Chemical Hygiene Plan

Overview

This Chemical Hygiene Plan (CHP) has been developed at Denison University in order to comply with the Occupational Safety and Health Administration (OSHA) Laboratory Standard Rules and Regulations. This laboratory standard is published as an amendment to 29CFR 1910, Subpart Z, and identified as Section 1910.1450. The title of that amendment is "Occupational Exposure to Hazardous Chemicals in Laboratories" (see Appendix D). The laboratory standard applies only to certain laboratories. OSHA defines a hazardous chemical as a substance for which there is statistically significant evidence, based on at least one scientific study, showing acute or chronic harm may result from exposure to that chemical.

At Denison University, the following have been designated as laboratories for the purpose of applying the laboratory standard:

    • Department of Art
    • Department of Biology
    • Department of Chemistry
    • Department of Geology and Geography
    • Department of Physics
    • Department of Psychology

Purpose

The purpose of the laboratory standard is to protect laboratory employees from harm due to chemicals while they are working in a laboratory. In addition to academic and administrative employees who spend a significant amount of their time working or teaching in a laboratory, the Laboratory Standard also includes as "laboratory employees" those office, custodial, and maintenance persons who, as part of their duties, regularly spend a significant amount of their working time within a laboratory environment. Students, as laboratory assistants paid by Denison University, are also covered by the Laboratory Standard.

Denison University, in meeting the requirements of the Laboratory Standard, will keep records of employee exposure to hazardous chemicals, provide employees with training and information regarding chemical and physical hazards (see Appendix A), and access to medical consultation and examination (see Appendix B). Training will include information about material safety data sheets (MSDS), chemical labels; permissible exposure limits (PEL) or threshold limit values (TLV). Measurement of the concentration of any chemical will be made for which a PEL or TLV may have been exceeded. Where this Laboratory Standard applies, it supersedes the Hazard Communication Standard, 29CFR 1910.1200 for those laboratories designated above.

 

Responsibility

For the Denison University CHP, Philip Waite is designated as the Chemical Hygiene Officer (CHO). This person acts as the representative of the president of the University who has the ultimate responsibility for chemical safety. The CHO also reports to the Vice President for Finance as that person designated by the President for overseeing any financial implications of the CHP and chemical safety; the CHO also reports to the Provost in regard to academic matters of the CHP.

The CHP will be distributed to all full time employees of the laboratories designated above and copies will be accessible to any other "laboratory employees", student laboratory assistants, or other interested parties. The CHP will be reviewed at least annually and updated as necessary.

 

General Chemical Safety

+ Chemical Storage

Chemical Storage

General Guidelines

  1. Do not store excessive quantities of chemicals in research laboratory. Purchase the minimum amount required and dispose of unneeded chemicals in a timely fashion.
  2. Date bottles of chemicals when they are opened. Peroxidizable chemicals such as isopropyl ether should be tested periodically or discarded according to the time limits. Discard any chemical of dubious purity (by the usual waste disposal procedures) if it cannot be purified safely.
  3. Store reagents on shelves or in cabinets. Store large bottles of chemicals on the lowest shelves of any chemical storage area. Do not allow bottles to extend over the edge of a shelf.
  4. Do not store chemicals on benchtops. They are more readily knocked over and are unprotected from potential exposure to fire.
  5. Hoods should not be used for chemical storage. Hood storage interferes with air flow in the hood, causes clutter, and increases the fuel load in the event of a hood fire. If small quantities of chemicals are stored in the hood, they should be placed on an elevated shelf.
  6. No chemicals (either reagents or waste chemicals) should be stored on the floor. Floor storage presents a major safety hazard because bottles can break if knocked over or struck together.
  7. Chemicals requiring refrigerated storage should be properly labeled and sealed to prevent escape of any vapors. Use only refrigerators designated for chemical storage. Flammable liquids MUST be stored only in explosion-safe refrigerators. Do not refrigerate chemicals unnecessarily.
  8. Seal caps of open bottles of volatile chemicals using Parafilm. This will prevent odor problems and deterioration of air/moisture sensitive reagents.
  9. Inspect storage areas periodically for damaged containers such as cracked bottles or caps or rusted cans. Replace loose or deteriorating labels.

Storage of Specific Classes of Chemicals

  1. Provide separate storage areas for corrosive chemicals, solvents, oxidizing agents, pyrophoric materials, and air- or water-reactive materials.
  2. Store acids separate from bases. Store ammonium hydroxide in a separate cabinet, preferably ventilated.
  3. Store oxidizers, including oxidizing acids such as nitric and perchloric acids separate from oxidizable compounds such as acetic acid. Perchloric acid MUST be stored where it cannot contact organic material.
  4. Store highly toxic chemicals in unbreakable secondary containers labeled with a description of the contents. Cyanides and sulfides MUST be kept safe from any contact with acids. Store cyanides in a closed cabinet, not in a location visible to passersby. Dispose of cyanides for which you have no current use.
  5. Store pyrophoric materials separate from flammable materials, in a dry, inert atmosphere such as a nitrogen-filled desiccator or a glove box.

Solvent Storage

  1. Solvents are classified by the National Fire Protection Association (NFPA) by flash point (Fp) and boiling point (bp) as follows:
Flammable liquid Class Flash Point Range
Class I F.P. less than 100o F (37.8o C)
Class IA F.P. less than 73o F (23o C) boiling point less than 100o F (37.8o C)
Class IB F.P. less than 73o F (23o C) boiling point greater than 100o F (37.8o C)
Class IC F.P. greater than 73o F (23o C) boiling point less than 100o F (37.8o C)
Class IIA F.P. greater than 100o F (38o C) boiling point less than 140o F (60o C)
Class IIIA F.P. greater than 140o F (60o C) boiling point less than 200o F (93o C)
Class IIIB F.P. greater than 200o F (38o C)
  1. Flash point is defined as the minimum temperature at which a liquid gives off vapor in sufficient concentration to form an ignitible mixture with air near the surface of the liquid. Many common solvents such as acetone, ethanol, and hexane are Class IB liquids. Ethyl ether and low-boiling petroleum ether are class IA liquids. Storage of flammable and combustible liquids is regulated by fire codes. The following storage procedures and regulations are taken largely from NFPA codes 45 and 30.
  2. Store flammable and combustible liquids in approved flammable liquid storage cabinets. Such cabinets may be vented, but this is not required. If the cabinet is not vented, the vent openings should be sealed with the bungs supplied with the 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. No more than 3 cabinets may be located in a single fire area (laboratory).
  3. 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.
  4. The largest allowable laboratory container for a Class IA solvent is 1 gallon (4 L) for glass, plastic, or metal, or 2 gallon ( 8L) for approved safety cans. Five gallon (20 L) cans may not be stored or used anywhere in the department except in the stockroom solvent storage rooms. It is recommended that the Class IA solvents such as ethyl ether be purchased only in 1 gallon (4 L) or smaller containers. If you require a larger quantity, you should order more than one bottle of the 1 gallon size.
  5. Solvents such as acetone and ethanol that are stored in plastic carboys for dispensing purposes should be positioned with the spigot over a sink, or over a tray large enough to contain the entire contents in the event of leakage from the spigot.
+ Safe Transport of Chemicals

Safe Transport of Chemicals

General Guidelines

  • Use a hand-held rubber safety bottle carrier for liquids and hazardous solids in glass containers. These carriers are mandatory for 2.5 L and 4 L bottles of liquids. Carriers may be borrowed from the stockroom but please return the carrier as soon as you have reached your destination with the hazardous reagent.
  • Do not attempt to carry an armful of bottles. Use a cart with side panels if transporting several chemicals at once. Do not allow containers to collide with each other during transport.
  • Always use a hand truck for cylinders of compressed gases. Remove regulators and replace protective cylinder cap before transport. Do not drag or roll cylinders. Chain the cylinder to the hand truck as soon as cylinder is in place before transport.
  • Never pick up a bottle by the cap or lid.
  • Wear eye protection while transporting chemicals.
  • Plan to transport the extremely hazardous chemicals during times of reduced traffic in the halls.
  • Do not transport extremely hazardous materials by yourself.
  • Bring a spill kit when transporting hazardous liquids.
  • Place bottles of extremely toxic or carcinogenic chemicals in an unbreakable outer container before transport.
  • Always wear protective gloves and laboratory coat.
  • Extremely hazardous materials should be sent in an empty elevator to a second person waiting at the desired floor.
  • Transport dry ice in an elevator without passenger or by using the stairs. A relative small block can produce enough CO2 gas to displace all oxygen in the enclosed area should the elevator become disabled.

 

 

Department of Transportation Hazardous Materials Regulation

The Transportation Uniform Safety Act became law in 1990. It defined Federal vs. state authority, introduced required training for hazmat employees, and required a 24 hour emergency response number. It became known as Hazardous Material Regulation 181 (HM-181). This 10 year phase-in plan is intended to better regulate the transport of hazardous materials and to bring U.S. regulations on packaging and transportation of hazardous materials in line with the United Nations Standards used extensively throughout the world.

The regulation of transportation of hazardous materials has been going on for a long time. In 1866, the federal government regulated the transport of nitroglycerine for obvious reasons. In 1966 The Department of Transportation (DOT) was established and assumed the responsibility of regulating hazardous materials from the Bureau of Explosives. In 1974 the Transportation Safety Act authorized the DOT to enforce hazardous materials regulations for all modes of domestic transportation.

