Management of Shock Sensitive
Reactive Chemicals

• Thousands of containers of chemicals are in use
  at DOE facilities and laboratories. Amongst
  these are several classes of chemicals that may
  pose significant health and safety risks to the
  worker. These include
• - Shock
• - Reactive Chemicals, and
• - Energetic Compounds

3
Identification and Management of Shock Sensitive
Reactive Chemicals

• This presentation focuses on the following
  aspects of chemical management
• - Identification of Highly Hazardous
  Chemicals
• - Management and Handling of Highly
  Hazardous Chemicals
• - Treatment and Disposition of Shock
  Sensitive Chemicals
• - Identification of Energetic Compounds

4
Identification and Management of Shock Sensitive
Reactive Chemicals

• - Management of Energetic Compounds
• - Handling and Disposition of Energetic
  Compounds
• - Regulatory Issues
• - Recent Chemical Disposition Efforts at
  Mound
• - Questions and Answers

5
Identification and Management of Shock Sensitive
Reactive Chemicals

• Identification of Highly Hazardous Chemicals
• - Over 60,000 chemicals, trade names and
  synonyms
• - Many of these pose high hazards through
  their reactive or highly toxic nature
• - Many of these are present at DOE
  facilities and laboratories

6
Identification and Management of Shock Sensitive
Reactive Chemicals

• Identification (cont..)
• - REACTIVE CHEMICALS are those chemicals
  that react with air, water or other materials
  resulting in the generation of toxic gases or
  large quantities of heat. The gas and heat
  generation may result in significant pressures
  when the material is compressed or contained.

7
Identification and Management of Shock Sensitive
Reactive Chemicals

• Identification (cont)
• - PEROXIDIZABLE COMPOUNDS are
• solvents and reagents (i.e., ether, dioxane,
  THF) that form reactive peroxides by
  reacting with molecular oxygen through a
  process called autoxidation or
  peroxidation.
• Peroxides in solutions greater than 1 percent
  present a
• significant hazard
• Lower concentration may still be hazardous if
  peroxides
• have accumulated on the walls of the container
  or near
• the cap

8
Identification and Management of Shock Sensitive
Reactive Chemicals

• Identification (cont)
• - Reactive Chemicals May Cause
• Spontaneous combustion, conflagration or
  explosion
• Generation of toxic gas such as hydrogen cyanide
  or
• hydrogen Sulfide
• - Peroxidizable Chemicals Become More
• Dangerous as Time Passes
• Formation of shock sensitive peroxides
• Common in certain highly volatile chemicals
• Also possible with Organometallic compounds

9
Identification and Management of Shock Sensitive
Reactive Chemicals

• Management Handling Highly Hazardous Chemicals
• - Have an Effective Chemical
  Management Program at Your Site
• - Have Written Procedures and Training at
• Your Facility for Proper Management
• - Have Procedures that Specify Actions to
• be Taken When Problems are Identified

10
Identification and Management of Shock Sensitive
Reactive Chemicals

• Inventory Control
• - Maintain Up-to-Date Chemical Inventory
• - Create a Subcategory on Inventory to
• Track High Hazard Chemicals, Especially
• Peroxidizable Chemicals
• - Use Chemicals on a First-In / First-Out
  Basis
• - Purchase and Store Small Quantities (Only
• what will be used in a three to twelve
  month
• period)
• - Look for Less Hazardous Substitutes
• - Ensure Proper Labeling
• 
  
  

11
Identification and Management of Shock Sensitive
Reactive Chemicals

• Management Handling (cont.)
• Storage and Use
• - Proper Storage, as Applicable, for
  Chemicals
• Flammable Cabinets
• Temperature Control
• Inert Atmosphere
• Keep Containers Sealed Tight
• - Refer to MSDS for Special Requirements
• Store out of Light and Away from Heat
• or Ignition Sources

12
Identification and Management of Shock Sensitive
Reactive Chemicals

• Management Handling (cont..)
• - Sunlight is Especially Dangerous
• - Treat all Peroxidizable Chemicals as if
  They Have Peroxide Accumulation
• - Test Peroxidizable Compounds for
  Peroxide Accumulation
• - Dispose of Older or Unused Chemicals
• - Use Caution When Distilling or
  Evaporating Peroxidizable Chemicals

13
Identification and Management of Shock Sensitive
Reactive Chemicals

• Management Handling (cont..)
• - Testing for Peroxidization
• Test every three or twelve months depending on
  the chemical
• Use the proper test methods (iodide test,
  ferrous
• thiocyanate test, and test strips)
• Test only actively used chemicals
• - Inspect Containers Prior to Each Use
• Check for discoloration
• Check for crystallization

14
Identification and Management of Shock Sensitive
Reactive Chemicals

• Treatment Disposition
• - Do Not Handle or Open Containers Suspected
  of Containing Accumulated Peroxides
• - Do Not Open Containers That Have Been
  Stored For Long Periods Without Testing
• - Keep Personnel Out of the Area
• - Post and Control Access to the Area
• - Contact Trained Specialist, the Fire
• Department, or the Bomb Squad

15
Identification and Management of Shock Sensitive
Reactive Chemicals

• Treatment Dispositions
• - Treatment by Passing Through a Column of
  Activated Alumina
• - Treatment of Water-Soluble Compounds
• With a concentrated Ferrous Salt
  Solution
• - There are Several Other Reduction Methods
  Each Specific to the Type of Peroxidized
  Compound
• - Controlled Detonation by Bomb Squad

