CHEMICAL HYGIENE PLAN CRAWFORD HALL OF SCIENCE LAKE SUPERIOR STATE UNIVERSITY

Version 2.0
Version 2.0 July, 2007, Ben Zoppa and Roxann Huisman Version 1.0 May, 1994, Dr. David Myton Copyright Lake Superior State University

TABLE OF CONTENTS
LIST OF ACRONYMS AND ABBREVIATIONS INTRODUCTION ACKNOWLEDGMENTS CHAPTER 1 STANDARD OPERATING PROCEDURES

1 7 8 9 9 9 9 10 10 11 11 11 11 12 13 15 16 16 17 17 17 19 20 20 21 21 21 22 22 22 23 23 23 24 25

OVERVIEW OPERATING PROCEDURES o Working With Laboratory Chemicals o Selection of Chemicals

o o o o o o o o

Obtaining and Transporting Chemicals Personal Protective Equipment Location and Equipment to be used for Specific Procedures Personal Hygiene Measures Accident, Spill and Leak Procedures Chemical Storage Waste Disposal Procedures for Lab Operations

CHAPTER 2 CONTROL MEASURES

OVERVIEW ENGINEERING CONTROLS o Ventilation o Laboratory Safety Equipment PERSONAL PROTECTIVE EQUIPMENT o Eye Protection o Hand Protection o Foot Protection o Protective Clothing CHEMICAL HYGIENE PRACTICES o Safety Planning for New Experiments o Unattended Laboratory Experiments o Housekeeping

CHAPTER 3 LABORATORY HOODS AND PROTECTIVE EQUIPMENT

OVERVIEW VENTILATION FUME HOOD PERFORMANCE

CHAPTER 4 EMPLOYEE INFORMATION AND TRAINING

OVERVIEW EMPLOYEE INFORMATION EMPLOYEE TRAINING

25 25 26 28 28 28 29 29 30 30 30 31 31 32 32 32 33 33 33 33 34 34 34

CHAPTER 5 APPROVAL OF OPERATIONS

OVERVIEW PRE-APPROVAL

CHAPTER 6 MEDICAL CONSULTATION AND EXAMS

OVERVIEW

CHAPTER 7 CHEMICAL HYGIENE RESPONSIBILITIES

OVERVIEW PERSONNEL o Crawford Hall Safety Committee o Laboratory Inspections

CHAPTER 8 SPECIAL PRECAUTIONS

OVERVIEW o Class 1: Select Carcinogens o Class 2: Reproductive Toxins

o Class 3: High Acute Toxicity Compounds SPECIAL OPERATIONAL PROCEDURES o Designated Work Areas o Containment Devices o Handling of Hazardous Waste o Decontamination Procedures

APPENDICES APPENDIX A REFERENCES APPENDIX B OSHA STANDARDS SUBPART Z, 29 CFR 1910.1200 TOXIC AND HAZARDOUS SUBSTANCES HAZARD COMMUNICATION AND APPENDIX A OF SAID STANDARD APPENDIX C MIOSHA STANDARD: HAZARDOUS WORK IN LABORATORIES APPENDIX D MIOSHA STANDARD: HAZARDOUS WASTE OPERATIONS EMERGENCY RESPONSE PLAN 35 36

67 80

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APPENDIX E LABORATORY INSPECTION FORM APPENDIX F HOOD INSPECTION FORM APPENDIX G EMPLOYEE TRAINING PROGRAM APPENDIX H INCOMPATIBILITY OF COMMON LABORATORY CHEMICALS APPENDIX I GLOVE RESISTANCE TO VARIOUS CHEMICALS APPENDIX J COMMON LABORATORY FLAMMABLE AND COMBUSTIBLE CHEMICALS APPENDIX K FLAMMABLE LIQUID STORAGE LIMITS FOR LABORATORIES APPENDIX L COMMON LABORATORY CORROSIVES APPENDIX M COMMON LABORATORY OXIDIZERS APPENDIX N CLASSES OF PEROXIDIZABLE CHEMICALS APPENDIX O SHOCK SENSITIVE AND EXPLOSIVE CHEMICALS APPENDIX P CARCINOGENS APPENDIX Q NIOSH RECOMMENDED EXPOSURE LIMITS APPENDIX R EXPLANATION OF THE NFPA DIAMOND APPENDIX S RESISTANCE OF SELECTED CLOTHING MATERIALS TO VARIOUS CHEMICALS

111 113 114 125 128 130 132 134 135 136 139 140 150 157 159

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LIST OF ACRONYMS AND ABBREVIATIONS

ACGIH American Conference of Governmental Industrial Hygienists 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. Acute An adverse effect with symptoms of high severity that develop over a short period of time Allergen An agent capable of producing an immunologic reaction Assistant Secretary means the Assistant Secretary of Labor for Occupational Safety and Health, U.S. Department of Labor, or designee. Carcinogen (see select carcinogen). CFR Code of Federal Regulations 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 employer's 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. CHP Chemical Hygiene Plan Chronic An adverse effect with symptoms that develop slowly over a long period of time or that frequently recur 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 A liquid having a vapor pressure exceeding 40 psi at 100 deg. F (37.8 C) as determined by ASTM D-323-72.

(iii)

CRW Crawford Hall of Science 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, an area of a laboratory or a device such as a laboratory hood. DOT Department of Transportation 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 An individual employed in a laboratory workplace who may be exposed to hazardous chemicals in the course of his or her assignment EPA Environmental Protection Agency 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; 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.

(ii)

(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 selfsustained 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 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 Setaflash Closed Tester (see American National Standard Method of test for Flash Point by Setaflash Closed Tester (ASTM D 3278-78)).

(ii)

(iii)

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, hepatotoxins, 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.

IARC International Agency for Research on Cancer 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 nonproduction basis.

Laboratory scale means work with substances in which the containers used for reactions, transfers, and other handling of substances is 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 use of hazardous chemicals means handling or use of such chemicals in which all of the following conditions are met: (i) (ii) (iii) (iv) Chemical manipulations are carried out on a "laboratory scale;" Multiple chemical procedures or chemicals are used; The procedures involved are not part of a production process, nor in any way simulate a production process; and "Protective laboratory practices and equipment" are available and in common use to minimize the potential for employee exposure to hazardous chemicals.

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 employee's 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.

LC 50 The concentration of a substance in air that causes death in 50% of the animals exposed by inhalation, a measure of acute toxicity LD 50 The dose that causes death in 50% of the animals exposed by swallowing a substance, a measure of acute toxicity LSSU Lake Superior State University 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. MIOSHA Michigan Occupational Safety and Health Act MSDS Material Safety Data Sheet Mutagen Chemical which causes chromosomal damage (mutations) NTP National Toxicology Program

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. PEL Permissible Exposure Limit. The legally allowed concentration in the workplace that is considered a safe level of exposure for an 8-hour shift, 40 hours per week. Physical hazard means a chemical for which there is scientifically valid evidence that it is a combustible liquid, a compressed gas, explosive, flammable, an organic peroxide, an oxidizer pyrophoric, unstable (reactive) or water-reactive. PPE Personal protective equipment. 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. REL Recommended Exposure Level Reproductive toxin means 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) (ii) It is regulated by OSHA as a carcinogen; or 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 It is listed under Group 1 ("carcinogenic to humans") by the International Agency for research on Cancer Monographs (IARC)(latest editions); or 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.

(iii) (iv)

Sensitizer Chemical capable of creating an allergic reaction in certain individuals after an initial exposure SOP Standard Operating Procedure Target Organ Effect The organ system to which a chemical will specifically attack. Categorized as the following: (i) (ii) (iii) Hepatotoxins: chemicals which produce liver damage. Signs & Symptoms: Jaundice; liver enlargement. Chemicals: Carbon tetrachloride; nitrosamines. Nephrotoxins: Chemicals which produce kidney damage. Signs & symptoms: Edema; proteinuria. Chemicals: Halogenated hydrocarbons; uranium. Neurotoxins: Chemicals which produce their primary toxic effects on the nervous system. Signs & Symptoms: Narcosis; behavioral changes; decrease in motor functions. Agents which act on the blood or hematopoietic system: Decrease hemoglobin function; deprive the body tissues of oxygen. Signs & Symptoms: Cyanosis; loss of consciousness. Chemicals: Carbon monoxide; cyanides. Agents which damage the lung: Chemicals which irritate or damage pulmonary tissue. Signs & Symptoms: Cough; tightness in chest; shortness of breath. Chemicals: Silica; asbestos. Reproductive toxins: Chemicals which affect the reproductive capabilities include chromosomal damage (mutations) and effects on fetuses (teratogenesis). Signs & Symptoms: Birth defects; sterility. Chemicals: Lead; DBCP. Cutaneous hazards: Chemicals which affect the dermal layer of the body. Signs & Symptoms: Birth defects; sterility. Chemicals: Lead; DBCP. Eye hazards: chemicals which affect the eye or visual capacity. Signs & symptoms: Conjunctives; corneal damage. Chemicals: Organic solvents; acids.

