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Hazardous Materials Handling and Storage OP-G-4.2

Table of Contents Purpose What is a Hazardous Material? C lassification of a Hazardous Material Training Requirements Storage of Hazardous Materials Handling Hazardous Materials First Aid Procedures for Hazardous Materials Disposal of Hazardous Materials Appendix 1: Incompatible Materials Appendix 2: Hazardous Waste Accumulation Point Requirements Appendix 3: Rules for Storing C hemicals Safely Appendix 4: Suggested C hemical Storage Pattern Appendix 5: Suggested Storage Time Limits for C ommon Peroxidizable C ompounds References

Purpose
The purpose of this policy is to provide University Faculty, Staff, and Students with guidance in the safe and proper storage and handling of Hazardous Materials. While this document does not cover all regulatory requirements concerning the handling and storage of hazardous materials, it is a good starting point. More information is available in the references listed below. C ontact the FSU Department of Environmental Health and Safety at 644-6895 for help in accessing these references. Back to Index

What is a Hazardous Material?

A hazardous material is a material which is capable of producing harmful physical or health effects. Harmful physical effects include fire, sudden release of pressure, explosion, and other violent reactions. Harmful health effects include acute conditions and chronic conditions. Acute conditions develop soon after over-exposure to hazardous materials and include burns, rashes, respiratory distress, convulsions, and possibly even death. C hronic conditions develop after long term exposure to hazardous materials and include cancers, nervous system disorders, and damage to other organ systems. Many Federal, State, and Local agencies regulate hazardous materials in order to protect human health and the environment. Back to Index

Classification of a Hazardous Material

In order to safely and properly handle and store hazardous materials, it is important to know the hazards of those materials. University personnel working with hazardous materials must be aware of the hazards those materials present. (See also FSU Hazard C ommunication Program.) Hazardous materials may generally be assigned to one or more of the following classifications. Flammable liquid - any liquid having a flash point below 1000 F (37.80 C ); i.e., at 1000 F or less the C ombustible liquid- any liquid having a flash point between 100 and 2000 F (37.8-93.30 C ). liquid produces enough vapors to ignite if exposed to an ignition source. Flammable solid - a substance that can cause a fire through friction, absorption of moisture or spontaneous chemical changes and, when ignited, will burn so vigorously that it creates a hazard. Oxidizer - a substance that readily yields oxygen or other electron acceptor to stimulate the combustion of organic matter (fuel). C orrosive - a liquid that corrodes steel (SAE 1020) at a rate greater than 6.35 mm (0.250 in.) at a test temperature of 1300 F (550 C ) or has a pH less than 2 or greater than 12.5. Organic Peroxide - an organic compound containing the chemical bond -0-0- (oxygen joined to oxygen). Poison - a substance so toxic that it presents a risk to life or health. Explosive- any chemical compound, mixture or device that reacts or decomposes with substantial

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instantaneous release of gas and heat. C ompressed Gas - a substance in gas or liquid form contained in a vessel under pressure. This includes cylinders, lecture bottles, and aerosol cans. These substances may be flammable, non-flammable, or poisonous. C ryogenics - substances which are extremely cold such as liquid nitrogen, liquid helium and dry ice. These substances may also become asphyxiation hazards if spilled in non-ventilated areas. Radioactive - any material having a specific activity greater than 0.002 microcuries per gram (uC i/g). See FSU Radiation Safety Manual for use of radioactive materials. Biomedical - tissues, organs, and blood from humans and primates. Sryinges, needles, sharps, and other objects containing materials above. Back to Index

Training Requirements
University personnel working with any of the hazardous materials listed above must receive Hazard C ommunication Training, also known as "Right-To-Know Training". EH&S will provide general hazard communication training; however, supervisors must train subordinates about specific hazards in their areas. Other training may be required as dictated by Federal and State regulations. Training sessions for Laboratory Safety, and Hazardous Waste Disposal are offered by FSU EH&S as well. Specific training requirements are outlined in other sections of the FSU Safety Manual. Back to Index

Storage of Hazardous Materials

Hazardous materials must be stored based on their compatibility, not simply in alphabetical order. Store materials of the same hazard together i.e. flammables with flammables and oxidizers with oxidizers. Hazardous substances should be stored in an orderly manner with older products most accessible and the newer products least accessible. Good housekeeping must be practiced in areas where hazardous products are stored. All hazardous materials must be properly labeled including their exact contents, hazardous properties, date of receipt, and if appropriate, date of expiration. Hazardous substances should be stored in original containers in which they were packaged at the manufacturing plant. If this is not practical, these products should be transferred according to manufacturers' recommendations into containers that are constructed to withstand the effects of the product over the maximum storage time. Incompatible materials must not be stored such that they may come in contact with each other. If incompatible materials are allowed to mix dangerous conditions will result. C ombining these materials may result in the following: heat or pressure; fire or explosion; violent reaction; toxic dusts, mists, vapors, or gases; flammable vapors or gases. Information regarding incompatible materials is summarized in Appendix 1 of this policy. Back to Index

