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FOREWORD

All UCI laboratory personnel who work with laboratory chemicals must know and follow the standard operating procedures outlined in this plan. All laboratory operations involving particularly hazardous chemicals must be planned and executed in accordance with the standard operating procedures described in this plan. In addition, each laboratory worker is expected to practice safe personal chemical hygiene habits aimed at reducing exposures to potential hazards.

This document was developed to comply with applicable federal and state requirements, and professional standards, including California Code of Regulations 8CCR §5191 "Occupational Exposure to Hazardous Chemicals in Laboratories" . This Chemical Hygiene Plan (CHP) will be reviewed and evaluated for effectiveness at least annually and updated as necessary. It must be readily available to laboratory employees, their representatives and any regulatory agency inspector during normal working hours.

Last Reviewed: September 2006

Rebecca Lally - Chemical Hygiene Officer
Chris Younghans-Haug -College of Health Sciences Coordinator
David Melitz - School of Biological Sciences & School of Social Ecology Coordinator
Joe Rizkallah - School of Engineering Coordinator
Rama Singh - School of Physical Sciences Coordinator

NOTE:

Contact your school's EH&S Coordinator or Campus Chemical Hygiene Officer at (949) 824-6200 with any corrections or suggestions for change in this Chemical Hygiene Plan.

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IMPORTANT PHONE NUMBERS FOR UC Irvine

EH&S SERVICES

Anonymous Hazard Reporting : To anonymously report a hazard or health and safety concern, call 824-6200. If you are concerned about the caller ID system, consider using a pay phone.

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TABLE OF CONTENTS

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1.1 Applicability

This Chemical Hygiene Plan (CHP) applies to all personnel handling hazardous chemicals in research laboratories at UC Irvine. The CHP provides written safety procedures for conducting research laboratory chemical operations in a manner that protects people from harmful chemical exposures.

1.2 Exclusions

The CHP does not cover work with radiation-producing devices, radioactive materials, biological agents, or the disposal of these wastes. Use of radioactive materials and biological agents must have prior approval of the UCI Radiation Safety Committee or Institutional Biosafety Committee. Permit forms and procedures can be obtained from EH&S at 824-6200. Please consult the UCI Radiation Safety Manual or UCI Biosafety Manual and related documents for additional information.

2.1 Laboratory Supervisor

The Supervisor's duties are the responsibility of the faculty member (Principal Investigator or Instructor) in charge of each laboratory. The Supervisor has direct responsibility for the health and safety of all personnel under his/her direction. The Supervisor's duties include the following:

1. Ensure that all laboratory workers under their control receive instructions and training to work safely with hazardous chemicals, respond appropriately when chemical accidents occur, and how to report injury and illnesses associated with occupational exposure to hazardous chemicals.
2. When injuries or illnesses occur at work, follow procedures outlined in the What to do in a Medical Emergency flyer. For non-emergencies, employee injuries and illnesses must still be reported: please visit the Worker's Compensation website for details. The Supervisor should investigate all accidents and near-misses and take measures to help prevent reoccurrence, with consultation from the School's EH&S Coordinator when necessary.
3. Assist the school's EH&S Coordinator with the execution of his/her duties whenever necessary.
4. Seek ways to improve chemical hygiene and laboratory safety.
5. Inform non-laboratory personnel (e.g., UCI Facilities Management and contract workers) of potential hazards when non-laboratory personnel are required to work in the laboratory environment. These laboratory hazards must be mitigated to provide a reasonably safe environment for repairs and renovations.
6. Identify hazardous conditions or operations, determine safe procedures and controls, and implement and enforce standard safety procedures.
7. Ensure that engineering controls (e.g., fume hoods, emergency showers and eyewashes) are operable and that personal protective equipment is available and used properly by laboratory staff working with hazardous chemicals.
8. Ensure delegated safety duties are completed on a timely basis.

2.2 EH&S Coordinator

UC Irvine EH&S Coordinator's responsibility is to support the Laboratory Supervisor to implement the policies and procedures described in this CHP. These duties include the following:

1. Review standard operating procedures for work involving hazardous substances upon request.
2. Conduct periodic laboratory safety surveys and safety survey follow-ups.
3. Assist Lab Supervisors and Laboratory Workers to implement EH&S policies and procedures.
4. Investigate accidents and provide written reports to EH&S Workers Compensation when appropriate.
5. Consult with the Laboratory Supervisor and the Campus Chemical Hygiene Officer (CHO) on hazard assessment and control in labs.
6. Consult with Facilities Management and contractors regarding potential lab hazards and provide information to minimize their risk of exposure to hazardous substances.

2.3 Safety Representative

A Safety Representative ( SR ) may be designated by the lab supervisor to be responsible for ensuring that hazardous chemicals are handled, stored, and disposed in accordance with this CHP.

1. Be designated by the Laboratory Supervisor.
2. Ensure completion of the Hazard Assessment and Corrections Tool.
3. Develop standard operating procedures for avoiding lab hazards as needed.
4. Assist with providing and documenting work-unit Specific Safety Training beyond EH&S provided courses.
5. Conduct laboratory safety self-assessments as needed.
6. Assist with maintaining the Chemical Inventory Database.
7. Monitor the disposal of chemicals used in laboratory operations.

2.4 Laboratory Employees & Workers

All persons working with laboratory chemicals must know how to work safely with the chemicals they use and are responsible for following prudent chemical safety practices. If any person is unsure of a chemical hazard or safety procedure, he/she should consult with his/her supervisor. While the California Code of Regulations 8CCR §5191 "Occupational Exposure to Hazardous Chemicals in Laboratories" imposes standards on employers and employees, UC Irvine attempts to have all persons working with hazardous chemicals in research laboratories implement the prudent practices described in this Chemical Hygiene Plan, including students and volunteers.