HM-181 affects all persons involved with hazardous materials in commerce. Basically, if you transport any quantity of a hazardous material over a public highways, (or streets), you are governed by these regulations.

The transitions dates and regulations are:

  • October 1, 1991 -- Items identified as poisonous by inhalation must include the words "POISON-INHALATION HAZARD" or "INHALATION HAZARD" on the shipping papers in association with the proper shipping name.
  • October 1, 1992 -- Items identified as poisonous by inhalations are subject to the new communication requirements, including placarding
  • October 1, 1993 -- Performance packaging requirements for all items identified as poisonous by inhalation are in affect. New requirements for segregation during transportation are in effect. All hazardous materials offered for transportation are subject to the new classification and communication requirements.
  • January 1, 1994 -- Items identified as infectious substances, (included regulated medical waste), are subject to all applicable requirements including classification, communications, and packaging.
  • October 1, 1994 -- Packaging manufactured on or after this date must comply with performance packaging standards. All packaging must now be tested and certified and may be subject to vibration, leakproffness, pressure, drop and stacking test. Each packaging used to transport hazardous materials must be designed and constructed and have its contents so limited that under conditions normally incident to transportation, there will be no release of the contents to the environment and the packaging integrity will not be compromised. The packaging must be compatible with their contents. New regulations for placarding are effective.
  • October 1, 1996 -- All shipment of hazardous materials must meet new performance packaging requirements.
  • October 1, 2001 -- Placard format and content must comply with new specification requirements.

Another important aspect of HM-181 is employee training. Employers must ensure that each hazmat employee (any person who in the course of employment directly effects hazardous materials transportation safety) is trained and tested about hazardous material safety. The training should include general awareness which should provide familiarization with the requirements of the regulations as well as recognize and identify hazardous materials. Function specific training on matters specifically applicable to the functions the employee performs. And safety training should include emergency response information, accident avoidance, and safe handling of hazardous materials. HM-181 requires the hazmat employee to receive this training at least once every two years.

How is Denison University affected by HM-181?

First, employees who use public roads to transport hazardous materials must comply with all requirements includingsafety training. Second, if anyone wants to ship a hazardous material, the container must be constructed to meet performance packaging standards and have appropriate labels and identification numbers on the container. After October 1, 1996, all containers must not have been previously used. The reasoning behind this is many people do not take the time to remove IDs and labels that may not be applicable to the new contents.

Third, it you do want to ship a hazardous material, you will be required to supply a 24 hour emergency response number with a person able to give details as to appropriate clean up and exposure hazards. Therefore, these regulations will make shipping hazardous materials much more difficult. However, if the quantity is small, (less than 25 grams), then the shipment is exempt from HM-181 regulations. If you have a larger quantity then consider breaking it down into small quantities to avoid having to meet the requirements of HM-181

+ Hazard Communication Standard

Hazard Communication Standard

The Federal government enacted the Hazard Communication standard in response to the dramatic increase in the use of chemicals in the workplace. Many of these chemicals can cause illness and injury if used or handled improperly. The law requires employers to provide their employees with the information and training they need to protect themselves from chemical hazards in the workplace.

  • Hazard Evaluation -- The standard requires employers to figure out what materials in their workplace are hazardous. Most of the chemicals used are purchased from companies who manufacture and/or distribute chemicals. This law requires these companies to tell employers if these materials are hazardous at the time they are purchased. Included with any hazardous material, the companies are required to supply a Material Safety Data Sheet (MSDS) and container labels.

    An employer may produce its own hazardous materials as products for sale or as by-products of research. When this happens, the employer is responsible for developing MSDSs and container labels for these materials.

    What this means to persons at Denison University is that any purchase of hazardous materials should include MSDSs for every item. Many companies only supply the MSDS upon request. Therefore, if you receive a hazardous material without an MSDS, it is your responsibility to contact the company and request it. In addition, if you are doing research and produce a compound, do not send this compound off campus. If you do, technically, the law requires you to evaluate its hazards and develop an MSDS to be included when shipped.

  • Hazardous Materials Inventory -- Employers must prepare and maintain an inventory itemizing all of the hazardous materials present in their workplace. This list becomes the focus of employers' efforts to obey the standard. The inventory should list each materials by the same name used on the MSDS for the material. The employee should have access to this inventory upon request.

    Here at Denison, each department should have an updated inventory. If a student or staff wishes to see the inventory, contact the department head. Its also worth noting that Superfund Amendments and Reauthorization Act (SARA), enforced by EPA, Title III grants any member of the community, in which the school is located, access to information on chemicals present on campus. SARA also requires that the institution provide EPA, the state government, and local community officials with an inventory of hazardous material located on campus.

  • Material Safety Data Sheet (MSDS) -- As mentioned above, an MSDS must be available for every hazardous material in the inventory. The MSDSs are one of the key ingredients in the hazard communication process. Their purpose is to provide information about the hazardous materials. See the section of this training program for more information on MSDSs and how to interrupt them. Also note the Security and Safety Home Page as to the location of MSDSs on Denison's Campus.

  • Labeling -- Employers must make sure that all containers of hazardous materials are properly labeled. Hazardous materials must haveproper labels before they can be shipped.

    OSHA requires the following information:

    1. Identity of the hazardous material.
    2. Appropriate hazard warnings (specific hazards, target organ effected, precautions, flammability, etc).
    3. Name and address of the material's manufacturer.

    If the manufacturer's label falls off or if the material is repacked into another container, a label of equal warning must be placed on the container.

    An important consideration on Denison's campus is when a compound is transferred into laboratory glassware. The glassware should always be labeled with its contents. Many times, hazardous solutions are left by laboratory workers with no label and therefore create risk to others in the lab. Also, when products of research are placed in vials or laboratory glassware, these containers should be labeled with their contents, dates they were made, and names of the researchers.

  • Employee Training -- The last part of the Hazard Communication standard requires employers to provide their employees with information and training on the hazardous materials they may be exposed to. When new employees are hired, or when an employee may be exposed to a new hazard, training must be provided.

    The training information should include:

    1. An explanation of the Hazard Communication Standard.
    2. Identification of the hazardous materials, potential health effects, and location on the material.
    3. The location and availability of the written hazard communication program and MSDSs.
    4. Procedures to be used to detect and measure workplace contaminants.
    5. Safe work practices and protective equipment employees can use to reduce risk.
    6. An explanation of the labeling system.

    Here at Denison University, training is carried out by department. The training should be scheduled as soon as possible after the beginning of the new school year. Student employees are required to take this training before they can work in the laboratory as teaching assistants, laboratory assistants and stockroom assistants. It is encouraged that all students taking science laboratory courses, be given the opportunity to join this training.

    This training program provided by Campus Security and Safety is meant to supplement the departmental training, not to replace it. However, this general training will provide you with a sound foundation of laboratory safety.

+ Hazard Identification System
nfpa.gif

National Fire Protection Association Hazard Identification System

Health

  1. Only slightly hazardous to health; May cause irritation.
  2. Hazardous to health; harmful if inhaled or absorbed.
  3. Extremely hazardous to health; Corrosive or toxic, avoid skin contact or inhalation.
  4. Fatally hazardous to health; specialized protective equipment required.

Flammability

  1. Only slightly flammable, must be pre-heated to burn.
  2. Flammable if moderately heated; flash point between 100 - 200 o F (38 - 100 o C).
  3. Flammable under normal temperature conditions; flash point under 100o F (38o C).
  4. Very flammable gases or very volatile flammable liquids.

Reactivity

  1. Normally stable but may become unstable at elevated temperatures.
  2. Unstable and readily undergo violent chemical change but do not detonate.
  3. Capable of detonation or explosive decomposition but require strong initiating source.
  4. Readily capable of detonation or explosive decomposition at normal temperatures.

Additional Markings

This space is used to place special codes to further identify safety hazards

  • W with a line through its center -- Used to indicate material reacts violently with water.
  • OXY -- Used to indicate a strong oxidizing chemical.

+ Handling Hazardous Chemicals

Handling Hazardous Chemicals

Be aware that all chemicals are hazardous to some degree, and protect yourself from accidental skin, eye, and respiratory contact.

Know the hazards of the materials you are working with. If you are using an unfamiliar procedure or chemical, conduct a literature search for reports of known or suspected hazards. Material Safety Data Sheets, (MSDSs), are an important primary source of information on physical properties, health hazards, reactivity, and spill cleanup procedures.

General Guidelines

  1. Whenever possible, perform hazardous reactions in a properly functioning hood using appropriate shielding.
  2. Never taste a laboratory chemical.
  3. Take special precautions when scaling up a reaction. A reaction that is safe under published conditions may be violent when multiplied in scale.
  4. Read labels carefully, and keep labels clean so that they are legible. Replace deterioration labels before a chemical becomes unidentifiable
  5. Clearly labels ampoules, product vials, reaction vessels, and all other containers. Labels should include chemical names, structures when appropriate, date and name of owner. If you know of special risk, include appropriate warnings. Unidentified materials cannot be disposed of and can cause serious accidents.
  6. If it is necessary to smell a chemical, do so by wafting the vapors toward your nose with your hand so that the minimum amount is inhaled.
  7. Never pour a chemical back into its original bottle after measuring out too much. This can contaminate the original contants.
  8. Never combine the contents of two or more bottles of the same reagent. If one of the bottles is contaminated, the resulting combination is now contaminated.
  9. Be aware of chemical incompatibilities before mixing to avoid explosive or uncontrollable reactions, generation of toxic gases, etc.