Handling Hazardous Materials

Protective Measures Whenever it is feasible, engineering controls must be used to reduce employee exposures to hazardous materials. The two most common engineering controls are the use of local exhaust and general ventilation. These measures limit an employee's exposure to airborne contaminants. When engineering controls are not available, or they fail to adequately reduce hazards, other personal protective equipment is required. Examples of personal protective equipment include: safety glasses, hearing protection, gloves, respirators, etc.

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Personal protection devices must be provided and worn in accordance with the manufacturer's recommendations indicated on the label of the product or as stated in the Material Safety Data Sheet for the product. Spill Procedures Hazardous chemical spills can be handled effectively when plans of action have been developed. Spill procedures should include the following: the potential location of possible spills; the quantities of material that might be released; chemical and physical properties of the material. This information may be obtained from the Material Safety Data Sheet or label; hazardous properties of the material (consult the MSDS); the types of personal protection equipment that may be needed for cleanup; location and contents of spill kits that should be made available where possible. These kits might include the following: neutralizing agents such as sodium carbonate, sodium bicarbonate or sodium bisulfite absorbents such as vermiculite, "super sorb," or absorbant pillows or dikes. Paper towels, rags and sponges may be used, but caution should be exercised because some chemicals may ignite upon contact with them; plastic scoops and shovels, disposable mops, disposable protective clothing and containers to receive the spilled material and all items used in the cleanup The following general procedure may be used, but should be tailored to the individual needs of the handlers and the specific hazard associated with the hazardous material: If the spilled material is flammable, turn off ignition and heat sources. Attend to any person who may have been contaminated (see First Aid). Notify individuals in the area about the spill. Evacuate nonessential personnel. Avoid breathing vapors of spilled material. Establish an exhaust or ventilation, if it is safe to do so. Air handling units are not to be used because they re-circulate the hazardous vapors. C ontact EH&S for information about the proper ventilation or exhaust required. If a spill is relatively large, or involves a highly toxic material, a carcinogen or flammable material, contact EH&S for assistance in cleaning up the spill and disposing of the hazardous waste resulting from the cleanup. Back to Index

First Aid Procedures for Hazardous Materials

Eye C ontact: If a chemical has been splashed into the eyes, immediately wash the eye and inner surface of the eyelid with copious amounts of water for 15 minutes. C heck for and remove any contact lenses at once. Seek medical attention immediately. Ingestion: C onsult MSDS, a chemical first aid manual or call the Poison C ontrol Information C enter at 1-800-2823171. Follow directions and seek medical attention immediately. Minor Skin C ontact: Promptly flush the affected area with water and remove any contaminated clothing. If symptoms persist after washing, seek medical attention. Major Skin C ontact: If chemicals have been spilled over a large area of the body, quickly remove all contaminated clothing while using the shower. Repeat if pain returns. Wash off chemicals by using a mild detergent or soap and water, do not neutralize chemicals or apply salves. Seek medical attention immediately. Remember that for some chemicals, such as hydrofluoric acid, effects resulting from exposure may not become apparent until hours or days later. C onsult the MSDS for any chemical to which someone has been exposed, even if no immediate injury is apparent. If clothing is on fire, help the individual to the floor and roll him around to smother the flames. If a safety shower is immediately available, douse the person with water; running to a remote shower will only fan the flame. Fire blankets are primarily used as a first aid measure for prevention of shock rather than against smoldering or burning clothing. A fire blanket may direct flames toward the face.