2.5 Campus Chemical Hygiene Officer (CHO)

The Campus Chemical Hygiene Officer is responsible for the development, implementation, and periodic review of the Chemical Hygiene Plan to comply with state and federal standards concerning occupational exposure to hazardous chemicals in laboratories.

2.6 School Facilities Manager/Director

The School Facilities Manager/Director is responsible for coordinating activities related to building repairs, maintenance, improvements, and laboratory moves and closures. The School Facilities Manager/Director will inform the EH&S Coordinator or EH&S of building repairs, maintenance, improvements, and laboratory moves and closures so that safety assessments can be performed. The Facilities Manager/Director has the responsibility for communicating to outside contractors and UC Irvine maintenance staff about potential hazards in the laboratories.

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Substances in the laboratory have properties that could cause harm to laboratory workers and others if handled improperly. Many lab chemicals are toxic or corrosive, or both. Compounds that are potentially explosive and/or highly flammable pose another significant hazard in laboratories. New and untested substances may be hazardous. The most important guideline for chemical safety is to treat all compounds as potentially harmful and minimize your chemical exposure. Before starting an experiment using hazardous chemicals, learn about its hazards and use this knowledge to plan the experiment. Hazards of two combined substances may be significantly greater than the hazards of either substance alone (e.g. toxic synergism).

3.1 Carcinogens

Carcinogens are chemical or physical agents that cause cancer. Carcinogens are toxic substances causing damage to cells after repeated or chronic exposure. Their effects may only become evident after a long latency period and may cause no immediate harmful effects.

Carcinogens are classified as “Particularly Hazardous Substances” and must be handled using the special precautions described in Section 5. Comprehensive lists of known & suspected carcinogens from peer-reviewed authoritative sources are available on the Internet. Many other compounds have limited evidence of carcinogenicity from animal studies. These compounds should be handled using the general procedures for work with hazardous substances outlined in Section 4.

Lab workers should recognize that many chemicals in research laboratories have not been tested for carcinogenicity. Researchers should be familiar with the specific classes of compounds and functional group types that have been correlated to carcinogenic activity. The following section lists representative compounds in each class that are “ reasonably anticipated to be carcinogens ” based on animal tests. All new and untested compounds should be treated as hazardous substances and handled using to the procedures described in Section 4.

Classes of Carcinogenic Compounds

*Cal/OSHA regulated (Section 5.5 applies)

Exposure to certain combinations of compounds (not necessarily simultaneously) can cause cancer even at exposure levels where neither of the individual compounds would have been carcinogenic. 1,8,9- trihydroxy­anthracene and certain phorbol esters are examples of “tumor promoters” that while not themselves carcinogenic can dramatically amplify the carcinogenicity of other compounds.

3.2 Reproductive Toxins

Reproductive toxins include substances that cause chromosomal damage (mutations) and substances causing lethal or malformation effects on fetuses (teratogenesis). Many reproductive toxins cause damage after repeated low-level exposures. Effects only become evident after long latency periods.

Information on reproductive toxicity of a specified chemical may be obtained from the Material Safety Data Sheets . See Section 14 for additional references and recommended reading.

The following table lists materials present in some UC Irvine research labs that are suspected or known to be reproductive toxins:

Partial List of Reproductive Toxins

The above list is not complete. The Laboratory Supervisor determines whether a chemical should be handled as a reproductive toxin. Laboratory workers should also consult with their personal physician regarding concerns about reproductive toxins.

3.3 Toxic and Highly Toxic Agents

The California Code of Regulations 8CCR§5194 defines toxic and highly toxic agents as substances with median lethal dose (LD 50 ) values in the following ranges:

3.4 Hazardous Substances with Toxic Effects on Specific Organs

Substances included in this category are:

1. Hepatotoxins - substances that produce liver damage (e.g. nitrosamines, carbon tetrachloride).
2. Nephrotoxins - agents causing damage to the kidneys (e.g. certain halogenated hydrocarbons).
3. Neurotoxins - substances that produce their primary toxic effects on the nervous system (e.g. mercury, acrylamide, carbon disulfide).
4. Agents that act on the hematopoietic system - substances that decrease hemoglobin function and deprive the body tissues of oxygen (e.g. carbon monoxide, cyanides).
5. Agents that damage lung tissue - (e.g. asbestos, silica).

3.5 Sensitizers

A sensitizer (allergen) is a substance that causes exposed people to develop an allergic reaction in normal tissue after repeated exposure to the substance. Examples of sensitizers used in some UC Irvine labs include chromium, nickel, formaldehyde, isocyanates, arylhydrazines, diazomethane, benzylic and allylic halides and many phenol derivatives.

3.6 Irritants

Irritants are defined as chemicals that cause reversible inflammatory effects on living tissue by chemical action at the site of contact. A wide variety of organic and inorganic compounds are irritants and consequently skin contact with all laboratory chemicals should always be avoided.

3.7 Corrosive Substances

Corrosive substances cause visible irreversible destruction of, or visible alterations in living tissue by chemical action at the site of contact. Major classes of corrosive substances include strong acids (e.g., sulfuric, nitric, phosphoric, hydrochloric, and hydrofluoric acids), strong bases (sodium hydroxide, phosphoric potassium hydroxide, and ammonium hydroxide), and dehydrating agents (sulfuric acid, sodium hydroxide, phosphorus pentoxide, and calcium oxide).`

3.8 Flammables and Potentially Explosive Substances

A number of highly flammable substances are in common use in UC Irvine laboratories. Potentially explosive substances are materials that decompose under conditions of mechanical shock, elevated temperature, or chemical action, with the release of large volumes of gases and heat.

