Lab Safety Plan: Chemical Storage and Inventory

10.  Chemical Storage and Inventory.

10.1 Regulatory Requirements

Implementation of the necessary work practices, procedures, and policies outlined in this chapter is required by the following: 

 

• OSHA 1910.1450 “Occupational Exposures to Hazardous Chemicals in Laboratories” 
• OSHA 1910.1200 “Hazard Communication”
• NFPA 45, Standard on Fire Protection for Laboratories Using Chemicals.
• DHS CFATS, Chemical Facility Anti-terrorism Standard

10.2 Chemical Inventories

10.2.1. Faculty members and other supervisors with chemicals are required to use the campus inventory system to maintain a current, accurate and complete chemical inventory that includes the hazardous materials, solids, liquids, gases, and gels used and stored in the rooms to which they are assigned.  The information maintained in the inventory includes the name of the chemical, the concentration, the chemical abstracts number, the size of the container, the amount on hand, the physical state, the type of the container, whether it is pure or a mixture and both the storage pressure and temperature. Chemical inventories are used to provide the required information to the fire department, ensure compliance with fire code storage limits, and homeland security reporting thresholds. The chemical inventory can also be used in an emergency to identify potential hazards for emergency response operations and more.

10.2.2. The chemical inventory list should be reviewed prior to ordering new chemicals and only the minimum quantities of chemicals necessary for the research should be purchased.  As new chemicals are added to the inventory, each laboratory group can confirm that they have access to the Safety Data Sheet (SDS) for that chemical through  UNHCEMS® (kent.edu).  Where practical, each chemical should be dated so that expired chemicals can be easily identified for disposal.  Inventory the materials in your laboratory at least annually to avoid overcrowding with materials that are no longer useful and note the items that should be replaced, have deteriorated, or show container deterioration. The Department of Homeland Security (DHS) maintains a list of “DHS Chemicals of Interest,” and requires a report to be submitted within 60 days if specific chemicals on that list exceed set threshold aggregate amounts.  Unneeded items should be given to EHS and should be discarded as chemical waste.  If substances are usable, these may be added to the CEMS database as surplus.   Attributes that may indicate the materials need to be disposed are cloudiness in liquids, a change in color, evidence of liquids in solids, or solids in liquids, “puddling" of material around outside of containers, pressure build-up within containers and obvious deterioration of containers in addition to exceeding a manufacturer’s expiration date.

10.2.3. Access to hazardous chemicals, including toxic and corrosive substances, should always be restricted.  These materials must be stored in laboratories or storerooms that are kept locked when laboratory personnel are not present.  Locked storage cabinets or other precautions are always recommended, and in some cases may be required in the case of unusually toxic or hazardous chemicals. Unusually toxic chemicals may include those that are immediately dangerous to life or health (IDLH).  

10.2.4. On termination or transfer of laboratory personnel, all related hazardous materials should be properly disposed of, or transferred to the laboratory supervisor or a designee.  

10.2.5. To facilitate improved inventory management and reporting, Kent State has implemented a systemwide(https://chemicalmgmt.kent.edu/program for maintaining inventory. Information on how to use the Kent State Chemical Database system is available on the EHS page. This program allows Kent State to comply with both long more easily-standing and new regulations requiring chemical inventory maintenance and reporting. OSHA’s “Hazard Communication” standard requires that employers develop and maintain a list of hazardous chemicals known to the workplace. This is a long-standing regulatory requirement and is an important component of  lab safety evaluations. Maintenance of the chemical inventory by individual labs allows for accurate compliance with this mandate.” requires that employers develop and maintain a list of hazardous chemicals known to the workplace.

10.3 Chemical Labeling

10.3.1. All containers (including diluted chemical solutions and those with abbreviations) of hazardous materials must be labeled with the identity of the hazardous substance and all applicable hazard warning statements or abbreviations. If abbreviations are used, a list of the abbreviations used, the full chemical names and the hazards warning statement associated with each, must be prominently displayed in each room.  In either case, all containers not actively being used, in transfer, or a reaction must be labeled. New synthesized compounds must be labeled, to the best of your knowledge,  with the appropriate hazard warnings based on the knowledge of the chemical and physical properties of that substance.   Unlabeled compounds should be assumed as highly hazardous chemicals, until proved otherwise.

10.3.2. Labels must be legible, in English, and clearly displayed.  Label the containers as thoroughly as possible.   Lewis structure should be used if no other information is available. Secondary containers (such as spray bottles) must be labeled with the identity of the substance and appropriate GHS hazard warnings.

