OEH&S Chemical Safety Manual Chapter 2

CHEMICAL PROCUREMENT, DISTRIBUTION, AND STORAGE

Controlling procurement, distribution and storage of chemicals is the essential part of any Chemical Safety Program. Every laboratory should have an up-to-date written inventory of the chemicals present, including quantities on hand, date of receipt, and location in the laboratory. The major areas include:

A. PURCHASING CHEMICALS

The decision to procure a specific quantity of a specific chemical is a commitment to handle it responsibly from receipt to disposal. Chemicals are procured on campus in at least three ways:

• Regular orders from campus storehouse or off-campus suppliers,
• Low-value blanket orders, and
• Personal acquisition, or transfer from other laboratories.

Irrespective of the route of procurement, the same safe procedures are required. Chemicals which are carcinogens or controlled substances are subject to additional legal regulations. Most chemicals may present hazards. In this instance the Office of Environmental Health and Safety (OEH&S), and the Chemical Safety Committee (CSC) are authorized to limit the quantity, purchase, or specify the conditions of use of any chemical it deems hazardous.

Do not purchase a greater quantity of chemicals than is actually needed or can be safely stored.

Users are expected to be knowledgeable about the hazards of the chemicals that they work with. Material Safety Data Sheets (MSDS), see Appendix C, and other published safety information must be readily available for use in an emergency. This information should be requested from the manufacturer when purchasing the chemical if it is not already available. OEH&S is the central repository for MSDSs; contact your Departmental Safety Advisor for assistance.

The Hazardous Waste Source Reduction and Management Review Act (SB14) requires a waste minimization program. This includes source reduction (limiting purchase to the minimum quantities required) and substituting hazardous chemicals with non-hazardous (or less hazardous) chemicals when practical.

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1. CHEMICAL INVENTORIES

Under the “Emergency Planning and Community Right to Know Act” of 1986 all facilities are required to provide certain information to local agencies. The San Francisco Department of Public Health, Bureau of Environmental Management requires that UCSF submit a detailed inventory of chemicals and update it annually. In addition,

UCSF must report any changes in facilities or usage which impacts the validity of a previous submittal within 30 days of such changes. OEH&S administers this program and obtains the necessary permits for the Campus. Each laboratory or unit using or storing chemicals is notified by OEH&S when these submissions are due.

To assist in maintaining current inventories, and reducing the burden of annual inventories, please make sure that you inform OEH&S:

• When you purchase a chemical that you did not use previously.
• When there is a change in usage of more than 25% per year.
• When your laboratory is moving, relocating or being remodeled.

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B. TRANSPORTING CHEMICALS

Transporting chemicals inappropriately can result in spills and, in some instances, chemical exposures and fire hazards. The obvious preventive approach lies in ensuring that the chemical is packaged in an appropriate container, protected from external forces, and secured in an appropriate cart.

Chemicals are to be transported in containers made of materials that are compatible with the chemical. This is extremely important for waste chemicals that are removed through the Campus Chemical Waste Program.

Chemicals are expected to be transported through public corridors in boxes or external containers which can reasonably be expected to withstand moderate forces that might be expected with accidental dropping.

Chemicals are transported in freight or service elevators only. If necessary, chemicals can be transported on carts; consideration must be given to the weight and balance of the load. No loose bottles or containers of chemicals shall be carried by hand down public corridors or in elevators. Use boxes and/or carts.

Note:
Off campus transportation of chemicals requires proper packaging and labeling, please contact OEH&S for assistance.

Hazardous materials shall not be transported on UCSF Shuttle buses.