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Disposal of Hazardous Materials

The disposal of most hazardous materials is strictly regulated by federal law. Do not dispose of any hazardous material in the sewer, on the ground or in the trash. The EH&S is responsible for collecting hazardous waste and treating it or preparing it for shipment to an approved hazardous waste disposal facility. Waste products must be clearly labeled with the complete names of the contents and they must be stored in nonleaking, safe containers. EH&S may be contacted for pickup by calling 644-6895 and giving the name of the products to be picked up, the location, the person in charge of the area, his phone number and the approximate quantity of the materials to be picked up. By law, the University is required to strive to reduce the amount of hazardous waste it generates; therefore, University departments should take the following measures: Buy only those amounts of hazardous materials which can be used before the expiration date of the material. Use up the hazardous material by using it for the purpose for which it is intended. Determine if someone else in the department has a legitimate need for, and can use, the product. EH&S provides training for those who generate hazardous waste. Further guidance on the disposal of hazardous waste and materials can be found in Appendix 2 of this policy. Back to Index

Appendix Appendix 1
Short list of incompatible materials Do Not C ontact ALKALI METALS such as calcium, potassium, and sodium with: water, carbon dioxide, carbon tetrachloride, and other chlorinated hydrocarbons. AC ETONE with: concentrated sulfuric acid and nitric acid mixtures. AMMONIA, ANHYDROUS with: mercury, halogens, calcium hypochlorite, or hydrogen fluoride. AC ETIC AC ID with: chromic acid, nitric acid, hydroxyl containing compounds, ethylene glycol, perchloric acid, peroxides, and permanganates. AC ETYLENE with: copper (tubing), fluorine, bromine, chlorine, iodine, silver, mercury, or their compounds. AMMONIUM NITRATE with: acids, metal powders, flammable liquids, chlorates, nitrates, sulfur, and finely divided organics or other combustibles. BROMINE with: ammonia, acetylene, butadiene, butane, hydrogen, sodium carbide, turpentine, or finely divided metals. C HROMIC AC ID with: acetic acid, naphthalene, camphor, alcohol, glycerine, turpentine, and other flammable liquids. C YANIDES with: acids.

ANILINE with: nitric acid, hydrogen peroxide, or other strong oxidizing substances. C HLORATES with: ammonium salts, acids, metal powders, sulfur, carbon, finely divided organics or other combustibles. C HLORINE with: ammonia, acetylene, butadiene, benzene and other petroleum fractions, hydrogen, sodium carbides, turpentine, and finely divided metals.

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HYDROGEN PEROXIDE HYDROGEN SULFIDE with: copper, chromium, iron, most metals with: nitric acid, oxidizing gases. or their respective salts, flammable liquids and other combustible materials, aniline, and nitromethane. HYDROC ARBONS IODINE

generally, with: fluorine, chlorine, bromine, p>with: acetylene or ammonia. chromic acid, or sodium peroxide. MERC URY NITRIC AC ID

with: acetylene, fluminic acid, or hydrogen. with: acetic, chromic, or hydrocyanic acids, aniline, carbon, hydrogen sulfide, flammable liquids or gases, or other substances which are readily nitrated. OXYGEN with: oils greases, hydrogen, flammable liquids, solids, or gases. PERC HLORIC AC ID with: acetic anhydride, bismuth and its alloys, alcohol, paper, wood, and other organic materials. POTASSIUM PERMANGANATE with: glycerine, ethylene glycol, benzaldehyde, or sulfuric acid. OXALIC AC ID with: silver or mercury PHOSPHOROUS PENTOXIDE with: water.

SODIUM PEROXIDE with: any oxidizable substances, for instance: methanol, glacial acetic acid, acetic anhydride, benzaldehyde, carbon disulfide, glycerine, ethylene glycol, ethyl acetate, furfural, etc.

SULFURIC AC ID with: chlorates, perchlorates, permanganates, and water NOTE: This list is not a complete list of incompatible materials. It contains some of the more common incompatible materials. Always research the materials you work with in order to be safe. Back to Index

Appendix 2
Hazardous Waste Accumulation Point Requirements Please, post this notice at your accumulation point and ensure that it remains in place. All chemical containers must be properly labeled. Hazardous waste containers must be marked with the words Hazardous Waste and the chemical and/or chemicals in question. In addition, for those containers with mixtures, a breakdown of the components by percentage or volume is critical to proper disposal (i.e. organic solvent container of 1 gallon of Acetone, 0.5 gallon of Hexanes, 0.5 gallon of Ethyl Acetate). All hazardous wastes shall be collected in sealable containers. Foil or film closures are not acceptable. Do not put hazardous wastes into sinks, drains, or the trash. The waste must be compatible with other wastes in the container, and with the type of container it is stored in. The exterior of the container must be free of chemical contamination. Leaking containers will not be picked up. Store containers of incompatible waste apart from each other (i.e. keep oxidizers away from flammable solvents). Also consider safe temperature storage requirements. Containers shall be kept closed during accumulation except when adding waste to a container. EH&S provides 5 gallon safety containers for hazardous waste solvent accumulation. Container tag instructions shall be followed. It is important to separate halogenated and non-halogenated solvents. In other words, please do not pour halogenated solvents into the non-halogenated solvent container. Keep acids, bases, heavy metals and pesticides from solvent containers. These steps are critical for safety and proper disposal. All chemicals placed in any hazardous waste container must be compatible. You shall not accumulate more than 55 gallons of waste (or 1 quart of acutely hazardous waste) at any one time. The allowable quantity for flammable liquids is less than 55 gallons. To keep the waste accumulation at a level much less than 55 gallons, EH&S provides 5 gallon safety solvent containers.

