By Michael McCann, Ph.D., C.I.H. Spills and leaks of chemicals can result in significant fire and health risks.
The Occupational Safety and Health Administration (OSHA), under its Hazardous Waste Operations and Emergency Response Standard (29 CFR 1910.120), requires schools, colleges, and other employers to develop procedures for emergency response to spills and leaks. Employers who do not operate an EPA or state-permitted hazardous waste treatment, storage, and disposal facility must comply only with paragraph (q) of this standard. The Environmental Protection Agency also has emergency response requirements under Section 304 of the Superfund Amendments and Reauthorization Act (SARA) and the Resources and Conservation Recovery Act (RCRA). OSHA 1910.120 and Emergency Response According to paragraph (a)(3) of this standard, an "Emergency Response" means "a response effort by employees from outside the immediate release area or by other designated responders (e.g., mutual-aid groups, local fire departments, etc.) to an occurrence which results, or is likely to result, in an uncontrolled release of a hazardous substance. Responses to incidental releases of hazardous substances where the substance can be absorbed, neutralized, or otherwise controlled at the time of release by employees in the immediate release area, or by maintenance personnel, are not considered to be emergency responses within the scope of this standard. Responses to releases of hazardous substances where there is no potential safety or health hazard (i.e., fire, explosion, or chemical exposure) are not considered to be emergency responses." Emergency Response Plan Paragraph (q) of this standard requires employers to develop a written emergency response plan. If the employer has a policy of immediate evacuation of their employees from the danger area when an emergency occurs, and does not permit any of their employees to assist in handling the emergency, then the employer is exempt from the requirements of 29 CFR 1910.120(q), provided they have an emergency action plan in accordance with 29 CFR 1910.38(a). This emergency action plan should include information on procedures for small spills that can be cleaned up quickly, how to recognize and report spill emergencies, and immediate evacuation of all employees for larger, more dangerous spills. Employees who might discover a spill or leak should have first responder awareness training. Emergency Response Procedures The OSHA standard has detailed requirements on who is in control in emergency response situations, and procedures to be followed. The standard also has procedures for medical surveillance and consultation, chemical protective clothing, the proper disposal of hazardous substances and contaminated materials, and personal protective equipment test methods. Training Many colleges have a health and safety department with personnel trained and equipped to handle hazardous spills and leaks. This department should be consulted to determine whether spill response services are available. The OSHA standard defines the amount and frequency of training and certifications needed for different levels of emergency response personnel. In order of the amount of training required and competence, the types of emergency response personnel are: 1) first responder awareness level; 2) first responder operations level; 3) hazardous materials technician; and 4) hazardous materials specialist. In addition, there are training requirements for the on-scene incident commander and skilled support personnel. More detailed information on emergency response procedures and training can be found in CSA's book Art Safety Procedures: A Health and Safety Manual for Art Schools and Art Departments. SARA and RCRA Emergency Procedures If a spill or leak into the environment has the potential to expose the public to hazardous substances, and if the size of the spill is in excess of SARA reportable quantities for the chemical, then section 304 of SARA requires emergency notification of the appropriate authorities. If there is a toxic release of a chemical on the CERCLA list in excess of the reportable quantity for that chemical, then the National Response Center (NRC) must be notified (telephone 800/424-8802). The NRC must also be notified if the spill involves hazardous waste. If the chemical is listed by SARA as an Extremely Hazardous Substance (EHS), then local emergency authorities (the local emergency planning committee and the state emergency planning committee) must also be notified. Large and small quantity generators are required by RCRA to appoint an emergency coordinator who is present or on call, and to develop an emergency/contingency plan for spills or leaks of hazardous waste that could expose the public or contaminate the environment (40 CFR 262.34). OSHA emergency response plans could meet this requirement. Cleaning Up Spills and Leaks Many of the basic steps involved in cleaning up emergency and non-emergency spills and leaks are similar. The primary differences are the degree of hazard, the level of training, and the types of personal protective equipment necessary to clean up the spill safely. Even non-emergency spills and leaks require knowledge and training to be cleaned up safely. This can be done in standard Right-To-Know training given in compliance with the OSHA Hazard Communication Standard. Standard Spill Control Procedures 1. Get away. The first person to notice the spill or leak should get away from the immediate area of the spill in order to evaluate the situation without exposing himself. Obviously, this might not be needed if the nature of the spill is known and is minor. 