(iv)

(v)

(vi)

(vii) (viii)

Teratogen Chemical which affects fetal development TLV Threshold Limit Value. The amount of exposure allowable for an employee in an 8hour day. TWA Time Weighted Average 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 A chemical that reacts with water to release a gas that is either flammable or presents a health hazard.

INTRODUCTION
R 325.70106 Chemical Hygiene Plan. Sub rule (1) Where hazardous chemicals as defined by these rules are used in the workplace, an employer shall develop and carry out the provisions of a written chemical hygiene plan that provides for both of the following: (a) Protecting employees from health hazards that are associated with hazardous chemicals in that laboratory. (b) Keeping exposures below the limits specified in R 325.70104. The Michigan Occupational Safety and Health Act (MIOSHA) standard: Hazardous Work in Laboratories (R 325.70101 - R 325.70114) extends new protections to employees who are assigned to a laboratory workplace. This standard supersedes all other MIOSHA standards except as provided in the standard and also supersedes the OSHA hazard communication standard 29 C.F.R. 1900.1200. The MIOSHA standard quoted above requires employers to develop a Chemical Hygiene Plan (CHP) to protect workers from hazards in the laboratory. The two broad performance goals for the Crawford Hall of Science Chemical Hygiene Plan can be stated as follows. First, to insure adequate protection of faculty, staff, and students from any hazards associated with the laboratory use chemicals within LSSU laboratories. Second, to keep employee and student exposure to chemicals below MIOSHA specified permissible exposure limits (PEL's). The LSSU Chemical Hygiene Plan is available to all employees, their representatives, and if necessary, representatives of MIOSHA. It is available to students and student employees, for whom its implementation is mandatory. Indeed, student employment involving the laboratory use of hazardous chemicals is contingent upon following the described safety and environmental guidelines in the plan. The LSSU Chemical Hygiene Plan for Crawford Hall of Science has been reviewed and approved by the Crawford Hall Safety Committee, University OSHA committee, the dean of the School of Science and Natural Resources, departmental chairs, and the president of the university or their designee. The effectiveness of the chemical hygiene plan will be reviewed and evaluated at least annually and updated as necessary. Discussion of the plan is encouraged, and improvements, proposed changes or questions relating to policy should be directed to the Chemical Hygiene Officer. The Chemical Hygiene Officer, working with the CRW Safety Committee, will reevaluate, revise, and update the plan periodically to reflect new safety information, better safety practices, and greater ease of implementation in accordance with the Laboratory Standard. The Chemical Hygiene Plan contains eight distinct elements and safety measures specified by the MIOSHA standard. These measures are designed to ensure employee protection in each of the following areas: [1] Standard Operating Procedures to be used when working with hazardous chemicals [2] Criteria to be used to determine and implement control measures to reduce exposure to hazardous chemicals [3] Measures to be taken to ensure that fume hoods and other protective equipment are functioning properly [4] The employee information and training program

[5] Particular operations or procedures that are hazardous enough that prior approval will be required before employees carry them out [6] A medical examination and consultation policy [7] Designation of a Chemical Hygiene Officer [8] Additional provisions for work with "select carcinogens", reproductive toxins, and substances with "high acute toxicity" Each of these elements is discussed in the eight chapters of this Hygiene Plan. Each chapter begins with an excerpt from the MIOSHA standard Rule 6, Sub rule (3) describing the required content. ACKNOWLEDGMENTS The chemical hygiene plan, while addressing the specific hygiene practices for the science laboratories at LSSU, draws many general concepts and principles from other sources. These sources included the appendices to the MIOSHA laboratory standard, the Model Chemical Hygiene Plan for Kentucky School Districts, The Chemical Hygiene Plan: Putting It All Together by TnT Partners, Compliance System for Hazardous Chemicals in Laboratories by Chemical Communications Systems, Inc, and a working draft of this plan prepared by Dr. Gene Wicks. Furthermore, the entirety of this article is based off and closely resembles the prior version written by Dr. David Myton in 1994. The major changes to be found are in the appendices, where missing information is now provided and extra materials have been added, mainly in an attempt to mimic other Michigan Universities and their Chemical Hygiene Plans.

CHAPTER 1 STANDARD OPERATING PROCEDURES

R 325.70106 Chemical Hygiene Plan Subrule (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: (a) Standard operating procedures relevant to safety and health considerations to be followed when laboratory work involves the use of hazardous chemicals. OVERVIEW Standard operating procedures are work practices and policies which have been deemed necessary to protect employees from chemical hazards in the laboratory. While these policies cannot anticipate every possible hazard or situation, they do describe those practices fundamental to good chemical hygiene under most circumstances. Many of the principles that should be used when working with laboratory chemicals can expressed in four general rules. (a) Minimize personal exposure to all laboratory chemicals, even to those of no known risk. Since few laboratory chemicals are without hazard, and specific lists for each and every chemical would require many volumes, general guidelines are adopted for all laboratory work. In all cases skin contact, inhalation or ingestion of with laboratory chemicals should be avoided. (b) Do not underestimate risks. Take special precautions for substances which present special hazards. (c) Maintain adequate ventilation. The best way to prevent exposure to airborne substances is to provide adequate ventilation, through the use of hoods and other ventilation devices. (d) Do not exceed the Permissible Exposure Limits (PEL's) established by OSHA, or the Threshold Limit Values (TLV's) set by the American Conference of Governmental Industrial Hygienists. OPERATING PROCEDURES Working with Laboratory Chemicals General guidelines for working with laboratory chemicals are found throughout the chemical hygiene plan. Specific guidelines and procedures are also described in later sections of the Chemical Hygiene Plan. Most of these guidelines are simple, "common-sense" safety practices. Identifying potential laboratory hazards, anticipating the consequences, and reducing or eliminating the risks by using appropriate "common-sense" safety precautions is the BEST approach to working with laboratory chemicals.

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Selection of Chemicals Before a chemical substance is selected for use in an operation, process or laboratory experiment, the supervisor or supervising faculty member should review the potential hazards of the substance under the conditions it will be used, and determine whether safer alternatives are available. The conditions in the lab at the time of use should also be considered to assure adequate ventilation, compatibility with other chemicals in use and the relative risk to exposure ratio. Other general approaches include: (a) Seek information and advice about hazards, plan appropriate protective procedures, and plan positioning of equipment before beginning any new operation. (b) Prior to obtaining a chemical, review the MSDS for that substance with attention given to the reactivity and health hazard sections, considering specifically how the chemical will be used. (c) At all times select the chemical with the least toxicity and lowest degree of physical hazard. Obtaining and Transporting Chemicals R 325.70109 Subrule (1) With respect to labels and material safety data sheets (MSDS) for hazardous chemicals, both of the following provisions apply: (a) Employers shall ensure that labels on incoming containers of hazardous chemicals are not removed or defaced (b) Employers shall maintain any MSDS that are received with incoming shipments of hazardous chemicals and ensure that MSDS are readily accessible to laboratory employees In accordance with the Federal and Michigan Occupational Safety and Health Acts, Lake Superior State University has established a written hazard communication program. This program is described in the LSSU Procedures Manual in the section entitled Business & Support Operations: Safety, Security and Health - Hazardous Materials Communication. The program identifies the shipping/receiving clerk as responsible for the proper labeling of incoming containers and maintaining the master file of Material Safety Data Sheets. Supervisors or Department heads are responsible for maintaining complete labeling of secondary containers and for maintaining a departmental MSDS file on materials employees will be exposed to in their work. A copy of the LSSU hazard communication program available in the department offices, the complete MIOSHA hazard communication standard is reproduced in Appendix B. The provisions of the Laboratory Standard, 325.70109 as quoted above, are addressed within this procedure. In addition to the content of the Hazardous materials communication, the following precautions and procedures should be observed: (a) The time and route of chemical transport should be planned to minimize potential for exposure to large numbers of people in the event of an incident (b) All containers of chemicals should be carried within a second container capable of containing the substance if the first container breaks or leaks. Employees should use a rubber pail or a cardboard box and appropriate cart as necessary. (c) The total amount transported should be kept small on any single trip (5 gallons is commonly recommended as a maximum quantity) (d) Only freight elevators should be used to transport chemicals, not stairs.