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Keep the waste containers near the process generating the waste. Keep open flame and ignition sources away from all chemicals, especially hazardous waste and chemical containers. NO SMOKING RULES APPLY. Do not overfill waste containers. Leave enough headspace to allow for expansion and to prevent spills. Designate an accumulation point manager and an alternate. Keep all containers properly labeled and complete all requested information on the Hazardous Waste C ontainer Tag. Inspect waste containers weekly for leaks and proper labeling. This must be documented. If the tag or container is not properly labeled the container cannot be picked up for disposal. All employees working in the area must have had HAZCOM/RIGHT-TO-KNOW TRAINING. All employees and students responsible for hazardous waste generation must have had HAZARDOUS WASTE AWARENESS AND HANDLING TRAINING. Dispose of PEROXIDE FORMING CHEMICALS (i.e. Ethers, Dioxanes, Tetrahydrofuran) before the expiration date written on the label. Realize that certain chemicals with the passage of time can become shock-sensitive explosives. Attention to this detail could save someone's life, and will save the University a significant amount of time and money. Your assistance is needed to prevent the generation of UNKNOWN CHEMICALS. Unknown chemicals are a safety hazard and cost a great deal to identify and dispose of. Proper labeling, inventory, and reporting, especially for those who may be leaving the University, would eliminate a great deal of this problem. EH&S requires that departments make every effort to identify unknown wastes. A special consultation with EH&S will be required before unknown waste will be picked up. Please call the Hazardous Materials Manager at 644-6895. It is critical that every effort be made to fully and correctly identify all chemical constituents and their respective concentrations on the container labels. Incorrectly labeled containers could result in improper disposal and subsequent fines being assessed to the University. An improper label could also cause serious and potentially fatal injuries to both laboratory and EH&S personnel. C ontainer labels can be obtained free of charge by calling EH&S at 644-6895. For Hazardous Waste Pick-up Service call EH&S at 644-6895. Your waste will be picked up as soon as possible after the request is received. Major laboratory chemical clean-outs must be planned well in advance of waste removal. To arrange for this service please call EH&S at 644-6895. Radioactive Materials are managed and disposed of by Radiation Safety. For information please call 644-8801. NEVER MIX HAZARDOUS AND RADIOAC TIVE WASTE. All FIRES regardless of size must be reported to the FSU Police by telephone (911) and by pulling the fire alarm pull station. All FIRE EXTINGUISHERS used for any fire or discharged to any degree must be reported immediately to EH&S 644-6895 for service. All CHEMICAL SPILLS AND OR RELEASES must be cleaned up properly and safely. All spills must be reported to EH&S at 644-6895. All spills in amounts greater than 1/2 Liter or 1 pound, or of any acutely hazardous materials, require a response by EH&S personnel. Any size spill directly to the ground or water must be immediately reported to EH&S. After normal working hours EH&S personnel can be contacted by calling the FSU Police at 644-1234 or dialing 911. If you have questions, please call EH&S at 644-6895 and ask for the Hazardous Materials Manager. Please post this notice at your accumulation point and ensure that in remains in place! Back to Index

Appendix 3: Rules for Storing Chemicals Safely

Segregate all incompatible chemicals for proper storage of chemicals for hazard class codes. In other words, store like chemicals together and away from other groups of chemicals that might cause reactions if mixed. Do not simply store chemicals in alphabetical order. Flammable materials should be stored in an approved, dedicated, flammable materials storage cabinet or room if the volume exceeds ten (10) gallons. C hemicals shall be stored separately from non-compatible hazard classes. The following is a recommended storage scheme to minimize incompatibility of chemicals: Inorganic: metals, hydrides. halides, sulfates, sulfites, thiosulfates, phosphates, halogens.