3.9 Select Agents (Toxins of Biological Origin)

In recognition of the growing number of microbiological and biomedical laboratories working with toxins of biological origin, the following list of select agent toxins requires authorization from the campus Biosafety Officer (824-9888) prior to purchase or transfer of the material.

All users must obtain a Biological Use Authorization Number (BUA). The BUA is designed to track the acquisition and transfer of these specific agents and to establish a system of safeguards to be followed when specific agents are in use.

Select Agents fall under the category of Particularly Hazardous Substances. Special handling procedures must be followed as listed under Section 5.0 and 5.5.

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4.0 Standard Operating Procedures for Working with Hazardous Chemicals in UCI Laboratories

4.1 Chemical Procurement

To minimize the duplication of hazardous chemicals within research groups, use chemicals currently available in the group's inventory. Furthermore, use hazardous chemicals from other research groups when possible. Both procedures are cost-effective and will reduce the quantity of hazardous chemicals stored and help minimize hazardous waste.

1. The decision to buy a hazardous chemical must be a commitment to handle and use the chemical safely from receipt to disposal.

2. Prior to the purchase of a new hazardous chemical, check your lab's current inventory or, when reasonably feasible, in the inventories of other research groups. Everyone has an obligation to reduce workplace exposures and environmental releases of hazardous chemicals to the lowest achievable levels (See Section 4.14 for more information on source reduction and waste minimization).

3. Checking in hazardous chemical shipments must follow these procedures:

a. Any package showing signs of leakage or breakage should not be accepted. If the damage to the package is minor or if the damage to the inside chemical container is uncertain, do not accept the package until it is opened in a fume hood by lab staff. If the delivery person insists on leaving the package, sign for the package but also record on the receipt that the package is damaged.

b. Chemical containers must not be accepted without legible and intact labels.

c. Staff working with the chemical must be familiar with the information on the Material Safety Data Sheet (MSDS). This information must be maintained for employees to access at all times when working with hazardous chemicals. See Accessing Material Safety Data Sheets . If you have problems with Internet access, contact MSDS Specialist at 824-6200.

d. All peroxide-forming chemicals containers should be marked with the manufacturer's expiration date. The researcher should write on the container the date when it is first opened.

e. Chemicals that have limited shelf life should be labeled “Dispose after (date) ”

f. All containers of ether should be labeled “Use by (6 months from receipt) or Dispose.”

4. Shipping of hazardous chemicals should only be performed by trained staff or under the direction of trained staff. See the Shipping Dangerous Goods webpage for details.

4.2 Hazardous Chemical Storage

1. Chemicals received must be moved as soon as possible to the designated storage area. Glass containers larger than 1 liter (L) must be placed in carrying containers or kept in shipping containers during transportation.

2. The storage area must be well illuminated and have local exhaust ventilation, with all storage maintained below eye level. Bottles larger than 4 L must be stored on the lowest shelf of the storage area. All storage areas must have seismic safety restraints.

3. Chemicals must be segregated by hazard classification and compatibility in a well-identified area, as follows:

a. Oxidizing acids, including mineral acids, must be separated from flammable and combustible materials. Acid-resistant trays must be placed under bottles of acids.

b. Cyanides and sulfides must be separated from acids or protected from contact with acids.

c. Oxidizers must be separated from flammables, organic materials and oxidizable inorganic substances.

d. Acids and bases must be separated from each other.

e. Chemicals that exhibit air and moisture sensitivity (e.g., organometallics, metal hydrides, etc) must be stored in a segregated area with provisions made to minimize the possibility of breakage, and other air or moisture contact.

f. Carcinogens, suspected carcinogens, and other highly toxic materials must be stored in a secure area with restricted access.

4. Chemical storage areas must not be used as a preparation or repackaging area.

5. The storage area must be accessible during normal working hours. The storage area must be under the control of the Safety Representative ( SR ).

6. The amount of chemicals at the laboratory bench must be as small as possible. The container size must be selected to keep amounts of chemicals to the minimum needed to work efficiently. Exposure to sunlight or heat must be minimized.

7. Stored chemicals must be checked by the SR for deterioration and container integrity, and by lab workers before each use. The inspection must also determine whether any corrosion, deterioration, or damage has occurred to the storage facility as a result of leaking chemicals. The SR must notify the Principal Investigator of any problems.

8. Inventories must be maintained in the laboratory and be updated at least annually. A copy of the inventory must be delivered to EH&S for the campus to keep permits current. If necessary, consult with the School EHS Coordinator for procedural updates for submitting chemical inventories.

9. The SR must conduct inspections of the laboratory for chemicals outside of the storage area. Chemicals not in current use must be returned to the storage area.

10. Substances that have been synthesized for the first time in the research laboratory must be stored in a manner consistent with their potential hazard as determined by analogy to known chemicals of similar composition.

4.3 Handling Hazardous Chemicals

General precautions to be followed for the handling and use of all laboratory chemicals are:

1. Inhalation, ingestion, and skin contact with all chemicals must be avoided.

2. All laboratory workers must wash all areas of skin that may have been exposed to chemicals prior to leaving the laboratory.

3. Pipetting or siphoning by mouth is prohibited.

4. Eating, drinking, smoking, gum chewing, and application of cosmetics in areas where laboratory chemicals are present must be avoided. See Clean Area procedures . Hands must be washed thoroughly prior to performing these activities in clean areas or outside of the lab.

