Guidelines forPotentially Explosive Chemical
Identification and Handling
University of California
Hazardous Waste Action Group
EH&S Guidelines for PEC ID and Handling, Revised April 7, 1999Page 1
Table of Contents
1.Introduction
a. Problem Statement
b. Scope of Work
c. PEC Definition
2.Personnel Qualifications
a. Training
3.Health and Safety
a. PPE
b. OSHA Buddy System
c. Handling Suspect PEC's During Inspections
d. Campus and National Laboratories Site Safety Requirements
4.PEC Identification and Handling Decision
a. Inspection
I.Role of Inspectors
b. PEC Worksheet
5.Material Management
a. Storage
b. Signage and Chemical Inventory
c. Isolation Distance
6.CUPA Notification
7.Vendor Services
8.Follow-up
a. Reports
b. Document Control
c. Generator Training
9.PEC Program
10.Attachments
- Chemical Information References
- Contacts
- PEC Handling Decision Procedures
- Warning Signs
- PEC Worksheet
- High Hazard Gas Cylinder Inspection Sheet
EH&S Guidelines for PEC ID and Handling, Revised April 7, 1999Page 1
1.Introduction
a. Problem Statement
Highly reactive/potentially explosive materials [a.k.a potentially explosive chemicals (PECs) such as ethers, nitro compounds, cylinderized chemicals and self-reactive compounds] are used at UC campuses and National Laboratories. If not handled properly, these materials can pose a serious threat to the health and safety of laboratory personnel, emergency responders, building occupants, chemical waste handlers, and disposal companies. Health, safety, disposal and financial issues arise from dealing with these materials.
In the past the UC campuses and National Laboratories have used different criteria for the identification, handling and disposal of these materials. For the safest and most cost effective reactives material management, these differences should be examined and the best management practices proposed.
b. Scope of Work
To develop guidelines for the recognition, safe handling and disposal of potentially explosive chemicals managed by University hazardous waste staff. In addition, source reduction practices and materials management recommendations for University personnel will be identified.
The intent of these Guidelines is to provide clear, consistent, and specific information to EH&S staff who dispose of PEC's and establish a protocol for identifying, handling, documenting and record keeping. In addition, these Guidelines provide a platform from which campuses and National Laboratories can develop a PEC program. The suggested contents of a PEC program are listed at the end of this document.
c. PEC Definition
PEC's are or are suspected of being explosives because they meet the following definitions or because of self propagating chemical reactions with light, oxygen, degradation by-products, impurities or contaminants that cause the substance to transform to an explosive condition.
An explosive is any chemical or mechanical mixture that, when subjected to heat, impact, friction, detonation, or other suitable initiation, undergoes rapid chemical change, evolving large volumes of highly heated gases that exert pressure on the surrounding medium. The term also applies to materials that detonate or deflagrate. (1995 Prudent Practices in the Laboratory. NationalAcademy Press. pg. 54.)
An explosive means any substance or article, including a device, which is designed to function by explosion (i.e. an extremely rapid release of gas and heat) or which, by chemical reaction with itself, is able to function in a similar manner even if not designed to function by explosion, unless the substance or article is classed otherwise. (49 CFR 173.50(a) Class 1 - Definitions)
A review of the relevant literature and discussions with outside waste disposal vendors indicates that PEC's may be old peroxide forming chemicals such as isopropyl ether, and sodium amide; nitrated aromatics such as old dehydrated or metal contaminated picrates, and contaminated tetranitromethane; azide compounds such as metal contaminated sodium azide, and crystalline lead azide; highly concentrated oxidizing acids such as >72% perchloric acid; devices such as explosive bolts, blasting caps, small arms ammunitions; other manufactured explosives or other compounds that degrade; or chemicals that were improperly synthesized and are potentially explosive.
2.Personnel Qualifications
a. Training
Besides recognizing known explosive chemicals or devices, certain EH&S staff need to be aware of chemicals that tend to become PECs and know the accepted procedures for dealing with them.
