West Virginia University Laboratory Training Module 4. Chemical Safety

Topics to be covered Chemical Waste Disposal Emergency Response Chemical Spills

1. Chemical Waste Disposal Complete the online Hazardous Chemical Disposal form at: http://www.wvu.edu/~ehs If you have questions contact Environmental Health and Safety (EH&S) at 293-3792. EH&S will pick up the unwanted chemicals. Chemicals, in containers, must be compatible and labeled with the common name of each chemical (no formulas)

Chemical Waste Disposal Continued Chemical containers should be no more than 95% full to allow for expansion and must have a screw cap closure or equivalent. WVU has a licensed contractor to transport and properly dispose of hazardous chemical waste

Storage of Waste Chemicals Waste chemical must be stored in a compatible manner. A typical segregation of waste chemicals involve the following: Acids Caustics Chlorinated Solvents Non-chlorinated Solvents Mercury Wastes Oxidizing Agents PCB Wastes Reactive Wastes Waste Oil Wastes with Heavy Metal Contamination These chemicals need to be accumulated in separate containers and isolated in such a way to isolate spills and leaks from each other.

Characteristics of Hazardous Waste If a waste meets one or more of the following four “characteristics” it is considered a hazardous waste for the purposes of disposal 1. Ignitable 2. Corrosive 3. Reactive 4. Toxic

Ignitability Any liquid having a flashpoint of less than 140 degrees F is an “ignitable” material. This includes almost all organic solvents. Compressed gas (propane, methane, etc.).

Ignitability continued: Oxidizers (e.g., potassium nitrate, sodium nitrite) It is not a liquid and is capable, under standard temperature and pressure, of causing fire through friction, absorption of moisture, or spontaneous chemical changes and, when ignited, burns so vigorously and persistently that it creates a hazard.

Corrosivity: Any aqueous material having a pH less than or equal to 2.0 or greater than or equal to 12.5 is a corrosive material. Any liquid or solid, which corrodes steel at a rate greater than 0.25 inch per year. All common organic and mineral acids are considered corrosives. Common bases such as solid sodium hydroxide and potassium hydroxide are also corrosive.

Reactivity: Reacts violently with water or forms potentially explosive mixtures with water or, when mixed with water forms toxic vapor or fumes. Can form hydrogen cyanide or hydrogen sulfide gas when exposed to pH conditions between 2 and 12.5. Readily capable of detonation or explosive decomposition if it is subjected to a strong initiating source or is heated under confinement.

Toxicity: Any waste product is considered “TCLP toxic” by RCRA regulations if it contains any one of 40 named metals, solvents or pesticides in specific quantities. Regulated quantities are in fractions of, or parts per million.

Chemicals found under the Toxicity characteristic and are regulated in parts per million concentration: Metals Arsenic Barium Cadmium Chromium Lead Mercury Selenium Silver Organics Benzene Carbon tetrachloride Chlorobenzene Chloroform Cresol Dichloroethane Methyl ethyl ketone Nitrobenzene Pyridine

toxic metal-containing compounds used at WVU: Barium hydroxide Nickel chloride Cacodylic acid Osmium tetroxide Cadmium chlorid Potassium dichromate Chromic acid Selenous acid Copper sulfate Silver (used photography fixer) Lead subacetate Sodium arsenate Mercuric nitrate Sodium cacodylate

Segregation of Chemical Waste: Chemical waste must be segregated in such a manner that only chemically compatible wastes are allowed to be mixed together.

The following guidelines must be followed when collecting solid chemical waste: Segregate and collect solid chemical waste according to their compatibilities. Contact EH&S for guidance. Do not mix solid waste and liquid waste. Collect these wastes separately. Label the chemical with the chemical IUPAC name and concentration. Needles, syringes, and sharps must be collected separately in a plastic needle discard container.

Incompatible Chemical Mixtures: Caution and common sense must be used when collecting chemical waste in the laboratory so that incompatible materials are not mixed together. Empty waste containers should be properly rinsed if they held a material, which is incompatible with the waste to be collected.

The following dangerous chemical mixtures must be avoided: Acid mixed with most cyanide salts or solutions generate highly toxic hydrogen cyanide gas. Acid mixed with most sulfide salts or solutions generate highly toxic hydrogen sulfide gas. Acid mixed with bleach generates highly toxic chlorine gas. Oxidizing acids (e.g., nitric, perchloric) react violently with combustible materials (paper, common solvents) and may cause a fire. Solid oxidizers (e.g., nitrates, iodates, permanganates) react with combustible materials (paper, common solvents) and may cause a fire. Hydrides (e.g., sodium hydride) react with water to form flammable hydrogen gas.

