Laboratory Safety Manual
Section 2
Chemical Safety
Introduction
All laboratories using hazardous chemicals are required to comply with the Occupational Safety and Health Administrations 29 CFR 1910.1450, Occupational Exposure to Hazardous Chemicals in Laboratories. This standard requires that the employer develop a written Chemical Hygiene Plan (CHP), which is capable of protecting employees from the health hazards associated with hazardous chemicals in the laboratory.
This section of the Laboratory Safety Manual is Duke University's CHP and is intended to highlight those laboratory practices that are necessary for protecting workers from exposure to hazardous chemicals. Additionally, site specific standard operating procedures must be developed for all particularly hazardous substances. This task is the responsibility of the principal investigator.
Chemical Hygiene Responsibilities
Department Head
Principal Investigator/Supervisor
Laboratory Employees and Students
The Occupational and Environmental Safety Office
Material Safety Data Sheets
The Occupational Safety and Health Administration (OSHA) requires that all chemical manufacturers, wholesalers, and distributors provide Material Safety Data Sheets (MSDS) for the products which they produce and sell. OSHA also requires that employers maintain in the workplace, copies of the MSDS for each hazardous chemical. These are required to be accessible at all times work is being conducted.
Typically, MSDS are shipped with the chemical order, or alternatively you may
contact the manufacturer to request one. The Occupational and Environmental Safety Office (OESO)
also maintains a MSDS collection as a resource to all Duke employees.
You may utilize this resource by filling out the
MSDS request form, and fax or return it through campus mail to the noted address. Additionally, OESO has posted several MSDS
resources
With any chemical, it is prudent to consult the MSDS before use. Material Safety Data Sheets list the products chemical, physical and toxicological properties along with suggestions for safe handling practices and emergency first aid procedures.
In general, a MSDS consists of several sections:
| 1. Chemical
Identification 2. Composition/ Information on Ingredients 3. Hazards Identification 4. First-Aid Measures 5. Fire-Fighting Measures 6. Accidental Release Measures 7. Handling and Storage 8. Exposure Controls/Personal Protection |
9. Physical/ Chemical
Properties 10. Stability and Reactivity 11. Toxicological Information 12. Ecological Information 13. Disposal Considerations 14. Transport Information 15. Regulatory Information 16. Other Information |
Labels on chemical containers can be a very useful source of information. Chemical manufacturers are required by the Hazard Communications Standard (29 CFR 1910.1200) to list at the very least their name and address, the chemicals name, and the potential hazards associated with the chemicals use on every container they ship. Most chemical manufacturers also include additional information such as the physical properties, and emergency first aid measures on the label.
Laboratory personnel who use chemicals should be conscientious
about the labeling of chemical containers. The OSHA Lab Standard
(29 CFR 1910.1450) states employers shall ensure that
labels on incoming containers of hazardous chemicals are not
removed, or defaced. What this means for laboratories is
that containers where solvents, other chemicals, or aging has
damaged the label should be re-labeled. All
containers in which small amounts of chemicals are kept for temporary purposes
must be labeled as well; however, in this case only the name of the chemical and
the hazard class is necessary.
NFPA
System for Classification of Hazards
The NFPA diamond is a symbol used to identify
the hazards associated with a given chemical to rescue workers. Frequently this symbol is found on the sides of buildings where
chemicals are stored and on chemical containers. Below are shown
the various hazards symbolized by the diamond and the numerical
code which indicates the severity of the hazard.
| HEALTH HAZARD 4 Deadly 3 Extreme Danger 2 Hazardous 1 Slightly Hazardous |
FIRE HAZARD Flash Points: 4 Below 73° F 3 Below 100° F 2 Above 100 F°, Not Exceeding 200° F 1 Above 200° F 0 Will not burn |
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| SPECIFIC HAZARD Oxidizer OX Acid ACID Alkali ALK Corrosive CORR Use NO WATER Radioactive |
REACTIVITY 4 May detonate 3 Shock and heat may detonate 2 Violent chemical change 1 Unstable if heated 0 Stable |
Standard operating procedures (SOPs) are detailed work practices which are developed to provide guidance for the safe handling of hazardous chemicals. Site-specific standard operating procedures (SOPs) must be written for each particularly hazardous substance used in the lab. SOPs include procurement, distribution, storage, disposal and emergency procedure practices for the particular chemical or hazard group. Click here to view several example SOPs. You may also click here for a blank SOP template. More extensive information on specific chemicals can be obtained by viewing the MSDS Resources on the OESO Website or calling our office.
Procurement
When procuring chemicals for the laboratory, less hazardous alternatives to chemicals used in various protocols should be discussed. By choosing suitable substitutes for hazardous chemicals, risk to laboratory personnel is reduced. Not all protocols for experiments can be easily adjusted, or when adjusted, achieve the same results. For this reason, the lab must carefully review each protocol and determine if safer, less hazardous chemicals may be substituted.
Another consideration when procuring chemicals for the laboratory is duplication. If a lab with multiple researchers does not control ordering and maintain an accurate inventory, duplication of inventory items will result. This consumes lab storage space, and increases the amount of hazardous, and flammable chemicals in the lab.
Handling Powdered Chemicals
Many hazardous chemicals are purchased in powder form, and are later mixed into solution when needed. To reduce the risk of generating "dust-clouds", which may pose an inhalation hazard to workers and potentially contaminate laboratory surfaces, the following should be considered:
- It is optimal to purchase the chemical in a pre-made solution, thus eliminating the need to handle a hazardous powder.
- Purchase the chemical in pre-weighed quantities. This will eliminate the need to weigh out the material which reduces your risk of exposure. Many pre-weighed powders are shipped in vials that are capped with a septum. This allows the injection of a diluent without opening the vial.
- If a powder must be weighed out in the laboratory, the following practices should be considered:
- Choose an enclosed balance if available. This will help contain airborne dust.
- Move your balance to the fume hood or biological safety cabinet if possible.
- Use spatulas or scoops to carefully move the powder from its container to the balance. Avoid direct pouring or shaking from the container!