EH&S staff who handle PECs should have inorganic and organic chemistry courses, and have experience with or have been trained to: use chemical references, be able to confer with PEC disposal vendors, use personal protective equipment, understand and know inspection protocols, handling decisions and peer review processes, use the PEC worksheet to document research, handling decision, and disposal efforts. It is recommended that training be performed as a component of the annual training.
3. Health and Safety
These guidelines are written to reduce the risk for personnel inspecting PEC's of being exposed to an explosion. If the situation warrants the use of explosion protective clothing (such as a Kevlar® flack jacket), then the situation should be handled by a properly equipped and trained contractor, or the bomb squad.
- Personal Protective Equipment
The following personal protective equipment should be used during PEC inspections:
Close toed shoes
Lab coat or coveralls
Protective eye wear
Face shield
Appropriate chemically resistant gloves
Appropriate respiratory protection if conditions require it
- OSHA Buddy System
The "buddy system" should be used for PEC inspections. OSHA defines the buddy system as: A system of organizing employees into work groups in such a manner that each employee of the work group is designated to be observed by at least one other employee in the work group. The purpose of the buddy system is to provide quick assistance to employees in the event of an emergency.
c. Handling Suspect PECs During Inspections
Do not pick up a PEC container to inspect it unless you know that picking it up, or accidentally dropping it will not cause the chemical to explode.
Before handling a PEC, as much information as available about the chemical should be obtained. The PEC Worksheet ‘Research’ sections should be completed.
If it is determined that the PEC will not explode if picked up, but may explode if it is dropped, and if it is absolutely necessary to move the PEC, handle it with GREAT care and consider evacuating the area before moving it. Only essential personnel should be allowed in the area. Place the chemical in a container and surround it with cushioning material such as bubble wrap or vermiculite. If it is being moved to another room, have someone walk ahead of you to ensure the path is clear. Take precautions to avoid dropping or jarring the chemical. If the chemical is stored in an unsafe area, and it is not safe to move to a proper storage area (e.g., lifting the chemical could cause it to detonate), then it should be handled by experts immediately, as per the PEC Worksheet-Handling Decision section.
- Campus and National Laboratories Site Safety Requirements
Each campus and National Laboratory may have specific site safety requirements. For example UC Berkeley is a compact campus with few large outdoor open spaces that could be used to set up a revetment for open air detonations of PECs. Therefore, all PEC stabilization performed on the UC Berkeley campus should not use the detonation option.
4. PEC Identification and Handling Decision
a. Inspection
Before inspecting the PEC inform your immediate supervisor, the Department Safety Coordinator (DSC), and the PI of the situation. At the site, locate the fire extinguisher, an eyewash/safety shower, emergency exit and the telephone.
Equipment used during a field inspection may include, pens and lab markers, tape, peroxide test strips (if appropriate), and flashlight.
I. Role of Inspectors
The role of the inspection team is to determine the appropriate method for disposal of the PEC.
The PEC lead inspector should complete the following tasks or responsibilities:
•Be the main contact for the department needing service
•Complete the PEC Worksheet
•Coordinate peer review of the PEC Handling Decision
•Coordinate with PEC removal and disposal vendor or bomb squad
It is recommended that one of the inspectors of the inspection team be designated as the “Lead” inspector. This will help to ensure that the above tasks are completed.
b. PEC Worksheet
The PEC Worksheet attached is designed to:
•Provide a place to document researched information, inspection notes, expert consultations and handling decisions regarding the PEC
•Guide the inspector to identify the hazards and appropriate method for handling, packaging and disposal of the PEC to the TSDF
•Serve as a PEC database data entry form. The database can be used for documentation, future reference, and statistical analysis.
The PEC Worksheet database is available upon request.
Following are PEC Worksheet section descriptions and advice to assist the inspectors in completing the worksheet.
Preliminary InformationThis is the initial information available about the chemical of concern describing who, what, and where.