10.3.3. Symbols and/or other languages may be provided for non-English speaking employees. Use the symbols in the Globally Harmonized System of Classification and Labeling of Chemicals. 
 
10.3.4. Peroxide forming chemicals (e.g., ethers) must be labeled with a date on receipt and the date when the bottle is first opened. Any unopened chemicals that are listed in Classes A through D that have been listed in the chemical inventory for a minimum of one year must be opened and tested for peroxides.   See appendix for a guide to peroxide formers.  These chemicals can degrade to form shock sensitive, highly reactive compounds and should be stored and labeled very carefully.

10.3.5. Particularly Hazardous Substances require additional labeling to identify the specific hazard associated with each of these chemicals (carcinogen, reproductive toxin, acutely toxicant). In addition, the storage area where they are kept must be labeled with the type of hazard. These chemicals should be segregated from less hazardous chemicals to help with proper access control and hazard identification.

10.4.  Chemical Storage & Segregation

Establish and follow safe chemical storage & segregation procedures for your laboratory. 
10.4.1. Storage and segregation guidelines are included for materials that are flammable, oxidizing, corrosive, water reactive, explosive, and highly toxic.

10.4.2. For general guidelines on segregation and storage, EHS has developed a Chemical Segregation Guidance Sheet  to assist with developing storage plans for hazardous chemicals. The specific Safety Data Sheet (SDS) should always be consulted when doubts arise concerning chemical properties and associated hazards.

10.4.3. All procedures employed must comply with PERRP(Public Employee Risk Reduction Program), OSHA, Fire Code and building code regulations.  

10.4.4. Always wear appropriate personal protective equipment (e.g., laboratory coat, safety glasses, gloves, safety goggles, apron) when handling hazardous chemicals.

10.4.5. Be aware of the locations of the safety showers and emergency eyewash stations.  Each laboratory is required to provide appropriate laboratory-specific training on how to use this equipment prior to working with hazardous chemicals.  

10.5. Safe Chemical Storage Priorities

Keep in mind that most chemicals have multiple hazards, and a decision must be made as to which storage area would be most appropriate for each specific chemical. First you must determine your priorities:

1. Flammability. When establishing a storage scheme, the number one consideration should be the flammability characteristics of the material. If the material is flammable, it should be stored in a flammable cabinet or, if necessary an explosion proof refrigerator.
2. Isolate. If the material will contribute significantly to a fire (e.g., oxidizers), it should be isolated from the flammables. If there were a fire in the laboratory and response to the fire with water would exaggerate the situation, isolate the water reactive material away from contact with water.
3. Corrosivity. Next look at the corrosivity of the material, and store accordingly.
4. Toxicity.  Finally, consider the toxicity of the material, with particular attention paid to regulated materials. In some cases, this may mean that certain chemicals will be isolated within a storage area. For example, a material that is an extreme poison but is also flammable, should be locked away in the flammable storage cabinet to protect it against accidental release.
5.  There will always be some chemicals that will not fit neatly in one category or another, but with careful consideration of the hazards involved, most of these cases can be handled in a reasonable fashion.

10.6. General Recommendations for Safe Storage of Chemicals

10.6.1. Each chemical in the laboratory should be stored in a specific location and returned there after each use.

10.6.2. Acceptable chemical storage locations may include corrosive cabinets, desiccators, flammable cabinets, laboratory shelves, or appropriate refrigerators or freezers. In general, fume hoods should not be used as permanent storage areas for chemicals, as this may seriously impair the ventilating capacity of the hood.  

10.6.3. Chemicals should not be routinely stored on bench tops or stored on the floor.  Additionally, bulk quantities of chemicals should be stored in a separate storage area, such as a flammable cabinet or stockroom or supply room.

10.6.4. Laboratory shelves should have a raised lip along the outer edge to prevent containers from falling. Hazardous liquids, toxic or corrosive chemicals should not be stored on shelves above eye-level and chemicals which are highly toxic, or corrosive should be in unbreakable secondary containers. 

10.6.5. Chemicals must be stored at an appropriate temperature and humidity level and should never be stored in direct sunlight or near heat sources, such as laboratory ovens.  

10.6.6. Incompatible materials should be stored in separate cabinets, whenever possible.  If these chemicals must be stored in one cabinet, due to space limitations, adequate segregation and secondary containment must be ensured to prevent adverse reactions.  