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1. LABELING CHEMICALS

Many of the chemicals utilized in research laboratories are hazardous, while others may be hazardous only when mixed with other chemicals (see Glossary for definintion of hazardous material). Therefore, it is important that containers of hazardous chemicals or mixtures be properly labeled.

a. Labeling of Hazardous Chemicals

Minimum requirements on the label are:

1. Name of user
2. Date
3. Description of contents
4. Concentration
5. Appropriate hazard labels Chemicals in the original container, as supplied by the manufacturer, are usually correctly labeled.

b. Laboratory Labeling Requirements

1. All chemical containers must be properly labeled.
2. All chemicals in supplier's containers should have the following information written on the manufacturer's label for identification purposes:
   • Date of receipt in laboratory
   • Name of person who purchased the chemical
3. Containers of dilutions made from the original stock bottle, should have the following information:
   • Date of preparation
   • Name of person who prepared the solution
   • Name of chemical or mixture and percent concentration(s)
   • Appropriate hazard labels
4. All peroxide-forming chemicals must have a label which indicates the expiration date and date opened. Be familiar with the hazards of peroxidizable chemicals (see Appendix B3). For specifics on types and explanation of labeling see Chapter 7.

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C. STORING CHEMICALS

1. GENERAL GUIDELINES

1. Do not store excessive quantities of chemicals in the laboratory. Purchase the minimum amount required, and dispose of unneeded chemicals in a timely fashion (contact OEH&S for support in disposing of chemicals).
2. All chemicals and chemical mixtures must be plainly and permanently labeled (see Labeling Requirements section above).
3. Each chemical in the laboratory should have a definite storage space, consistent with the properties of that chemical.
4. Stored chemicals must have secondary containment of sufficient volume to hold the bottle’s contents should it leak, and of a material resistant to the effects of the chemical.
5. Store reagents in cabinets or on shelves. Store largest bottles of chemicals on the lower shelves. Do not allow bottles to extend over the edge of the shelf. Be mindful of earthquake risks when storing chemicals on shelves.
6. When storing chemicals above bench level, it is preferable to store them in cabinets with sliding doors; the next preferable location is in cabinets with latched doors.
7. Storing chemicals on open shelves requires that the shelves have a minimum of ¾ -inch lip. A solid metal, wood, or Lucite strip or strong wire may be used to modify shelves.
8. Do not store chemicals on benchtops. They are more readily knocked over and are unprotected from potential exposure to fire.
9. Chemicals requiring refrigeration should be properly labeled, and sealed to prevent escape of vapors. Only refrigerators designated and approved for chemical storage should be used (see Appendices E4 and E5).
10. Fume hoods should not be used for chemical storage. Such storage interferes with the air flow in the hood, causes clutter, and increases the fuel load in the event of a hood fire. If small quantities of highly hazardous chemicals must be stored in the hood, they should be placed on an elevated shelf.
11. No chemicals (either reagents or waste chemicals) should ever be stored on the floor. Floor storage presents a major hazard because bottles can be knocked over and broken.
12. Flammable, toxic, and corrosive chemical liquids in quantities greater than 250 ml. must be stored in cabinets, below bench level.
13. Highly toxic chemical liquids, such as carcinogens, cyanides, hydrofluoric acid and perchloric acid must be double-contained. The outer container must be properly labeled.
14. Flammable liquids requiring cold storage must be stored only in approved explosion-safe refrigerators or freezers. Do not refrigerate chemicals unnecessarily.
15. Volatile chemicals must be tightly closed when not in use.
16. Date bottles of chemicals when they are opened.
17. Peroxidizable chemicals, such as ethyl ether and tetrahydrofuran, should be discarded within six months of opening the container.
18. Storage areas should be inspected periodically for damaged containers, such as cracked bottles or caps, or rusted metal containers. Loose or deteriorated labels must be replaced.
19. Plan chemical storage with personal safety in mind. Make certain all personnel will be able to exit the laboratory, should there be a spill or fire.

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2. SECONDARY CONTAINMENT

Secondary containment is required in circumstances where there is a possibility that the chemicals may spill and contaminate the area. This containment can be achieved in a variety of ways, such as:

1. Use of chemical resistant trays, or other containers, placed under the chemical container.
2. Using storage cabinets which are designed to contain spilled chemicals.