Responsible PersonnelThese are the names of people in the department who may need to be notified. As a courtesy, contact both the PI and the DSC and inform them that you are investigating a PEC.
Container and ChemicalContainer History
InformationThis includes detailed information on the age, storage and chemical name verification.
Literature Search
This describes the appearance, physical and chemical characteristics of the suspect chemical in its new condition and what one can expect to see in a degraded condition. This information is available through books, internet websites, chemical manufacturers, MSDS’s, experts in the field and, over time, the PEC Worksheet database.
Questions to be answered during the Literature Search are:
(This information should be known before visually inspecting the chemical.)
Does the new chemical have PEC characteristics?
Does the chemical degrade and are the degradation by-products sensitive to heat, shock, or friction?
What are the visual signs of such degradation?
What storage conditions would prevent or enhance degradation?
Does the chemical require an inhibitor to arrest degradation by-product generation?
Does the chemical require a stabilizing solvent (water, hydroquinone, acetone, etc.) to be present?
Chemical Observations
The Literature Search information can now be used to assist the inspectors with on site observations. First describe the appearance of the chemical and then complete the appropriate section:
1) solvent peroxide formers, and
2) all other PEC’s
Record your observations on the PEC Worksheet. Compare the information discovered in the literature search with your site observations.
Expert ConsultationConsulting with experts in the PEC field will help you to determine whether or not the chemical in question is a PEC, and the best course of action for handling the chemical. Discuss the literature and observations with the expert and get guidance as needed to fill out this section of the worksheet. You must determine the chemical stability before proceeding with a handling decision. Attachment 2 should be a listing of your chemical experts.
PEC Handling DecisionThis section consists of PEC handling decision possibilities. (Note: This list is not all inclusive. New situations may require different actions.) The handling decision is made case by case and is based upon the information found in literature, site observations, expert guidance, disposal site requirements, and possibly other extenuating circumstances. Handling decisions should be peer reviewed by another EH&S PEC trained person or by the designated EH&S Manager. (See Attachment 3 for a list of handling decisions).
5. Material Management
PECs should be stored safely while researching proper handling and TSDF disposal options. Check with the lab contact to ensure the PEC is stored in a space where it won't be disturbed, and is away from light and heat sources.
- Storage
•Store the chemical away from heat, flame, or direct sunlight.
•Store the chemical away from high use areas to avoid accidental bumping or knocking into the container.
•Store the chemical so that it will not fall to the floor during an earthquake.
- Signage and Chemical Inventory
•Complete the warning sign label (see Attachment 4— Warning Sign), include the hazard information
•Place the label on the original chemical container.
•If the chemical is inside a refrigerator or a chemical storage cabinet, place a completed warning sign on the outside of the storage area where it can be easily seen.
•In some cases you may need to label the door of the room with a completed warning sign and include a detailed container location description on the sign*.
•Update chemical inventory database to reflect that the room contains a PEC.
*Note: This should be done only if access to the room needs to be restricted and action on removing the chemical will occur quickly. The warning sign on the door should be removed promptly when the chemical is removed.
- Isolation Distance
Isolation distances are usually not necessary because most PECs are not capable of self propagating explosions without some kind of initiation. If during the literature research phase of the PEC investigation it is discovered that the chemical is capable of self propagating explosions, then the area should be evacuated and a vendor (capable of handling the situation) or the bomb squad should be called to handle the emergency.
6. CUPA Notification
Certified Unified Program Agencies may wish to be notified of any PEC that is left on Campus and National Laboratories property if it could reasonably be expected to present a hazard during an emergency response. In addition, when warranted, putting a warning sign (Attachment 4; also, see section 5.) on the outside of the door leading into the area where a PEC is being kept will ensure emergency responders know of its presence.