Dangerous chemical mixtures that must be avoided continued: Phosphides (e.g., sodium phosphide) react with water to form highly toxic phosphine gas. When silver salts are mixed with ammonia in the presence of a strong base, an explosively unstable solid is generated. Alkali metals (e.g., sodium, potassium, calcium, etc.,) react with water to form flammable hydrogen gas. Oxidizers (e.g., nitric acid) react with reducers (e.g., hydrazine) to yield fires or explosions. Unsaturated compounds (carbonyls, double bonds, etc.) may polymerize violently in the presence of acids or bases. Hydrogen peroxide/acetone mixtures may explode when heated in the presence of acid. Hydrogen peroxide/acetic acid solutions may explode when heated. Hydrogen peroxide/sulfuric acid mixtures are susceptible to spontaneous and unpredictable chemical detonation.

Materials Prohibited in the Chemical Waste Stream 1. Radioactive Materials 2. Uranium Compounds (uranyl acetate, uranyl nitrite) 3. PCB’s (polychlorinated biphenyls, arochlor, chlorextol, chlorodiphenyl) 4. Infectious Waste or Etiological Agents (human blood, serum, body fluids, etc.) 5. Dioxin Waste (TCDD, pentachlorophenol, tri- and tetrachlorophenol) 6. Asbestos

Guidelines which must be followed when collecting chemical waste: Containers must be clearly labeled with the IUPAC chemical name (no abbreviations) and concentration. Unused chemical reagents in original containers with intact labels need no further labeling. Chemical waste containers must be sealed airtight with a proper lid. Rubber stoppers, corks, and parafilm are not allowed.

Continued: An air gap of 5-10% must be left in the container to allow for expansion of the liquid. Before collecting waste in a used container, rinse the container. Chemical waste must be collected in a chemically compatible container to prevent the chemical from dissolving the container. For example, if waste acetic acid is collected in a steel container, the acid will soon corrode the container’s wall and an unwanted leak will occur. The original container that a chemical was shipped in is a good container to collect the waste.

Empty Chemical Container Disposal Procedure Empty chemical containers that held a material, which was flammable, corrosive, reactive, or toxic, must be picked up by EH&S. Fill out the chemical waste to request a pickup. Non-hazardous containers may be discarded in the domestic trash as long as they are not made of glass. Empty non-hazardous containers may be discarded in the regular trash.

Gas Cylinders Empty gas cylinders and lecture bottles present a special disposal problem because it is not always obvious when they are empty. Contact EH&S for assistance. Remember gas cylinders must be stored in an upright position and secured to prevent falls!

Trace Contaminated Waste (Carcinogen, Mutagen, Toxic) Laboratory chemicals, which are extremely toxic, or are a potent mutagen, teratogen or carcinogen must be handled in a manner that minimizes personal exposures.

Trace Contaminated Waste (Carcinogen, Mutagen, Toxic) Laboratory workers must identify which chemicals they work with are hazardous. A Material Safety Data Sheet (MSDS) should be consulted for each chemical so a proper assessment can be made regarding its toxicity. Trace contaminated wastes should be collected for materials that have been in contact with chemicals that are carcinogenic, potent mutagens, or are extremely toxic. Contact EH&S for waste disposal advice before actually collecting trace contaminated waste products. EH&S will help you determine whether these waste products warrant special collection.

Continued When collecting trace contaminated waste the following guidelines apply: Collect solid and liquid waste separately. Collect syringes and sharps in plastic needle buckets. Dispose full buckets into infectious waste stream. Collect trace contaminated waste separately from all other wastes. All waste must be collected in airtight containers. Properly label all waste containers. Dispose of all trace contaminated waste through EH&S.

Universal Waste As part of the EPA’s commitment to reduce waste, the Agency has issued the Universal Waste Rule. This rule has been designed to reduce the amount of material that is being disposed of as hazardous waste. It includes: Nickel-cadmium batteries Lead-acid batteries Some agricultural pesticides Thermostats Fluorescent Bulbs

Batteries: Most batteries can be recycled by sending them back to the company or using a recycling facility. Please contact EH&S for information regarding recycling. Each battery must be clearly marked as “Universal Waste Batteries”, or “Used Batteries” with the date. Leaking or damaged batteries must be stored in a closed, structurally sound container, with secondary containment. Have the batteries collected by or deliver them to an authorized battery recycler.

Fluorescent Lamps A variety of vendors are available in many areas to recycle fluorescent light bulbs. Please contact Environmental Health and Safety for a list of recycling companies. Fluorescent lamps must be must be labeled “Universal Waste Electric Lamps” or “Used Lamps” with the date on which your first began storing the lamps. Lamps must be packaged in a way to minimize breakage and to prevent release of lamp fragments if breakage were to occur. Store unbroken lamps in a box or fiber drum. Have the lamps collected by an authorized universal waste handler within one year of the date marked on the container. Broken or damaged bulbs will be treated as hazardous waste. All the spill debris from broken or damaged bulbs must be cleaned up and placed into a sealed bag. Please contact EH&S for assistance with spill cleanup.

Used Oil A variety of vendors exist to recycle oil. Call EH&S for information regarding oil recycling. Used oil must be stored in a fail proof container and must be clearly labeled with the type of oil.