- Always wear appropriate personal protective equipment when handling hazardous chemicals. For guidance, contact the OESO-Hygiene & Safety Division at 684-5996.
- Clean off all potentially contaminated work surfaces when finished. Keeping the work area clean will not only reduce the risk of exposing others, it will also reduce the risk of contamination of the the next user's material.
Transportation of Chemicals
When transporting chemicals, precautions should
be taken to avoid dropping or spilling chemicals.
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Proper storage of chemicals in laboratories is
always a major concern. Chemicals that have been stored
improperly could react, forming hazardous products. Sometimes
improper storage results only in a mess, but at other times, it
has resulted in loss of life and property. Here are some general
guidelines for avoiding obvious incompatibilities.
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The following tables show partial list of incompatible chemicals, and general classes of incompatible materials.
Partial List of Incompatible Chemicals
(Reactive Hazards)
Substances in the left hand column should be
stored and handled so that they cannot accidentally contact
corresponding substances in the right hand column under
uncontrolled conditions.
| Chemical | Separate From |
| Acetic Acid | Chromic acid, nitric acid, peroxides, permanganates |
| Acetic anhydride | Hydroxyl-containing compounds such as ethylene glycol, perchloric acid |
| Acetone | Concentrated nitric and sulfuric acid mixtures, hydrogen peroxide |
| Acetonitrile | Strong acids and bases |
| Acetylene | Chlorine, bromine, copper, silver, fluorine, mercury |
| Alkali and alkaline earth metals, such as sodium, potassium, lithium, magnesium, calcium, powdered aluminum | Carbon dioxide, carbon tetrachloride, other chlorinated hydrocarbons (also prohibit the use of water, foam, and dry chemical extinguishers on fires involving these metalsdry sand should be employed) |
| Ammonia (anhydrous) | Mercury, chlorine, calcium hypochlorite, iodine, bromine, hydrogen fluoride |
| Ammonium hydroxide | Strong acids, hydrogen peroxide, acidic metals |
| Aniline | Nitric acid, hydrogen peroxide |
| Chromic acid and chromium trioxide | Acetic acid, naphthalene, camphor, lycerol, turpentine, alcohol, other flammable liquids |
| Chlorine | Ammonia, acetylene, butadiene, butane, other petroleum gases, hydrogen, sodium carbide, turpentine benzene, finely divided metals |
| Chloroform | Alkali metals (e.g. sodium, potassium), acetone, strong bases |
| Copper | Acetylene, hydrogen peroxide |
| Fluorine | Isolate from everything |
| Formaldehyde | Nitric acid, sulfuric acid, hydrochloric acid, perchloric acid, anhydrides, inorganic acids |
| Hydrazine | Hydrogen peroxide, nitric acid, any other oxidant |
| Hydrocarbons (benzene, butane, propane, gasoline, turpentine, etc.) | Fluorine, chlorine, bromine, chromic acid, peroxides |
| Hydrochloric acid | Strong bases, permanganates, chlorates, chlorites |
| Hydrocyanic acid | Nitric acid, alkalis |
| Methanol | Perchloric acid, sulfuric acid, nitric acid, highly reactive metals (e.g., potassium, sodium, magnesium) |
| Nitric Acid | Acetic anhydride, acetone, acetonitrile, alcohols, thiols, amines, dichloromethane, DMSO, benzene, bases |
| Phenol | Nitric acid, perchloric acid, sulfuric acid |
| Pyridine | dinitrogen tetroxide, acid chlorides, anhydrides, perchloric acid |
Click here to view Classes of Incompatible Chemicals
Housekeeping
General housekeeping is one of the most overlooked aspects of Laboratory Safety. Labs that are cluttered with unnecessary trash, broken/ unused equipment, empty chemical bottles, and old ordering catalogs are not only messy in appearance, but also represent a potential fire hazard. Removing such unnecessary items from the laboratory creates more space for research, and storage.
Occasionally the lab should be cleaned. The floors should be
mopped and the benchtop wiped down. Where repeated spills of
reagent have been allowed to dry on the benchtop there is a
possibility of
contaminating ones work, or clothing.
Food and Drink
Food and drink shall not be consumed nor stored in areas in which hazardous chemicals are used. Designated areas of the lab may be used for eating and drinking provided that everyone in the lab practices good hygiene. This entails wearing gloves while working with chemicals, and taking the gloves off and washing hands before entering clean areas of the lab. Items that are used in areas of the lab that are contaminated with chemicals should be left in those areas. Carrying a notebook from the area where it may have been contaminated with chemicals to a clean area puts lab workers at risk of exposure.
Flammable Materials
Flammable materials include aerosols, gases,
liquids, and solids. In most laboratory situations, gases,
liquids, and solids will be the main concern. Flammable gases are
defined by OSHA to be (A) a gas that, at ambient
temperature and pressure, forms a flammable mixture with air at a
concentration of 13% by volume or less; or (B) a gas that, at
ambient temperature and pressure, forms a range of flammable
mixtures with air wider than 12% by volume, regardless of the
lower limit. Flammable liquids mean any liquid having a
flashpoint below 100°F. Flammable solid means a solid,
other than a blasting agent or explosive, that is liable to cause
fire through friction, absorption of moisture, spontaneous
chemical change, or which burns so vigorously and persistently as
to create a serious hazard. The Material Safety Data Sheet
is a good source for determining if a chemical is flammable. In
addition, most flammable substances are labeled as such. The
following recommendations should be observed when working with
flammable materials:
Other regulations apply to the use and storage of flammable materials here at Duke.
All laboratory use refrigerators and freezers are required by the Durham Fire Marshal to be labeled as Approved, or Not Approved for Flammable Storage.
Corrosive Materials
Corrosive materials are those that cause visible destruction of, or irreversible alterations in, living tissue by chemical action at the site of contact. There are many examples of these in the labs here at Duke. The ones that most people who work in labs are familiar with are strong acids and strong bases. Strong oxidizing materials can also cause burns and damage to the eyes and skin. Corrosive material should be stored in well ventilated areas with secondary containment. The secondary containment, usually a plastic wash basin or the like, not only contains leaks and spills, but also prevents some of the metallic corrosion these materials can promote. The Material Safety Data Sheet is a good source for determining if a material is corrosive. In addition, corrosive materials are labeled as such.