As a general rule all chemicals should be stored with secondary containment. However, the following require mandatory secondary containment:


3. Waste storage containers.
4. Chemicals which are being poured into other containers.
5. Operations which require handling of large quantities of liquids (100’s cc)

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3. COMPATIBILITY OF STORED CHEMICALS

a. General Guidelines:

1. Do not store all chemicals in one area. Segregate chemicals according to the chemical and physical properties of the chemicals. Consult the MSDS for reactivity information. Do not store hazardous chemicals alphabetical.
2. Provide separate storage areas for corrosives, solvents, oxidizing agents, pyrophoric materials, and air - or water-reactive chemicals.
3. Acids should be stored separately from bases.
4. Organic acids should be stored separately from inorganic acids.
5. Solvents should be stored separately from acids.
6. Store ammonium hydroxide in a separate cabinet, preferably vented.
7. Store oxidizers, including oxidizing acids such as nitric and perchloric acids separate from oxidizable compounds, such as acetic acid.
8. Perchloric acid must be stored where it cannot come in contact with organic material.
9. Cyanides and sulfides must be kept safe from any contact with acids. Store cyanides in closed cabinets, away from easy reach.
10. Dispose of cyanides which have no current use (contact OEH&S for support).
11. Store pyrophoric materials separate from flammable materials in a dry inert atmosphere (for example, a nitrogen-filled desiccator).
12. Store highly toxic chemicals in unbreakable secondary containers prominently labeled with a description of the contents.

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Table 2.1 A Suggested Shelf Storage Pattern - Inorganic

INORGANIC SULFUR, PHOSPOURS, ARSENIC, PHOSPORUS PENTOXIDE INORGANIC HALIDES, SULFATES, SULFITES, THIOSULFATES, PHOSPATES, HALOGENS, ACETATES INORGANIC AMIDES, NITR ATES (Not AMMONIUM NITRATE) NITRITES, AZIDES (Store away from ony water) (Store Ammonium Nitrate away from all other substances - ISOLATE IT !) INORGANIC METALS & HYDRIDES (Store away from any water) (Store flammable solids in flammables cabinet) INORGANIC HYDROXDES, OXIDES, SILICATES, CARBONATES, CARBON

INORGANIC ARSENATES, CYANIDES, CYANALES (Store away from any water) INORGANIC SULFIDES, SELENIDES, PHOSPHIDES, CARBIDES, NITRIDES INORGANIC BORATES, CHROMATES, MANGANATES, PERMANGANATES INORGANIC CHLORATES, PERCHLORATES, CHLORITES, PERCHLORIC ACID, PEROXIDES, HYPOCHLORITES, HYDROGEN PEROXIDE MISCELLANEOUS

INORGANIC ACIDS, except NITRIC ACID (Acids are best stored in dedicated cabinets) Store Nitric Acid away from other acids unless your acid cabinet provides a separate compartment for Nitric Acid. If possible avoid using the floor

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2.1 A Suggested Shelf Storage Pattern – Organic

ORGANIC ALCOHOLS, GLYCOLS, AMINES, AMIDES, IMINES, INIDES (Store flammables in a dedicated cabinet) ALDEHYDES (Store flammables in a dedicated cabinet) ORGANIC ETHERS, KETONES, KETENES, HALOGENATED HYDROCARBONS, ETHYLENE OXIDE (Store flammables in a dedicated cabinet) ORGANIC EPOXY COMPOUNDS, ISOCYANATES ORGANIC SULFIDES, POLYSULFIDES, ETC.

ORGANIC PHENOL CRESOLS ORGANIC PEROXIDES, AZIDES, HYDROPEROXIDES ORGANIC ACIDS, ANHYDRIDES, PERACIDS (Store certain organic acids in acid cabinet) MISCELLANEOUS MISCELLANEOUS

STORE SEVERE POISONS IN POISONS CABINET ORGANIC ALCOHOLS, GLYCOLS, ETC. ORGANIC HYDROCARBONS, ESTERS, ETC ORGANIC ETHERS, KETONES, ETC STORE FLAMMABLES IN A DEDICATED CABINET FLAMMABLES If possible avoid using the floor

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Table 2.1.B is intended to provide general information on chemical incompatibilities for storage. It is by no means a complete listing. Consult the MSDS for each particular chemical for more information.