16
Identification and Management of Shock Sensitive
Reactive Chemicals

• Treatment Disposal
• - Reactive Metals Can be Placed Into Stable
  Environments
• Handling Methods
• - Handle with Remote Equipment
• - Handle in Inerted Containment
• - Use of Intrinsically Safe Tools and
  Equipment
• - Use Proper Personal Protective
  Equipment

17
Identification and Management of Shock Sensitive
Reactive Chemicals

• Disposal
• - Disposal by Detonation or Burning
• - Disposal through Professional Waste
• Management Company

18
Identification and Management of Shock Sensitive
Reactive Chemicals

• Special Conditions for Radiological Facilities
• - Must Address Radiological Facilities
• - Detonation not a Viable Method
• - Stabilize/Reduce Peroxides and Add an
• Inhibitor
• - Sample for Radiological Contamination
  and Attempt Unrestricted Release to a Waste
  Disposal Facility
• - Solidify in Polymer if Contaminated

19
Identification and Management of Shock Sensitive
Reactive Chemicals

• Identification of Explosive Compounds
• - Numerous Energetic Compounds Have Been and
  are Still in Use at DOE Facilities
• - Used for Manufacture of Explosive
• Components
• - Discovered Frequently at Facilities
• Undergoing Decommissioning
• - Usually in Gram Quantities or Less
• - Can Present Significant Risk to Workers

20
Identification and Management of Shock Sensitive
Reactive Chemicals

• Identification of Explosives
• Types of Energetic Material
• PETN Lead Axide
• TATB HMX
• HNS PBX
• HNAB N Lead Styphnate
• RDX TIHX

21
Identification and Management of Shock Sensitive
Reactive Chemicals

• Managing Energetic Compounds
• - Follow the Requirements of the DOE
• Explosives Manual
• - Have Written Procedures for Management of
  These Materials
• - Have Trained and Qualified Personnel
• - Maintain an Up-to-Date Inventory

22
Identification and Management of Shock Sensitive
Reactive Chemicals

• Managing Energetic Compounds
• - Proper Storage
• - Grounded Work Surfaces
• - Intrinsically Safe Tools and Equipment
• - Store and Transport Using Explosives Cases
• - Follow Posted Guidelines and Quantity
• Restrictions
• - Proper Personal Protective Equipment

23
Identification and Management of Shock Sensitive
Reactive Chemicals

• Disposition of Energetic Materials
• - Package and Ship to a Waste Disposal
• Company Licensed to Handle Explosives
• - Mound Used Safety Kleen (Formerly
  Laidlaw Thermal Services) in Louisiana
• - Determine if Other Facilities can Use
• These Materials or Devices
• - Special Requirements for Shipping and
  Transportation

24
Identification and Management of Shock Sensitive
Reactive Chemicals

• Radiological Issues
• - No Commercial Disposal Option if Energetic
  Materials have Radiological Contamination
• - Dissolve Material in Appropriate Solvent
• - Sample for Radiological Activity
• - Attempt Unrestricted Release to
  Commercial Waste Disposal Facility
• - Solidify/Polymerize Material if
  Contaminated

25
Identification and Management of Shock Sensitive
Reactive Chemicals

• Regulatory Issues
• - OSHA (Lab Safety and Industrial
  Standards) for Storage and Handling
• - OSHA (HAZWOPER) for Disposition
• - RCRA (Hazardous Waste Requirements-
• Most of These Chemicals will be D001
  Ignitable and/or D003 Reactive Waste)
• - RCRA (Emergency Treatment Permit,
• Temporary Treatment Permit, or Generator
• Treatment)

26
Identification and Management of Shock Sensitive
Reactive Chemicals

• Recent Efforts At Mound
• - Mound Chemical Disposition Project 1998
• Disposed of more than 8000 containers of
• excess chemicals
• gt 1000 Gas Cylinders
• gt 1000 RCRA Hazardous Chemicals
• gt 750 Mixed (Radioactive/RCRA) Chemicals
• gt 2200 Non-Radioactive Chemicals
• gt 3000 Radioactive Chemical
• gt 750 Unknowns Sampled Characterized

27
Identification and Management of Shock Sensitive
Reactive Chemicals

• Mound (cont.)
• - 15 Container of Ether, Dioxane, and THF
• Stabilized and Inhibited. These were
  then Sampled, Released and Sent to Off- Site
  Waste Disposal
• - 2 Containers of Potassium Metal were
• Surveyed, then Stabilized in an Inerted
  Glove Box with Mineral Oil, and Released for
  Off-Site Disposal

28
Identification and Management of Shock Sensitive
Reactive Chemicals

• Mound (cont)
• - 17 Classified Energetic Components were
  Machined on a Remote Operation Lathe to
  Remove Energetic Material and Declassify the
  Component
• - 27 Energetic Powders from a Radiological
  Contamination Area were
• Dissolved in Acetone or DMSO, Sampled, and
  Released for Off-Site
• Waste Disposal

29
Identification and Management of Shock Sensitive
Reactive Chemicals

• Mound (cont.)
• - Packaged and Shipped Remaining 95
• Energetics Off-Site for Disposal
• - Disposed of 48 Reactive Pyrotechnic
• Powders
• - No Contamination Incidents
• - No Spills or Releases
• - No Accident or Injuries to Workers

30
Identification and Management of Shock Sensitive
Reactive Chemicals

• Questions Answers
• Credits
• - Babcock Wilcox of Ohio (Mound)
• - John Ross, Los Alamos Technical
• Associates