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amides, nitrates, nitrites, azides, nitric acid. hydroxides, oxides, silicates, carbonates, carbon. sulfides, selenide, phophides, carbides, nitrides. chlorates, perchlorates, perchloric acid, chlorites, hypochlorites, peroxides, hydrogen peroxide. arsenates, cyanides, cyanates. borates, chromates, manganates, permanganates. Organic: acids, anhydrides, peracids alcohols, glycols, amines, amides, imines, imides. hydrocarbons, esters, aldehydes. ethers, ketones, detenes, halogenated hydrocarbons, ethylene oxide. epoxy compounds, isocyanates. peroxides, hydroperoxides, azides. sulfides, polysulfides, sulfoxides, nitriles. phenols, cresols. Liquids should be stored in unbreakable or double-contained packaging, or the storage cabinet should have the capacity to hold the contents if the container breaks. Avoid floor chemical storage (even temporary). C hemicals should be stored no higher than eye level and never on the top shelf of a storage unit. Shelf assemblies should be firmly secured to the walls. Avoid island shelves. Each shelf should have an anti-roll lip. Store acids in a dedicated acid cabinet. Nitric acid may be stored there also, if it is kept isolated from the others. Store severe poisons in a dedicated poison cabinet. All chemicals should be labeled and dated. Look for unusual conditions in chemical storage areas, such as: improper storage of chemicals leaking or deteriorating containers spilled chemicals temperature extremes (too hot or cold in storage area) lack of or low lighting levels blocked exits or aisles doors blocked open, lack of security trash accumulation smoking or open lights or matches fire equipment blocked, broken or missing lack of information or warning signs ("No Smoking", "Flammable Liquids", "Acids", "C orrosives", "Poisons", C hemical Storage") Any of these conditions should be corrected immediately. Inspections of chemical storage areas on a routine basis will help to correct deficiencies and prevent accidents. Back to Index

Appendix 4: Sugggested Chemical Storage Pattern

Inorganic Organic

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Alcohols, Glycols, etc. (store flammables in dedicated cabinets) Hydrocarbons, Esters, etc. (store flammables in dedicated cabinet) Ethers, Ketones, etc. (store flammables in dedicated cabinet) Epoxy compounds, Isocyanates

Sulfur, Phosphorus, Arsenic, Phosphorus Pentoxide

Halides, Sulfates, Sulfites, Thiosulfates Phosphates, etc. Amides, Nitrates (not ammonium nitrate), Nitrites, etc. Metals, Hydrides (store away from water) Hydroxides, Oxides, Silicates, etc. Arsenates, C yanides (store above acids) Sulfides, Selenides, Phosphides, C arbides, Nitrides Manganates, C hromates, Permanganates, Borates C hlorates, C hlorites, Perchlorates, Peroxides, Perchloric acid Acids. except nitric. (store acids in dedicated cabinets) Back to Index

Sulfides, Polysulfides, etc. Phenol, C resols

Peroxides, Azides, etc. Acids, Anhydrides, Peracids, etc. Miscellaneous

Miscellaneous (Nitric Acid)

Appendix 5: Sugggested Storage Time Limits for Common Peroxidizable Compounds

MOST DANGEROUS: Discard after 3 months. Peroxide formation hazard during storage. isopropyl ether divinyl acetylene vinylidene chloride potassium metal sodium amide

DANGEROUS: Discard after one year. Peroxide formation hazard during storage and on concentration (i.e. distillation) of compound. diethyl ether tetrahydrofuran dioxane acetal methyl isobutyl ketone ethylene glycol dimethyl ether vinyl ethers Safety Hints dicyclopentadiene diacetylene methyl acetylene cumene tetrahydronaphthalene cyclohexene methylcyclopentane

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Ethers should be stored in the dark and under nitrogen if possible. Always check for the presence of peroxides before distilling any peroxide former. C onsult safety references before working with peroxidizable compounds. Back to Index

1. Do not purchase these compounds in quantities greater than can be used in the specified storage time period.

References
1. 2. 3. 4. 5. 6. Hazard C ommunication Standard (OSHA) 29 C FR 1910.1200, C hapter 442 F.S., Rule 38I-20.003 F.A.C . Hazardous Waste Management (EPA) 40 C FR Parts 260-299, Rule 62-730 F.A.C . Occupational Exposure to Hazardous C hemicals in Laboratories (OSHA) 29 C FR 1910.1450, Rule 38I- 20.003 F.A.C . Safety in Academic C hemistry Laboratories"; American C hemical Society, Washington D.C .,1991. Prudent Practices for Handling Hazardous C hemicals in Laboratories; National Academy of Sciences, Washington D.C ., 1981. "Flammable and C ombustible Liquids C ode"; NFPA Standard 30, National Fire Protection Association, Quincy, MA, 1992 li Back to Index

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