 

Handling of Organic Peroxides

Peroxides are a group of compounds that contain an oxygen-oxygen bond. As a class, organic peroxides are the most explosive substances that are normally found in the laboratory. Peroxides are sensitive to light, heat, and friction, as well as to strong oxidizing and reducing agents. Explosions involving peroxides are unpredictable and violent.

  1. Store peroxides away from sources of light, heat, friction, and mechanical disturbance.
  2. A solid peroxide can often be stored more safely if it is dissolved in a nonperoxidizable inert solvent such as an aliphatic hydrocarbon. Do not allow solutions of peroxides to evaporate, because the concentration of peroxide may reach a dangerous level.
  3. Store solutions of peroxides at a cool temperature, but do not refrigerate peroxides at a temperature below which precipitation or freezing out of solid material may occur; in this form, peroxides are extremely sensitive to shock and heat.
  4. Do not store peroxides or solutions of peroxides in glass bottles with ground glass or screw caps. The friction caused by opening the bottle can initiate an explosion. Polyethylene bottles with screw caps may be used.
  5. Use ceramic spatulas for handling peroxides; metal spatulas can catalyze an explosive reaction.
  6. Use no flames in areas where peroxides are being handled.
  7. Purchase, store, and use the minimum quantity of peroxide necessary. Use special caution when scaling up reactions that use peroxides.
  8. Perform experiments involving peroxides in a hood and behind a safety shield.
  9. Clean up all spills immediately by absorption on vermiculite or other suitable absorbent.

 

Peroxide-Forming Chemicals

Some chemicals can easily form peroxide when exposed to atmospheric oxygen. These peroxidizable chemicals are especially dangerous because the presence of peroxides may not be known. Check a list of peroxidizable compounds before using a organic solvent in a distallion or reaction.

Compounds that form peroxides include:

  • Ethers and acetals. Especially dangerous are cyclic ethers (e.g., Tetrahydrofuran and dioxane) and ethers derived from primary and secondary alcohols, particularly diisopropyl ether. Ethers having an aromatic group bonded to the oxygen generally do not peroxidize under normal conditions.
  • Compounds containing benzylic hydrogen atoms, especially tertiary hydrogens, (e.g., cumene, tetralin).
  • Compounds containing allylic hydrogens (CH2=CHCH2R), including most alkenes (e.g., cyclohexene, cyclooctene).
  • Ketones, especially cyclic ketones
  • Dienes and vinylacetylenes (e.g., divinylacetylene, butadiene).
  • Paraffinic and alkylaromatic hydrocarbons with tertiary hydrogens (e.g., decalin, methylcyclopentane).
  • Vinyl and vinylidene compounds (e.g., vinyl acetate, vinylidene chloride).
  • Aldehydes (particularly anhydrous acetaldehyde); ketones with an alpha- hydrogen (methyl isobutyl ketone); ureas, amides, lactams.
  • Potassium metal (actually forms the yellow superoxide KO2) and alkali metal amides such as sodium amide.

Peroxidizable Compounds Hazard Classification

  • Class A -- Includes compounds that form dangerous explosive peroxides without concentration. These include diisoproply ether, divinylacetylene, vinylidene chloride, potassium metal, and sodium amide.
  • Class B -- Includes compounds that form peroxides but are only dangerous when concentrated by evaporation or distillation. Examples are diethyl ether, dioxane, THF, tetralin, and cyclohexene.
  • Class C -- Includes monomers in which peroxide formation may initiate explosive polymerization. Examples are styrene, butadiene, and vinyl monomers.

 

Handling of Peroxide-Forming Chemicals

Buy and use the minimum quantities of Peroxidizable substances necessary.

  1. Store peroxide-forming chemicals for the shortest possible time. Date the container when it is opened. Test for peroxide formation when first opened and every 3 months. If peroxide levels are acceptable, date the container when the test was performed. If the material contains hazardous concentrations, either treat to remove peroxides or discard.
  2. Peroxide formation in ethers and hydrocarbons can be prevented if they are stored under an inert atmosphere, for example, argon or nitrogen. The container should be well sealed.
  3. Store peroxidizable chemicals away from source of heat, light, sparks, other ignition sources, and mechanical shock.
  4. Peroxide-forming compounds should be kept at a cool temperature. Do not refrigerate peroxides if solid peroxide may precipitate or freeze out. Solid material is especially sensitive to shock.
  5. Do not store peroxide-forming compounds in glass bottles having ground glass or screw caps, or metal cans with metal screw caps. Serious explosions can occur by merely unscrewing the top of a glass bottle that contains peroxides. Metal cans with plastic caps and polyethylene bottles are safer containers for ethers and other peroxidizable compounds. The safest container is the one supplied by the manufacturer.
  6. Test peroxidizable substances before using, and periodically in storage as specified in item 2 above. Chemicals test using Quantofix Peroxide Test Papers (available from Aldrich). Chemistry stockroom keeps a supply of these on hand.
  7. Peroxides may be removed from solvents by passing the solvent through a column of alumina or Dowex-1 resin. The column MUST NOT be allowed to run dry and the packing should be handled as other peroxide waste. It is less dangerous, however, to use a new bottle of peroxide-free solvent than to purify solvent containing peroxides.
  8. Serous accidents can occur when substances capable of forming peroxides are distilled. Consider other methods of purification. If distillation is necessary, the following precautions should be observed where peroxide formation is suspected.
    • Test for peroxides before distilling. The peroxide test strips can indicate the concentration of peroxide in ppm. allowing you to know just how much peroxides are present.
    • Do the distillation under an inert atmosphere. Do not allow air to come in contact with hot solvent.
    • Add a suitable reducing agent to the distillation flask, such as sodium/benzophenone for ethers. Make sure that no compounds that react vigorously with the reducing agent are present in the distillation flask.
    • Do not carry the distillation to dryness; leave at least 10% liquid in the flask.
    • Wear goggles, face shield and use a free standing safety shield when distilling peroxidizable chemicals. Conduct the distillation in a hood with the sash closed.
    • Be aware that freshly distilled peroxidizable material may reform peroxide with two weeks of distillation.
  9. Spills should be cleaned up immediately by absorption on solusorb or other suitable absorbents. These are located in the issue rooms or main stockroom.

 

Handling of Common Chemicals that are Particularly Hazardous

Many compounds found in older literature have been found in recent years to be more hazardous than once thought. When the research was preformed, these compounds were readily available and the chronic effects were not known. Therefore, if you use a procedure not recently published, you must check the MSDSs of the reagents to get the most recent information on hazardous health affects. For the compounds listed below, consider finding a substitute solvent or reactant to avoid possible risk. If you cannot find as substitute, then take special precaustions to avoid exposure.

  1. Benzene is considered a Category I Carcinogen by OSHA. Chronic poisoning can occur by inhalation of relatively small amounts over a long period of time. The toxic action is primarily on the blood-forming organs. Benzene has been documented to cause leukenia. Benzene is readily absorbed through the skin. Toluene should be substituted whenever possible. OSHA permissible exposure limit is 1 ppm.
  2. Carbon Tetrachloride is another dangerous solvent found in many literature references. At one time, carbon tetrachloride was used in fire extinguishers (if you ever find an old extinguisher with CCl4, contact the Chemical Hygiene Officer immediately). Keep exposure to the liquid and its vapors to an absolute minimum. High concentration in the air can lead to death from respiratory failure. Less severe exposure can lead to kidney and liver damage. In addition to inhalation hazard, it can be readily absorbed through the skin. Methylene chloride, (dichloromethane), is a much safer chlorinated hydrocarbon. However, almost all chlorinated hydorcarbons have been found to be toxic to some degree. The current threshold limit value for carbon tetrachloride is 5 ppm.
  3. Chloroform is a compound similar to carbon tetrachloride with one less chlorine atom (CHCl3). Therefore, it has many of the adverse health affects as carbon tetrachloride. Repeated exposure can cause kidney, liver and heart damage. In laboratory animals it has been shown to be a carcinogen and mutagen. Use methylene chloride as a substitute. The PEL for chloroform is 2 ppm.
  4. Formaldehyde use as preservative of biological tissue has been found to be a a human carcinagen. Repeated inhalation can cause cancer of the lungs, nasopharynx, and/or nasal passages. It can cause respiratory tract irritation and edema. It can also cause eye and skin irritation. Formaldehyde is a colorless, pungent, irritant gas that is water soluble and most frequently found in 37% aqueous solution commonly known as formalin. Alway use formalin in a hood and wear gloves and splash-proof goggles. The threshold limit value for formaldehyde is 0.75 ppm.
  5. Ethyl ether is an extremely flammable solvent use in Grinard reactions and extractions. The greatest danger of ethyl ether is its very low flash point (-30o C). The vapors of ether are heavier than air and can "crawl" along the benchtop to a source of ignition. It tends to form peroxides especially anhydrous. It is a depressant to the central nervous system and can cause unconciousness or even death on severe exposure. Carry out reactions using ethyl ether in the hood.
  6. Perchloric Acid usually found as 72% aqueous solution is a very strong oxidizing acid. Contact with combustible materials at elevated temperatures may cause fire or explosion. Handle with extreme care as severe burns can result from skin contact. Wear heavy rubber gloves and apron in addition to splash-proof goggles.