2. Identify the spill to the extent possible. Do so without being at risk. This includes identifying: a) the type of material spilled (e.g., from the label); b) the size of the spill and whether the leak has stopped; c) whether two chemicals are involved in the leak and could react with each other; and d) any unusual features such as foaming, odor, fire, etc. 3. Is this an emergency? Leaks that can be cleaned up by personnel on the spot or by maintenance personnel are not emergencies. If this is not clear, consider it an emergency. The following are examples of spills and leaks that should be considered emergencies: Type of spill Amount Examples extremely flammable liquids > 1 pint rubber cement flammable liquids > 1 quart toluene combustible liquids > 1 quart mineral spirits toxic, volatile liquids > 1 quart ammonia concentrated acids > 1 gallon sulfuric acid concentrated alkalis > 1 gallon lye solution poisonous, reactive materials any cyanides, sulfides oxidizing agents > 1 pound conc. nitric acid leaks from gas cylinders uncontrolled oxygen, acetylene In addition, any fires involving hazardous substances (e.g. solvents, oxidizers, corrosive chemicals), or any spill or leak that causes any injury such as unconsciousness, should be considered an emergency. If there is an emergency situation as defined above, initiate the emergency procedures defined in the Emergency Response Plan. The following steps might be part of the Emergency Response Plan. If the plan involves immediate evacuation, then do not proceed any further. Sound the alarm and assist evacuation.
4. Get help for all but very minor spills. In emergency situations, the amount of training determines the degree of participation in the clean-up.
5. Identify the material spilled. Is it flammable, combustible, toxic and volatile, toxic/corrosive and nonvolatile, or an oxidizing agent? The label and Material Safety Data Sheet for the product should give information on safe clean-up.
6. Plan how to clean up the spill or leak. Procedures for common types of spills and leaks are discussed below.
7. Obtain the proper spill control materials. These would include pillows, leak patches, and sparkproof tools.
8. Put on appropriate personal protective equipment. This can include respirators, gloves, and goggles.
9. Stop the source of the spill or leak by turning off the valve of a leaking gas cylinder, patching a leaky hose, or uprighting a knocked over container of liquid, among others.
10. Stop the spill from spreading. This can include using appropriate spill control pillows or other spill control materials for spilled liquids to build a dike, shutting down ventilation systems to keep gases and vapors from spreading, and plugging drains to prevent contamination of the water supply. Flammable liquids in the sewer system, for example, can be an extreme explosion hazard. Allowing hazardous chemicals to enter the sewer system may also be a violation of EPA, state, or local disposal regulations.
11. Clean up the spill using the appropriate absorbing materials and equipment. In general, paper towels or rags should not be used for liquids that evaporate quickly since they will not prevent further evaporation. For very small spills, you can use paper towels if they are immediately placed in a proper oily waste can.
12. Dispose of contaminated materials properly. Contaminated spill control materials and disposable personal protective clothing must be disposed of as hazardous waste. Contaminated tools and non-disposable personal protective equipment should be safely decontaminated.
13. File an incident report. The incident report should be filed with the health and safety program director for every spill, including non-emergency spills, detailing the nature of the spill, how it occurred, how it was cleaned up, any problems that arose, and recommendations for preventing further spills of the type. The spill might also have to be reported to local, state, or federal authorities. Specific Recommendations The following section gives the hazards and specific recommendations for cleaning up a variety of common spills and leaks that could occur in an art department. When a spill is large enough for clean-up to be considered an emergency response, the Emergency Response Plan should be followed. The recommendations below should be incorporated into the emergency response procedures. Flammable Liquid Spills Spills of flammable liquids are among the most dangerous types of spills because they are potential health hazards as well as a fire hazard at room temperature and below. A spill of a flammable liquid will spread out and evaporate very quickly to reach high vapor concentrations. The lower explosive limit (LEL), the lowest concentration of the flammable vapor in air that can burn, can be achieved very easily. All it takes is a spark, flame, or other source of ignition to cause a fire or explosion. Spills of more than one pint of an extremely flammable liquid or one quart of a flammable liquid should be considered emergency response situations. The following are procedures to be followed for flammable liquid spills:
1. Immediately shut off any flames. For large, emergency spills, shut off the power to any electrical equipment, lights, etc. in the spill area using a control outside the spill area (e.g. a fuse box) to prevent sparks setting off a fire or explosion.