Oxidizers
Oxidizers are agents that initiate or promote combustion in other materials, thereby causing fire either of itself or through the release of oxygen or other gases. Examples of oxidizers include potassium permanganate (KMnO 4 ), sodium chlorate (NaClO 4 ), concentrated nitric acid (HNO 3 ), and ammonium nitrate (NH 4 NO 3 ). Oxidizers form explosive combinations with flammable, or combustible material. For this reason, they should be stored away from solvents, and in a cool, dry location. (Not under the sink!) The Material Safety Data Sheet is a good source for determining if a material is an oxidizer.
Water Reactive Materials
Water reactive materials are chemicals which
react violently with water to produce heat and flammable or toxic
gas. Most water reactive materials are found in chemistry,
however a few hydrides and alkali metals like sodium are used in
other research areas throughout the University. Examples of water
reactive materials include calcium hydride, lithium aluminum
hydride, sodium, potassium, and lithium metals. These type of
materials should be stored in cool, dry locations; never under a sink. Alkali metals are stored under mineral
oil to prevent reaction with moisture in the air. The Material
Safety Data Sheet is a good way to determine if a material is
water-reactive.
| Water-Reactive Chemicals Alkali metals Alkali metal hydrides Alkali metal amides Metal alkyls, such as lithium alkyls and aluminum alkyls Grignard reagents Halides of nonmetals, such as BCl 3 , BF 3 , PCl 3 , PCl 5 , SiCl 4 , S 2 Cl 2 Inorganic acid halides, such as POCl 3 , SOCl 2 , SO 2 Cl 2 Anhydrous metal halides, such as AlCl 3 , TiCl 4 , ZrCl 4 , SnCl 4 Phosphorus pentoxide Calcium carbide Organic acid halides and anhydrides of low molecular weight |
Pyrophoric Materials
Pyrophoric means a chemical that will ignite
spontaneously in air at a temperature of 130°F (54°C) or
below.
| Classes of Pyrophoric Chemicals
Grignard reagents, RMgX Metal alkyls and aryls, such as RLi, RNa, R 3 Al, R 2 Zn Metal carbonyls, such as Ni(CO)4 , Fe(CO)5 , Co 2 (CO)8 Alkali metals such as Na, K Metal powders, such as Al, Co, Fe, Mg, Mn, Pd, Pt, Ti, Sn, Zn, Zr Metal Hydrides, such as NaH, LiAlH 4 Nonmetal hydrides, such as B 2 H 6 and other boranes, PH 3 , AsH 3 Nonmetal alkyls, such as R 3 B, R 3 P, R 3 As Phosphorus (white) |
Peroxide Forming Materials
Peroxide forming materials are chemicals which can form shock sensitive peroxide crystals over time or upon exposure to air. There are a few examples of these types of chemicals at Duke. The most common peroxide forming chemicals in use are diethyl ether and tetrahydrofuran (THF). Peroxide formation cannot be prevented once the chemical has been opened unless the chemical is maintained under an inert atmosphere (impractical). For this reason, it is recommended that all peroxide formers be dated when received, and periodically evaluated using test strips to indicate peroxide formation. It is prudent practice to maintain only the inventory necessary to complete ongoing work. DO NOT STOCKPILE! The Material Safety Data Sheet is a good source for determining if a material is capable of forming peroxides.
Classes of Chemicals That Can Form Peroxides Upon Aging
Class I: Unsaturated materials, especially those of low
molecular weight, may polymerize violently and hazardously due to
peroxide initiation.
| Acrylic acid Acrylonitrile Butadiene Chlorobutadiene (chloroprene) Chlorotrifluoroethylene Methyl methacrylate Styrene |
Tetrafluoroethylene Vinyl acetate Vinyl acetylene Vinyl chloride Vinyl pyridine Vinylidene chloride |
Class II: The following chemicals are a peroxide hazard
upon concentration (distillation/ evaporation). A test for
peroxide should be performed if concentration is intended or
suspected.
| Acetal Cumene Cyclohexene Cyclooctene Cyclopentene Diacetylene Dicyclopentadiene Diethylene glycol dimethyl ether (diglyme) Diethyl ether (ether) |
Dioxane (r-dioxane) Ethylene glycol dimethyl ether (glyme) Furan Methyl acetylene Methyl cyclopentane Methyl-i-butyl ketone Tetrahydrofuran Tetrahydronaphthalene Vinyl ethers |
Class III: Peroxides derived from the following
compounds may explode without concentration.
| Organic | Inorganic |
| Divinyl ether Divinyl acetylene Isopropyl ether Vinylidene chloride |
Potassium metal Potassium amide Sodium amide (sodamide) |
NOTE: Lists are illustrative but not exhaustive.
Cryogenic Gases and Liquids
Cryogenic materials can be defined as liquefied
or solidified gases at low temperatures. Examples of cryogenics
are liquid helium, nitrogen, oxygen, and dry ice (solidified
carbon dioxide). The hazards involved in using cryogenics are
tissue damage (frostbite) asphyxiation due to oxygen
displacement, and potential explosion due to pressure buildup.
Another hazard associated with the use of liquid hydrogen,
helium, and nitrogen in particular is potential condensation of
liquid oxygen. If liquid oxygen comes in contact with an
oxidizable material an explosion is possible. The following
guidelines should be used when working with cryogenic gases and
liquids:
Explosives
Explosive means a chemical that causes a sudden release of
pressure, gas, and heat when subjected to sudden shock, pressure
or high temperature. The table below contains a list of
potentially explosive combination of common laboratory reagents.
| Potentially Explosive Combinations of Some
Common Reagents Acetone + Chloroform in the
presence of a base |
Poisons
Poisons are chemicals that cause damage to target organs such as liver, lungs or the reproductive system if inhaled, ingested, injected or absorbed through the skin.