For notification, be prepared to give the agency the following information:
•Chemical name
•Amount
•Hazard
•Building
•Room
•Location in the room
•EH&S contact name and number
•Expected date the chemical will be removed
•Condition of material
7. Vendor Services
Potential vendor services for PECs should include the following:
•Site visits/job walks/expert chemical assessments
•Obtaining on-site treatment permits if necessary
•Site Safety Plan
•On-site transportation to stabilization area
•Remote opening and/or stabilization
•Specialized personal protective equipment
•Packaging supplies
•Packaging, labeling, manifesting
•Transportation to permitted disposal site
• Disposal
8. Follow-up
- Reports
Using the PEC Worksheet, document the actions taken and hazardous waste information related to disposal.
- Legal Review
Campus-specific guidelines should be submitted to the Office of General Counsel for legal review (where they differ in material respects from these guidelines).
c. Generator Training
- Inventory Controls
Departmental chemical inventory systems should include a mechanism by which laboratory personnel can keep track of chemicals that may be or (because of aging) may become PECs. The inventory should be updated regularly and have some “flag”when a PEC is nearing an expiration date and is in need of testing, purification, stabilization or disposal.
- Waste Minimization
Chemicals should be ordered only in necessary and sufficient quantities and in a timely manner. Whenever possible, scientists should use less hazardous chemical substitutes. Process changes or engineering controls are also good methods for waste minimization to minimize excess purchases and to assure fresh supplies, thus preventing unnecessary hazards and disposal costs.
9. PEC Program
Each campus or National Laboratory should develop a PEC program consisting of the following basic elements:
•Develop campus or National Laboratory PEC guidelines for EH&S staff to maintain a safe, consistent approach to PEC management. Use guidelines as a working document. Refine & evaluate as often as necessary.
•Get outside professional and legal review of PEC guidelines and procedures
•Assign qualified staff to the PEC Team
•Develop and give training for EH&S staff on the program and PEC guidelines:
Office awareness of the PEC Program (general training)
Hazardous Waste Management Team (identification and disposal)
Emergency Response personnel (training on ER Procedures)
PEC Team and support members (more specific handling procedures)
•Prepare a PEC Fact/Help Sheet for campus or National Laboratory guidance
•Form an Outreach Workgroup to focus on PEC generation prevention
Determine prevention issues
Develop documents, tools, ideas for educating the campus or National Laboratory and increasing awareness and safety (including labels)
Implement program for campus or National Laboratory departments, laboratories, field stations
10. Attachments
1. Chemical Information References
2. Contacts
3. PEC Handling Decision Procedures
4. Warning Signs
5. PEC Worksheet
6. High Hazard Gas Cylinder Inspection Sheet
EH&S Guidelines for PEC ID and Handling, Revised April 7, 1999Page 1
Attachment--1
Chemical Information References
(EXAMPLE)
People:The Laboratory's PI, Chemical User
WHATWHERE
Databases:UC TOMES database Internet access
Sigma-Aldrich-Fluka MSDS
PEC Database
Internet:Internet MSDS or other WWW locationsEH&S Website links or
/links.html
Files:MSDS File Laboratory or EH&Soffice
Books:Bretherick's Handbook of Reactive
Chemical Hazards
The Merck Index
Chemical Supply Catalogs (i.e. Aldrich)
Explosives
Hawley's Condensed Chemical Dictionary
Dangerous Properties of Industrial Materials
ETSC Training Manual
Chemical Hygiene Plan
College/School/Department Safety Manual
Other:List of PECs from ETSC Training ManualETSC Manual
Rick Kelly's Paper (on peroxide formers)
College/School/Department references
Attachment—2
CONTACTS
(EXAMPLE)
Notification Contacts
Berkeley Fire Department (BFD)
David Orth, Assistant Fire Chief
Phone: (510) 644-6665
Pager:(510) 840-3235
University of California Police Department Bomb Unit (UCPD)
Captain Bill Foley
Phone: (510) 642-6760
PEC Contractor Contacts/Experts
WMIS–Advanced Environmental Technology Services