 

+ Proper Handling of Gas Cylinders

Proper Handling of Gas Cylinders

Hazards of Compressed Gases

  • Mechanical failure of the cylinder, cylinder valve, or regulator can result in rapid diffusion of the pressurized contents into the atmosphere, leading to explosion, fire runaway reaction, or burst reaction vessels.
  • Unsecured cylinders can be knocked over very easily, causing serious injury and damage. Impact can shear the valve from an uncapped cylinder, especially if a regulator is attached, causing a rocking action or penwhelling leading to personal injury.
  • Gas cylinders may contain flammable, toxic, or corrosive gases; asphyxiants; or oxidizers.

Storage and Handling of Compressed Gases

  1. Check to make sure that a label is attached or the identification of the contents is stencilled on the cylinder when a cylinder is brought to you. Do not accept a cylinder if the contents are not clearly identified. Do not rely on color coding to identify the contents of a gas cylinder; color coding is not standardized.
  2. To transport a cylinder, use a hand truck equipped with a chain or belt for securing the cylinder. Make sure the protective cap covers the cylinder valve. Never move a cylinder while a regulator is attached. Do not move cylinders by carrying, rolling, sliding, or dragging them across the floor. Do not transport oxygen and combustible gases at the same time.
  3. Secure gas cylinders to prevent them from falling over. Chains or a clamp-plus-strap assembly are the most common methods of keeping cylinders upright. Make sure the chain is high enough on the cylinder to keep it from tipping over. Cylinder supports are available from the stockroom.
  4. Do not store incompatible gases together. Store cylinders of oxygen at least 20 feet away from cylinders of hydrogen or other flammable gases.
  5. Store cylinders away from heat (never in areas above 125 C ), including steam or hot water pipes, and away from areas where they might be subjected to mechanical damage.
  6. Store full and empty tanks in volatile solvent room. Place "Empty" ring around the top of the tanks when removing them from service to avoid accidental connection to an empty to a pressurized system, causing backflow into the tank.
  7. Ground cylinders of combustible gases (e.g., to a water pipe) to prevent buildup of static electricity. Keep cylinders away from locations where they might form part of a electrical circuit.
  8. Keep the protective cap that comes with a cylinder of gas on the cylinder when it is not in use. The cap prevents the main cylinder valve from being damaged or broken.
  9. 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 of liquefied flammable gases; and three 4' X 15" cylinders (or volume equivalent of gases with high Health Hazard Ratings (see NFPA 45).
  10. Corrosive or unstable gases should be ordered in the minimum quantities necessary and stored in a hood or other safe, dry area. Corrosive gases, if stored for long periods, will corrode the valve internally and may be impossible to open or if opened, may not close.
  11. Gases with Health Hazard Ratings of 3 or 4, or a rating of 2 with no physiological warning properties, MUST be kept in an hood or other ventilated enclosure. No more than three cylinders with ratings of 3 or 4 may be kept in one enclosure.
  12. 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.
  13. 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 in the Volatile solvent room.
+ Hazardous Waste Disposal

Hazardous Waste Disposal

Waste Minimization

Disposal of waste chemicals, strictly regulated by EPA and DOT, is becoming increasingly expensive and difficult. Virtually all hazardous chemicals are now banned from landfills, leaving incineration as the main disposal route.

It is imperative that researchers work to minimize disposal problems through the following measures:

  1. Purchase the smallest reasonable quantity of chemicals. Avoid the need to dispose of a surplus. Disposal cost is frequently much higher than the original cost of the chemical.
  2. Exchange surplus chemicals with other research groups. Check the inventory to be sure that the reagent in not already on hand. If a dated bottle is available, consider purification and using it.
  3. Reduce the scale of reactions whenever possible.
  4. Before running a reaction, consider the waste products produced and determine a safe disposal method. The Chemical Hygiene Officer may also be able to provide you with additional information.
  5. When possible, treat waste to reduce their hazards before packaging for disposal. A simple neutralization or oxidation may considerably downgrade the hazards of a reaction waste and make it easier to dispose of it.
  6. Consider alternative methods using less hazardous reagents.
  7. Recover and reuse solvents when feasible.
  8. Determine methods of decontaminating disposable (such as filter paper, tubing, weighing boats, etc) to allow disposal in trash or reuse. Contaminated non-chemical waste cannot be disposed of with the chemical waste.
  9. Above all, remember that it is the responsibility of the individual researcher to determine acceptable disposal procedures. If you do not know how to dispose of the waste safely and legally, do not buy the chemical and do not run the reaction! The department may be left with waste material that cannot be legally disposed of.

Disposal Methods

    Most waste chemicals are disposed of annually through the supervision of the CHO. Waste solvent container located in some labs are for routine waste solvent of volumes of less than one liter. If you anticipate more than one liter of waste will be generated, it is better to collect the waste in a labelled bottle. When the bottle is full or you will no longer be adding waste to it, it can be stored in a safe place until the annual disposal.

    A few chemicals cannot be disposed of in this manner, such as radio-actives, metallic mercury and asbestos. Some nonhazardous materials, such as chromatographic supports, low-toxicity inorganic salts, and some water-soluble organics, may be disposed of in the trash or down the drain. Special procedures are given below for these exceptions.

    Storage of Waste -- Each research group should establish chemical waste holding points. An enclosed cabinet is the preferred location, although open shelving may be acceptable. Storage of waste on the floor, with or without a tray , is unacceptable. Active collection bottles should be capped and generally should be kept in a hood. But do not allow the waste to accumulate more than one four-liter bottle.

    Packaging

    • Glass bottles are preferred for all waste. Polyethylene is acceptable for nonreactive solid waste. The main stockroom can supply small numbers of glass and polyethylene containers if your emptied reagent bottles are inadequate.
    • Metal cans are not acceptable because they may corrode.
    • Screw caps are required. Corks, rubber stoppers, and ground glass stoppers are unacceptable because they are not secure. An exception is a permanently frozen ground glass stopper. Indicate on the label that the stopper is frozen.
    • Leaking containers are not acceptable. The most common cause of leakage is use of a cap from a different brand of solvent bottle. Caps are not always interchangeable and may not seal properly. Check for leakage by tilting the bottle. Vented caps also leak and are unacceptable.
    • Fill containers only to the shoulder of the bottle to allow for thermal expansion.
    • Size the container to the contents, e.g., do not dispose of one liter of liquid in a four liter bottle.
    • Compatible chemicals may be combined to fill containers. For example, common non-halogenated solvents such as acetone, ethanol, hexane and toluene may be combined. Do not combine halogenated and nonhalogenated solvents if at all possible; halogenated solvents must undergo more rigorous (and more expensive) treatment.
    • The outside of containers must be free of chemical residues to avoid injury to personnel picking up the waste.

    Labeling

    1. Before using a bottle as waste container, obliterate the original label unless it accurately describes the contents. Even if it does describe the contents, mark the label clearly "WASTE" while using it as a collection container, to prevent someone mistaking it for a pure reagent.
    2. Keep a running list, securely attached to the bottle, of each chemical added to the bottle. Do not rely on memory, especially if several people are using the same waste container. The final waste label MUST accurately reflect the contents of the bottle.
    3. Use a ballpoint pen or waterproof marker.
    4. Fill out the label completely, including the chemical names of all chemicals present. Generic classes such as "halogenated organics" are not acceptable. Waste chemicals cannot be disposed of without chemical names. "unknown" chemicals MUST be identified by the generator.

    Metallic Mercury, Mercury Solutions, and Compounds -- Metallic mercury should be collected for recycling. Mercury should be taken to Philip Waite in the chemistry main stockroom (ground floor, Ebaugh Laboratories). Mr. Waite maintains mercury containers into which you may deposit your mercury. This is for mercury only, not mercury compounds or debris from mercury spill cleanups. Solutions of mercury should be treated with sulfide to precipitate the mercury compounds before submitting for disposal. The resulting HgS is acceptable for disposal. Decant the supernatant liquid; do not filter it because you will not be able to dispose of the mercury-contaminated filter paper. Label mercury salts and arrange disposal in the normal manner.

    Asbestos-Containing Materials -- The use of asbestos should be avoided if at all possible. However, if you do need to dispose of asbestos, first place it in plastic bags, label its origins and give it to the Chemical Hygiene Officer, Mr. Waite, for disposal.

    Pump Oil and Mineral Oil -- Uncontaminated waste oils (meeting specified levels of arsenic, chromium, lead, sulfur, halogens, and PCBs) are not considered hazardous waste. Vacuum pump or heating bath oil that you have no reason to believe is contaminated will be accepted for disposal by the Chemical Hygiene Officer, Mr. Waite.

    The following procedures apply:

    • Plastic bottles are acceptable containers.
    • Clearly label the bottle "Waste Pump Oil" (or mineral oil, as appropriate). Take it to the chemistry main stockroom and submit it to Mr. Waite.
    • Do not use this procedure to dispose of oil mixed with solvents or other contaminants.
    • Motor oil will not be accepted. Dispose of this through one of the local garages that accepts used motor oil, (BP station on Columbus Rd.).