Compressed Gases
Compressed gas cylinders in the laboratory pose both chemical and physical hazards. Gases accidentally released can result in a depleted oxygen atmosphere which can lead to asphyxiation of laboratory personnel. Many gases used in laboratories also present a fire hazard due to their high degree of flammability. Finally, if a valve is damaged as the result of the tank being knocked over, the cylinder can become a projectile capable of causing severe injury.
Transporting Compressed Gas Cylinders
Compressed gas tanks should always be transported on cylinder
carts which are equipped with straps or chains. It is always
prudent to keep the valve cover in place while in transport and
until the tank is secured in place and ready for use.
Storage Precautions and Procedures
The following are prudent work procedures for
handling compressed gas cylinders once in the laboratory.
Particularly Hazardous Substances
Particularly hazardous substances (PHS) are those chemicals which may present extreme risk potential to laboratory workers if not handled appropriately; therefore, these substances may require additional control measures when used in the laboratory. PHS include select carcinogens, reproductive toxins, and those substances with a high degree of acute toxicity. The Duke PHS List can be searched at Duke University's Particularly Hazardous Substance List. Click here to open a printable version of the list, which is sorted by CAS number (unique identifier).
OSHA defines PHSs as the following:
Select Carcinogens
Substances that meet one of the following criteria: Regulated by
OSHA as a carcinogen Is listed as known carcinogen in
the latest Annual Report on Carcinogens issued by the National
Toxicology Program (NTP) Is listed under IARC Group 1 Is listed
under Group 2A or 2B of IARC or under the category,
reasonably anticipated to be carcinogens by NTP, and
causes statistically significant tumor incidence in experimental
animals
Reproductive Toxins
Substances that cause chromosomal damage (mutagens) and
substances with lethal or teratogenic (malformation) effects on
fetuses. This category also includes substances that can affect
the male or female reproductive organs and ability to reproduce.
Highly/Acutely Toxic
Substances which fall into one of the following: Median lethal
dose of 200 milligrams or less per kilogram of body weight when
administered orally to albino rats weighing between 200 and 300
grams each (Note: Oral exposures are not considered to be
significant in labs, therefore substances meeting this criteria
are not included in this list.) Median lethal dose of 200
milligrams or less per kilogram of body weight when administered
by continuous contact for 24 hours with the bare skin of albino
rabbits weighing between two and three kilograms each Substance
that has a median lethal concentration in air of 200 parts per
million by volume or less of gas or vapor, or 2 milligrams per
liter or less of mist, fume, or dust, when administered by
continuous inhalation for one hour to albino rats weighing
between 200 and 300 grams each
Chemical Fume Hoods
A Chemical Fume Hood is the primary containment device used to
protect both personnel and the laboratory environment from
hazardous chemicals. As a general rule, a chemical fume hood
should be used whenever a substance is appreciably volatile, or is
recognized as a Particularly Hazardous Substance whose primary
route of exposure is through inhalation. All chemical fume hoods
shall be certified by an OESO-approved contractor on an
annual basis. The following rules should be adhered to when using
chemical fume hoods:
Before using perchloric acid in any hood, contact the OESO for
approval. Unless periodically washed and steam cleaned, a hood in
which perchloric acid is being used can accumulate
dangerous perchlorate salts in the exhaust ducts. These
salts are potentially explosive. There are hoods that are
specifically designed for perchloric acid use.
Local Ventilation
Duke University Facilities Management Department, and Medical Center Engineering and Operations handles all local ventilation maintenance for the University and Medical Center respectively. Concerns about ventilation in your lab area should be addressed to the appropriate maintenance department, or to the OESO at 684-5996.
Air Sampling/Biological Monitoring
The OESO will measure an employees exposure to any substance regulated by a standard which requires monitoring when there is reason to believe that an employees exposure levels for that substance regularly exceeds the Permissible Exposure Level (PEL). Employees concerned about possible exposures should call the OESO Hygiene, Safety & Environmental Programs Division at 684-5996. If the employee has been involved in a laboratory accident in which they were exposed to a hazardous substance, they should first go to Employee Occupational Health and Wellness (684-3136) and complete a Report of Work Related Injury or Illness form.
Emergency Eyewashes and Showers
Emergency eyewashes and showers are required through OSHA
standard 1910.151(c) to be present in all areas where the
eyes or body of any person may be exposed to injurious corrosive
materials. Emergency eyewashes and showers should be
located no more than 75 ft, or ten seconds travel time, from an
area where hazardous materials are being used according to ANSI Z358.1-2004 (American National Standard for Emergency Eyewash and
Shower Equipment). Emergency eyewashes and showers should clearly
identified by a highly visible sign.
Eyewashes should be flushed periodically to clear anything
that might be present, and verify proper operation. All labs are required to do this weekly. Documentation of this testing should be
kept in the lab by initialing each week on an eyewash
maintenance sheet. Emergency drench showers are tested on a periodic basic by Duke
Maintenance.
Coverings over the spray nozzles of eyewashes should be maintained. This prevents airborne contamination. The removal of these coverings should not require a separate motion by the operator when activating the unit.
Click here to view Duke's Emergency Eyewash and Shower policy.
Personal protective equipment is the primary means of preventing chemical exposures via absorption, or inhalation.
1. General
One of the main forms of general protection is the lab coat. Lab coats should be worn whenever there is a possibility of splashes, spills, or other clothing contamination to lab personnel. In situations, such as acid washes, where the possibility of a splash is high, plasticized aprons and shoe coverings should be worn. Closed-toed shoes should always be worn in laboratories. This reduces the risk of injury to the feet from spills, or objects dropped in the lab. Eye and/or face protection should be worn whenever there is a procedure being performed on the bench top/chemical fume hood where there is a risk of splashes, explosion, or implosion.
2. Glove Types
It is important to use the proper glove for the type of chemical that is being used. There are no gloves that are perfect for every situation, but many gloves have a broad spectrum of resistance to many chemicals. Some important things to keep in mind when using gloves are:
3. Respirators
Occasionally, work being performed in the lab may require the use of a respirator because it cannot be performed in a chemical fume hood, or glove box. Before respirators are worn, the wearer must be fit tested to ensure that the respirator will function properly. Fit testing, and assistance in selecting the appropriate respirator for a given task may be found by contacting the Hygiene, Safety & Environmental Programs Division of OESO at 684-5996.