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(e) Gas cylinders must be stored and transported with their caps in place. Large cylinders must be transported using a cylinder cart. Personal Protective Equipment Some measure of protection is required for all persons present during the laboratory use of hazardous chemicals. The exact nature and extent of the protection is dependant on what is being used and under what circumstances. Protective equipment includes, but is not limited to, safety glasses, splash goggles, face shields, gloves, aprons, lab coats, and respirators. Refer to Personal Protective Equipment requirements found in Chapter 2 Control Measures. Location and Equipment to be used for Specific Procedures Because of the specific hazards associated with some laboratory chemicals and processes, some specific operations should be confined to limited areas in the lab to minimize exposure. Each supervisor or supervising faculty member should identify those processes in their labs requiring special handling and assign those chemicals or processes to the available fume hoods. The following guidelines should also be observed: (a) Fume hoods should be used for all procedures involving concentrated acids, alkalis and toxic chemicals with PEL's less than 50 ppm. (b) When using the fume hood, keep chemicals away from the face. (c) Monitor the operation of the hood and report any problems immediately. (d) Never use a closed system for carrying out chemical reactions that involve heating or evolution of a gas. Always vent experiments to either a fume hood or to the laboratory. (e) Use scrubbers to remove toxic chemicals from gaseous waste streams (e.g. a chilled, stirred 5 % sodium hydroxide scrubber for an acidic waste stream). (f) Check gloves, glove boxes or glove bags for leaks and test for adequate airflow before use. Personal Hygiene Measures The key to minimizing personal exposure to hazardous chemicals is the practice of good personal hygiene. In addition to the discussion of good hygiene practices found in Chapter 2, the following guidelines should be emphasized: (a) Minimize exposure to chemicals via the eyes, skin, nose, and mouth by using appropriate personal protective equipment and ventilation controls including a laboratory fume hood. (b) Wash hands before eating, drinking, or using gum or tobacco products. (c) Never eat, drink, smoke, or chew gum or tobacco inside a laboratory. (d) Never taste or smell chemicals. Do not use mouth suction to pipette chemicals or to start a siphon. Accident, Spill and Leak Procedures OSHA's Hazardous Waste Operations and Emergency Response Rule require all facilities to have a written emergency response plan for those spills that may involve significant risk. A copy of this MIOSHA regulation is included in Appendix D. The response plan should contain provisions for several key elements including the following: (a) Evacuation for people from the spill area and restriction of access to the area (b) Notification of proper authorities and individuals who will take charge of the incident
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(c) Appropriate containment and control measures (d) Equipment to be used (e) Decontamination The written emergency response plan should include procedures for ventilation failure, evacuation (including alarms for isolation areas), medical care, reporting and drills. For small to moderately-sized chemical spills of minimal risk in the lab, wear gloves, safety glasses or goggles, proper shoes, and a lab coat or lab apron, and clean up the spill using the clean-up kits provided in the lab. Contain the spilled material for subsequent treatment or disposal. Discard any broken glass into the special lab receptacles provided. Assure the proper disposal of the adsorbent or pillows used in the clean-up process. Metallic mercury and its compounds are subtle poisons which can be easily absorbed into the body by inhalation, ingestion, or skin contact. The chronic effects of mercury inhalation due to metallic mercury lost in the lab are cumulative and not readily reversible. Pools or droplets of metallic mercury should be collected by suction or cleaned up using a designated "mercury-spill cleanup kit." Mercury collected for reclamation should be stored in a high-density polyethylene bottle, and rags, sponges, or other such materials used in cleanup should be placed in a sealed plastic bag, labeled, and disposed of properly. In the case of accident requiring medical attention or assistance, contact Central Dispatch (911 from cell phones, or 9-911 from campus phones) immediately to arrange for an escort and any necessary transportation. All accidents must also be reported through the departmental office using the appropriate forms. Copies of the accident and incident forms are to be present in each laboratory and are available in the departmental office. The following guidelines regarding accidents in the laboratory do not replace the need for proper medical consultation and treatment. These guides are general recommendations only, taken from Appendix A of the Laboratory Standard. In the case of eye contact: promptly flush eyes with water for a prolonged period (15 minutes) and seek medical attention. In the case of ingestion: encourage the victim to drink large amounts of water, contact the poison control center if necessary and seek medical attention. In the case of skin contact: promptly flush the affected area with water and remove any contaminated clothing. If symptoms persist after washing, seek medical attention. Personnel trained in first aid should be available during working hours and an emergency room with medical personnel should be readily available. The most common injuries in the lab involve broken glass and heat burns. Treat minor burns as needed with antiseptic/antibacterial creams. For small cuts, the affected area should be washed with cold water and a band-aid should be applied. For larger cuts which may require stitches, severe burns, or for instances where chemicals may have been absorbed into the cut, medical attention should be sought. Have someone call the doctor before the injured person leaves the building, and make sure that the person is accompanied by a friend or staff member. Chemical burns may result when corrosive materials like strong acids, bases, oxidizers, and reducing agents are handled improperly. For chemical splashes, wash the affected area with water for 15 minutes and remove all contaminated clothing. Use the lab shower for spills over large areas of the body. After rinsing thoroughly, seek medical attention. Chemical Storage

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Chemical Classes The primary concerns for chemical storage are minimizing the amounts, avoiding contact between incompatible chemicals and ensuring that hazardous storage conditions (inadequate ventilation, light, heat, etc) are not present. The following guidelines should be used when storing various classes of chemicals: (a) Flammables, both liquid and solid, should be kept in a locking, fireproof cabinet. If flammables must be stored cold, an "explosion-proof" or "explosion-safe" refrigerator or cold room should be used. (b) Corrosives should be stored in a cool, dry place separate from all other chemicals. There are four general types of corrosive compounds: acids, bases, oxidizers, and reducing agents. The four different types should be stored separately from one another. (c) Reactive compounds which cannot be exposed to air or water should be stored separately in appropriate air or water-tight containers respectively. They should be kept in a cool, dry place. (d) Certain types of reactive compounds should receive special treatment. For example: cyanides, sulfides and sulfites should be stored separately away from acids in a cool, dry place. (e) Peroxides present a special storage hazard and should be monitored carefully. Diethyl ether, p-dioxane, tetrahydrofuran, and other commonly used peroxide-forming materials should be labeled with the date the container was first opened, and disposed of within six to twelve months of the opening date. (f) All other compounds not covered in the above categories should be stored alphabetically in a clean, ventilated stockroom storage area. General Guidelines The following procedures and guidelines apply to all storage of laboratory chemicals, both for long term storage and for temporary storage in the lab. Quantities present in the lab should be kept to minimums and be limited to only those materials needed for the current procedures. (a) Stockrooms/storerooms should not be used as preparation or repackaging areas, should be open during normal working hours, and should be controlled by one person. (b) Do not store chemicals above eye level and do not store them on the floor. (c) Avoid storing chemicals in fume hoods not designated for storage. If short term storage in fume hoods must take place, insure that the fume hood will be in continuous operation overnight and on weekends. (d) Store chemicals on lipped shelves which are securely attached to the wall. (e) Use chemically resistant trays for storage of corrosive liquids and solvents. (f) Store chemicals away from heat, out of direct sunlight, and away from high traffic areas. (g) Return chemicals to the stockroom when they are no longer being used for a class experiment or for research. (h) Store large gas cylinders upright, away from heat sources, and securely chained. (i) All gas cylinders not in use should be stored with the cap in place. (j) Passageways, stairways and hallways should not be used as storage areas. Access to exits, emergency equipment and utility controls should never be blocked. Waste Disposal The objective of the waste disposal program is to ensure that minimal harm to people, to other organisms, and to the environment will result from the disposal of waste laboratory chemicals. The hazards associated with such waste are present for the individual handling the material, for other occupants of the building who may be downstream from the disposal and for the

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environment as a whole. For these reasons the disposal of laboratory chemicals to the drain is forbidden without proper chemical evaluation, treatment and/or dilution. The LSSU Procedures Manual section on Hazardous Waste Disposal provides guidance for the on-site hazardous waste, storage, inventory, labeling, classification and the transport to disposal facilities in compliance with all Environmental Protection Agency and Department of Transportation regulations. The procedures manual, with section: Hazardous Waste Disposal, is available at the departmental offices. The following general guidelines provide additional information about waste handling in the lab. (a) Whenever feasible, chemicals should be recovered and recycled for reuse in the laboratory. Metals may often be recovered by extraction or precipitation procedures, and solvents may be recovered by distillation. (b) Return unused reagent chemicals to the Supply room for redistribution. (c) Treat wastes to make them less hazardous. Many hazardous wastes can be treated to become less hazardous or non-hazardous for disposal purposes. Acids and bases may be neutralized, oxidizing agents may be reduced, strong carcinogens may be oxidized, highly reactive substances may be converted to less reactive substances, and cyanides may be carefully treated with bleach. The treatment process should be done under carefully controlled addition, rate and temperature conditions, and under close supervision. (d) Consolidation of Wastes. As a general rule, the larger the mass or volume of a waste, the more expensive it is to dispose of the waste. It is more economical to concentrate wastes if this can be done safely. Sometimes a hazardous material will precipitate to form a solid and a non-hazardous liquid upon concentration. (g) Temporary storage of lab wastes is permitted in accordance with departmental policies. Appendix H describes a chemical compatibility system which may assist employees in determining and assessing the risks of chemical waste handling. Procedures for Handling Wastes Each faculty member is responsible for the proper handling of the wastes generated in their respective labs. Suitable collection points should be established for all used laboratory chemicals allowing for the segregation of those chemicals by compatibility, type and/or hazard. Where ever possible the used chemicals should be recovered, treated, consolidated or clearly labeled as unrecoverable laboratory wastes. Wastes should be removed from the laboratories to a central waste storage area at least once per week, and from the central waste storage area at regular intervals to long term storage. Each laboratory should provide suitable containers labeled Used Laboratory Solutions or Student Preparation: (compound name here) to receive materials unsuitable for direct disposal to the drain. Used laboratory chemicals which will be treated, consolidated or in some way handled to reduce the potential hazards shall NOT be labeled as wastes until the hazardous components have been consolidated or removed. Only the portions which are not treatable shall be declared nonrecoverable waste. All non-recoverable-waste containers must be labeled with a complete list of contents, the appropriate instructor's name, the course number, the experiment number, and the accumulation period. Such waste containers should have no labels other than the special orange lab waste label. Some dilute solutions of selected low-toxicity cations and anions may be suitable for disposal into septic drains. The following list, taken from Prudent Practices for Disposal for Chemicals from Laboratories, National Research Council, Washington, D.C.: National Academy Press. 1983 may be used to evaluate used laboratory solutions. Compounds whose anion and cation both

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come from this list are typically suitable for drain disposal with excess water, in quantities up to about 100 g at a time. Strongly acidic or basic compounds should be neutralized before disposal.