    If you know or have good reason to believe that waste oil is contaminated, label it as hazardous waste, including the chemical names and approximate levels of all contaminants.

    Drain Disposal of Chemical Wastes -- Many organic and inorganic chemicals are suitable for disposal down the drain if they are water soluble to at least 3%, low toxicity, and (for organics) readily biodegradable. This includes many low-molecular weight organics containing oxygen or nitrogen, and soluble in-organics containing both cations and anions of low toxicity.

    Avoid flushing inorganic salts containing heavy metals such as: chromium, lead, mercury, nickel, silver, cadmium, and antimony. In addition never flush down the drain cyanide or sulfide salts. These inorganic compounds should be precipitated out of the solution, separated from the supernatant liquid, and packaged and labelled for disposal.

    If you are not sure the solution may be flushed down the drain, first check with a lab supervisor or the CHO to be sure it is not harmful to the environment.

    If it is okay to flush, follow these precautions:

    1. Flush down the drain with large volumes of excess water.
    2. Neutralize acidic or basic inorganics before disposal.
    3. Dispose of only small quantities at one time (less than 100 g).

    Disposal of Non-Hazardous Chemical Waste In Trash -- Some solid chemical waste are considered nonhazardous by EPA criteria and may be disposed of by simply placing them in the trash baskets. These include sugars and starches; naturally occurring alpha-amino acids and their salts; citric acid and its salts; various insoluble or otherwise innocuous sulfates, oxides, carbonates, and other salts; and chromatographic adsorbents (silica gel, alumina) and molecular sieves, if not contaminated with hazardous chemicals.

    These may be disposed of in the ordinary trash using the following precautions:

    1. Remove solvents from adsorbents.
    2. Package materials in at least two layers e.g., plastic bags or jars, packed in a cardboard box.
    3. Affix an identifying label to the inner packaging so its identity may be determined in cast the packaging breaks open. Do not label as Hazardous Waste.
    4. Deposit the package in the dumpster yourself. The custodians will not handle even nonhazardous chemical waste.

    Empty Glass Containers -- Bottles and unbroken glassware MUST be empty and cleaned inside and out before they are placed without a cap in the trash. It is imperative that no flammable vapors are remaining in bottles when they are placed in the trash. If the contents are water soluble and not toxic, rinsing them with water several times should suffice. If the contents are not water soluble, the bottle should be rinsed several times with an appropriate solvent such as alcohol or acetone and the rinsing treated as waste solvent. Traces of residual water can remain in the bottles; residual solvents should be allowed to evaporate in the hood before the bottle is discarded. Discard only clean containers to avoid injury to persons emptying the trash.

    Broken Glassware -- In each laboratory a "sharps container" should be available for broken glassware. If you break a common piece of laboratory glassware such as a beaker or flask, the pieces should be collected in a dust pan and deposited into one of the sharps container. The exception to this is any glassware that might have salvageable parts such as ground glass joints. Ask the laboratory supervisor if you are not sure. These sharps container are not intended for sample vials or empty glass containers. Broken mercury thermometers should not be placed in these containers.

 

 

Chemical Hygiene Outline

A. Standard Operating Procedures

    + General Rules

    A. Standard Operating Procedures

      A1. General Rules

      1. Never work alone in a laboratory or chemical storage area except for work done in photographic darkrooms and in studio art areas. It is expected that there will be more than one person working in a building at any time of day or night.
      2. Contact lenses is permitted to be worn when working in a laboratory or chemical storage area but splash proof goggles should be worn.
      3. Wear appropriate eye protection at all times.
      4. When working with flammable chemicals, be certain that there are no sources of ignition near enough to cause a fire or explosion in the event of a vapor release or liquid spill.
      5. Use a tip-resistant shield for protection whenever an explosion or implosion might occur.

      For the chemicals they are working with, all employees should know and constantly be aware of:

      1. The chemical's hazards, as determined from the NFPA label, the MSDS and other appropriate references.
      2. Appropriate safeguards for using that chemical, including personal protective equipment.
      3. The location and proper use of emergency equipment.
      4. How and where to properly store the chemical when it is not in use.
      5. Proper personal hygiene practices.
      6. The proper methods of transporting chemicals within the facility.
      7. Appropriate procedures for emergencies, including evacuation routes, spill cleanup procedures and proper waste disposal.
    + Personal Hygiene

    A. Standard Operating Procedures

      A2. Personal Hygiene

      1. Wash promptly whenever a chemical has contacted the skin.
      2. Avoid inhalation of chemicals; do not "sniff" to test chemicals.
      3. Do not use mouth suction to pipet anything; use suction bulbs or other pipet filling devices.
      4. Wash well with soap and water before leaving the laboratory; do not wash with solvents.
      5. Do not eat, drink, smoke or apply cosmetics in the laboratory.
      6. Do not bring food, beverages, tobacco, or cosmetic products into areas where chemicals are stored or used.
      7. Confine long hair and loose clothing. Wear shoes at all times in the laboratory, but do not wear sandals or perforated shoes.
    + Protective Clothing and Equipment

    A. Standard Operating Procedures

      A3. Protective Clothing and Equipment

      1. Eye protection worn when working with chemicals should meet the requirements of the American National Standards Institute (ANSI) Z87.1. When working with more than 10 mL of a corrosive liquid, also wear a face shield, type N, large enough to protect the chin, neck and ears, as well as the face.
      2. When working with corrosive liquids, also wear gloves made of material known to be resistant to permeation by the corrosive chemical and tested by air inflation (do not inflate by mouth) for the absence of pin-hole leaks.
      3. When working with hazardous chemicals, wear either a high-necked, calf-or ankle-length, rubberized laboratory apron or a long-sleeve, calf-or ankle-length, chemical and fire resistant laboratory coat. It is better to wear long-sleeved/long legged clothing and not to wear short-sleeved shirts, short pants, or short skirts.
      4. When working with allergenic, sensitizing or toxic chemicals, wear gloves made of material known to be or tested and found to be resistant to permeation by the chemical and tested for the absence of pin hole leaks.
      5. Always wear low-heeled shoes with fully covering "uppers"; do not wear shoes with open toes or with uppers constructed of woven material.
      6. Whenever exposure by inhalation is likely to exceed the threshold limits described in the MSDS or other reference, use a fume hood. If this is not possible, use a proper respirator.
      7. Carefully inspect all protective equipment before using. Do not use defective protective equipment.
      8. Know the location of safety equipment: emergency shower, eye wash station, fire extinguisher, fire blanket, fire alarm pull station.
      9. Electrically ground containers using approved methods before transferring or dispensing a flammable liquid from a large container.
    + Housekeeping

    A. Standard Operating Procedures

      A4. Housekeeping

      1. Access to emergency equipment, showers, eyewash stations, and exits should never be blocked by anything, not even a temporarily parked cart.
      2. All chemical containers must be labeled with at least the identity of the contents and an indication of the hazards those contents present to users such as the NFPA warning label.
      3. Keep all work areas, especially laboratory benches, clear of clutter. Clean up the work area on completion of an operation or at the end of each work day.
      4. Keep all aisles, hallways, and stairs clear of all chemicals.
      5. All chemicals should be placed in their assigned storage areas at the end of each work day.
      6. At the end of each work day, the contents of all unlabeled containers are to be considered wastes and disposed of accordingly.
      7. Wastes should be properly labeled and kept in their proper containers until collected for disposal.
      8. Promptly clean up all spills; properly dispose of the spilled chemical and cleanup materials. (See Section A6)
      9. All working surfaces and floors should be cleaned regularly.
      10. No chemicals are to be stored in aisles or stairwells, on desks or laboratory benches (when not regularly used), on floors or in hallways, or to be left overnight on shelves over the workbenches.
      11. Apparatus which may discharge toxic chemicals such as vacuum pumps and distillation columns, should be vented to a fume hood or provided with a suitable trap.
      12. Avoid practical jokes or horseplay or other behavior which might confuse, startle or distract another worker.
    + Prior Approval

    A. Standard Operating Procedures

      A5. Prior Approval

      Employees, other than faculty, must obtain prior approval to proceed with a laboratory task from the employer or his or her designee whenever:

      1. A new laboratory procedure or test is to be carried out.
      2. It is likely that toxic limit concentrations could be exceeded or that other harm is likely.
      3. There is a change in a procedure or test, even if it is very similar to prior practices. "Change in a procedure or test" means:
        1. A significant increase or decrease in the amount of one or more chemicals used.
        2. A substitution or deletion of any of the chemicals in a procedure.
        3. Any change in other conditions under which the procedure is to be conducted.
      4. There is a failure of any of the equipment used in the process, especially of safeguards such as fume hoods or clamped apparatus.
      5. There are unexpected results.
      6. Members of the laboratory staff become ill, suspect that they or others have been exposed, or otherwise suspect a failure of any safeguards.
    + Spills and Accidents

    A. Standard Operating Procedures

      A6. Spills and Accidents

      Minor spills of hazardous chemicals should be taken care of immediately using proper cleanup and disposal methods such as spill cleanup kits located in laboratories and stockrooms.

      Major spills of toxic substances or accidents involving any hazardous chemical should be resolved immediately according to Denison University's emergency procedure plan (see Appendix C).