Occasionally, and in spite of our best efforts to prevent them, accidents will occur in the laboratory. The most frequent accident in the laboratory is generally a chemical spill. For this reason, Duke has a chemical spill response team that is on call 24 hours a day, 7 days a week. This team is managed by the Environmental Programs Division of the OESO, and can be reached by calling 911 from a campus or medical center phone.
The following procedures (also outlined in the
red Emergency Response Guide flipchart) should be followed in the
event of a MINOR chemical spill in your laboratory:
In the event of a MAJOR chemical spill,
the following procedures should be followed:
All laboratories that produce regulated chemical waste must adhere to the requirements of Duke Universitys Chemical Waste Policy, and the The Laboratory Chemical Waste Management Practices.
An effective written chemical waste management program is essential to the proper management of Dukes hazardous waste. The Chemical Waste Policy serves as a resource to help laboratory personnel understand their role in the waste management system.
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Prudent chemical waste handling and storage practices:
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Chemicals Produced in the Laboratory
Special requirements have been established for determining and communicating the hazards related to chemicals produced in the laboratory. Specific provisions vary based on intended use.
Use of Chemicals Whose Hazards are Well Characterized
When a chemical is produced which is known to have hazardous characteristics (e.g., carcinogenicity, toxicity), the principal investigator or laboratory supervisor must ensure that the personnel who use this chemical are provided appropriate training and personal protective equipment/ engineering controls. The Occupational and Environmental Safety Office (OESO) can provide information about the hazards of, and recommendations on appropriate personal protective equipment/ engineering controls for, chemicals which are already well characterized.
Use of Chemicals Whose Hazards Have Not Been Characterized
Chemicals produced in the laboratory, whose hazards are unknown, must be considered as Particularly Hazardous Substances (i.e., mutagens, carcinogens, teratogens, toxins, etc.) and handled accordingly. Each principal investigator, or laboratory supervisor, has the responsibility to identify potential hazards associated with the newly synthesized chemical as soon as possible so that appropriate personnel protective equipment and engineering controls can be determined.
Chemicals Produced for Inter-Laboratory Use
If chemical substances are produced for distribution to other
laboratories, then all requirements of 29 CFR 1910.1200,
Hazard Communication Standard must be met. The
provisions of this standard are presented in Dukes Hazard
Communication Program and include:
Hazard Determination Development of Labels Preparation of
Material Safety Data Sheets (MSDS)
References
Duke University Safety Manual, Current Edition.
The MSDS Pocket Dictionary, Second Edition. Schenectady,
NY: Genium Publishing Corporation, 1996.
CRC Handbook of Chemistry and Physics, 73rd Edition. Boca
Raton, FL: CRC Press, Inc., 1992.
Prudent Practices in the Laboratory: Handling and Disposal of
Chemicals. Washington, DC: National Academy Press, 1995.
Fundamentals of Industrial Hygiene, 4th Edition. Itasca,
Illinois: National Safety Council, 1996.
Code
of Federal Regulations, Title 29, Part 1910.1450
Occupational Exposure to Hazardous Chemicals in
Laboratories.
(a) Scope and Application
(1) This section shall apply to all employers engaged in the laboratory use of hazardous chemicals as defined below.
(2) Where this section applies, it shall supersede, for laboratories, the requirements of all other OSHA health standards in 29 CFR part 1910, subpart Z, except as follows:(i) For any OSHA health standard, only the requirement to limit employee exposure to the specific permissible exposure limit shall apply for laboratories, unless that particular standard states otherwise or unless the conditions of paragraph (a)(2)(iii) of this section apply.
(ii) Prohibition of eye and skin contact where specified by any OSHA health standard shall be observed.
(iii) Where the action level (or in the absence of an action level, the permissible exposure limit) is routinely exceeded for an OSHA regulated substance with exposure monitoring and medical surveillance requirements paragraphs (d) and (g)(1)(ii) of this section shall apply.(3) This section shall not apply to:
(i) Uses of hazardous chemicals which do not meet the definition of laboratory use, and in such cases, the employer shall comply with the relevant standard in 29 CFR part 1910, subpart 2, even if such use occurs in a laboratory.
(ii) Laboratory uses of hazardous chemicals which provide no potential for employee exposure. Examples of such conditions might include:(A) Procedures using chemically-impregnated test media such as Dip-and-Read tests where a reagent strip is dipped into the specimen to be tested and the results are interpreted by comparing the color reaction to a color chart supplied by the manufacturer of the test strip; and
(B) Commercially prepared kits such as those used in performing pregnancy tests in which all of the reagents needed to conduct the test are contained in the kit.
(b) Definitions
Action level means a concentration designated in 29 CFR part 1910 for a specific substance, calculated as an eight (8)-hour time-weighted average, which initiates certain required activities such as exposure monitoring and medical surveillance.
Assistant Secretary means the
Assistant Secretary of Labor for Occupational Safety and Health,
U.S.
Department of Labor, or designee.
Carcinogen (see select carcinogen).
Chemical Hygiene Officer means an employee who is designated by the employer, and who is qualified by training or experience, to provide technical guidance in the development and implementation of the provisions of the Chemical Hygiene Plan. This definition is not intended to place limitations on the position description or job classification that the designated individual shall hold within the employers organizational structure.
Chemical Hygiene Plan means a written program developed and implemented by the employer which sets forth procedures, equipment, personal protective equipment and work practices that (i) are capable of protecting employees from the health hazards presented by hazardous chemicals used in that particular workplace and (ii) meets the requirements of paragraph (e) of this section.
Combustible liquid means any liquid
having a flashpoint at or above 100 deg. F (37.8 deg. C), but
below 200 deg. F (93.3 deg. C), except any mixture having
components with flashpoints of 200 deg. F (93.3 deg. C), or
higher, the total volume of which make up 99 percent or more of
the total volume of
the mixture.