Cations Aluminum (III), Calcium (II), Copper (II), Iron (II) and (III), Hydrogen, Potassium, Lithium, Magnesium, Sodium, Ammonium, Tin (II), Strontium (II), Titanium (III) and (VI), Zinc (II), Zirconium (II) Procedures for Lab Operations

Anions Borate, Tetraborate, Bromide, Carbonate, Chlorate, Chloride, Bisulfite, OCN,Hydroxide, Iodide, Nitrate, Phosphate, Sulfate, Thiocyanate

In addition to the general procedures discussed above, each specific laboratory operation that involves significant hazards should have its own standard operating procedure developed. These procedures must be developed in a manner appropriate to the circumstances around such use. Procedures may differ for use of the same material in different settings and when used in different quantities. Guidelines illustrated here apply to normal use of hazardous materials, while other sections of the CHP apply to extremely hazardous chemicals or special measures. Each supervisor or supervising faculty member should develop similar procedures for the safe handling of hazardous laboratory chemicals used within the context of their respective laboratories. Two sample procedures are provided below. (a) Pouring, mixing or reacting significant volumes (greater than 10 mL) of severely irritating or corrosive chemicals: [1] Goggles or face shield, gloves and lab coat must be worn [2] The operation should be carried out under the hood or in the sink [3] At least one other person must be in the lab at the time (b) Use of volatile toxic chemicals: [1] All such chemicals will be handled under the hood [2] Hood operation will be checked before beginning the procedure [3] Employees will wash hands after handling [4] Any symptoms or accidental over-exposure must be reported

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CHAPTER 2 CONTROL MEASURES

R 325.70106 Chemical Hygiene Plan Subrule (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: (b) 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 particularly hazardous. OVERVIEW Control measures must be used when personal safety issues or health hazards are present. This chapter examines when and what types of protective control measures should be used. Protective apparel must be compatible with the required degree of protection for the substances being handled. There must be easily accessible drench-type safety showers, eyewash fountains, and fire extinguishers for each lab. Available in or near each lab should be fire alarms and telephones for emergency use, and any other items designated by the laboratory supervisor or supervising faculty. Harmful chemicals can inadvertently be introduced into the body by four general routes of exposure: inhalation, ingestion, skin contact, and injection (i.e. chemicals entering the body though cuts or skin punctures). There are three strategies to prevent exposure or to reduce harm in the event of exposure. Each of these strategies is introduced and discussed in the three subsequent sections of this chapter. Engineering Controls include approaches to reduce contact to hazardous materials through physical barriers, ventilation and equipment. Adequate ventilation is extremely important in experiments involving hazardous compounds, corrosive, flammable, or potentially explosive compounds. Such experiments should always be done inside a fume hood. Potentially explosive reactions should be done behind a lab shield. Compounds that are highly reactive toward air and water should be handled using proper syringe technique, in a dry box, or in a glove bag contained inside a fume hood. Personal protective equipment, properly used, can prevent significant exposure to chemicals. Safety glasses and proper footwear may be required in any LSSU laboratory based on the procedures in use. Gloves are mandatory protection from compounds that are infectious, toxic or corrosive. In addition, a lab apron or lab coat should be worn when working with relatively large amounts of these materials. If a pressure buildup or implosion is possible due to a chemical reaction or other laboratory operation such as vacuum distillations, a face shield should be worn as well. Good personal hygiene practices are the third strategy to reduce chemical exposure in the laboratory. Unnecessary contact with chemicals should be avoided. Washing the hands or exposed skin frequently is a good practice, and bathing after significant exposure or at the end of

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a workday is recommended. In the event of an accident, contaminated clothing should be removed immediately and fresh clothing should be worn. ENGINEERING CONTROLS Engineering controls include those physical accommodations within the laboratory facility designed to ensure and protect the health and safety of employees. These include the ventilation system, and the laboratory safety equipment. Routine laboratory safety equipment, such as fire extinguishers, fire blankets, eyewash stations, safety showers, and spill control kits are all important control devices to minimize personal harm and to prevent an accident from getting out of control. Ventilation Proper ventilation is essential to the safe operation of laboratories. Each laboratory must have an appropriate general ventilation system with air intakes and exhausts located so as to avoid intake of contaminated air. There must be adequate, well ventilated stockrooms and storerooms. Laboratories should be at negative pressure relative to the halls and surrounding classrooms so that contaminated air is not drawn out of the laboratory. All chemical hygiene related equipment and systems should undergo continuing appraisal and modifications when necessary. Furthermore the work conducted and its scale must be appropriate to the physical facilities available, and especially to the quality of the ventilation. Chapter 3 of this chemical hygiene plan is devoted to the proper functioning and operational performance of laboratory hoods and other protective equipment. Laboratory Safety Equipment Fume Hoods Laboratory type fume hoods are extremely important in providing adequate ventilation when working with hazardous compounds in the laboratory. They are to be present in all laboratories in Crawford Hall where hazardous chemicals are handled. The fume hoods are to be inspected periodically to insure adequate face velocities, and any necessary maintenance should be requested promptly. Chapter 3 describes the plan to ensure proper and adequate operation of fume hoods and other protective equipment. Portable Chemical Shields A Portable chemical shield is available it should be used whenever there is the potential for a chemical explosion or glass breakage due to high pressure or vacuum inside a vessel. The experimental apparatus and entire chemical shield should be used inside a laboratory hood if possible. Fire extinguishers Fire extinguishers are to be available in or near each laboratory. Four general fire classes exist with a different type of fire extinguisher appropriate for use on each class. Table 2-1 shows the four general classes of fire, the types of fuel present in each class, and the types of fire extinguishers that can be safely used to put the corresponding fire out. With regard to the information in Table 2-1, there are a few cautionary notes. Water-based extinguishers are useful only for Class A fires and should not be used for extinguishing fires of any other type. Aqueous film-forming foam extinguishers (AFFF) conduct electricity and should not be used on Class C fires. Using multipurpose dry chemical extinguishers in a confined area may produce a cloud that reduces visibility. Also, halon 1211 may be toxic if inhaled (at >4 % halon/unit air volume) and can decompose to give dangerous by products at 900F (480C). It is

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also important to note that carbon dioxide fire extinguishers may cause frostbite, and suffocation is possible if they are used in a confined area. Carbon dioxide extinguishers with a metal discharge horn will also conduct electricity and should never be used on a Class C fire. Finally, a Class ABC rated fire extinguisher should NEVER be used on a Class D fire since it may make the fire worse. Class D fires should be smothered with sand or a Class D fire extinguisher Fire Blankets Fire blankets should be provided in all Crawford Hall laboratories where flammable compounds may be used for instructional and/or research purposes. Emergency Eyewash Stations Eyewash stations should be checked bimonthly to make sure that they are working properly; any required maintenance is to be performed promptly. Eyewash stations should be present or immediately available in all Crawford Hall laboratories, storerooms, or stockrooms where hazardous chemicals are handled or stored. Prominent signs should identify the presence and location of this and other safety and first aid equipment in the lab.

TABLE 2.1 General Classes of Fires and Fire Extinguishers Class Fuel Source (examples) Appropriate Fire Extinguisher Type

Ordinary Combustibles: (wood, Water based; Aqueous film-forming paper, rubber, natural foam (AFFF); Multipurpose dry fibers, some plastics) chemical; Halon 1211 Flammable Liquids: (Flammable liquids and gases, greases, tars, oil-base paints, and other volatile liquids)

Carbon dioxide; Dry chemical; Halon 1211; Multipurpose dry chemical; Filmforming foam (AFFF)

Electrical: (energized Dry chemical; Halon; Multipurpose dry electrical wiring or chemical; Carbon dioxide without a electrical equipment) metal discharge horn

Combustible Metals: (solid sodium metal or Specialized class D; Do NOT use an lithium metal) ABC type fire extinguisher

This information was obtained from Gold, David T., Fire Brigade Training Manual, National Fire Protection Association, Quincy, MA, 1982, pp. 58-71.