5. Refrigerators, glassware, containers, and utensils used for laboratory operations must never be used for the storage, handling, or consumption of food. Mark items “NOT FOR FOOD USE” or equivalent to prevent inadvertent use of laboratory items for food.

6. Substances of unknown hazards must be assumed to be hazardous, and any chemical mixture must be assumed to be as hazardous as its most hazardous component.

7. Laboratory workers must be familiar with the chemical's hazard information from the container label, the Material Safety Data Sheet and other appropriate references. This familiarization must include symptoms of exposure and the precautions necessary to prevent exposure.

8. Specific precautions based on the hazardous characteristics of individual chemicals must be implemented as deemed necessary by Principal Investigator/Laboratory Supervisor.

9. If warranted, any lab specific practices can be documented in a written Standard Operating Procedure (SOP); complete sections 1-7 of the Standard Operating Procedure Template .

4.4 Handling Flammable and Potentially Explosive Substances

1. Flammable Substances

Flammable substances are among the most common of the hazardous materials found in UC Irvine laboratories. Flammable substances are materials that readily catch fire and burn in air. A flammable liquid itself does not burn; rather it is the vapors from the liquid that burn. The rate at which different liquids produce flammable vapors depends on their vapor pressure and increases with temperature. The degree of fire hazard also depends on the ability to form combustible or explosive mixtures with air, the ease of ignition of these mixtures, and the relative densities of the liquid with respect to water and of the gas with respect to air.

To illustrate this point, an open beaker of diethyl ether set on the laboratory bench next to a Bunsen burner will ignite, whereas a similar beaker of diethyl phthalate will not. Ether has a much lower flash point. The flash point is the lowest temperature at which a liquid gives off vapor in sufficient concentration to form an ignitable mixture with air near the surface of the liquid. Many common laboratory solvents and chemicals have flash points that are lower than room temperature and have the potential to ignite and burn.

These following basic precautions should be followed in handling flammable substances:

a. Flammable substances should only be handled in areas that are free of ignition sources. Ignition sources include: open flames, electrical equipment (especially motors), static electricity, and hot surfaces.

b. If you will be using a hot plate, stirring plate or heating mantle, do not proceed with your laboratory work until you know the autoignition temperatures of the chemicals likely to be released and can ensure that the temperatures of all exposed surfaces are less than those autoignition temperatures. Make certain that the temperature control device and the stirring/ventilating motor (if present) do not spark.

c. Never heat a flammable substance with an open flame.

d. When transferring flammable liquids to and from metal containers, use bonding and grounding wires to avoid static-generated sparks.

e. Ventilation is one of the most effective ways to prevent the formation of flammable mixtures. A laboratory hood should be used whenever any more than a few milliliters (mL) of flammable substances are handled in any way that produces vapors.

2. Potentially Explosive Substances

Potentially explosive substances are materials that decompose under conditions of mechanical shock, elevated temperature, or chemical action, with the release of large volumes of gases and heat. Special precautions are required for the safe use of potentially explosive materials. Each researcher must evaluate the explosive hazards involved in his/her work and consult with the Laboratory Supervisor to develop adequate standard operating procedures. Work with potentially explosive materials will require the use of special protective apparel (face shields, goggles, gloves, laboratory coats) and protective devices such as explosion shields and barriers. Place the shields in suitable positions to protect yourself and others. Be sure that the shields are stabilized with weights or fasteners so that they cannot be knocked over.

Organic peroxides are among the most hazardous substances handled in research laboratories. As a hazard class, they are low-power explosives, and hazardous because of their sensitivity to shock, sparks, and even friction (as little as a cap being twisted open). Many peroxides that are routinely handled in laboratories are far more sensitive to shock than most primary explosives such as trinitrotoluene (TNT). All organic peroxides are highly flammable, and most are sensitive to heat, friction, impact, light, as well as strong oxidizing and reducing agents. Organic peroxide procedures should be carried out only by knowledgeable laboratory workers..

Some peroxides in use at UC Irvine are commercial compounds such as m- chloroperoxy­benzoic acid, benzoyl peroxide, hydrogen peroxide, and t-butyl hydroperoxide. However, common solvents and reagents are known to form peroxides on exposure to air, and these chemicals often become contaminated with sufficient peroxides to pose a serious hazard. Classes of compounds that form peroxides by auto oxidation include:

a. Ethers with primary and/or secondary alkyl groups, including acyclic and cyclic ethers, acetals, and ketals. Examples include diethyl ether, diisopropyl ether, dioxane, dimethyl ether, tetrahydrofuran, ethyl vinyl ether and alcohols protected as tetrahydropyran ethers.

b. Hydrocarbons with allylic, benzylic, or propargylic hydrogens. Examples of this class of peroxide-formers include cyclohexene, cyclooctene, methyl acetylene, isopropylbenzene (cumene), and tetralin (tetrahydronaphthalene).

c. Conjugated and unconjugated dienes and terpenes among which divinylacetylene is particularly hazardous.

d. Saturated hydrocarbons with exposed tertiary hydrogens; common peroxide-formers include decalin (decahydronaphthalene) and 2,5-dimethylhexane.

e. Aldehydes including acetaldehyde and benzaldehyde

Compounds belonging to the classes listed above cannot form peroxides without exposure to oxygen (or other oxidizers). After use and prior to storing these materials, flush the container with an inert gas such as nitrogen or argon before sealing. If the compound is not volatile, it may be advisable to degas the sample by vacuum or bubbling techniques. In some cases it may be appropriate to add an oxidation inhibitor, such as hydroquinone or BHT (2,6-di- t -butyl-4-methylphenol), to the sample. Containers should be tightly sealed and dated.