Compressed gas means:
(i) A gas or mixture of gases having, in a container, an absolute pressure exceeding 40 psi at 70 deg. F (21.1 deg. C); or
(ii) A gas or mixture of gases having, in a container, an absolute pressure exceeding 104 psi at 130 deg. F (54.4 deg C) regardless of the pressure at 70 deg. F (21.1 deg. C); or
(iii) A liquid having a vapor pressure exceeding 40 psi at 100 deg. F (37.8 C) as determined by ASTM D-323-72.
Designated area means an area which may be used for work with select carcinogens, reproductive toxins or substances which have a high degree of acute toxicity. A designated area may be the entire laboratory, such as a laboratory hood.
Emergency means any occurrence such as, but not limited to, equipment failure, rupture of containers or failure of control equipment which results in an uncontrolled release of a hazardous chemical into the workplace.
Employee means an individual employed in a laboratory workplace who may be exposed to hazardous chemicals in the course of his or her assignments.
Explosive means a chemical that causes a sudden, almost instantaneous release of pressure, gas, and heat when subjected to sudden shock, pressure, or high temperature.
Flammable means a chemical that falls into one of the following categories:
(i) Aerosol, flammable means an aerosol that, when tested by the method described in
16 CFR 1500.45, yields a flame protection exceeding 18 inches at full valve opening, or a flashback (a flame extending back to the valve) at any degree of valve opening;
(ii) Gas, flammable means:(A) A gas that, at ambient temperature and pressure, forms a flammable mixture with air at a concentration of 13 percent by volume or less; or
(B) A gas that, at ambient temperature and pressure, forms a range of flammable mixtures with air wider than 12 percent by volume, regardless of the lower limit.(iii) Liquid, flammable means any liquid having a flashpoint below 100 deg F (37.8 deg. C), except any mixture having components with flashpoints of 100 deg. C) or higher, the total of which make up 99 percent or more of the total volume of the mixture.
(iv) Solid, flammable means a solid, other than a blasting agent or explosive as defined in 1910.109(a), that is liable to cause fire through friction, absorption of moisture,
spontaneous chemical change, or retained heat from manufacturing or processing, or which can be ignited readily and when ignited burns so vigorously and persistently as to create a serious hazard. A chemical shall be considered to be a flammable solid if, when tested by the method described in 16 CFR 1500.44, it ignites and burns with a self-sustained flame at a rate greater than one-tenth of an inch per second along its major axis.
Flashpoint means the minimum temperature at which a liquid gives off a vapor in sufficient concentration to ignite when tested as follows:
(i) Tagliabue Closed Tester (See American National Standard Method of Test for Flash Point by Tag Closed Tester, Z11.24 - 1979 (ASTM D 56-79)) - for liquids with a viscosity of less than 45 Saybolt Universal Seconds (SUS) at 100 deg. F (37.8 deg. C), that do not contain suspended solids and do not have a tendency to form a surface film under test; or
(ii) Pensky-Martens Closed Tester (See American National Standard Method of Test for Flashpoint by Pensky-Martens Closed Tester, Z11.7 - 1979 (ASTM D 93-79)) - for liquids with a viscosity equal to or greater than 45 SUS at 100 deg. F (37.8 deg. C ), or that contain suspended solids, or that have a tendency to form a surface film under test; or
(iii) Setaflash Closed Tester (see American National Standard Method of test for Flash Point by Setaflash Closed Tester (ASTM D 3278-78)).Organic peroxides, which undergo auto accelerating thermal decomposition, are excluded
from any of the flashpoint determination methods specified above.
Hazardous chemical means a chemical for which there is statistically significant evidence based on at least one study conducted in accordance with established scientific principles that acute or chronic health effects may occur in exposed employees. The term health hazard includes chemicals which are carcinogens, toxic or highly toxic agents, reproductive toxins, irritants, corrosives, sensitizers, Hepato-toxins, nephrotoxins, neurotoxins, agents which act on the hematopoietic systems, and agents which damage the lungs, skin, eyes, or mucous membranes. Appendices A and B of the Hazard Communication Standard (29 CFR 1910.1200) provide further guidance in defining the scope of health hazards and determining whether or not a chemical is to be considered hazardous for purposes of this standard.
Laboratory means a facility where the laboratory use of hazardous chemicals occurs. It is a workplace where relatively small quantities of hazardous chemicals are used on a non-production basis.
Laboratory scale means work with substances in which the containers used for reactions, transfers, and other handling of substances are designed to be easily and safety manipulated by one person.
Laboratory scale excludes those workplaces whose function is to produce commercial quantities of materials.
Laboratory-type hood means a device located in a laboratory, enclosure on five sides with a movable sash or fixed partial enclosed on the remaining side; constructed and maintained to draw air from the laboratory and to prevent or minimize the escape of air contaminants into the laboratory; and allows chemical manipulations to be conducted in the enclosure without insertion of any portion of the employees body other than hands and arms. Walk-in hoods with adjustable sashes meet the above definition provided that the sashes are adjusted during use so that the airflow and the exhaust of air contaminants are not compromised and employees do not work inside the enclosure during the release of airborne hazardous chemicals.
Laboratory use of hazardous chemicals means handling or use of such chemicals in which all of the following conditions are met:
(i) Chemical manipulations are carried out on a laboratory scale;
(ii) Multiple chemical procedures or chemicals are used;
(iii) The procedures involved are not part of a production process, nor in any way simulate a production process; and
(iv) Protective laboratory practices and equipment are available and in common use to minimize the potential for employee exposure to hazardous chemicals.
Medical consultation means a consultation which takes place between an employee and a licensed physician for the purpose of determining what medical examinations or procedures, if any, are appropriate in cases where a significant exposure to a hazardous chemical may have taken place.
Organic peroxide means an organic compound that contains the bivalent -O-O- structure and which may be considered to be a structural derivative of hydrogen peroxide where one or both of the hydrogen atoms has been replaced by an organic radical.
Oxidizer means a chemical other than a blasting agent or explosive as defined in 1910.109(a), that initiates or promotes combustion in other materials, thereby causing fire either of itself or through the release of oxygen or other gases.