Table 2.1.B

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D. STORAGE OF SPECIFIC CLASSES OF CHEMICALS

1. FLAMMABLE LIQUID STORAGE

a. Definitions

1. Flammable Liquid: A liquid with a flash point below 1000^F (370^C) (NFPA Class I liquids).
2. Combustible liquid: A liquid with a flash point at or above 1000^F (600^C) (NFPA Class II, Class IIIA and Class IIIB)

Note:
UCSF consists of many interconnected high-rise buildings. Because several of these are hospital patient areas, NFPA Class II liquids are treated as Class I liquids, i.e., flammable. Flash points of commercial and unknown chemical solutions can be obtained by request to your DSA or the Campus Fire Marshal.

b. General Guidelines

Class IA solvents, such as ethyl ether, should be purchased only in one gallon (4 liter) or smaller containers. If a larger quantity is required, purchase an additional one gallon container. Because of the extreme flammability of the Class I liquids, only quantities needed for immediate use should be stored.

Solvents such as acetone and ethanol that are stored in spigoted plastic carboys for dispensing should be positioned with the spigot over a tray (secondary container) large enough to contain the entire contents of the carboy in the event of leakage from the spigot.

The hazardous nature of each chemical in this category must be considered individually with respect to reactivity and flammability, and in relation to other flammable chemicals which may be stored in the same area.

The quantity of chemicals stored is a consideration in fire prevention. The current fire control approach is directed toward limiting the quantity of unprotected chemicals. Amounts and types of chemicals to be stored are related to the structure of the facility, the availability of sprinklers and other fire protection, and the rated occupancy of the building. Assistance in developing a chemical storage plan is available from your DSA or the Campus Fire Marshal.

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2. CONDITIONS FOR STORAGE AND USE OF FLAMMABLE CHEMICALS

a. General Guidelines:

1. Dispensing of flammable liquids from a shipping container greater than one gallon is not permitted.
2. Dispensing of flammable liquids should be performed in a fume hood.
3. Dispensing of flammable liquids near open fire or flame is prohibited.
4. Refrigerators which are used for storage of flammable liquids must be approved as laboratory safe and so labeled.
5. Flammable liquids shall be stored in containers no larger than the following:
   • Glass Container:
     • 1 pint of Class IA flammable liquids (flash point <73 degree F, boiling point <100 degree F)
     • 1 quart of Class IB flammable liquids (flash point <73 degree F; boiling point >100 degree F)
     • 1 gallon of Class IC flammable liquids (flash point >73 degree F, boiling point <100 degree F)
   • Metal Container:
     • 1 gallon of all Class I and Class II liquids
     • > 1 gallon of all Class I and Class II liquids must be stored in approved safety containers.
   • Storage Volume:
     • No more than 10 gallons in aggregate of flammable liquids shall be stored outside of an approved and labeled storage cabinet.
     • No more than 60 gallons of flammable liquids may be stored inside of an approved flammable liquid storage cabinet. The use of more than one flammable storage cabinet in the laboratory must be approved by the Campus Fire Marshal.
   • Flammable Liquid Storage Cabinets:
     • Flammable liquid storage cabinets must meet approval requirements of Factory Mutual or Underwriters Laboratories. A list of approved flammable liquid storage cabinets is available from the Campus Fire Marshal. Such cabinets may be vented, but this is not required. If the cabinet is not to be vented, the vent openings should be sealed with the bungs supplied with the cabinet.
     • Storage of flammable and combustible liquids is regulated by fire codes.
     • Storage of flammable and combustible liquids must be in an approved flammable liquid storage cabinet.
     • The total volume of flammable and combustible liquids stored in the cabinet should not exceed the maximum quantities recommended by the manufacturer of the cabinet, or 60 gallons, whichever is less.
     • Quantities of flammable liquids greater than one liter should be stored in approved safety cans. Glass containers no larger than 1 gallon (4 L) are acceptable if purity would be adversely affected by storage in metal.