3. Visual Identifiers

Organic solvents in glass bottles provide the investigator with the ability to visually inspect the container and its contents. A flashlight can be used to either backlight or sidelight the bottle. Look for the following signs:

a. Gross Contamination

Hard crystal formation in the form of chips, ice-like structures, crystals, solid mass or cloudy media, are critical signs of gross organic peroxide contamination. Do not handle the container. Contact EH&S for proper disposal.

b. Contamination

Clear liquid presenting wisp-like structures floating in suspension indicate early signs of peroxide contamination.

Peroxide crystals may be found on the bottom of the container, side walls of the glass, threaded cap, and may also be found on the outside of the container. If an old container is found, every attempt should be made to inspect the container without picking up or moving the container.

4. Detection and Removal of Peroxides

Refer to Procedures for Detecting and Removing Peroxide Contamination for specific procedures. Most labs will find it easier and more economical to use inventory management to prevent the problem of undesirable peroxide formation.

5. Labeling of Peroxidizable Compounds

Many compounds form explosive peroxides or can be explosively polymerized by the presence of peroxides. Commercially available samples of these compounds normally contain stabilizers or inhibitors to extend the shelf storage lifetime. Upon long term storage, the effect of the stabilizer becomes depleted. In addition, most distillation and purification steps normally separate stabilizers from the peroxidizable compound.

Test samples of potential peroxide former before each use, especially if you intend to distill or concentrate a large volume (greater than one liter) of the solvent.

Use the following lists as guidance for storage times. If a compound stored longer than the indicated periods is not disposed immediately, samples must be tested for peroxides before each use, especially if distillation is being planned.

Ethers have limited shelf life and should be purchased in the smallest practical containers. Each container should have the manufacturer's expiration date and date when first opened.

For isopropyl and diethyl ethers, even unopened containers should be disposed prior to the manufacturer's expiration date. Containers of isopropyl ether, divinyl acetylene, and vinylidene chloride should be tested for peroxide every 3 months after opening or should be discarded. If the peroxide concentration is within acceptable limits, the container can be closed and re-dated for the next scheduled test.

Other peroxidizable compounds, such as ethyl ether, dioxane, tetrahydrofuran, etc. should be tested every 6 months after opening or discarded. If peroxide concentration is within acceptable limits, the container can be closed and re-dated for the next scheduled test.

Contact EH&S for assistance in disposing of peroxides or other explosive materials.

For additional information about peroxides and peroxide forming chemicals, refer to NFPA 43B, “Code of Organic Peroxide Formulations”. The following recommendations for discard or testing timeframes were obtained from Prudent Practices for Disposal of Chemicals from Laboratories , Appendix I, National Academy Press, Washington D.C., 1983, pp.245-246.

A Polymerizable monomers should be stored with a polymerization inhibitor which the monomer can be separated by distillation just before use.

A Polymerizable monomers should be stored with a polymerization inhibitor which the monomer can be separated by distillation just before use.

A Polymerizable monomers should be stored with a polymerization inhibitor which the monomer can be separated by distillation just before use.

B Although air will not enter a gas cylinder in which gases are stored under pressure, these gases are sometimes transferred from the original cylinder to another in the laboratory, and it is difficult to be sure that there is no residual air in the receiving cylinder. An inhibitor should be put into any such secondary cylinder before one of these gases is transferred; the supplier can suggest inhibitors to be used. The hazard posed by these gases is much greater if there is a liquid phase in such a secondary container, and even inhibited gases that have been put into a secondary container under conditions that create a liquid phase should be discarded within 12 months

C The hazard from peroxides in these compounds is substantially greater when they are stored in the liquid phase and, if so stored without inhibitors, they should be considered as in List A.

6. Specific Hazards that May Lead to Fires or Explosions

(See Section 12 for Control of Fires)

The combination of certain compounds or classes of compounds can result in a violent chemical reaction leading to an explosion or fire. Other compounds pose explosion or fire hazards when exposed to heat, shock, or other conditions. Some of the specific compounds and combinations of compounds that may pose explosion or fire hazards and may be encountered in laboratories are listed below. This list is not complete. Researchers are expected to learn about the hazardous properties of chemicals involved in their research before using them. Use explosion shields to protect yourself and others.

a. Acetylenic compounds are explosive in mixtures of 2.5%-80% with air. At pressures of 2 or more atmospheres, acetylene

subjected to an electrical discharge or high temperature decom­poses with explosive violence. Dry acetylides can detonate with the slightest shock. Many heavy metal acetylides are also shock sensitive explosives.

b. Aluminum chloride should be considered a potentially dangerous material. If moisture is present, there may be sufficient decomposition (generating hydrochloric acid (HCl)) to build up considerable pressure. If a bottle is to be opened after long standing, it should be completely enclosed in a heavy towel.

c. Ammonia reacts with iodine to give nitrogen triiodide, which is explosive, and with hypochlorites to give chlorine. Mixtures of ammonia and organic halides sometimes react violently when heated under pressure.

d. Dry benzoyl peroxide is easily ignited and sensitive to shock and may decompose spontaneously at temperatures above 50 °C. It has reported to be desensitized by the addition of water to 20%.

e. Carbon disulfide is both very toxic and very flammable; mixed with air, its vapors can be ignited by a steam bath or steam pipe, a hot plate, or a glowing light bulb.