    + Chemical Waste Disposal

    A. Standard Operating Procedures

      A7. Chemical Waste Disposal

      In order to assure that minimal harm is done to people, other organisms and the environment from the disposal of waste laboratory chemicals, indiscriminate disposal by pouring them down the drain or adding them to mixed refuse for landfill burial is unacceptable.

      The following procedures should be followed in disposing of waste chemicals:

      1. Whenever possible, spent solvents should be recovered and recycled by distillation or chromatographic purification for reuse.
      2. Aqueous solutions of acids and bases should be neutralized before flushing down the drain with large volumes of water.
      3. Solutions containing toxic heavy metals such as mercury, lead, chromium, silver, etc. should be precipitated and the metal recovered in solid form for subsequent disposal as a solid waste.
      4. Fume hoods should not be used as a means of disposal of volatile chemicals.
      5. Liquid organic wastes should be emptied into labeled plastic containers kept in vented metal cabinets in each laboratory. Waste containers should be labelled "polar", meaning alcohols, acids, amines and other compounds capable of forming hydrogen bonds, and "non-polar" meaning anything else including halogenated hydrocarbons. Liquid waste containers should be removed and replaced when full and safely stored for disposal by a licensed waste hauler.
      6. Highly reactive wastes such as acid chlorides should be converted to a less reactive form before disposing in the waste containers.
      7. Dry solid wastes should be stored in labelled plastic containers until removed by a licensed waste hauler. A running inventory should be maintained of each waste container's contents.
      8. Old or unneeded chemical stocks should be removed from storage and disposed of at least annually.
      9. Before a worker's employment in a laboratory ends, chemicals for which that person was responsible should be discarded or returned to storage.

B. Specific Safety Procedures

    + Toxic Chemicals

    B. Specific Safety Procedures

      B1. Procedures for Toxic Chemicals

      The Material Safety Data Sheets (MSDS)for many of the chemicals used in the laboratory will state recommended limits or OSHA-mandated limits, or both, as guidelines for exposure. Typical limits are threshold limit values (TLV), permissible exposure limits (PEL), and action levels. When such limits are stated, they will be used to assist the chemical hygiene officer in determining the safety precautions, control measures, and safety apparel that apply when working with toxic chemicals.

      1. When a TLV or PEL value is less than 50 ppm or 100 mg/m3 the user of the chemical must use it in an operating fume hood or else in a glove box, vacuum line or similar device which is equipped with appropriate traps and/or scrubbers. If none are available, no work should be performed using that chemical.
      2. If a TLV, PEL or comparable value is not available for that substance, the animal or human median inhalation lethal concentration information, LC50, will be assessed. If that value is less than 200 ppm or 2000 mg/m3, (when administered continuously for one hour or less), then the chemical must be used in an operating fume hood or else in a glove box, vacuum line, or similar device which is equipped with appropriate traps and/or scrubbers. If none are available, no work should be performed using that chemical.
      3. Whenever laboratory handling of toxic substances with moderate or greater vapor pressures will be likely to exceed air concentration limits, laboratory work with such liquids and solids will be conducted in a working fume hood or in a glove box, vacuum line or similar device which is equipped with appropriate traps and/or scrubbers. If none are available, no work should be performed using that chemical.
    + Flammable Chemicals

    B. Specific Safety Procedures

      B2. Procedures for Flammable Chemicals

      In general, the flammability of a chemical is determined by its flash point, the lowest temperature at which an ignition source can cause the chemical to ignite momentarily under certain controlled conditions.

      1. Chemicals with a flash point below 200oF (93.3oC) will be considered "fire hazard chemicals".
      2. OSHA standards and the National Fire Protection Association (NFPA) guidelines on when a chemical is considered flammable apply to the use of flammable chemicals in the laboratory. In all work with fire-hazard chemicals, follow the requirements of 29 CFR, subparts H and L; NFPA Manual 30, "Flammable and Combustible Liquids Code"; and NFPA Manual 45, "Fire Protection for Laboratories Using Chemicals".
      3. Fire-hazard chemicals should be stored in a flammable-solvent storage area or in storage cabinets designed for flammable materials.
      4. Fire-hazard chemicals should be used only in vented hoods and away from sources of ignition.
    + Reactive Chemicals

    B. Specific Safety Procedures

      B3. Procedures for Reactive Chemicals

      The most complete and reliable reference on chemical reactivity is found in the current edition of "Handbook of Reactive Chemical Hazards" by L. Bretherick, published by Butterworths. Reactivity information is sometimes given in manufacturers' MSDSs and on labels. Guidelines on which chemicals are reactive can be found in regulations promulgated by the Department of Transportation (DOT) in 49 CFR and by the Environmental Protection Agency (EPA) in 40 CFR. Also see NFPA Manual 325M, "Fire Hazard Properties of Flammable Liquids, Gases, Volatile Solids"; Manual 49, "Hazardous Chemicals Data"; and Manual 491M, "Manual of Hazardous Chemical Reactions".

      1. A reactive chemical is one that:
        1. Is described as such in Bretherick or the MSDS
        2. Is ranked by the NFPA as 3 or 4 for reactivity
        3. Is identified by the DOT as:
          • An oxidizer
          • An organic peroxide
          • An explosive, Class A, B, or C.
        4. Fits the EPA definition of reactive in 40 CFR 261.23
        5. Fits the OSHA definition of unstable in 29 CFR 1910.1450
        6. Is known or found to be reactive with other substances.
      2. Handle reactive chemicals with all proper safety precautions, including segregation in storage and prohibition on mixing even small quantities with other chemicals without prior approval and appropriate personal protection and precautions.
    + Corrosive Chemicals and Contact Hazard Chemicals

    B. Specific Safety Procedures

      B4. Procedures for Corrosive Chemicals and Contact-Hazard Chemicals

      Corrosivity, allergenic, and sensitizer information is sometimes given in manufacturers' MSDS's and on labels. Also guidelines on which chemicals are corrosive can be found in other OSHA standards and in regulations promulgated by DOT in 49 CFR and the EPA in 40 CFR.

      1. A corrosive chemical is one that:
        1. Fits the OSHA definition of corrosive in Appendix A of 29 CFR 1910.1200
        2. Fits the EPA definition of corrosive in 40 CFR 261.22 (has a pH greater than 12 or less than 2.5)
        3. Is known or found to be corrosive to living tissue.
      2. A contact hazard chemical is an allergen or sensitizer that:
        1. Is so identified or described in the MSDS or on the label
        2. Is so identified or described in the medical or industrial hygiene literature
        3. Is known or found to be an allergen or sensitizer.
      3. Handle corrosive chemicals with all proper safety precautions, including wearing both safety goggles and face shield, gloves tested for absence of pin holes and known to be resistant to permeation or penetration, and a laboratory apron or laboratory coat.

C. Control Measures and Equipment

    + Ventilation

    C. Control Measures and Equipment

      C1. Ventilation

      The Material Safety Data Sheets (MSDS) for many of the chemicals used in the laboratory will state recommended limits or OSHA-mandated limits, or both, as guidelines for exposure. Typical limits are threshold limit values (TLV), permissible exposure limits (PEL), and action levels. When such limits are stated, they will be used to assist the chemical hygiene officer in determining the safety precautions, control measures, and safety apparel that apply when working with toxic chemicals.

      1. Laboratory ventilation should be not less than eight air changes per hour (calculated). This flow is not necessarily sufficient to prevent accumulation of chemical vapors. Work with toxic chemicals that have low air concentration limits, or that have high vapor pressures, should always be done in a hood, if available.
      2. Fume hoods should provide 70 to 90 linear feet per minute of air flow.
      3. Laboratory employees should understand and comply with:
        1. A fume hood is a safety backup for condensers, traps, or other devices that collect vapors and fumes. It is not used to "dispose" of chemicals by evaporation unless the vapors are trapped and recovered for proper waste disposal.
        2. The apparatus inside the hood should be placed on the floor of the hood at least six inches away from the front edge.
        3. Fume hood windows should be lowered at all times except when necessary to raise (open) them to adjust the apparatus that is inside the hood.
        4. The hood fan should be kept "on" whenever a chemical is inside the hood, whether or not any work is being done in the hood.
        5. Personnel should be aware of the steps to be taken in the event of power failure or other hood failure and, if necessary, contact maintenance or repair personnel.
        6. Inspect hood vent ducts and fans at frequent intervals to be sure they are both clean and clear of obstructions. This maintenance is to be performed by maintenance or repair personnel.
        7. Hoods should never be used as storage areas for chemicals, apparatus or other materials.
    + Flammable Liquid Storage

    C. Control Measures and Equipment

      C2. Flammable Liquid Storage

      1. Fire hazard chemicals (see paragraph B2) in quantities greater than 1000 mL should be kept in metal safety cans designed for such storage. The cans should be used only as recommended by the manufacturer, including the following safety practices:
        1. Never disable the spring-loaded closure.
        2. Always keep the flame-arrestor screen in place; replace if punctured or damaged. Note: Fire hazard chemicals are often purchased in glass containers. Use considerable caution in storing chemicals in such containers.
      2. Cabinets designed for the storage of flammable materials should be properly used and maintained, including electrical grounding. Read and follow the manufacturer's information and also follow these safety practices:
        1. Store only compatible materials inside a cabinet.
        2. Do not store paper or cardboard or other combustible packaging material in a flammable-liquid storage cabinet.
        3. The manufacturer establishes quantity limits for various sizes of flammable-liquid storage cabinets; do not overload a cabinet.
    + Eyewash Fountains and Safety Showers