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3. STORAGE OF CORROSIVE CHEMICALS

a. General Guidelines:

1. i. Storage areas should be constructed of materials that are resistant to the corrosive chemicals used.
2. ii. Corrosive chemicals may be stored under a fume hood; the fume hood should have vertical separations to provide for incompatible storage.
3. iii. Consult the MSDS for information on incompatible storage.
4. iv. All corrosive compressed gases shall be stored in a chemical fume hood or approved ventilated cabinet.
5. v. Water sensitive corrosives should not be stored under sinks.

4. STORAGE AND HANDLING OF COMPRESSED GASES

a. General Guidelines

1. Mechanical failure of the cylinder, cylinder valve, or regulator can result in rapid dispersion of the pressurized contents into the atmosphere.
2. Unsecured cylinders can be knocked over very easily, causing serious injury and damage.
3. Impact can shear the valve from an uncapped cylinder, especially if a regulator is attached, causing a rocking or rocket action leading to personal injury.
4. Gas cylinders containing flammable, toxic or corrosive gases, asphyxiant, or oxidizers must only be handled by trained personnel.
5. A label identifying the contents of the cylinder must be attached. Alternatively, the identification may be etched or printed on the cylinder.
6. Do not accept a cylinder if the contents are not clearly identified.
7. Do not rely on color coding to identify the contents of a gas cylinder; for a given gas the color coding is not standardized.
8. Open cylinder valves slowly to prevent damage to the pressure regulator.
9. Always use the proper regulator for the gas in the cylinder.
10. To transport a cylinder, use a hand truck equipped with a chain or belt for securing the cylinder.
11. Make sure the protective cap covers the cylinder valve. Never move a cylinder while a regulator is attached.
12. Do not move cylinders by carrying, rolling, sliding, or dragging them across the floor.
13. Do not transport oxygen and combustible gases at the same time.

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b. Secure gas cylinders to prevent them from falling over:

1. Two chains or straps must be used to secure cylinders - one across the lower third and one across the upper third of the cylinder.
2. Attach the chain(s) to a holding plate or rack which is securely fixed to structural membrane.
3. Do not use bench side clamps.
4. Base plates may be used for securing the cylinders.
5. Do not store incompatible gases together. Store cylinders of oxygen at least 20 feet away from cylinders of hydrogen or other flammable gases.
6. Store cylinders away from heat (never in areas above 125 degree C). Heat sources may include steam or hot water pipes.
7. Store cylinders away from areas where they might be subjected to mechanical damage. Store full and empty tanks separately, place “Empty” sign around the top of the empty tanks to avoid accidental connection of an empty cylinder to a pressurized system, causing backflow into the tank.
8. Electrically ground cylinders of combustible gases (e.g., to a water pipe) to prevent buildup of static electricity.
9. Keep cylinders away from locations where they might form part of an electrical circuit.
10. Keep the protective cap on the cylinder when the cylinder is not in use. The cap prevents the cylinder valve from being damaged or broken.
11. National Fire Protection Association (NFPA) codes specify maximum quantities and sizes of hazardous gas cylinders in laboratory areas. A typical laboratory in the department may have no more than:
    • Three standard cylinders of flammable gases and/or oxygen
    • Two standard cylinders of liquefied flammable gases
    • Three 4’X15” cylinders (or volume equivalent) of gases with high Health Hazard Ratings). Gases with Health Hazard Ratings of 3 or 4, or a rating of 2 with no physiological warning properties, MUST be kept in a hood or other ventilated enclosure. No more than three cylinders with ratings of 3 or 4 may be kept in one enclosure.
12. Corrosive or unstable gases should be ordered in the minimum quantities necessary and stored in a hood or other safe, dry area.
13. Corrosive gases, if stored for long periods, will corrode the valve internally and may be impossible to open, or if opened, may not close.
14. Cylinders not needed for current use should not be stored in laboratories. Recommended maximum retention periods for gases are:
    • 36 months for liquefied flammable gases, flammable gases, and oxygen;
    • 6 months for corrosive or unstable gases or those with a Health Hazard Rating of 3 or 4.
15. When a cylinder is empty (preferably not less than 25 psi residual pressure):
    • Close the valve to prevent air and moisture from entering the tank,
    • Remove the regulator (purging it if necessary to safely remove toxic or corrosive gases),
    • Replace the cylinder cap, and label the tank "EMPTY."
    