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Emergency Safety Showers An easily accessible drench-type safety shower or drench hose should be present wherever hazardous chemicals are stored or used. Prominent location signs should identify the presence and location of this and other safety and first aid equipment in the lab. The proper operation of safety showers should be checked every 3 to 6 months, and prompt maintenance provided if necessary. Spill Control Supplies Spill control equipment should be present in each laboratory, stockroom, and storeroom where significant quantities of hazardous chemicals are stored or used. A basic spill kit should include Hazorb spill control pillows, acid neutralizing powder, caustic (base) neutralizing powder, a solvent adsorbent, a brush, and a dustpan. Additional or specialized spill materials may be required for the specific processes or needs of individual laboratories, as determined by the department head or supervising faculty. A mercury spill cleanup kit is available in the chemistry stockroom and special attention must be given to the complete and proper cleanup of mercury spills. Signs and Labels Prominent signs and labels of the following types should be posted: emergency telephone numbers; identity labels showing the contents of containers not in immediate use by a worker, and the associated hazards; location signs for safety showers, eyewash stations, other safety and first aid equipment, exits, and areas where food and beverage consumption and storage is permitted/prohibited; warnings at areas or equipment where special or unusual hazards exist. Specific examples of signs and labels concerning chemically-related safety, health, and environmental issues in Crawford Hall are given below. 1. A laboratory authority list must be on the door of each lab showing the faculty member(s) who use the lab as well as a phone number where each can be reached. 2. In the event of a fire, accident, flood, or hazardous chemical spill, a faculty member must be contacted. 3. A laboratory's specific safety policies must be posted inside the lab for all students to read and consult. 4. Location signs for safety equipment and/or spill cleanup equipment must be present. 5. Hazard warning signs must be posted in appropriate areas where flammable materials, biological hazards, or other potentially hazardous materials may be present. 6. All laboratory chemical containers should have appropriate labels. Student unknowns should be labeled in accordance with departmental policy. 7. The date that all peroxidizable compounds like ethyl ether, p-dioxane, and tetrahydrofuran are opened, and their expiration date, should be written on the respective labels. 8. Chemical solutions that are prepared for a class should reflect the contents, the course number, and the date on the label. 9. All used chemical containers and unrecoverable waste containers must be labeled with a complete list of contents, the appropriate instructor's name, the course number, the experiment number, and the accumulation period. 10. LSSU chemical waste containers should have no labels other than the special orange lab waste label. PERSONAL PROTECTIVE EQUIPMENT Personal protective equipment (PPE) is a term used to describe variety of products worn by laboratory workers designed to protect those workers from safety and health hazards. Protective equipment is required anytime there is a possibility that the worker may be exposed to a

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hazardous chemical. The level of protection required depends on the specific hazards involved and the quantities of materials handled. There are clear limitations to all types of PPE. Such limitations must be considered when selecting equipment for any given task. Limiting factors for PPE protection include: proper fit and selection; comfort vs. protection; restrictions to sight, hearing, touch, and movement; proper maintenance; equipment lifetimes. All personal protective equipment should be examined before use to ensure the equipment will be able to provide the needed level of safety. The following sections discuss some types of PPE, each supervisor or supervising faculty must assess the operations within their own labs and determine the types and levels of protection required for the assigned tasks. Eye Protection Proper eye protection should be worn at all times in laboratories where people may come in contact with hazardous chemicals. Eye protection may be required in all laboratories (Chemistry, Biology, Geology and Physics) depending on the specific operations performed. Supervisors and supervising faculty must assess the operation and require a level of eye protection appropriate to the assigned task. Some general considerations regarding the choice of eye protection include the following. Contact lenses are NOT appropriate in cases where hazardous chemicals may contact the eye, and in fact contacts may actually increase the chance of injury if a chemical splash into the eye takes place. Prescription eyewear offers little to no protection against chemical splash or impact resistance to flying particles unless they are ANSI Z87.1 rated. Visitor type glasses do not provide sufficient protection against chemical splashes and should not be used when handling hazardous chemicals and solutions which may be splashed. Indirectly vented chemical splash goggles should be used when handling concentrated reagents or hazardous materials. Full face shields should be used when working with systems under pressure. In all cases select a level of eye protection with ensures adequate protection for the tasks assigned. Hand Protection Proper hand protection is very important when working with toxic, corrosive, or flammable materials. Since the physical properties of hazardous compounds vary, there have been several different types of glove materials developed to work with different compounds. Table 2.2 gives some common examples of proper glove materials for use with acids, bases, and solvents. Wear appropriate gloves when the potential exists for contact with toxic materials, materials that may cause irritation, allergic sensitization or skin absorption. Consult the MSDS for the chemical to ensure that the type of glove material used is protective for the substance. Latex gloves can be used safely for handling many solids and for handling dilute aqueous solutions of many inorganic materials. Latex gloves are quite popular due to their flexibility, it is easier to manipulate lab equipment while wearing them, and they may seem more comfortable. Latex gloves are, however, the poorest protection of any of the glove materials discussed for use with acids, bases, and organic solvents. This is well known from "breakthrough studies" where the average time of chemical breakthrough for glove materials is determined with respect to a given compound. While it is mandatory that all students and employees have proper hand protection when working with potentially hazardous materials, it is also recognized that certain common laboratory operations can be performed safely without gloves. Should contamination occur, the hands can be washed in the sink with soap and water.

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Supervisors and supervising faculty should determine the type of gloves and level of protection required for the assigned laboratory tasks. Adequate glove protection should be made available as necessary. Before each use, inspect gloves carefully for discoloration, punctures, and tears. Discard them when they become contaminated or damaged. Foot Protection Adequate protection for employee feet includes a prohibition against open-toed shoes (e.g. sandals, flip-flops, and bare feet) in the laboratory. This guards against foot injury due to glass breakage or accidental chemical spills. Furthermore canvas or cloth shoes which may absorb any material spilled on them should be discouraged. TABLE 2.2 GLOVE MATERIALS Chemical compatibility and breakthrough time test data are available from glove suppliers (for example Lab Safety Supply January 97 catalog 7A p288). Breakthrough times are based on controlled conditions; users are advised to conduct their own backup tests to confirm suitability for the application desired. Protective Clothing A lab coat or lab apron should be used when working with potentially toxic, corrosive, or flammable compounds that may inadvertently be splashed onto clothing. It is much less expensive to buy a lab apron than it is to replace expensive jeans, shirts, blouses, or other street clothing. Chemical suits are routinely worn in industry and in environmental cleanup situations where a large amount of uncontained hazardous material may be present. A face shield should be used in conjunction with a fume hood or a laboratory safety shield when working with substances that may react violently or create pressure. CHEMICAL HYGIENE PRACTICES Personal hygiene practices are direct and easily implemented methods to reduce exposure to hazardous materials. In addition to those practices discussed in other sections of the CHP, hygiene practices may include the following: 1. Use a properly operating fume hood to vent gases or to work with potentially hazardous or noxious materials. 2. Never taste or smell chemicals in the laboratory. 3. Do not use mouth suction to pipette chemicals or to start a siphon; use a pipetting device or aspirator to create a vacuum. 4. Wash the hands and arms thoroughly before leaving the laboratory, even if gloves have been worn. 5. Take a bath after work or after lab if clothes have been inadvertently contaminated. Note: In the event of an accident, contaminated clothing should be removed immediately and fresh clothing should be worn. 6. Wash contaminated clothing separately from other clothing items. 7. Never eat, drink, smoke, or chew tobacco or gum inside a laboratory, and do not store food or beverages meant for consumption in lab refrigerators.

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8. Avoid working alone in the laboratory if you are working with hazardous materials or doing potentially hazardous work. 9. Keep lab spaces, including fume hoods, clean and uncluttered to prevent accidental spills and glass breakage. 10. Avoid practical jokes or other behavior which might confuse, startle, or distract another worker. 11. Follow proper handling procedures for biological specimens and infectious wastes. 12. Dispose of broken glass only in approved containers, not the regular trash. 13. Always be alert to unsafe conditions or actions and correct them immediately. Remember that someone else's accident can be as dangerous to you as any YOU might have. 14. Minimize exposure to chemicals via the eyes, skin, nose, and mouth by using appropriate personal protective equipment and ventilation controls, including a laboratory fume hood. Safety Planning for New Experiments The approach used for safety planning of new experiments in academic laboratories should be the same as that used by safety planners in industry. When designing a new experiment, search for potential hazards in each of three major areas--the physical properties of the chemicals, the experimental procedure, and the manipulation of the equipment. Also consider what may happen if equipment breaks down, the electricity is shut off, the water is shut off, a fire occurs, or you are burned by a corrosive chemical. Evaluate the probability of a potential hazard happening and the severity of its consequences. Then attempt to reduce the risks by one or both of the following approaches: by reducing the probability that a given hazard might happen or by reducing the severity of the consequences if it really does happen. Unattended Laboratory Experiments Unattended laboratory experiments are permitted only if the supervisor or supervising faculty in charge of a project knows and approves of the unattended operation. In such a case, the experiment should be well secured and some thought must be given to anything that might go wrong during the experimenters absence. Before leaving, the experimenter should affix a sign on or near the experiment giving his/her name and telephone number, the date, the time, the chemical reaction or chemicals involved in the experiment, and the advisor's name (if applicable). If anything goes wrong with the experiment or if anyone has any questions about it, the experimenter or his/her advisor (if any) should be contacted. Housekeeping Lab instructional and research areas, storage rooms, and preparation rooms should be kept clean and free from obstructions. There should not be any chemicals or any glassware cluttering the benches nor should carts and chairs block the aisles. Likewise, the fume hoods should have neither chemicals nor glassware cluttering them, and the hoods should be used only in accordance with the designated purposes. Once chemicals and equipment are no longer in use, they should be returned to their proper storage area. Equipment should be cleaned before being returned to the stockroom.