f. Chlorine may react violently with hydrogen or with hydrocarbons when exposed to sunlight.

g. Diazomethane and related compounds should be treated with extreme caution. They are very toxic (potent carcinogens), and the pure gases and liquids explode readily.

h. Dimethyl sulfoxide decomposes violently on contact with a wide variety of active halogen compounds. Explosions from contact with active metal hydrides have been reported.

i. Diethyl, diisopropyl, and other ethers (particularly the branched-chain type) sometimes explode during heating or refluxing because of the presence of peroxides. Ferrous salts or sodium bisulfite can be used to decompose these peroxides, and passage over basic active alumina will remove most of the peroxidic material. In general, however, old samples of ethers should be disposed properly through EH&S.

j. Ethylene oxide has been known to explode when heated in a closed vessel. Experiments using ethylene oxide under pressure should be carried out behind suitable barricades.

k. Halogenated compounds such as chloroform, carbon tetrachloride, and other halogenated solvents should not be dried with sodium, potassium, or other active metals. Violent explosions are usually the result of such attempts.

l. Hydrogen peroxide in concentrations greater than 3% can be dangerous. Contact with the skin may cause severe burns. Thirty percent (30%) hydrogen peroxide may decompose violently if contaminated with iron, copper, chromium, or other metals or their salts.

m. Liquid-nitrogen cooled traps that are open to the atmosphere rapidly condense liquid air. When the coolant is removed, an explosive pressure buildup occurs, usually with enough force to shatter glass equipment. Only sealed or evacuated equipment should be cooled.

n. Lithium aluminum hydride should not be used to dry methyl ethers or tetrahydrofuran. Fires from this practice are very likely. The products of a LiAlH 4 reaction with carbon dioxide have been reported to be explosive. Carbon dioxide or bicarbonate extinguishers should not be used on lithium aluminum hydride fires, which should be smothered with sand or some other inert substance. LiAlH4 reactions should be carried out in a fume hood, behind an explosion shield, and with proper safeguards to avoid exposure of the effluent hydrogen gas to spark or flame. Any stirring device must be spark-proof.

o. Oxygen cylinders : Serious explosions have resulted from contact between oil and high-pressure oxygen. Oil should not be used on connections to any cylinder.

p. Ozone is a highly reactive and toxic gas. Ozone is formed by the action of ultraviolet light on oxygen (air) and, therefore, certain ultraviolet sources may require venting to the exhaust hood. Liquid and solid ozone are explosive substances.

q. Palladium on carbon, platinum on carbon, platinum oxide, Raney nickel, and other catalysts should be filtered from catalytic hydrogenation reaction mixtures carefully. The recovered catalyst is usually saturated with hydrogen and highly reactive and, thus, will inflame spontaneously on exposure to air. Particularly in large-scale reactions, the filter cake should not be allowed to become dry. The funnel containing the still-moist catalyst filter cake should be put into a water bath immediately after completion of the filtration.

Another hazard in working with such catalysts is the danger of explosion if additional catalyst is added to a flask in which hydrogen is present.

r. Parr bombs used for hydrogenations have been known to explode. Parr bombs should be handled with care behind explosion shields, and the operator should wear goggles.

s. Perchlorates : The use of perchlorates should be avoided whenever possible. Perchlorates should not be used as drying agents if there is a possibility of contact with organic compounds, or in proximity to a dehydrating acid strong enough to concentrate the perchloric acid to more than 70% strength (e.g., in a drying train that has a bubble counter containing sulfuric acid). Safer drying agents should be used. Seventy-percent perchloric acid can be boiled safely at approximately 200 ° C, but contact of the boiling undiluted acid or the hot vapor with organic matter, or even easily oxidized inorganic matter (such as compounds of trivalent antimony), will lead to serious explosions. Perchlorate esters have the same shattering explosive effect as nitroglycerine. Oxidizable substances must never be allowed to contact perchloric acid. Beaker tongs, rather than rubber gloves, should be used when handling fuming perchloric acid. Perchloric acid evaporations should be carried out in a hood that has a good draft and a built-in water spray for the ductwork behind the baffle. After use, washing out the hood and ventilator ducts with water is necessary to avoid danger of spontaneous combustion.

t. Permanganates are explosive when treated with sulfuric acid. When both compounds are used in an absorption train, an empty trap should be placed between them.

u. Peroxides (inorganic) : When mixed with combustible materials, barium, sodium, and potassium peroxides form explosives that ignite easily.

v. Phosphorus (red and white) forms explosive mixtures with oxidizing agents. White phosphorus should be stored under water because it is spontaneously flammable in air. The reaction of phosphorus with aqueous hydroxides forms phosphine, which may ignite spontaneously in air or explode.

w. Phosphorus trichloride reacts with water to form phosphorous acid, which decomposes on heating to form phosphine, which may ignite spontaneously or explode. Care should be taken in opening containers of phosphorous trichloride, and samples that have been exposed to moisture should not be heated without adequate explosion shielding to protect the operator.

x. Potassium is in general more reactive than sodium. It ignites quickly upon exposure to humid air and, therefore, should be handled under the surface of a hydrocarbon solvent such as mineral oil or toluene. Oxidized coatings should be very carefully scraped away before cutting the metal (explosions can otherwise occur). Potassium metal can form explosive peroxides. Metal that has formed a yellow oxide coating from exposure to air should not be cut with a knife, even when wet with a hydrocarbon, because an explosion can be promoted.

y. Residues from vacuum distillations have been known to explode when the still was vented to the air before the residue was cool. Such explosions can be avoided by venting the still pot with nitrogen, by cooling it before venting, or by restoring the pressure slowly.

