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Chapter 45
CHEMICAL HYGIENE AND SAFETY PLAN

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Work Process N. Specific Controls and Procedures — Flammables and Combustible Liquids

1. General Information

1. Flammable and combustible chemicals include liquids such as organic solvents, oils, greases, tars, oil-based paints, and lacquers, as well as flammable gases. Flammable gases are discussed in ESH Manual programs Chapter 7, Pressure Safety, and Chapter 13, Gas Safety. The emphasis of this section is on flammable and combustible liquids.
2. Flammable and combustible liquids are defined by their flashpoints. The flashpoint of a liquid is the minimum temperature at which it gives off sufficient vapor to form an ignitable mixture with the air near its surface or within its containment vessel. A liquid’s flashpoint is a function of its vapor pressure and boiling point. Generally, the higher the vapor pressure and the lower the boiling point of a liquid, the lower its flashpoint will be. The lower the flashpoint, the greater the fire and explosion hazard.
3. Flammable and combustible liquids are classified by the National Fire Protection Association (NFPA) and the California Fire Code (CFC) based on their flashpoints.

2. Flammable Liquids (Class I)

1.  Liquids with flashpoints below 100°F (37.8°C) and vapor pressures not exceeding 40 pounds per square inch (absolute) at 100°F (37.8°C). The boiling point is only considered when distinguishing between Class IA and IB flammables. Flammable Class I liquids are subdivided as follows:

3. Combustible Liquids (Classes II and III)

1. Liquids having flashpoints at or above 100°F (37.8°C). The boiling point is not considered. Combustible liquids in Classes II and III are subdivided as follows:

4. Control Measures

1. Work leads must identify flammable and combustible liquids used in the work area. Review sources such as SDSs for specific compounds.
2. An assessment of the hazards and controls in place is necessary to limit employee exposures to these agents. Contact an EHS Health and Safety Representative to provide assistance.
3. Work involving these materials shall be added to a Work Planning and Control Activity. Consult the Work Planning and Control program (EHS Manual Chapter 6).

5. Training and Information

1. Employees who either handle or who may be exposed to flammable and combustible liquids are required to complete Chemical Hygiene and Safety Training (EHS 0348; or EHS 0345 for Facilities personnel).
2. Activity leads are responsible for on-the-job training specific to hazards and controls of these materials for their work activities. Information on hazards and minimum PPE requirements must be available to workers accessing work areas where these hazards are present such as through the entrance placard and co-located hazards in WPC activities.   EHS Health and Safety Representatives are available to provide assistance.
3. Consult Work Process Y, Container Labeling, for labeling requirements for primary and secondary containers.
4.  The entrance to the work area should be posted with a Caution Placard depicting hazards and emergency contact information.

6. Substitution and Chemical Inventory Management

1.  Identify and use safer chemical alternatives (e.g., materials with higher flashpoints and higher boiling points) if possible.
2. If a safer chemical can’t be used, limit what you buy or borrow what you need from a colleague in your group or contact the Chemical Management System Coordinator (cms@lbl.gov) to assist you in finding a source of the chemical at Berkeley Lab.
3. Conduct periodic cleanouts to prevent accumulating unneeded chemicals.
4.  Keep working quantities of chemicals to a minimum. Don’t stockpile chemicals.
5. Enter these materials into the Chemical Management System (CMS).

7. Ventilation. A fume hood or other appropriate exhaust ventilation system should be used when handling flammable and combustible liquids in a manner that may produce an airborne hazard (such as fumes, gases, vapors, and mists). This includes procedures such as transfer operations, preparation of mixtures, blending, sonification, spraying, heating, and distilling. Consult Work Process N.11, “Transfer Operations,” for guidance and requirements regarding ventilation during transfers from one container to another.
8. Work Practices

1. Control all ignition sources when handling flammable and combustible liquids. Sources of ignition include open flames, smoking, hot surfaces, electrical and mechanical sparks, cutting and welding, static electricity, heat-producing chemical reactions, and anything that closes an electrical circuit (e.g., opening/closing a switch, plugging/unplugging a power cord, electrical motor or compressor switching on/off, etc.). Contact your EHS Health and Safety Representative or the Fire Marshal for assistance in identifying ignition sources.
2. Consult Work Process N.11, “Transfer Operations,” for guidance and requirements on transferring flammable and combustible liquids from one container to another, including bonding and grounding information.
3.  Keep containers closed when not in use.
4. Storing and consumption of food is permitted in designated areas only. See Work Process J, Work Practice Controls for additional information.
5. Use a mechanical aid or a pipette bulb for pipetting.
6. Open bottles or carboys slowly and carefully and wear protective equipment to guard hands, face, and body from splashes and vapors/gases.
7. Wipe drips/residues from containers and work surfaces.
8. Wash hands before leaving the work area and prior to consuming food/beverages.

9. Personal Protective Equipment (PPE). Skin and eye contact must be prevented. The following PPE should be worn when handling these materials. Additional information may be found in Work Process I, Personal Protective Equipment.