10.6.7. All stored containers and research samples must be appropriately labeled and tightly capped to prevent vapor interactions and to alleviate nuisance odors.  Caution should be used with flasks with only septa, cork, rubber or glass stoppers.

10.6.8. Laboratory refrigerators and freezers must be labeled appropriately with “No Food/Drink” and must never be used for the storage of food or drinks intended for human consumption.  Freezers should be defrosted periodically so that chemicals do not become trapped in ice formations. Never store flammables in a refrigerator not specifically designed for storage of flammable liquids. 

10.7. Flammable and Combustible Liquids

10.7.1. In general, flammables should not be stored alongside combustible materials like paper and packaging plastic bags.

10.7.2. Large quantities of flammable or combustible materials should not be stored in the laboratory. The Fire Code limits specific volume of flammable materials or other classes of hazardous chemicals depending on the original design and construction of the facility and varies from building to building.

10.7.3. In most labs, the maximum total quantity of class 1A, 1B and 1C flammable liquids must not exceed 60 gallons, which must all be stored in a flammable storage cabinet.

10.7.4. The maximum quantity allowed to be kept outside a flammable storage cabinet, safety can, or approved refrigerator/freezer is 10 gallons per room. Class 1A solvents, such as ethyl ether, should be purchased only in one gallon (4 liter) or smaller containers.

10.7.5. Because of the extreme flammability of the Class 1 liquids, only quantities needed for immediate use should be present in the work area.  The rest should be stored.    Examples of equipment that can be used for storage include flammable storage cabinets, flammable storage refrigerators or freezers that are designed and UL approved for the storage of flammable substances, or approved safety cans or drums that are grounded.

10.7.6.  Always segregate flammable or combustible liquids from oxidizing acids and oxidizers.  Flammable materials must never be stored in domestic-type refrigerators/freezers.

10.7.7.  Flammable or combustible liquids must not be stored on the floor or in any exit access.

10.7.8. Handle flammable and combustible substances only in areas free of ignition sources and use the chemical in a fume hood whenever practical.  Only the amount of material required for the experiment or procedure should be stored in the work area.

10.7.9.  Always transfer flammable and combustible chemicals from glass containers to glassware or from glass container/glassware to plastic. Transferring these types of chemicals between plastic containers may lead to a fire hazard due to static electricity. The transfer of flammable liquid from 5 gallon or larger metal containers should not be done unless the container is grounded and bonded.

Table 1:  Classification of Flammables.

10.8 Pyrophoric & Water Reactive Substances

10.8.1. The basic requirements for pyrophoric material usage are as follows:

The laboratory space must meet the requirements for safe use and storage of pyrophoric material.

• Ideally, material should be used and stored in a fully sprinklered lab, as approved by the Fire Marshal, and appropriate storage must be available and used.  Use caution if labs are not sprinklered.
• Inventory must be regularly managed, and annually certified, using the CEMS system.
• Review of the Kent State SOP on pyrophorics.
• Users of pyrophoric materials are required to take the Pyrophoric training course in Flashtrain.
• Users must use flame resistant gloves based on the PPE section of the SDS.

10.8.2. Because pyrophoric substances can spontaneously ignite on contact with air and/or water, they must be handled under an inert atmosphere and in such a way that rigorously excludes air and moisture. Some pyrophoric materials are also toxic and many are dissolved or immersed in a flammable solvent. Other common hazards include corrosivity, teratogenicity, or peroxide formation.

10.8.3. Only minimal amounts of reactive chemicals should be used in experiments or stored in the laboratory. These chemicals must be stored as recommended in the SDS. Reactive materials containers must be clearly labeled with the correct chemical name, in English, along with a hazard warning.

10.8.4. Suitable storage locations may include inert gas-filled desiccators or glove boxes; however, some pyrophoric materials must be stored in a flammable substance approved freezer.  If pyrophoric or water reactive reagents are received in a specially designed shipping, storage or dispensing container (such as the Aldrich Sure/Seal packaging system), ensure that the integrity of that container is maintained.  Ensure that sufficient protective solvent, oil, kerosene, or inert gas remains in the container while pyrophoric materials are stored.  Never store reactive chemicals with flammable materials or in a flammable liquid's storage cabinet.

10.8.5. Storage of pyrophoric gases

Gas cabinets, with remote sensors and fire suppression equipment, are required.  Gas flow, purge and exhaust systems should have redundant controls to prevent pyrophoric gas from igniting or exploding. Emergency back-up power should be provided for all electrical controls, alarms and safeguards associated with the pyrophoric gas storage and process systems.