Physical hazard means a chemical for which there is scientifically valid evidence tat it is a combustible liquid, a compressed gas, explosive, flammable, an organic peroxide, an oxidizer pyrophoric, unstable (reactive) or water-reactive.
Protective laboratory practices and equipment means those laboratory procedures, practices and equipment accepted by laboratory health and safety experts as effective, or that the employer can show to be effective, in minimizing the potential for employee exposure to hazardous chemicals.
Reproductive toxins means chemicals
which affect the reproductive chemicals which affect the
reproductive capabilities including chromosomal damage
(mutations) and effects on fetuses (teratogenesis).
Select carcinogen means any substance which meets one of the following criteria:
(i) It is regulated by OSHA as a carcinogen; or
(ii) It is listed under the category, known to be carcinogens, in the Annual Report on Carcinogens published by the National Toxicology Program (NTP)(latest edition); or
(iii) It is listed under Group 1 (carcinogenic to humans) by the International Agency
for research on Cancer Monographs (IARC)(latest editions); or
(iv) It is listed in either Group 2A or 2B by IARC or under the category, reasonably anticipated to be carcinogens by NTP, and causes statistically significant tumor incidence in experimental animals in accordance with any of the following criteria:(A) After inhalation exposure of 6-7 hours per day, 5 days per week, for a significant portion of a lifetime to dosages of less than 10 mg/m(3);
(B) After repeated skin application of less than 300 (mg/kg of body weight) per week; or
(C) After oral dosages of less than 50 mg/kg of body weight per day.
Unstable (reactive) means a chemical which is the pure state, or as produced or transported, will vigorously polymerize, decompose, condense, or will become self-reactive under conditions of shocks, pressure or temperature.
Water-reactive means a chemical that reacts with water to release a gas that is either flammable or presents a health hazard.
(c) Permissible exposure limits
For laboratory uses of OSHA regulated substances, the employer shall assure that laboratory employees exposures to such substances do not exceed the permissible exposure limits specified in 29 CFR part 1910, subpart Z.
(d) Employee exposure determination
(1) Initial monitoring. The employer shall measure the employees exposure to any substance regulated by a standard which requires monitoring if there is reason to believe that exposure levels for that substance routinely exceed the action level (or in the absence of an action level, the PEL).
(2) Periodic monitoring. If the initial monitoring prescribed by paragraph (d)(1) of this section discloses employee exposure over the action level (or in the absence of an action level, the PEL), the employer shall immediately comply with the exposure monitoring provisions of the relevant standard.
(3) Termination of monitoring. Monitoring may be terminated in accordance with the relevant standard.
(4) Employee notification of monitoring results. The employer shall, within 15 working days after the receipt of any monitoring results, notify the employee of these results in writing either individually or by posting results in an appropriate location that is accessible to employees.
(e) Chemical Hygiene Plan General
(Appendix A of this section is non-mandatory but provides guidance to assist employers in the development of the Chemical Hygiene Plan).
(1) Where hazardous chemicals as defined by this standard are used in the workplace, the employer shall develop and carry out the provisions of a written Chemical Hygiene Plan which is:
(i) Capable of protecting employees from health hazards associated with hazardous chemicals in that laboratory and
(ii) Capable of keeping exposures below the limits specified in paragraph (c) of this section.(2) The Chemical Hygiene Plan shall be readily available to employees, employee representatives and, upon request, to the Assistant Secretary.
(3) The Chemical Hygiene Plan shall include each of the following elements and shall indicate specific measures that the employer will take to ensure laboratory employee protection;(i) Standard operating procedures relevant to safety and health considerations to be followed when laboratory work involves the use of hazardous chemicals;
(ii) Criteria that the employer will use to determine and implement control measures to reduce employee exposure to hazardous chemicals including engineering controls, the use of personal protective equipment and hygiene practices; particular attention shall be given to the selection of control measures for chemicals that are known to be extremely hazardous;
(iii) A requirement that fume hoods and other protective equipment are functioning properly and specific measures that shall be taken to ensure proper and adequate performance of such equipment;
(iv) Provisions for employee information and training as prescribed in paragraph (f) of this section;
(v) The circumstances under which a particular laboratory operation, procedure or activity shall require prior approval from the employer or the employers designee before implementation;
(vi) Provisions for medical consultation and medical examinations in accordance with paragraph (g) of this section;
(vii) Designation of personnel responsible for implementation of the Chemical Hygiene Plan including the assignment of a Chemical Hygiene Officer, and, if appropriate, establishment of a Chemical Hygiene Committee; and
(viii) Provisions for additional employee protection for work with particularly hazardous substances. These include select carcinogens, reproductive toxins and substances which have a high degree of acute toxicity. Specific consideration shall be given to the following provisions which shall be included where appropriate:(A) Establishment of a designated area;
(B) Use of containment devices such as fume hoods or glove boxes;
(C) Procedures for safe removal of contaminated waste; and
(D) Decontamination procedures.(4) The employer shall review and evaluate the effectiveness of the Chemical Hygiene Plan at least annually and update it as necessary.
(f) Employee information and training
(1) The employer shall provide employees with information and training to ensure that they are apprised of the hazards of chemicals present in their work area.
(2) Such information shall be provided at the time of an employees initial assignment to a work area where hazardous chemicals are present and prior to assignments involving new exposure situations. The frequency of refresher information and training shall be determined by the employer.
(3) Information. Employees shall be informed of:(i) The contents of this standard and its appendices which shall be made available to employees;
(ii) the location and availability of the employers Chemical Hygiene Plan;
(iii) The permissible exposure limits for OSHA regulated substances or recommended exposure limits for other hazardous chemicals where there is no applicable OSHA standard;
(iv) Signs and symptoms associated with exposures to hazardous chemicals used in the laboratory; and
(v) The location and availability of known reference material on the hazards, safe handling, storage and disposal of hazardous chemicals found in the laboratory including, but not limited to, Material Safety Data Sheets received from the chemical supplier.(4) Training
(i) Employee training shall include:
(A) Methods and observations that may be used to detect the presence or release of a hazardous chemical (such as monitoring conducted by the employer, continuous monitoring devices, visual appearance or odor of hazardous chemicals when being released, etc.);
(B) The physical and health hazards of chemicals in the work area; and
(C) The measures employees can take to protect themselves from these hazards, including specific procedures the employer has implemented to protect employees from exposure to hazardous chemicals, such as appropriate work practices, emergency procedures, and personal protective equipment to be used.(ii) The employee shall be trained on the applicable details of the employers written Chemical Hygiene Plan.