1. At a minimum, safety glasses with side shields, laboratory coats (coveralls are acceptable in shop settings) and closed-toe shoes will be worn when handling these materials. This is to be considered as minimum protection and must be upgraded if necessary.
2. Additional PPE such as chemical goggles, face shields, chemical aprons, disposable coveralls, chemically resistant gloves and respiratory protection must be worn if there is a greater chance of chemical exposure. An EHS Health and Safety Representative may be contacted for assistance in selecting appropriate gloves and respiratory protection. The use of respiratory protection requires an industrial-hygiene hazard evaluation and a medical clearance followed by a fit test and training by the Industrial Hygiene Group.
3. Consult Work Process I.6, Eye and Face Protection, for guidance on the selection, uses, and limitations of safety glasses, chemical goggles, and face shields.
4. Because many chemicals are skin-absorbers (i.e., agents that readily pass through the skin) it is important to select gloves that are chemically resistant to the material. Consult the PPE section. This contains a list of skin-absorbing agents and provides detailed guidance for selecting chemically resistant gloves.
5. Gloves must be selected on the basis of their chemical resistance to the material(s) being handled, their suitability for the procedures being conducted, and their resistance to wear as well as temperature extremes. Improper selection may result in glove degradation, permeation of the chemical through the glove, and ultimately personal exposure to the chemical. This is a potentially serious situation. Consult Work Process Work Process I.5, Gloves, for guidance on the selection, uses, limitations, and disposal of chemically resistant gloves. An EHS Health and Safety Representative may also be contacted for assistance in selecting appropriate gloves.

10.  Storage

1. Consult Work Process K, Chemical Storage, for hazardous-materials storage requirements, recommendations, and information on chemical incompatibility. Additional requirements are provided below.
2. Store flammable and combustible liquids away from ignition sources. Sources of ignition include open flames, smoking, hot surfaces, electrical and mechanical sparks, cutting and welding, static electricity, heat-producing chemical reactions, and anything that closes an electrical circuit (e.g., opening/closing a switch, plugging/unplugging a power cord, electrical motor or compressor switching on/off, etc.). Contact your EHS Health and Safety Representative for assistance in identifying ignition sources.
3. Segregate flammable and combustible liquids from oxidizing acids and oxidizers.
4. Flammable-Storage Cabinets and Refrigerators/Freezers.

1. Store flammable and combustible liquids in an approved flammable-storage cabinet.

• Containers of flammable liquids (e.g., squeeze bottles or similar volume secondary containers with closed lids or tops) may be maintained outside of flammable liquid storage cabinets while in use or when staged for use. Staging requires the use of secondary containment as specified in the Chemical Hygiene and Safety Plan (Work Process K, Chemical Storage).
• Unless in use or staged for use, store flammable liquid containers in flammable liquid storage cabinets. Place all flammable liquid containers in flammable liquid storage cabinets when no longer needed.
• Limit the amount of flammable liquids staged for use to the smallest practical quantity.
• Note: Storage of nonflammable solvents such as chloroform and methylene chloride are permitted in flammable storage cabinets provided that (1) they are chemically compatible with the other stored chemicals and (2) storage of non-flammables does not displace flammable and combustible chemicals from the storage cabinet.
• Flammable-storage cabinets are designed to protect their contents from fires in the work area. They can be located under fume hoods or exist as stand-alone units. Approved flammable-storage cabinets are constructed of steel and are equipped with self-closing doors with a three-point latch arrangement. Flammable-storage cabinets installed as part of laboratory construction and renovation projects must be connected to the building’s supply and exhaust ventilation system. The top bung is connected to an outside source of supply air and the lower bung is connected to the exhaust system. This controls vapors and odors and prevents corrosion to the interior.

2.  No more than 120 gallons of Class I, Class II, and Class IIIA liquids, combined, may be stored in a flammable-storage cabinet. Of this total, no more than 60 gallons may be Class I and Class II liquids, combined. Refer to ES&H Manual Chapter 12, Fire Prevention and Protection, for detailed guidance on maximum quantities allowed in a single fire-control area (i.e., an area that is separated from other rooms/areas by minimum one-hour fire-rated barriers).
3. Do not store Class I liquids in any basement or pit unless it has an approved ventilation system designed to prevent the accumulation of flammable vapors (refer to OSHA 1910.106[f][2][iii][b]). A basement is a story of a building or structure having one-half or more of its height below ground level. For questions or further guidance, consult the Berkeley Lab's Fire Marshal.
4.  Ordinary domestic refrigerators/freezers contain electrical components (light bulbs, switches, contacts, and motors) that are potential ignition sources that may initiate a fire or an explosion if flammable vapors are present. Therefore, refrigerators/freezers used for storing flammable liquids must be designed, constructed, approved for that purpose. NOTE: This applies to aqueous ethanol solutions greater than or equal to 15%. Domestic refrigerator/freezers as well as units that have been modified to remove spark sources are not acceptable alternatives. Contact Procurement & Property Management for guidance on purchasing refrigerators and freezers.
5. Labeling: Refrigerators/freezers approved for storage of flammable materials must be labeled by the manufacturer to indicate this approval and any associated prohibitions, e.g., no smoking, keep flame or fire away, etc. In addition, they must be labeled to indicate no storage of food, beverages, or ice for human consumption. See Work Process K, Table K-1 Refrigerator/Freezer Labeling Requirements.