Chemical wastes should be disposed of properly as described previously in the CHP. Contents of unlabelled or improperly labeled containers should be disposed of promptly. Stairways and hallways should never be used to store chemicals and equipment even for
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short periods of time, and instructional laboratories should not be used for extended storage of equipment that no longer works.

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CHAPTER 3 LABORATORY HOODS AND PROTECTIVE EQUIPMENT

R 325.70106 Chemical Hygiene Plan Sub rule (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: (c) A requirement that laboratory-type hoods and other protective equipment are functioning properly and the specific measures that shall be taken to ensure the proper and adequate performance of such equipment. OVERVIEW The fume hood is probably the single most important equipment used to control employee exposure to hazardous chemicals in a laboratory. Fume hoods occupy a central position within the plan to control employee exposures. Laboratory fume hoods require regular monitoring, inspections, and maintenance to ensure proper and adequate performance. The level of performance for any given hood is dependant on the type of operations performed within the hood. In general however the minimum face velocity of hoods should be monitored and work within the hood kept a safe distance behind the face. Other equipment, such as glove boxes, isolation/incubation rooms, and freezers must also be included in a program of regular inspection and maintenance. VENTILATION A system of general ventilation must be provided for the laboratory. This system should provide a source of air for breathing and for input to local ventilation devices. This system should not be relied on for protection against toxic substances released into the laboratory. The system should ensure that laboratory air is continually replaced, preventing increase of air concentrations of toxic substances during the working day. This system should direct the air flow into the laboratory from non-laboratory areas and out to the exterior of the building. Exhaust outlets for vented air should be located at a site remote from any fresh air intake for the building. Such a system will leave the laboratories at a relative negative pressure when compared to the hallways. Ventilated storage cabinets, canopy hoods, etc. should be provided as needed, each with a separate exhaust duct. Modifications to the ventilation system should be made only if thorough testing indicates worker protection from airborne toxic substances will continue to be adequate. The performance of the general ventilation system should maintain 4-12 room air changes per hour, if local exhaust systems such as hoods are used as the primary method of control. If this is the case the hoods must be left in operation whenever the lab is in use. The air flow should not be turbulent and should be relatively uniform throughout the laboratory. Air flow into and within the hood should not be excessively turbulent, and hood face velocities should be adequate (typically 60-100 linear feet per minute). The quality and quantity of the ventilation should be regularly monitored and evaluated (at least every 3 months), and reevaluated whenever a change in the local ventilation devices is made.

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FUME HOOD PERFORMANCE The specific ventilation capacity of each laboratory type fume hood is dependent on the operations carried out in the hood and the hazards associated with the substances handled. In general, a laboratory hood with 2.5 linear feet of hood space per person should be provided for every two workers if they spend most of their time working with chemicals, and each hood should have a continuous monitoring device to allow convenient confirmation of adequate hood performance before use. If there are not enough of the proper types of hoods in the lab for the operations assigned, or the performance of the hoods and/or ventilation system are not adequate for those operations, then those operations must be restricted or additional hood capacity acquired. Regular inspection and monitoring of laboratory fume hoods is essential to ensure their proper and adequate performance. Contained within Appendix is the hood inspection checklist. Key points within the checklist include: the method of measurement; minimum standards for performance; frequency of inspection; communication within the university; hood condition and location; frequency and type of use; and the presence of other control measures (glove boxes, isolation rooms, etc.) The records and reports generated through the inspection program should be maintained by the chemical hygiene officer with the Crawford Hall of Science Safety Committee.

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CHAPTER 4 EMPLOYEE INFORMATION AND TRAINING

R 325.70106 Chemical Hygiene Plan Sub rule (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: (d) Provisions for employee information and training as prescribed in R 325.70107. OVERVIEW A regular and ongoing employee information and training program is an essential component of the universities efforts to ensure the health and safety of its employees. This chapter of the Chemical Hygiene Plan describes our program to provide this information and training, the content of that program, and employee records related to the program. R 325.70107 Sub rule (1) An employer shall provide employees with information and training to ensure that they are apprised of and understand the hazards of chemicals present in their work areas. Sub rule (2) Such information shall be provided at the time of an employee's initial assignment to a work area where hazardous chemicals are present and before assignments that involve new exposure situations. Refresher information and training shall be provided by the employer to ensure that an employee is aware of the risks of exposure to hazardous chemicals. EMPLOYEE INFORMATION The Laboratory Standard describes five mandatory topics of instruction within the category of employee information. The informational content required by the Standard is met at LSSU through a written communication, with the necessary information summarized in Table 4.1. Table 4.1 shall be provided to all employees at the time of initial hire and made available during all ongoing training activities. The mandatory topics to be included in employee information include the following:

The contents of R 325.70101-70114 "Hazardous Work in Laboratories", which shall be made available to employees The location and availability of the Chemical Hygiene Plan The permissible exposure limits for MIOSHA-regulated substances or the recommended exposure limits for other hazardous chemicals if there are no applicable MIOSHA rules Signs and symptoms associated with exposure to hazardous chemicals that are used in the laboratory The location and availability of known reference material on the hazards, safe handling, storage, and disposal of hazardous chemicals found in the laboratory, including material safety data sheets (MSDS) received from a chemical supplier.

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EMPLOYEE TRAINING The employee training program is comprised of classroom type instruction and is mandated to address three key topics. The employee training program must include:

Methods and observations that may be used to detect the presence or release of a hazardous chemical The physical and health hazards of chemicals in the work environment The measures employees can take to protect themselves from health hazards, including specific procedures that the employer has implemented to protect employees from exposure to hazardous chemicals.

The training program must also train the employee in the applicable details of this written chemical hygiene plan. An outline of the employee training program is provided in Appendix G, listing the key points which are covered in the training. Records of employee training, attendance logs, and other relevant notes are to be maintained by the CRW Safety Committee. TABLE 4.1 EMPLOYEE INFORMATION The following table contains mandatory information related to employee health and safety. This information is to be made available to all employees upon initial hire and during all subsequent training opportunities.

The contents of R 325.70101-70114 Hazardous Work in Laboratories: The MIOSHA Laboratory Standard has been provided to every faculty member assigned to or supervising laboratory courses, is contained within the appendices of the chemical hygiene plan, is available from the Crawford Hall Safety Committee, from the departmental office and from the LSSU employee relations office. The location and availability of the Chemical Hygiene Plan: The Crawford Hall chemical hygiene plan is available at each departmental office within Crawford Hall, from members of the CRW Safety committee and from the LSSU employee relations department. The permissible exposure limits for MIOSHA-regulated substances or the recommended exposure limits for other hazardous chemicals if there are no applicable MIOSHA rules: The appendices to the chemical hygiene plan contain complete listings of exposure limits as defined by OSHA, NIOSH, ACGIH and the EPA. These reference lists, along with MSDS sheets for all chemicals used in the laboratory should be consulted in evaluating the exposure risk and hazards for any material. Signs and symptoms associated with exposure to hazardous chemicals that are used in the laboratory: MSDS sheets for the chemicals used in each laboratory shall be consulted in determining the signs and symptoms of exposure. MSDS sheets are available in the departmental offices, LSSU Purchasing Office and Health Services Office. Additional sources of information on chemical exposure can be found in the Merck Index, copy available at the library. The location and availability of known reference material on the hazards, safe handling, storage, and disposal of hazardous chemicals found in the laboratory, including material safety data sheets (MSDS) received from a chemical supplier.

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MSDS sheets are available in departmental offices, at the LSSU Purchasing Office, and at the LSSU Health Services Office. Additional reference materials can be obtained from the CRW Safety Committee and from the departmental library. Consult supervisor for further guidance about the materials used in your laboratory.