2. Open the windows and turn on any explosion-proof fans exhausting to the outside (they should be on separate circuits from the rest of the room). Air conditioning and ventilation systems should be turned off to prevent vapors from spreading throughout the building.
3. Evacuate the area as a precaution against fire risk. In emergency response situations, trained emergency personnel would determine the degree of evacuation needed, unless the college has an immediate evacuation plan.
4. Wear gloves, goggles, and air-purifying respirators for small spills (although minor spills might not require a respirator). Cleaning up large spills or unknown spills requires positive-pressure self-contained breathing apparatus (SCBA) because of high vapor concentrations that could be present. The fire department might be able to do this if no one in-house is qualified and trained with SCBA. Other protective clothing and equipment that might be needed for large spills include goggles and face shield, impermeable clothing, and boots.
5. Control the spread of large spills by diking with spill control pillows or similar materials. Make sure the flammable liquid does not enter drains.
6. Use appropriate spill control materials to clean up the spill. Dry clay or vermiculite will work if proper spill control materials are not available. Paper towels should not be used for more than tiny amounts of volatile liquids because the paper will aid evaporation.
7. Pick up contaminated spill control materials using spark-proof tools (e.g. plastic, aluminum), and place in garbage bags. This material must be treated as hazardous waste under EPA regulations. Flush the affected area with water afterwards. Combustible Liquid Spills Combustible liquids are not a fire hazard at normal room temperature since their flash point is above 100 F. In general, handle combustible liquid spills (e.g. mineral spirits) as a volatile liquid spill. However, if a spilled combustible liquid comes into contact with a hot surface, then heating of the liquid could result in a fire hazard. In that case, the spill should be handled as a flammable liquid spill. Volatile Liquid Spills Inhalation of vapors and possible skin absorption of the liquid are the major hazards associated with volatile liquid spills such as 1,1,1-trichloroethane, methylene chloride, acetic acid, and combustible liquids. Spills of solutions of gases dissolved in water (such as ammonia) and bleach are also discussed here. Flammable liquids are treated separately. Spills of more than one quart should be considered emergency response situations. The following are procedures for cleaning up spills of volatile liquids:
1. Open windows and turn on any fans exhausting to the outside. Ventilation systems should be turned off to prevent vapors from spreading throughout the building.
2. Evacuate the immediate area as a precaution against health risks. In emergency response situations, trained emergency personnel would determine the degree of evacuation needed, unless the college has an immediate evacuation plan.
3. Wear gloves, goggles, and air-purifying respirators for small spills (although minor spills might not require a respirator). Cleaning up large spills or unknown spills requires positive-pressure self-contained breathing apparatus (SCBA) because of the high vapor concentrations that could be present. The fire department might be able to do this if no one in-house is qualified and trained with SCBA. Other protective clothing and equipment that might be needed for large spills include goggles and face shield, impermeable clothing, and boots.
4. Control the spread of large spills by diking with spill control pillows or similar materials.
5. Use appropriate spill control materials to clean up the spill. Dry clay or vermiculite will also work if proper spill control materials are not available. Paper towels should not be used for more than tiny amounts of volatile liquids because the paper will aid evaporation.
6. Pick up contaminated spill control materials and place in approved waste disposal containers. This material must be treated as hazardous waste under EPA regulations. Flush affected area with water afterwards. Acid and Alkali Spills With acids and alkaline solutions, the concern is mostly skin contact due to the corrosive properties of concentrated acids and alkalis, and irritation from dilute solutions. Note that many concentrated acids react violently with water. Spills of more than a gallon of concentrated acids or alkalis should be considered an emergency response situation. All concentrated hydrofluoric acid spills should be considered an emergency and need special procedures. The following are recommended procedures:
1. Do not touch spilled material.
2. Wear protective clothing, gloves, goggles, and boots in order to avoid skin contact. For concentrated acids and alkalis, a face shield is needed in addition to goggles. For volatile concentrated acids, SCBA may be needed. The MSDS should be checked.
3. Control the spread of large spills of concentrated acids by diking with spill control pillows or similar materials for later disposal as hazardous waste.
4. Small acid spills can be neutralized with sodium bicarbonate or sodium carbonate, and alkali spills with sodium bisulfate or citric acid. Commercial absorbent spill control materials can also be used.