5. Flammable and Combustible Storage Cans and Other Containers. Flammable and combustible liquids may be stored in various containers. The allowed volume depends on the flammable/combustible class and container material (See Table N-1 below).

Table N-1. Maximum Container Sizes for Combustible and Flammable Fluids

a Glass containers of no more than 1 gallon capacity may be used for Class IA or IB flammable liquids if such liquid either would be rendered unfit for its intended use by contact with metal or would excessively corrode a metal container so as to create leakage hazard. NOTE: This exemption does not apply to the accumulation of non-corrosive ignitable hazardous waste.

b Underwriter Laboratory or Factory Mutual approved container equipped with a self-closing lid, pressure relief, flame arrester, bonding/grounding tab, and a funnel.

Note: Class I liquids are flammable, and Class II liquids are combustible; Class 1A liquids have a flashpoint (FP) below 73°F, and boiling point (BP) below 100°F; Class 1B — FP below 73°F, and BP at or above 100°F; Class 1C — FP at or above 73°F, but less than 100°F (BP not addressed); Class II — FP at or above 100°F, but below 140°F; Class III — FP at or above 140°F.

11.  Transfer Operations

1. All Classes of Flammable and Combustible Liquids

1. Keep ignition sources at least 3 feet away.
2. Bonding and grounding of conductive containers is required when the size of the source container is greater than 1 gallon or 4 liters. Bonding/grounding is recommended whenever a metal or conductive plastic container is involved. Click here for additional guidance and information on bonding and grounding.
3. Use secondary containment and have appropriate spill control supplies available.
4. Keep containers closed when not in use.

2. Class IA Flammable Liquids

1. All transfers of Class IA flammable liquids must be performed inside a fume hood or with appropriate local exhaust ventilation.
2. Class IA flammable liquids must never be transferred by gravity-dispensing (see 11.c. below).

3. Class IB and IC Flammable Liquids

1. Transfers of Class IB and IC flammable liquids must be performed inside a fume hood or with appropriate local exhaust ventilation.

Exception: A maximum of 2 liters of Class IB or IC flammable liquids may be transferred within a one-hour period outside of a fume hood or without local exhaust ventilation. Such transfers must take place with adequate room ventilation. Spaces that are enclosed or constricted must be avoided. Contact your EHS Health and Safety Representative for an exposure assessment if there are any concerns about the health hazard of the chemicals being handled. Refer to Work Process CC “Exposure Assessments, Monitoring, and Medical Consultation” for more information.

Note: This exception is based on a study performed by EHS in December 2016 in response to findings from an NFPA 45 inspection. Contact EHS for a copy of the report “Berkeley Lab Revised Assessment of Flammable Vapors and the Need for Local Exhaust Ventilation per NFPA 45 Requirements in Chapters 7.2.6 and 9.3.1” (CHESS ID# SIH-6352).

4. Class II and III Combustible Liquids

1. Transfers of Class II and III combustible liquids – when heated at or above the flashpoint during the transfer – must be performed according to the requirements listed for Class IB and IC flammable liquids above.
2. Transfers of unheated Class II and III combustible liquids must be performed in well-ventilated areas. A fume hood or local exhaust ventilation is required if there is a potential that the transfer may produce an airborne physical or health hazard. Contact your EHS Health and Safety Representative for assistance in determining potential for such airborne hazards.

5. Gravity-Dispensing Flammable IB and IC and Combustible Liquids.

1. Gravity-dispensing refers to transferring flammable or combustible liquids by means of gravity from large containers placed on the side or containers with a valve near the bottom. Container size is usually greater than 20 gallons (75 liters), but can be smaller.
2. Class IB, Class IC, Class II, and Class III liquids may be transferred from containers or tanks by gravity through piping, hoses, and self- or automatic closing valves that have been reviewed and approved by Berkeley Lab's Fire Marshal.
3. Such transfer operations must follow the general requirements as outlined in section 11.a above.
4. Moreover, the nozzle and conductive containers must be bonded to each other (i.e., electrically interconnected) to prevent static electricity discharge. The dispensing container (if conductive) must also be connected to an electrical ground.
5. Ventilation must be provided as outlined in sections 11.c and 11.d above.
6. Contact your EHS Health and Safety Representative and the Fire Marshal’s Office for assistance in setting up gravity-dispensing operations.

12.  Emergency Procedures

1. Consult Work Process V, Emergency Procedures and Equipment, for emergency actions regarding chemical spill and personal exposure to chemicals.
2. In addition to these requirements, the following applies to flammable and combustible liquid spills:

1. Never use combustible or reactive materials (such as paper towels) to clean up or absorb spills of flammable or combustible liquids. Keep an adequate number of appropriate spill kits to meet anticipated needs. These are commercially available through VWR Scientific. Typically, products containing diatomaceous earth are used for absorbing organic solvents.
2. An emergency eyewash and safety shower should be located in all areas where flammable or combustible liquids are used. In the event of skin or eye contact, flush the affected area for at least 15 minutes and report to Health Services for evaluation and treatment.

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