z. Sodium should be stored in a closed container under kerosene, toluene, or mineral oil. Scraps of sodium or potassium should be destroyed by reaction with n-butyl alcohol. Contact with water should be avoided because sodium reacts violently with water to create explosions and fire. Reactions with sodium should be carried out in a fume hood, behind an explosion shield, and with proper safeguards to avoid exposing the effluent gas hydrogen to spark or flame. Any stirring device must be spark-proof. Carbon dioxide, bicarbonate, and carbon tetrachloride fire extinguishers should not be used on alkali metal fires.

aa. m-chloroperbenzoic acid should only be stored in plastic containers. Researchers should take special care to do this after purifying commercial material to 99%. A sample of 99+% material stored in a glass sample bottle exploded in a laboratory in 1995 causing an injury to a researcher.

7. If warranted, any lab specific practices can be documented in a written Standard Operating Procedure (SOP); complete sections 1-7 of the Standard Operating Procedure Template . Also, examples of SOPs for many hazardous chemicals are located in the SOP Library .

4.5 Segregation of Incompatible Substances

When transporting, storing, using, or disposing of any chemical, ensure that the substance cannot accidentally come in contact with an incompatible material. Such contact could result in a serious explosion, the formation of substances that are highly toxic or flammable or both. See Table of Common Incompatibilities for more examples.

4.6 Handling Compressed Gases

Because of their high pressure, cylinders of compressed gases present physical hazards. Guidelines for handling compressed gas cylinders follow:

1. Except during transportation (see Section 4.6.4 below), compressed gas cylinders of all sizes must be restrained at all times by straps, chains, or a suitable stand to prevent the cylinder from falling.

2. When a cylinder is empty, mark it "EMPTY" or "MT" or use the tag system supplied by the vendor. Close the valve and replace the valve protection cap. Cylinders should not block egress from the laboratory.

3. During transportation of cylinders, the protective caps must be securely in place. For cylinders over 2 feet, an appropriate cart must be used.

4. Compressed gas cylinders must not be exposed to temperatures higher than 50°C (122°F).

5. Lecture bottles of reagent gases must be used according to the following guidelines:

a. Whenever possible, lecture bottles must be purchased from a supplier that allows the return of partially filled or empty cylinders.

b. Compatible regulators must always be used, taking into account any properties of the gas.

c. At least once a year, the SR must inspect the stored lecture bottles for signs of leakage and/or corrosion. The SR must determine which lecture bottles will not be used during the next 12 months and return these to a supplier for proper reuse or disposal.

6. Leaking cylinders of flammable, oxidizing, corrosive or toxic gases represent a serious hazard, and must be handled according to the following procedures:

a. DO NOT transport leaking cylinders of toxic gases in elevators or hallways. Leave the area and call EH&S for assistance.

b. If a minor leak is suspected, a flammable gas leak detector or a soapy solution (Snoop â ) must be used; under no circumstances must a flame be used for leak detection.

c. Shut off the main cylinder valve upon confirmation of a minor leak, the cylinder must be immediately transported to a fume hood or gas cabinet. EH&S must then be notified of the leak.

d. If a major leak of a hazardous gas develops, all personnel must be evacuated from the area (see Section 12 for further details).

e. Compressed gas cylinders that are leaking inside gas cabinets must be left in place and reported to the EH&S Emergency Response Team by dialing 824-6200 during normal working hours (M-F, 8AM-5PM) or 911 after hours.

7. Flashback or flame arresters are recommended when working with highly flammable fuel gases such as acetylene and hydrogen gas.

8. Ensure equipment is grounded when working around flammable gases.

A comprehensive Compressed Gas Safety Awareness Training Supplement is provided in the Appendices.

4.7 Laboratory Use of Anesthetics

Anesthesia commonly used in some research laboratories include: nitrous oxide, halothane, enflurane, methoxyflurane, trichloroethylene, and urethane. Exposure to waste anesthetic gases and vapors during surgical procedures is harmful to researchers. Open bench surgeries involving gaseous anesthetics should employ waste gas scavenging systems that are connected to non-recirculating exhaust systems.

1. Refer to the Controlling Waste Anesthetic Gases for procedures to minimize exposure to waste anesthetic gases.

2. Exhaust systems must be used in conjunction with scavenger systems. Contact EH&S prior to installation of scavenger systems to existing building ventilation.

4.8 Laboratory Equipment and Glassware

Each laboratory worker must keep the work area clean and uncluttered. All chemicals and equipment must be properly labeled in accordance with Section 4.11. The work area must be regularly cleaned and all equipment properly cleaned and stored.

The following procedures must apply to the use of laboratory equipment and glassware:

1. Laboratory equipment must be used only for its intended purpose.

2. All glassware will be handled and stored with care to minimize breakage; glassware must be disposed of in the following ways:

a. All broken glassware, Pasteur pipettes, slides, cover slips and other glassware which could puncture that are not contaminated with infectious material, radioactive material, or hazardous material must be placed in the assigned broken glass container in each laboratory. This container must be labeled both in English and Spanish with the words "BROKEN GLASS/VIDRIO ROTO”.

b. Pasteur Pipettes, slides and cover slips that are contaminated with infectious material must be disposed of in one of the following ways:

i. Sterilized in an autoclave permitted by Orange County Health Agency and EH&S and then disposed of in the broken glass container.

ii. Decontaminated with bleach or other appropriate decontaminant and then disposed of in the broken glass container.

iii. Transferred to a medical waste disposal site in a sharps disposal container.

