# Presentation: 479271

## Identification and Management of Shock Sensitive & Reactive Chemicals

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

## 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

## 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

## 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

## 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

## 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.

## 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

## 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

## 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

## 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

## 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

## 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

## 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

## 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

## 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

## 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

## Identification and Management of Shock Sensitive & Reactive Chemicals

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

## 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

## 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

## 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

## 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

## 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

## 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

## 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

## 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)

## 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:
-  > 1000 Gas Cylinders
-  > 1000 RCRA Hazardous Chemicals
-  > 750 Mixed (Radioactive/RCRA) Chemicals
-  > 2200 Non-Radioactive Chemicals
-  > 3000 Radioactive Chemical
-  > 750 Unknowns Sampled & Characterized

## 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

## 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

## 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

## Identification and Management of Shock Sensitive & Reactive Chemicals

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