    C. Control Measures and Equipment

      C3. Eyewash Fountains and Safety Showers

      1. Equip all laboratories with eyewashes and safety showers. These must be located so they can be reached from any point in the laboratory.
      2. Check the functioning of eyewash fountains and safety showers and measure the water flow at selected intervals. Promptly repair any facility that does not meet the water flow requirements.
      3. Be sure that access to eyewash fountains and safety showers is not restricted or blocked by temporary storage of objects or in any other way.
    + Respirators

    C. Control Measures and Equipment

      C4. Respirators

      1. Employees should wear respirators whenever it is possible that engineering controls or work practices could become or are ineffective and that employees might be exposed to vapor or particulate concentrations greater than the PEL, action level, TLV, or similar limit, whichever is the lowest.
      2. The requirements of 29 CFR 1910.134 should be followed, including in particular:
        1. Written standard operating procedures governing the selection and use of respirators.
        2. All employees who are likely to need to use respirators must be trained in their proper use, inspection and maintenance. (See "NIOSH Guide to Industrial Respiratory Protection", DHHS Publ. No. 87-0116, NIOSH, Cincinnati, 1987, for details.)
    + Vapor Detection

    C. Control Measures and Equipment

      C5. Vapor Detection

      Do not use odor as a means of determining that inhalation exposure limits are or are not being exceeded. Whenever there is reason to suspect that a toxic chemical inhalation limit might be exceeded, whether or not a suspicious odor is noticed, notify the supervisor.

      Laboratory workers should wear a respirator suitable for protection against the suspect chemical until measurements of the concentration of the suspect vapor in the air show that the limit is not exceeded. Under this circumstance and if there is no reason to anticipate an increase in the concentration of the chemical, and if the supervisor approves, the respirator can be removed and the work may continue.

    + Fire Extinguishers

    C. Control Measures and Equipment

      C6. Fire Extinguishers

      Fire extinguishers should be provided within 30 feet of travel and located along normal paths of travel. Access must be maintained and the location should be conspicuously marked in an appropriate manner. The fire extinguisher and type must be selected for the appropriate hazard.

    + Fire Alarms

    C. Control Measures and Equipment

      C7. Fire Alarms

      Fire alarms must be provided along normal paths of travel, along exit routes, and should be conspicuously marked. Alarms must be tested at regular intervals.

D. Procedures for Carcinogens, Toxins, and Chemicals of Unknown Toxicity

    + Chemical Hygiene Plan D

    D. Procedures for Carcinogens, Toxins, and Chemicals of Unknown Toxicity

      Procedures for Carcinogens, Reproductive Toxins, substances with a high degree of Acute Toxicity, and Chemicals of Unknown Toxicity

      Follow the procedures described in this section when performing laboratory work with greater than 10 mg of any carcinogen, reproductive toxin, substance that has a high degree of acute toxicity, or a chemical whose toxic properties are unknown.

      1. The following definitions will apply:
        1. Carcinogen: Any substance defined as such in 29 CFR 1910.1450 and any other substance described as such in the applicable MSDS.
        2. Reproductive toxin: Any substance described as such in the applicable MSDS, or any substance identified as a reproductive toxin by the Oak Ridge Toxicology Information Resource Center (TIRC), (615) 576-1746, or, for teratogens only, any substance identified as such in Thomas H. Shepard, "Catalog of Teratogenic Agents", 6th Ed., Johns Hopkins Press, 1989.
        3. Chemical whose toxicity is unknown: A chemical for which there is no known statistically significant study conducted in accordance with established scientific principles that establishes its toxicity.
        4. For the purpose of this CHP, chemicals in these four categories will be called "inimical".
        5. Designated area: A hood, glove box, portion of a laboratory, or an entire laboratory room designated as the only area where work with quantities of the inimical chemicals in excess of the specific limit shall be conducted. 
      2. Designated areas shall be posted and their boundaries clearly marked. Only those persons trained to work with inimical chemicals will work with those chemicals in a designated area. All such persons will:
        1. Use the smallest amount of chemical that is consistent with the requirements of the work to be done.
        2. Use high efficiency particulate air (HEPA) filters or high efficiency scrubber systems to protect vacuum lines and pumps.
        3. Store inimical chemicals or remove them from storage.
        4. Decontaminate a designated area when work is completed.
        5. Prepare wastes from work with inimical chemicals for waste disposal in accordance with specific disposal procedures consistent with the Resource Conservation and Recovery Act (RCRA) and as designted by Denison University's hazardous waste officer.
      3. Store all inimical chemicals in locked and enclosed spaces with a slight negative pressure compared to the rest of the building, if such space is available.
      4. Because the decontamination of jewelry may be difficult or impossible, do not wear any jewelry when working within designated areas.
      5. Wear long-sleeved disposable clothing and gloves known to resist permeation by the chemicals to be used when working in designated areas.

E. Records and Record-Keeping

    + Chemical Hygiene Plan E

    E. Records and Record-Keeping

      Records and Record-Keeping

      Follow the procedures described in this section when performing laboratory work with greater than 10 mg of any carcinogen, reproductive toxin, substance that has a high degree of acute toxicity, or a chemical whose toxic properties are unknown

      1. A detailed written report form should be completed for each accident or exposure incident and retained in file. OSHA form 200 should be used to record lost workdays that may occur as a result of accident or chemical exposure.
      2. Inventory and usage records for high risk substances should be kept including the amounts of these materials on hand, amounts used, and the names of the workers involved.
      3. Medical records should be retained by the institution in accordance with the requirements of state and federal regulations.
      4. A collection of Material Safety Data Sheets (MSDS) should be maintained in one or more locations and made accessible to all employees who require them. Documents relating to the distribution and maintenance of these materials should also be retained.
      5. Documents relating to the safety training of employees should be kept.
      6. Records of air concentration monitoring results, exposure assessments, medical consultations, and examinations must be maintained for at least 30 years and must be made accessible to employees or their representatives.
      7. Major safety suggestions from employees should be kept. A suggestion that is unusable today might be useful tomorrow. Even when a suggestion is clearly nonworkable, it should be taken seriously, examined and recorded.
      8. Near miss reports. Employees who participate in or witness events that could have caused harm, but fortunately did not, should prepare reports of the incidents. These reports are used to develop changes in procedures that will prevent a future more serious occurrence.
      9. Repair and maintenance records for control systems. These are useful as they suggest corrective actions and indicate that equipment was or was not well maintained and kept in working condition.
      10. Complaints from employees. It is useful to keep a record of all complaints, investigations, and outcomes. Even when not justified, especially when a complaint correctly or incorrectly involves defects in and difficulties with operating equipment, the record may prove to be invaluable if that equipment develops a defect or malfunction at a later date.
      11. The EPA and other Federal and state agencies have special recordkeeping requirements. For example: Recordkeeping of allegations and the reporting of suspect hazards from the adverse effects of chemical exposure are required under Sections 8(c) and 8(e) of the Toxic Substances Control Act; see 40 CFR 716 and 717.

Appendix A. Employee Information and Training

    + Employee Information and Training

    Appendix A

      Employee Information and Training

      It is Denison University's responsibility to provide the necessary information and training to all Denison employees so that they may work safely with hazardous chemicals and minimize their exposure to them. Training methods may vary from classroom lecture to commercial "canned" presentations or videotapes to printed handouts or booklets to posted notices to private discussions with employees. OSHA does not mandate the training method but requires that, if asked by an OSHA inspector, the employees must be able to answer to the issues. Training methods will vary depending on the background and the responsibilities of the employees.

      1. Employees who have professional degrees in chemistry, such as faculty members, may not need formal training since their professional training and graduate experience already qualify them to safely handle hazardous chemicals. These employees should, however, be provided with written material, as needed, and should be prepared to "pass" an evaluation of the effectiveness of instruction in matters pertaining both to safety and health hazards and to the precautions to be taken under the variety of circumstances extant in the laboratory where they work.
      2. New employees, including teaching assistants, should be provided, at the time of their assignment to a laboratory, information and training in the hazards associated with the materials or procedures that they will be using.
      3. Employees should have access to the PELs, action levels, and other recommended exposure limits for hazardous chemicals used in Denison University laboratories and with the signs and symptoms associated with exposures to these materials.
      4. Employees should know the location and have access to the MSDSs and other reference materials.
      5. In general, employee training should include:
        1. The methods and observations that may be used to detect the presence or release of a hazardous chemical.
        2. The specific hazards associated with the chemicals that they will be using.
        3. The measures employees can use to protect themselves from these hazards, including specific procedures such as appropriate work practices, personal protective equipment to be used, and emergency procedures.
        4. A copy of this Chemical Hygiene Plan and appropriate instruction as to its content and meaning.
        5. Instruction in the contents and requirements of the OSHA Laboratory Standard.