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CHAPTER 5 APPROVAL OF OPERATIONS

R 325.70106 Chemical Hygiene Plan Sub rule (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: (e) The circumstances under which a particular laboratory operation, procedure, or activity shall require prior approval from the employer or the employer's designee before implementation. OVERVIEW There may be a limited number of procedures in laboratories that are significantly more hazardous than all of the other activities of the lab. High hazard activities always should be performed by an individual well acquainted with all of the safety policies and a thorough understanding of the nature of the hazards. PRE-APPROVAL There are three factors to consider in deciding whether or not to require pre-approval of an operation. These factors include the potential hazard of the operation, the dependability and level of safety awareness of the employee, and finally what preventative measures are possible and the extent to which a pre-approval policy will enhance their use. Each supervisor and supervising faculty should consider the operations undertaken within their respective laboratory settings and assess whether a pre-approval policy may be needed. In doing so one should consider the worst-case scenario should the operation be performed in the most inappropriate manner possible. For example, what are the key elements in carrying out the procedure safely, and will pre-approval promote safe practices? Are the employees involved in the operation significantly less familiar with the hazards, their causes, or the logistical operation of the lab than the senior person who would give oversight and approval? Finally, how frequently is the operation performed and what is the availability of the supervisor to provide approval?

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CHAPTER 6 MEDICAL CONSULTATION AND EXAMS

R 325.70106 Chemical Hygiene Plan Sub rule (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: (f) Provisions for medical consultation and medical examinations in accordance with R 325.70108. OVERVIEW The MIOSHA Laboratory Standard rules require that employers make available to employees the opportunity to receive medical evaluation in cases where there is some reason to believe that the employee has been affected by exposure to a hazardous chemical. The Standard, whose full text is printed in Appendix C, describes the provisions for medical consultation and examination. Excerpts from several relevant sections of the Standard are included below. The complete text should be consulted for additional information. The LSSU employee relations office should be contacted directly by the employee to arrange for medical evaluation. Such evaluations are to be provided without cost to the employee, without loss of pay, and at a reasonable time and place. R 325.70104 For laboratory uses of MIOSHA-regulated substances, an employer shall assure that the laboratory employees' exposures to such substances to not exceed the permissible exposure limits specified in MIOSHA occupational health standards R 325.70105 Sub rule (1) An employer shall measure an employee's exposure to any substance that is 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 permissible exposure limits (PEL). R 325.70108 Sub rule (1) An employer shall provide all employees who work with hazardous chemicals an opportunity to receive the following medical attention, including any follow-up examinations which the examining physician determines to be necessary: (a) When an employee develops signs or symptoms that are associated with hazardous chemicals . . . (b) If exposure monitoring reveals an exposure level that is routinely above the action level . . . (c) When an event takes place in the work areas . . . that results in the likelihood of a hazardous exposure . . .

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CHAPTER 7 CHEMICAL HYGIENE RESPONSIBILITIES

R 325.70106 Chemical Hygiene Plan Sub rule (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: (g) Designation of personnel who are responsible for implementing the chemical hygiene plan, including the assignment of a chemical hygiene officer and, if appropriate, establishment of a chemical hygiene committee. OVERVIEW Responsibility for chemical hygiene and laboratory safety within LSSU laboratories rests upon all members of the university community. The safety of any one individual is vitally linked to the safe practices of the other members of the lab. As recommended in, and taken from, the appendices to the MIOSHA standard, section B, the following paragraphs outline the responsibilities and obligations of the university community as related to the standard. PERSONNEL Responsibility for chemical hygiene rests at all levels of the university, including those listed below: Chief Executive Officer, who has ultimate responsibility for chemical hygiene within the institution and must, with other administrators, provides continuing support for institutional chemical hygiene. Supervisor of the Department, or other administrative unit, who is responsible for chemical hygiene in that unit. Chemical Hygiene Officer, whose appointment is essential and who must: (a) work with administrators and other employees to develop and implement appropriate chemical hygiene policies and practices; (b) monitor procurement, use and disposal of chemicals used in the lab; (c) see that appropriate audits are maintained; (d) help supervisors and supervising faculty develop precautions and adequate facilities; (e) know the current legal requirements concerning regulated substances; and (f) seek ways to improve the chemical hygiene program. Laboratory Supervisors and Supervising Faculty, who have overall responsibility for chemical hygiene in the laboratory including responsibility to: (a) ensure that workers know and follow the chemical hygiene rules, that protective equipment is available and in working order, and that appropriate training has been provided; (b) provide regular, formal chemical hygiene and housekeeping inspections including routine inspections of emergency equipment; (c) know the current legal requirements concerning regulated substances; (d) determine the required levels of protective apparel and equipment; and (e) ensure that facilities and training for use of any material being ordered are adequate.

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Laboratory Worker, who is responsible for: (a) planning and conducting each operation in accordance with the institutional chemical hygiene procedures; and (b) developing good personal chemical hygiene habits. Crawford Hall Safety Committee The Safety Committee shall consist of the Chemical Hygiene Officer and at least four faculty and/or staff members from within Crawford Hall representing each academic discipline involved in the laboratory use of hazardous chemicals. The committee is expected to carry out the following duties with regard to the Chemical Hygiene Plan: 1. Assist the Chemical Hygiene Officer in periodic inspections for safety hazards and properly functioning safety equipment in Crawford Hall laboratories. 2. Schedule periodic laboratory safety seminars for all work-study students, faculty staff and interested students. 3. Assist the Chemical Hygiene Officer in reevaluating, improving, and updating the Chemical Hygiene Plan. 4. Assist faculty members in obtaining the proper protective equipment needed for instructional and/or research use. 5. Assist the department chairpersons in evaluating lab safety improvements and lab safety equipment. 6. Develop and update the inventory used in the chemical tracking process. 7. Maintain current records for safety inspections and for safety equipment (e.g. fume hood performance). Laboratory Inspections Comprehensive laboratory inspections will be done on a yearly basis while less rigorous inspections will be performed quarterly. The Crawford Hall Safety Committee will participate in the comprehensive safety and housekeeping inspections, while the quarterly inspections will be performed by the Chemical Hygiene Officer. The LSSU Laboratory Inspection form is included in Appendix . Included in the regular inspections are the following items: 1. 2. 3. 4. Check the fire extinguishers. Record the fume hood ventilation flow in fpm. Inspect safety equipment (e.g. safety shower, eyewash, spill control equipment). Evaluate housekeeping practices. 1. Spot check for safe chemical handling.

Formal records of the laboratory inspections will be kept on file as a part to the chemical hygiene plan by the CRW Safety committee.

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CHAPTER 8 SPECIAL PRECAUTIONS

R 325.70106 Chemical Hygiene Plan Sub rule (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: (h) Provisions for additional employee protection for work with particularly hazardous substances, such as select carcinogens, reproductive toxins, and substances that have a high degree of acute or chronic toxicity. OVERVIEW As described in the above MIOSHA rule there are three classes of compounds which must receive special consideration. Each of the three classes are defined by different criteria, described in the sections to follow. Class 1: Select Carcinogens Select carcinogens are defined as those substances that meet any of the following four criteria. The chemicals specified by these criteria are subject to expansion and revision. OSHA-regulated carcinogens The following substances are specifically designated as carcinogens and OSHA has written standards for these materials. Changes to this list can be identified through the local OSHA office or from the current Code of Federal Regulations (29 CFR 1910.1000). The following substances are OSHA-regulated carcinogens: Asbestos, Benzidine, Inorganic arsenic, 2,4-Nitrobiphenyl, 4-Aminodiphenyl, Benzene, a-Napthylamine, Ethyleneimine, Coke oven emissions, Methyl chloromethyl ether, beta-Propioactone, 1,2-dibromo-3-chloropropane, 3',3'-Dichlorobenzidine, 2-Acetylaminofluorene, Acrylonitrile (and its salts), 4Dimethylaminoazobenzene, Ethylene oxide, bis-Chloromethyl ether, N-Nitrosodimethylamine, beta-Napthylamine, Vinyl chloride National Toxicology Program (NTP) All the chemicals listed in the "Annual Report on Carcinogens" published by the National Toxicology Program as "known to be carcinogens". This list is reprinted in Appendix . International Agency for Research on Cancer (IARC) All the chemicals listed in the publication "International Agency for Research on Cancer Monographs" under the list titled: "Group 1 Carcinogenic to Humans". This list is reprinted in Appendix . Other Lists Chemicals that appear in the aforementioned NTP document on the list headed "reasonably anticipated to be carcinogens", or in the aforementioned IARC document on the lists headed 2A (probably carcinogenic to humans) and 2B (possibly carcinogenic to humans) and also meet the following criteria:

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"Causes a 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 levels of less than 10mg/m3 b. After repeated skin application of less than 300mg/kg of body weight per week; or c. After oral dosages of less than 50 mg/kg of body weight per day Class 2: Reproductive Toxins OSHA defines these chemicals as substances which affect reproductive capabilities including chromosomal damage (mutations), and effects on fetuses (teratogenesis). Employers and employees may be aware of this potential through inspection of the MSDS for the substances in use in the laboratory. Class 3: High Acute Toxicity Compounds The Hazard Communication Standard, is used by OSHA to define those compounds with high acute toxicity, uses the following criteria: a. median LD 50 of 50 mg/kg orally in albino rats weighing 200-300 grams b. median LD 50 of 200 mg/kg by continuous contact for 24 hours with the bare skin of albino rabbits weighing between two and three kilograms c. median LC 50 in air of 200 ppm (or 2 mg/liter) continuous inhalation for one hour All three classes of compounds described above fall into the single category in the laboratory standard: particularly hazardous substances. For any such chemical, when it is used in a lab, the employer must make provisions for additional protection where appropriate, to include special operational procedures. Supervisors or supervising faculty whose laboratory operations include the use of particularly hazardous substances must follow the guidelines described below for special operational procedures. SPECIAL OPERATIONAL PROCEDURES Designated Work Areas R 325.70106 Sub rule (3) Part (h) Specific consideration shall be given to the following provisions, which shall be included where appropriate: (i) The establishment of a designated area or areas that indicate the physical limits of exposure to particularly hazardous substances Separate areas shall exist for the departments of Geology, Biology, Chemistry, Physics, etc so as to minimize the amount of hazardous materials a student or faculty member will come into contact with on a day to day basis. Senior research involving hazardous materials, especially in the departments of biology and chemistry, will be kept to their assigned areas. Fume hood shall serve as further designation of work areas, as all hazardous-fume producing chemicals and experiments shall be kept in a well ventilated hood. Fume hoods shall be left in the closed or down position when not being used.