2. Emergency Response Know where your emergency equipment is; make sure the equipment is not blocked. Have emergency phone numbers posted near the phone.

Medical Emergencies: Call 911 to report emergency Provide minimum first aid to prevent further injury to the victim. Follow other department procedures (meet paramedics) Complete an accident report form.

Calling 911: Report the locations; nature of emergency Answer the dispatcher questions Meet emergency personnel at the door

Chemical Splashes: Get victim to safety shower and eyewash Flush for 15 minutes or until help arrives Remove contaminated clothing

Eyes: Quick response is important Flush for 15 minutes You may have to force the eye lids open Have the victim roll their eyes around

Safety Showers and Eyewashes

Fire Emergencies: (If a fire occurs) Pull the fire alarm to evacuate the building Call 911 and report the location of the fire If you do call 911, be sure to meet the emergency personnel to give them relevant information and direct them to the exact location of the emergency. Isolate the fire (close fume hood sash or lock door) Confine or control the fire if possible: Immediately turn off gas supplies and electrical power sources. Use an appropriate fire extinguisher

Which Fire Extinguisher Do I Use? CO2 extinguishers are for flammable liquids (Class B fires) or electrical fire (Class C). Solid or dry chemical fire extinguishers can be used for all fires; paper and wood (Class A), flammable liquids (Class B), or electrical (Class C) fires. Yellow “Class D” extinguishers are for metal fires.

3. Chemical Spills All chemical spills that occur at West Virginia University should be reported to the departmental chemical hygiene officer and your supervisor. The spill report needs to include the date, time, location, and the chemical(s) and their volume.

If a spill occurs: Contact Environmental Health and Safety with the location of the spill and, if known, the chemical and volume spilled. If the spill presents an immediate danger, leave the spill site and control entry to the spill site. Notify nearby persons and evacuate as necessary. If flammable vapors are involved, do not operate electrical switches.

Continued: If the substance involved is an unknown, then emergency spill response procedures are limited to self-protection, notification of EH&S, isolation of the chemical, and evacuating and securing the area involved. If the spill does not present immediate personal danger, try to control the spread or volume of the spill. Locate and retrieve the departmental spill kit for absorbent material. Do not touch the spill without protective clothing. Never assume gases or vapors do not exist or are harmless because of lack of smell.

Spilled Liquids: Confine the spill to small area. For small quantities of inorganic acids or bases, use a neutralizing agent or an absorbent mixture (soda ash or diatomaceous earth). For small quantities of other materials, absorb the spill with a nonreactive material (vermiculite, clay, sand, absorbent towels, pillows). For large spills contact Environmental Health and Safety and try to prevent the spill from spreading. Carefully pick up the bottles and the soiled absorbent material and place in a 5-gallon bucket with a label identifying the chemical. Contact EH&S for disposal.

Spilled Solids: Sweep spilled solids of low toxicity into a dustpan and place them into a suitable container. Additional precautions such as the use of a HEPA filter vacuum cleaner may be necessary. Contact EH&S for disposal.

Mercury Spills: Mercury is extremely dangerous and every effort should be taken to prevent spills. For small spills, a laboratory coat, safety glasses, and gloves should be used. The following gloves have been approved for use with mercury: Chlorinated polyethylene Polyurethane Viton Butyl Rubber Polyvinyl Chloride Nitrile Rubber Neoprene

Mercury Spills continued: Please use a mercury spill kit to clean up a mercury spill. Call EH&S for assistance. Wearing protective clothing, place the sponge, provided in the spill kit, rough side up on a level surface. The rough side contains the active material that will amalgamate mercury. Dampen the sponge with about 2ml of water. Spread the water evenly with a gloved finger and wait one minute. (Excessive water may reduce the ability of the sponge to pick up mercury).

Mercury Spills continued: With the active side down, slowly wipe the area contaminated with mercury. The mercury droplets will be amalgamated by the chemical layer of the sponge. The capacity of the sponge can be increased with a small amount of moistened HG Absorb Powder rubbed into the surface of the activated sponge. After finishing the Hg Absorb sponge should be returned to its plastic bag and disposed of. Contact Environmental Health and Safety for disposal. Air Monitoring: Any mercury spill has the potential to generate airborne concentrations in excess of regulated levels. Please contact EH&S at 293-3792 for air monitoring of the spill area.

Leaking Compressed Gas Cylinders If a leak is suspected contact EH&S at 293-3792 and they will advise you to follow the appropriate action.

Recommended Spill Kit Contents Supervisors in areas in which the potential exist for chemical spills, should store and maintain a spill kit. The contents of this kit (5 gallon bucket) include: 1 Universal Spill Boom (Snake) 3”X4’ 2 Universal Spill Pads 2.5 gallons of vermiculite 2 30 gallon trash bags Gloves Eye Protection 1 “Hazardous Waste” Label If you have any questions as to how to obtain these materials contact EH&S.