10.8.6. Never return excess reactive chemical to the original container. Small amounts of impurities introduced into the container may cause a fire or explosion.  For storage of excess chemical, prepare a storage vessel in the following manner:

a. Dry any new empty containers thoroughly.

b. Insert the septum into the neck in a way that prevents atmosphere from entering the clean  dry (or reagent filled) flask;

c. Insert a needle to vent the flask and quickly inject inert gas through a second needle to  maintain a blanket of dry inert gas above the reagent;

d. Once the vessel is fully purged with inert gas, remove the vent needle then the gas line. To introduce the excess chemical, use the procedure described in the handling section of the SOP;

e. For long-term storage, the septum should be secured with a copper wire or hose clamp

f. For extra protection a second same-sized septa (sans holes) can be placed over the first; and

g. Use “Parafilm M®” or equivalent around the outer septa and remove the Parafilm M® and      outer septum before accessing the reagent through the primary septum.

 Pyrophoric materials  Guidance

10.9.  Oxidizers

Oxidizers (e.g., oxygen, ozone, hydrogen peroxide, and other inorganic peroxides; fluorine, chlorine, and other halogens; nitric acid and nitrate compounds; persulfuric acids; chlorite, chlorate, perchlorate, and other analogous halogen compounds; hypochlorite and other hypohalite compounds, including household bleach; hexavalent chromium compounds such as chromic and dichromic acids and chromium trioxide, pyridinium chlorochromate, and chromate/dichromate compounds; permanganate compounds; sodium perborate; nitrous oxide; silver oxide; osmium tetroxide; Tollens' reagent; 2,2'-dipyridyldisulfide) should be stored in a cool, dry place and kept away from flammable and combustible materials (e.g., wood, paper, Styrofoam^TM, most plastics), flammable organic chemicals, and reducing agents (e.g. zinc, alkaline metals, and formic acid).

10.10. Peroxide Forming Chemicals

10.10.1.  Peroxide forming chemicals are able to form shock sensitive peroxide crystals. Peroxide crystals can be explosive when concentrated or as solids, which can occur if peroxide forming material is allowed to dry on the outside of a container. Many organic solvents are peroxide formers to some degree.

• Ethers, acetals, and ketals, especially cyclic ethers and those with primary and/or secondary alkyl groups
• Aldehydes, including acetaldehyde and benzaldehyde
• Compounds containing benzylic hydrogens, and
• Compounds containing allylic hydrogens, including most alkenes, vinyl, and vinyl diene compounds and dienes.

10.10.2. Some of the more common peroxide forming chemicals used in research laboratories are tetrahydrofuran (THF), dioxane, diethyl ether, and isopropyl ether. All peroxide forming chemicals should be stored in airtight containers in a dark, cool, and dry place and must be segregated from other classes of chemicals that could create a serious hazard to life or property should an accident occur (e.g., acids, bases, oxidizers, highly toxic materials).  The containers should be labeled with the date received and the date opened. This information, along with the chemical identity should face forward to minimize container handling during inspection. These chemicals must also be tested and documented for the presence of peroxides annually. Minimize the quantity of peroxide forming chemicals stored in the laboratory and dispose of peroxide forming chemicals before peroxide formation.

10.10.3. Carefully review all cautionary material supplied by the manufacturer prior to use. Avoid evaporation or distillation, as distillation defeats the stabilizer added to the solvents.  Ensure that containers are tightly sealed to avoid evaporation and that they are free of exterior contamination or crystallization. Never return unused quantities back to the original container and clean all spills immediately.

10.10.4.  If old containers of peroxide forming chemicals are discovered in the laboratory, (greater than two years past the expiration date or if the date of the container is unknown), do not handle the container. If crystallization is present in or on the exterior of a container, do not handle the container. Secure it and contact EHS for pick-up and disposal.

10.11. Corrosives

10.11.1. Corrosive materials cause irreversible damage to skin or metals. Store corrosive chemicals (i.e., acids, bases) below eye level and in secondary containers that are large enough to contain at least 10% of the total volume of liquid stored or the volume of the largest container, whichever is greater.  Acids must always be segregated from bases and from active metals (e.g., sodium, potassium, magnesium) at all times and must also be segregated from chemicals which could generate toxic gases upon contact (e.g., sodium cyanide, iron sulfide).

10.11.2.  Specific types of acids require additional segregation. Mineral acids must be kept away from organic acids and oxidizing acids must be segregated from flammable and combustible substances.  Perchloric acid should be stored by itself, away from other chemicals.  Picric acid is reactive with metals or metal salts and explosive when dry and must contain at least 10% water to inhibit explosion.   Glacial acetic acid shall be stored in a flammable cabinet.