3. All needles, scalpels, and blades must be disposed of in a sharps disposal container. Full sharp containers are brought to medical waste disposal sites for pickup and destruction off-campus.

4. All glass apparatus must be carefully inspected for cracks and other flaws before evacuation. Whenever feasible, evacuated or pressurized glassware must be taped or a shield placed between the glassware and the operator to contain glass fragments and chemicals in the event of implosion.

5. All laboratory equipment must be inspected on a regular basis by the laboratory workers, and replaced or repaired as necessary.

6. Frozen ground glass joints should be taken to the Glass Shop in Rowland Hall for “unsticking”. Cooling the glassware is sometimes effective. Serious cuts have occurred from researchers trying to do this themselves.

7. Use proper traps (filters or adsorbants) to protect house vacuum lines.

4.9 Personal Protective Equipment

1. Safety glasses meeting ANSI Z87.1 are required for laboratory workers and visitors to the laboratory as procedures dictate and will be worn at all times when in the laboratory.

2. Chemical goggles and/or a full-face shield must be worn during chemical transfer and handling operations as procedures dictate.

3. Laboratory coats are provided and must be worn at all times in the laboratory. Laboratory coats must be removed immediately upon discovery of significant contamination.

4. Appropriate chemical-resistant gloves must be worn at all times when skin contact with chemicals may occur. Wear two layers of gloves when added protection is needed.

Reusable gloves must be inspected and washed prior to re-use. Replace damaged or deteriorated gloves immediately. Gloves must be washed prior to removal from the hands.

Remove gloves immediately after working with toxic solvents that are readily absorbed through skin, such as phenol or carbon disulfide.

Many researchers use latex gloves for work with hazardous chemicals due to the wide availability of this type of glove. About 10% of the population will exhibit an allergic sensitivity to latex products.

Generally, nitrile gloves are preferable over latex and vinyl for most hazardous chemical work, but it is important to consult the Glove Selection Guidelines and Resources document, chemical vendor, or EH&S when selecting the proper glove for hazardous chemical work.

5. Thermal-resistant gloves must be worn for operations involving the handling of heated materials and exothermic reaction vessels. Thermal-resistant gloves must be asbestos free and should be replaced when damaged or deteriorated.

6. All personnel using respirators must obtain prior approval from EH&S and participate in the UC Irvine Respiratory Protection Program.

7. Remove all contaminated personal protective equipment before leaving the laboratory.

8. Refer to Personal Protective Equipment in the Laboratory Safety Guidelines for more information. Consult with your School EH&S Coordinator for assistance.

4.10 Personal Work Practices

1. The Laboratory Supervisor must ensure that each laboratory worker knows and follows the rules and procedures established in this plan. The Hazard Assessment and Corrections Tool is used to design a consistent and lab-specific laboratory worker training, in support of communicating the rules and procedures established in this plan.

2. All laboratory workers must remain vigilant to unsafe practices and conditions in the laboratory and must immediately report such practices and/or conditions to the Laboratory Supervisor. The Laboratory Supervisor must correct unsafe practices and/or conditions promptly. Recurring hazardous situations and unsafe practices should be incorporated into the work-unit Specific Training to increase laboratory workers understanding in the problematic areas.

3. Long hair and loose-fitting clothing must be confined close to the body or tied back to avoid being caught in moving machine/equipment parts and contaminated.

4. Do not wear high-heeled shoes, open-toed shoes, sandals, or shoes made of woven material.

5. Never perform unauthorized experiments.

6. Do not work alone in the laboratory without authorization.

7. Shorts, cutoffs, and miniskirts unnecessarily expose your skin to potential corrosives and are not safe.

8. Jewelry including rings, bracelets, and wristwatches in the laboratory can become contaminated and damaged by chemicals increasing chances of chemical exposure. Also, wearing jewelry increases probability of accidental contact with electrical sources or catch-points on equipment causing accidents.

9. Use volatiles inside the chemical fume hood.

10. Exposure to any laboratory chemical by any route--dermal, inhalation, ingestion, injection--must be avoided.

11. Chemicals must never be deliberately tasted or smelled.

12. Loose fitting, insulated gloves must be worn when handling cryogenics. Where splashing could occur during transfer of cryogenics, safety goggles and face shields should be worn. Boiling and splashing always occur when charging a warm container or when inserting warm objects into the liquid.

13. Never wear or bring lab aprons or lab coats or jackets into areas where food is consumed.

14. Do not prepare or store (even temporarily) food or beverages in the same area as hazardous chemicals. Never consume any food or beverage when you are in a chemical area. Do not chew gum or tobacco, and do not smoke or apply cosmetics in the laboratory.

15. Wash hands thoroughly after working with hazardous chemicals and before leaving the lab.

4.11 Container Labeling

1. All chemical containers in the laboratory must be labeled including waste containers. The label must be informative and durable, and at a minimum, will identify contents and hazards.

2. When hazardous chemicals are transferred out of the original container, a completed Hazardous Materials label must be affixed to the unlabeled container. View an example of a blank EH&S Hazardous Materials label at the EHS Website. EH&S recommends using the preprinted labels available in various electronic file formats from the Hazardous Waste Management website. Be careful to use the label designed for materials , not waste.

3. All waste container labels must include the words “Hazardous Waste,” the chemical name(s) of all constituents and the weight percentage, the Principal Investigator's name, department location (building name, room number and telephone number), and the date waste was first generated. View an example of a blank EH&S Hazardous Material Waste label at the EHS website. The EH&S preprinted waste labels—various electronic file formats available from the