Appendix B. Exposure Assessments, Medical Consultations, and Examinations

    A. Suspected Exposures to Toxic Substances

    + A1. Criteria for Reasonable Suspicion of Exposure

    Appendix B

      Exposure Assessments, Medical Consultations, and Examinations

        A. Suspected exposures to toxic substances

        There may be times when employees or supervisors suspect that an employee has been exposed to a hazardous chemical to a degree and in a manner that might have caused harm to the victim. If the circumstances suggest a reasonable suspicion of exposure, the victim is entitled to a medical consultation and, if so determined in the consultation, also to a medical examination at no cost with no loss of workday time attributed to the victim.

      • A1. Criteria for reasonable suspicion of exposure
        1. It is the policy of Denison University to promptly investigate all employee-reported incidents in which there is even a remote possibility of employee over-exposure to a toxic substance.
        2. Events or circumstances that might reasonably constitute overexposure include:
          1. A hazardous chemical leaked or was spilled or was otherwise rapidly released in an uncontrolled manner.
          2. A laboratory employee had direct skin or eye contact with a hazardous chemical.
          3. A laboratory employee manifests symptoms, such as headache, rash, nausea, coughing, tearing, irritation or redness of eyes, irritation of nose or throat, dizziness, loss of motor dexterity or judgement, etc., and 1) some or all of the symptoms disappear when the person is taken away from the exposure area and breathes fresh air, 2) the symptoms reappear soon after the employee returns to work with the same hazardous chemicals.
          4. Two or more persons in the same laboratory work area have similar complaints.
    + A2. Exposure

    Appendix B

      A2. Exposures

      All complaints and their disposition, no matter what the ultimate disposition may be, are to be documented. If no further assessment of the event is deemed necessary, the reason for that decision should be included in the documentation. If the decision is to investigate, a formal exposure assessment will be initiated.

    + A3. Exposure Assessment

    Appendix B

      A3. Exposure Assessment

      In cases of emergency, exposure assessments are conducted after the victim has been treated.

      It is not the purpose of an exposure assessment to determine that a failure on the part of the victim, or others, to follow proper procedures was the cause of an exposure. The purpose of an exposure assessment is to determine that there was, or was not, an exposure that might have caused harm to one or more employees and, if so, to identify the hazardous chemical or chemicals involved. Other investigations might well use results and conclusions from an exposure assessment, along with other information, to derive recommendations that will prevent or mitigate any future overexposures. However, exposure assessments determine facts, they do not make recommendations.

    • Unless circumstances suggest other or additional steps, these actions constitute an exposure assessment:
      1. Interview the complainant and also the victim, if not the same person.
      2. List the essential information about the circumstances of the complaint, including:
        • The chemical under suspicion.
        • Other chemicals used by the victim.
        • All chemicals being used by others in the immediate area.
        • Other chemicals stored in that area.
        • Symptoms exhibited or claimed by the victim.
        • How these symptoms compare to symptoms stated in the materials safety data sheets for each of the identified chemicals.
        • Were control measures, such as personal protective equipment and hoods, used properly?
        • Were any air sampling or monitoring devices in place? If so, are the measurements consistent with other information?
    + A4. Notification of Results or Monitoring

    Appendix B

      A4. Notification of Results or Monitoring

      Within 15 working days of receipt of the results of any monitoring, notify employees of those results.

    B. Medical Consultation and Examination

    + Medical Consultation and Examination

    Appendix B

      B. Medical Consultation and Examination

      The details of medical consultations and examinations are determined by the physician.

      The purpose of a medical consultation is to determine whether a medical examination is warranted. When, from the results of an exposure assessment, it is suspected or known that an employee was overexposed to a hazardous chemical or chemicals, the employee should obtain medical consultation from or under the direct supervision of a licensed physician.

      When warranted, employees also should receive a medical examination from or under the direct supervision of a licensed physician who is experienced in treating victims of chemical overexposure. The medical professional should also be knowledgeable about which tests or procedures are appropriate to determine if there has been an overexposure; these diagnostic techniques are called "differential diagnoses".

      These provisions apply to medical consultations and examinations:

      1. You must provide all employees who work with hazardous chemicals an opportunity to receive medical consultation and examination when:
        1. The employee develops signs or symptoms associated with a hazardous chemical to which the employee may have been exposed in the laboratory.
        2. Monitoring, routine or otherwise, suggests that there could have been an exposure above the action level, or PEL if there is no action level, for a chemical for which a substance-specific standard has been established.
        3. There is a spill, leak, or other uncontrolled release of a hazardous chemical.
      2. Provide the physician with:
        1. The identity of the hazardous chemical or chemicals to which the employee may have been exposed.
        2. The exposure conditions.
        3. The signs and symptoms of exposure the victim is experiencing, if any.
      3. Ordinarily, physicians will furnish to the employer in written form:
        1. Recommendations for follow-up, if determined to be pertinent.
        2. A record of the results of the consultation and, if applicable, of the examination and any tests that were conducted.
        3. Conclusions concerning any other medical condition noted that could put the employee at increased risk.
        4. A statement that the employee has been informed both of the results of the consultation or examination and of any medical condition that may require further examination or treatment.
      4. These written statements and records should not reveal specific findings that are not related to an occupational exposure.
    + B1. Documentation

    Appendix B

      B1. Documentation

      All memos, notes, and reports related to a complaint of actual or possible exposure to hazardous chemicals are to be maintained as a part of the record.

    + B2. Notification

    Appendix B

      B2. Notification

      Employees shall be notified of the results of any medical consultation or examination with regard to any medical condition that exists or might exist as a result of overexposure to a hazardous chemical.

Appendix C. Emergency Response

    + Emergency Response

    Appendix C

      A. Basic Steps for Emergency Response

    • A1. Determine the nature of the emergency
      1. High Hazard Emergency: If the emergency is immediately dangerous to life and health, involves a large area, major injury to personnel, is a threat to personnel and the public, involves radioactive materials, involves an infectious agent, or involves a highly toxic, corrosive or reactive hazardous material, then proceed with the plan below:
        1. Isolate the area, if possible, and evacuate.
        2. Call emergency response numbers and activate the building fire system.
          • Fire or other emergency: dial 6777
          • Campus Security and Safety: dial 6482
          • Licking County Emergency: dial 911
        3. When you call:
          • Identify yourself and the reason you are calling.
          • Identify the exact location of the emergency.
          • Identify the nature of the emergency, any injuries or symptoms involved, and any hazardous materials involved if you know them.
        4. Keep others out of the area and take action to protect life and limb.
        5. Provide rescue only if you are properly protected from the hazard. Never attempt to rescue someone who is unconscious unless you know what the problem is and you know you are properly protected from the hazard.
          • Do not move a seriously injured person unless he/she is in further danger.
          • Anyone overcome with smoke or chemical gases or vapors should be removed to uncontaminated air and treated for shock. Provide first aid if you have the capability.
          • For chemical splash in the eyes or on the skin, remove contact lenses and rinse affected area for at least 15 minutes in emergency eyewash or shower, or use other water source. Remove any contaminated clothing, including undergarments and jewelry. Call an ambulance.
        6. Identify yourself and be available to provide emergency response personnel information when they arrive. If possible, collect Material Safety Data Sheets for chemicals involved and provide these to the emergency response personnel.
      2. Low Hazard Emergency: If the emergency is small, there is no fire hazard, involves low to moderately toxic materials in small amounts, or involves a readily treatable injury, proceed the plans below:
        • For a minor injury, report to Whisler Hospital or local emergency room for treatment. All injuries which occur on the job should be treated at the hospital.
        • For a small spill, use an absorbent material that will neutralize the spill, if available. Spill kits are available from chemistry issue rooms and the main stockroom.
        • A dustpan and brush should be used, and protective clothing (e.g., rubber gloves and goggles) should be worn. The area should be decontaminated with soap and water after clean-up. Residue should be placed in an appropriate container for waste collection.
      3. Fire and Fire-related Emergency: If you discover a fire or fire-related emergency such as abnormal heating of material, hazardous gas leaks, hazardous material or flammable liquid spill, smoke, or odor of burning, immediately follow these procedures:
        1. Activate the building fire alarm system (pull fire station). If not available or operational, verbally notify persons in the building.
        2. Notify the fire department (6777 or 3-911)
        3. Isolate the area and evacuate the building:
          • Shut down equipment in the immediate area, if possible.
          • Close doors to isolate the area.
          • Use a portable fire extinguisher to:
            • Assist yourself to evacuate.
            • Assist another to evacuate.
            • Control a small fire if possible.
        4. Provide the fire/police teams with the details of the problem upon their arrival. Special hazard information you may know is essential.

            If fire alarms are ringing in your building:

          • Evacuate the building.
          • Move at least 200 feet away from the building.
          • Stay clear of driveways, sidewalks and other access ways to the building.
          • If you are a supervisor, try to account for your employees and report any missing persons to the emergency personnel at the scene.
          • Assist emergency personnel, as requested.
          • Do not re-enter the building until it is safe and you are directed to do so.
      4. Mercury Spills:
        • For small spills such as a thermometer break, use a trapped vacuum line attached to a tapered glass tube, similar to a medicine dropper, to pick up mercury droplets. Cover small droplets in accessible areas with powdered sulfur. Place residue in container for hazardous waste collection.
        • For large spills contact your supervisor for assistance or instructions.
      5. Radioactive Spills:
        • Evacuate the area and notify the Chief of Security and Safety immediately.

Appendix D. CRF 1910.1450 Occupational Exposure to Hazardous Chemicals in Laboratories

 

For more information, contact Mary Lindsey.


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