10.12. Special Storage Requirements

10.12.1. Compressed Gas Cylinders

Correct storage of compressed gas cylinders

10.12.2. Compressed gas cylinders that are stored in the laboratory must be chained or strapped to the wall or other stable building member, with the safety cap in place. The cylinders must be restrained by a chain, two chains preferred; one chain should be placed at one third from the top of the cylinder, and the other placed at one third from the bottom of the cylinder. If this is not practical, contact EHS for guidance. Bolted “clam shells” may be used in instances where gas cylinders must be stored or used away from the wall.  Store liquefied fuel-gas cylinders securely in the upright position.

Cylinders are not to be stored in a horizontal position. Do not expose cylinders to excessive dampness, corrosive chemicals, or fumes.

10.12.3. Certain gas cylinders require additional precautions. Flammable gas cylinders must use only flame-resistant gas lines and hoses which carry flammable or toxic gases from cylinders and must have all connections wired. Compressed oxygen gas cylinders must be stored at least 20 feet away from combustible materials and flammable gases.

10.12.4. Gas cylinder connections must be inspected frequently for deterioration and must never be used without a regulator. Never use a leaking, corroded or damaged cylinder and never refill compressed gas cylinders. When stopping a leak between cylinder and regulator, always close the valve before tightening the union nut. The regulator must be replaced with a safety cap when the cylinder is not in use. Move gas cylinders with the safety cap in place using carts designed for this purpose, and do not use carts for storage of cylinders. Please refer to the gas cylinder procedures on the  EHS website for more details.

10.12.5. Liquid Nitrogen.  Protection considerations should be addressed when storing liquid nitrogen in a laboratory.  The primary risk to laboratory personnel from liquid nitrogen is skin or eye thermal damage caused by contact with the material.  In addition, nitrogen expands 696:1 when changing from a cryogenic liquid to a room temperature gas.  The gases usually are not toxic, but if too much oxygen is displaced, asphyxiation is a possibility.  Consider an oxygen sensor in a small space.   Always use appropriate thermally insulated gloves when handling liquid nitrogen. Face shields may be needed in cases where splashing can occur.   A diffuser is recommended for dispensing liquid nitrogen.

10.13. Laboratory Security

10.13.1. Recently regulatory agencies have been implementing rules to ensure chemical security. While many of these rules are for large manufacturing facilities, it is critical that chemicals be secured to prevent theft from campus laboratories. Numerous federal agencies are involved in the maintenance of laboratory security, including the Drug Enforcement Agency, Federal Bureau of Investigations, and Department of Homeland Security. It is each laboratory’s responsibility to prevent and report any theft of chemicals from their laboratory.

10.13.2. Laboratories can increase their security by simply keeping lab doors closed and locked when unoccupied, maintaining a current and accurate chemical inventory, training personnel on security procedures, and controlling access to keys. Labs should report any suspicious activity to the Kent State Police department and EHS.

10.14. On-Campus Distribution of Hazardous Chemicals

10.14.1 Precautions must be taken when transporting hazardous substances between laboratories. Chemicals must be transported between stockrooms and laboratories in break-resistant, secondary containers such as commercially available bottle carriers made of rubber, metal, or plastic, that include carrying handle(s) and which are large enough to hold the contents of the chemical container in the event of breakage. A cart is also recommended when transporting chemicals.   Wear PPE, eg., safety glasses and gloves).

10.14.2. When transporting cylinders of compressed gases, always secure the cylinder with straps or chains onto a suitable hand truck and protect the valve with a cover cap. Avoid dragging, sliding, or rolling cylinders and use a freight elevator when possible. The figure below illustrates correct cylinder transport.   Do not ride elevators with liquified gases.

Gas cylinder cart

Liquified Gas Cart

10.14.3. The transportation of hazardous chemicals and compressed gases over public roads, or by air, is strictly governed by international, federal, and state regulatory agencies, including the U.S. Department of Transportation (DOT) and the International Air Transport Association (IATA).  Any person who prepares and/or ships these types of materials must ensure compliance with pertinent regulations regarding training, quantity, packaging, and labeling.  Without proper training and packaging, it is illegal to ship hazardous materials.  Those who violate the hazardous materials shipment regulations are subject to criminal investigation and penalties. Individuals who wish to ship hazardous materials off-campus must contact EHS.