    Use a hand truck to return the cylinder to the gas cylinder storage area and secure it until is removed.
16. Always use manufacturer-supplied valves and regulators. Do not mix-and-match valves and regulators from different units. xvii. Use manufacturer recommended techniques and tools for installation and removal of valves, regulators, etc.

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5. CRYOGENICS SAFETY

Cryogens are liquids with boiling points below 200K (-73 degree C). This extreme cold can cause some materials which come into contact with them to become brittle and lose their mechanical strength. Handling of cryogenic liquids requires special safety precautions. The following is a listing of some important precautions required.

1. Cryogenic liquids must be handled by personnel who are familiar with potential hazards.
2. Contact with skin can cause severe "cold burns"; therefore, use insulating gloves and wear lab coats when handling these liquids.
3. Use eye protection (goggles with side shields or face shields) when working with or handling cryogenics liquids.
4. Store and use cryogenic liquids in well ventilated areas to prevent excessive displacement of air.
5. Large liquid-to-gas ratios can cause a small spill to produce large volumes of gas. This, in turn, can displace air in confined spaces. Therefore, during spills be aware of potential oxygen deficiency.
6. Use only approved cryogenic storage vessels with pressure relief mechanism.
7. In addition to producing an oxygen deficiency by displacement of air, CO₂ also affects the breathing rate. Therefore, it must be used in well ventilated areas.
8. Use special shatter-resistant containers for cryogenic liquids whenever possible.
9. If it is necessary to use standard containers such as glass Dewars, tape the outside to prevent glass fragments from scattering in the event of breakage.
10. Avoid transferring of flammable cryogenic liquids within the buildings. Perform the transfers away from the sources of ignition.
11. Icing on the valves and hoses is caused by the solidification of moisture in air. DO NOT use force to remove the icing.
12. Do not dispose of dry ice by dropping it in water.

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6. CAL-OSHA REGISTERED CARCINOGENS

Table 2.2 Chemicals on the California Occupational Safety and Health Administration’s Registered Carcinogen List:

• 2-acetylaminofluorene
• 4-aminodiphenyl
• Benzidene and its salts
• 3,3’-dichlorobenzidene and its salts
• 4-dimethylaminoazobenzene
• alpha-Naphthylamine
• beta-Naphthylamine
• 4-nitrobiphenyl
• N-nitrosodimethylamine
• beta-propiolactone
• bis-chloromethyl ether
• Methyl chloromethyl ether
• ethyleneimine vinyl chloride
• coke oven emissions
• 1,2-dibromo-3-chloropropane (DBCP)
• Acrylonitrile Inorganic arsenic
• 4,4’-methylenebis(2-chloroaniline)
• Formaldehyde
• Benzene
• Ethylene Dibromide
• Ethylene Oxide
• Methylenedianiline
• Chromium
• Cadmium
• Asbestos
• 1,3 Butadiene
• Methylene Chloride

In order to purchase, store or use any of these chemicals, the facility must submit a registration to Cal-OSHA. To provide maximum flexibility for operations, UCSF OEH&S obtains site registrations for each Campus. This process requires that laboratories complete the application form and submit to OEH&S for review and processing. See Appendix D1 for details of registration program.

7. CONTROLLED SUBSTANCES

The use of Controlled Substances is governed by the US Drug Enforcement Agency and is subject to specific requirements outlined in UCSF Controlled Substances Program Manual. Please refer to the document, or contact your DSA, for registration requirements.

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