5. Neutralized acids and alkalis can then be mopped up. Wring out the mop in the sink or a pail with a wringer.
Cyanide and Sulfide Spills Reactive materials such as cyanide and sulfide powders and solutions are potentially very hazardous because of the risk of producing extremely toxic hydrogen cyanide and hydrogen sulfide gases, especially if the spill also involves acids. Cyanide solutions may also be absorbed through the skin. All spills of cyanide, sulfide, and other reactive materials should be considered emergency response situations. The following are recommended procedures:
1. Do not touch spilled material.
2. Wear a protective apron, goggles, gloves, and a positive-pressure SCBA. For small powder spills, air-purifying respirators with a HEPA filter would suffice.
3. Scoop up powder with clean shovel or other tool; place in a dry container approved by the Department of Transportation.
4. Adsorb liquid spills with spill control materials. Do not allow the spill to enter drains or sewer system.
5. Flush spill area with water.
6. Dispose of as reactive hazardous waste. Oxidizing Agent Spills Oxidizers such as dichromates, nitrates, chlorates, concentrated hydrogen peroxide, and concentrated nitric acid are strong oxidizing agents that can ignite solvents and other combustible materials. They are also skin and respiratory irritants and may have other health hazards. See Material Safety Data Sheets on individual materials for specific instructions on cleaning up spills. Spills of more than one pound of an oxidizing agent should be considered an emergency response situation. The following are general procedures for oxidizer spills:
1. Do not touch the spilled material. Keep away from combustible materials (wood, paper towels, oil, etc.)
2. Wear appropriate protective equipment (e.g. apron, goggles, gloves, respirators, etc.) For small powder spills, air-purifying respirators with a HEPA filter would suffice; for larger spills, SCBA is required.
3. Scoop up powder with a clean shovel or other noncombustible tool, and place in a dry container approved by the Department of Transportation.
4. Adsorb liquid spills with spill control materials. Do not allow the spill to enter drains or sewer system.
5. Concentrated hydrogen peroxide spills are not emergencies. The solution should be diluted with water, and then allowed to decompose to ordinary oxygen. The residue can be poured down the drain.
6. Flush spill area with water.
7. Dispose adsorbed material as flammable hazardous waste.
Organic Peroxide Spills Methyl ethyl ketone peroxide and benzoyl peroxide are hardeners used with various plastics resins and can be ignited by sparks, flames, and heat. They are normally dissolved in solvents to make them less reactive. Spills of organic peroxides should be handled as flammable liquid spills.
Water-Based Paint Spills Latex paints and other water-based paints are not an inhalation hazard even though they may contain small amounts of organic solvents. Even large spills of water-based paints are not considered emergency response situations. The following are basic procedures for clean-up:
1. Gloves and goggles should be worn for cleanup.
2. Wet mopping is the best method of cleanup.
3. The diluted paint can be flushed down the sewer if it does not contain lead, chromates, cadmium, or other toxic metals. If toxic metals are present, dispose of them as hazardous waste.
Compressed Gas Cylinders Leaking gas cylinders can be an emergency if the cylinder gas is oxygen (an oxidizer), a flammable gas such as acetylene or propane, or a toxic gas such as ammonia, and if the leak cannot be turned off by closing the cylinder valve. In this case, follow prescribed emergency response procedure. The following are recommended procedures:
1. If a leak is suspected, test with non-fat (detergent) soap or other leak detection solution. Do not use a flame.
2. If the leak cannot be stopped by turning off the cylinder valve, take the leaking cylinder outside well away from sources of ignition if the gas is oxygen or is flammable. (If the gas is toxic, wear positive-pressure SCBA.)
3. Try to temporarily stop the leak through the cylinder valve by attaching a regulator which is closed. 4. Reopen the cylinder valve slightly to allow gas to escape slowly.
5. Clearly tag and secure the cylinder. Post a sign warning people not to approach within 20 feet with cigarettes or other sources of ignition. If necessary, post a security guard.
6. Contact the supplier or manufacturer, and follow their further instructions. References
3M Occupational Health and Environmental Safety Division. (1989). Hazardous Spill Clean-Up. 3M Co., St. Paul, MN. McCann, M. (1992). Art Safety Procedures: A Health and Safety Manual for Art Schools and Art Departments. Center for Safety in the Arts, New York, NY. Occupational Safety and Health Administration. (1990). Hazardous Waste and Emergency Response (OSHA 3114). U.S. Department of Labor, Washington, DC. Office of Hazardous Materials Transportation. (1987). 1987 Emergency Response Guidebook. U.S. Department of Transportation, Washington, DC.