(g) Medical consultation and medical examinations
(1) The employer shall provide all employees who work with hazardous chemicals an opportunity to receive medical attention, including any follow-up examinations which the examining physician determines to be necessary, under the following circumstances:
(i) Whenever an employee develops signs or symptoms associated with a hazardous chemical to which the employee may have been exposed in the laboratory, the employee shall be provided an opportunity to receive an appropriate medical examination.
(ii) Where exposure monitoring reveals an exposure level routinely above the action level (or in the absence of an action level, the PEL) for an OSHA regulated substance for which there are exposure monitoring and medical surveillance requirements, medical surveillance shall be established for the affected employee as prescribed by the particular standard.
(iii) Whenever an event takes place in the work area such as a spill, leak, explosion or other occurrence resulting in the likelihood of a hazardous exposure, the affected employee shall be provided an opportunity for a medical consultation. Such consultation shall be for the purpose of determining the need for a medical examination.(2) All medical examinations and consultations shall be performed by or under the direct supervision of a licensed physician and shall be provided without cost to the employee, without loss of pay and at a reasonable time and place.
(3) Information provided to the physician. The employer shall provide the following information to the physician:(i) The identity of the hazardous chemical(s) to which the employee may have been exposed;
(ii) A description of the conditions under which the exposure occurred including quantitative exposure data, if available; and
(iii) A description of the signs and symptoms of exposure that the employee is experiencing, if any.(4) Physicians written opinion.
(i)For examination or consultation required under this standard, the employer shall obtain a written opinion from the examining physician which shall include the following:
(A) Any recommendation for further medical follow-up;
(B) The results of the medical examination and any associated tests;
(C) Any medical condition which may be revealed in the course of the examination which may place the employee at increased risk as a result of exposure to a hazardous workplace; and
(D) A statement that the employee has been informed by the physician of the results of the consultation or medical examination and any medical condition that may require further examination or treatment.(ii) The written opinion shall not reveal specific findings of diagnoses unrelated to occupational exposure.
(h) Hazard identification
(1) With respect to labels and material safety data sheets:
(i) Employers shall ensure that labels on incoming containers of hazardous chemicals are not removed or defaced.
(ii) Employers shall maintain any material safety data sheets that are received with incoming shipments of hazardous chemicals, and ensure that they are readily accessible to laboratory employees.(2) The following provisions shall apply to chemical substances developed in the laboratory:
(i) If the composition of the chemical substance which is produced exclusively for the laboratorys use is known, the employer shall determine if it is a hazardous chemical as defined in paragraph (b) of this section. If the chemical is determined to be hazardous, the employer shall provide appropriate training as required under paragraph (f) of this section.
(ii) If the chemical produced is a byproduct whose composition is not known, the employer shall assume that the substance is hazardous and shall implement paragraph (e) of this section.
(iii) If the chemical substance is produced for another user outside of the laboratory, the employer shall comply with the Hazard Communication Standard (29 CFR 1910.120) including the requirements for preparation of material safety data sheets and labeling.
(i) Use of respirators
Where the use of respirators is necessary to maintain exposure below permissible exposure limits, the employer shall provide, at no cost to the employee, the proper respiratory equipment. Respirators shall be selected and used in accordance with the requirements of 29 CFR 1910.134.
(j) Record keeping.
(1) The employer shall establish and maintain for each employee an accurate record of any measurements taken to monitor employee exposures and any medical consultation and examinations
including tests or written opinions required by this standard.
(2) The employer shall assure that such records are kept, transferred, and made available in accordance with 29 CFR 1910.1020.
(k) Dates
(1) Effective date. This section shall become effective May 1, 1990.
(2) Start-up dates.(i) Employers shall have developed and implemented a written Chemical Hygiene Plan no later than January 31, 1991.
(ii) Paragraph (a)(2) of this section shall not take effect until the employer has developed
and implemented a written Chemical Hygiene Plan.
Introduction
Purpose
It is the goal of Duke University to produce an environment that
protects the human conceptus, and the ability of each female
employee or the spouse of a male employee to conceive and
maintain a healthy pregnancy. The University recognizes the
responsibility of both the employee as well as management for
pregnancy and reproductive health protection and feel that
education of the work force is the cornerstone of an effective
program.
Responsibilities
Department Heads shall ensure that all employees with
reproductive health concerns have the opportunity to receive
consultations or workplace assessments as necessary. The OESO
shall provide hazard assessments of workplaces as requested by
Employee Occupational Health& Wellness.
Employee Occupational Health & Wellness shall provide medical
consultation for any employee with
reproductive health concerns.
Procedures
Employees with concerns about how their workplace may affect
their reproductive capacity, pregnancy, or the health of the
fetus, should contact Employee Occupational Health & Wellness
for a consultation.
Prior to the consult, the employee will be asked to perform a
self-audit of the workplace. The OESO will
be available for advice during the self-audit process.
Employees in work areas with reproductive hazards will be educated about the potential consequences of exposures. Employees who wish to alter their work situation to avoid a risk will be reviewed by EOHW to determine the necessity for alternation. If deemed necessary, the employee may request a transfer or appropriate leave of absence, consistent with University policy.
Exposure to some agents within the environment may pose a
hazard to the fetus while the same exposure would not represent a
hazard to the employee. Therefore, employees may be restricted
(by EOHW) from working in certain areas if it is determined that
the employee may be exposed to conditions that would negatively
affect reproductive health or the safety of the fetus. Any
alterations in job situation
will be consistent with existing University policy.
References
Public Law 91-589, The Occupational Safety and Health Act of
1970
Last Updated:
May 23, 2006
Safety@mc.duke.edu