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All hazardous materials shall be kept in their designated areas when stored during use in a laboratory, or in the chemical storage area when not needed. All efforts shall be made to reduce the amount of hazardous materials left in the laboratory and research areas. If at all possible, extremely hazardous materials should only be removed from designated storage areas only when in use, and then promptly returned. Containment Devices R 325.70106 Sub rule (3) Part (h) Specific consideration shall be given to the following provisions, which shall be included where appropriate: (ii) The use of containment devices, such as laboratory-type hoods or glove boxes. All attempts should be made to utilize the fume hoods located in laboratories. In the case of particularly dangerous experiments involving vacuums, high pressures, explosions, etc, a blast shield or the explosion hood should be utilized. See Chapter 3 fore more information regarding fume hoods. Handling of Hazardous Waste R 325.70106 Sub rule (3) Part (h) Specific consideration shall be given to the following provisions, which shall be included where appropriate: (iii) Procedures for the safe removal of contaminated waste. Only materials in containers labeled Hazardous Waste shall fall under this provision. All other materials shall be recycled internally if at all feasible. If the campus of LSSU cannot reclaim or neutralize a waste, it shall then be categorized as Waste and it shall be either given to a third party for reclamation or shall be the responsibility of the grounds manager to have the waste removed. Decontamination Procedures R 325.70106 Sub rule (3) Part (h) Specific consideration shall be given to the following provisions, which shall be included where appropriate: (iv) Decontamination procedures. Decontamination depends heavily on the material being used in the lab. See MSDS for specific decontamination instruction, and subsequent first aid procedures. However, some basic precautions should be followed especially in the case of acid/base spills. Many basic salts become more corrosive when water is added, and thus should be brushed off before flushing with water for 15-20 minutes. Likewise, most powders can be brushed off prior to showering to reduce the chances of a reaction with water. Anything in the eye is immediately exposed to the moist membranes, and thus should be flushed with water immediately (And for a long period of time, such as 20 minutes plus.) for nearly any contaminant. Basic decontamination equipment in the lab includes a variety of devices, such as eye wash stations, chemical showers, and everyday cleaning items such as soap or paper towel. Every lab worker should know the locations of the eyewash station and the shower, and should be prepared to use them in the case of an emergency.

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APPENDIX A REFERENCES

SELECTED REFERENCES Mahn, William J., Academic Laboratory Chemical Hazards Guidebook, Van Nostrand Reinhold, New York, 1991, pp. 1-77. Prudent Practices for Disposal of Hazardous Chemicals from Laboratories, National Academy Press, Washington, D.C., 1983, p. 133. Gold, David T., Fire Brigade Training Manual, National Fire Protection Association, Quincy, MA, 1982, pp. 58-71. Smith, Warren, ed., Safety in Academic Chemistry Laboratories, American Chemical Society, Washington, D.C., 1990, pp. 1-67.

REGULATION REFERENCES MIOSHA STANDARD: Hazardous Work in Laboratories, R 325.70101-325.70114 OSHA STANDARDS SUBPART Z, 29 CFR 1910.1200 - Toxic and Hazardous Substances Hazard Communication and Appendix A of said standard MIOSHA STANDARD: Hazardous Waste Operations Emergency Response Plan, R 325.52101 R 325.52137

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APPENDIX B OSHA STANDARDS SUBPART Z, 29 CFR 1910.1200 TOXIC AND HAZARDOUS SUBSTANCES HAZARD COMMUNICATION AND APPENDIX A OF SAID STANDARD
1910.1200(a) "Purpose." 1910.1200(a)(1) The purpose of this section is to ensure that the hazards of all chemicals produced or imported are evaluated, and that information concerning their hazards is transmitted to employers and employees. This transmittal of information is to be accomplished by means of comprehensive hazard communication programs, which are to include container labeling and other forms of warning, material safety data sheets and employee training. ..1910.1200(a)(2) 1910.1200(a)(2) This occupational safety and health standard is intended to address comprehensively the issue of evaluating the potential hazards of chemicals, and communicating information concerning hazards and appropriate protective measures to employees, and to preempt any legal requirements of a state, or political subdivision of a state, pertaining to this subject. Evaluating the potential hazards of chemicals, and communicating information concerning hazards and appropriate protective measures to employees, may include, for example, but is not limited to, provisions for: developing and maintaining a written hazard communication program for the workplace, including lists of hazardous chemicals present; labeling of containers of chemicals in the workplace, as well as of containers of chemicals being shipped to other workplaces; preparation and distribution of material safety data sheets to employees and downstream employers; and development and implementation of employee training programs regarding hazards of chemicals and protective measures. Under section 18 of the Act, no state or political subdivision of a state may adopt or enforce, through any court or agency, any requirement relating to the issue addressed by this Federal standard, except pursuant to a Federally-approved state plan. 1910.1200(b) "Scope and application." 1910.1200(b)(1) This section requires chemical manufacturers or importers to assess the hazards of chemicals which they produce or import, and all employers to provide information to their employees about the hazardous chemicals to which they are exposed, by means of a hazard communication program, labels and other forms of warning, material safety data sheets, and information and

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training. In addition, this section requires distributors to transmit the required information to employers. (Employers who do not produce or import chemicals need only focus on those parts of this rule that deal with establishing a workplace program and communicating information to their workers. Appendix E of this section is a general guide for such employers to help them determine their compliance obligations under the rule.) 1910.1200(b)(2) This section applies to any chemical which is known to be present in the workplace in such a manner that employees may be exposed under normal conditions of use or in a foreseeable emergency. 1910.1200(b)(3) This section applies to laboratories only as follows: 1910.1200(b)(3)(i) Employers shall ensure that labels on incoming containers of hazardous chemicals are not removed or defaced; ..1910.1200(b)(3)(ii) 1910.1200(b)(3)(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 during each work shift to laboratory employees when they are in their work areas; 1910.1200(b)(3)(iii) Employers shall ensure that laboratory employees are provided information and training in accordance with paragraph (h) of this section, except for the location and availability of the written hazard communication program under paragraph (h)(2)(iii) of this section; and, 1910.1200(b)(3)(iv) Laboratory employers that ship hazardous chemicals are considered to be either a chemical manufacturer or a distributor under this rule, and thus must ensure that any containers of hazardous chemicals leaving the laboratory are labeled in accordance with paragraph (f)(1) of this section, and that a material safety data sheet is provided to distributors and other employers in accordance with paragraphs (g)(6) and (g)(7) of this section. 1910.1200(b)(4) In work operations where employees only handle chemicals in sealed containers which are not opened under normal conditions of use (such as are found in marine cargo handling, warehousing, or retail sales), this section applies to these operations only as follows:

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1910.1200(b)(4)(i) Employers shall ensure that labels on incoming containers of hazardous chemicals are not removed or defaced; ..1910.1200(b)(4)(ii) 1910.1200(b)(4)(ii) Employers shall maintain copies of any material safety data sheets that are received with incoming shipments of the sealed containers of hazardous chemicals, shall obtain a material safety data sheet as soon as possible for sealed containers of hazardous chemicals received without a material safety data sheet if an employee requests the material safety data sheet, and shall ensure that the material safety data sheets are readily accessible during each work shift to employees when they are in their work area(s); and, 1910.1200(b)(4)(iii) Employers shall ensure that employees are provided with information and training in accordance with paragraph (h) of this section (except for the location and availability of the written hazard communication program under paragraph (h)(2)(iii) of this section), to the extent necessary to protect them in the event of a spill or leak of a hazardous chemical from a sealed container. 1910.1200(b)(5) This section does not require labeling of the following chemicals: 1910.1200(b)(5)(i) Any pesticide as such term is defined in the Federal Insecticide, Fungicide, and Rodenticide Act (7 U.S.C. 136 et seq.), when subject to the labeling requirements of that Act and labeling regulations issued under that Act by the Environmental Protection Agency; 1910.1200(b)(5)(ii) Any chemical substance or mixture as such terms are defined in the Toxic Substances Control Act (15 U.S.C. 2601 et seq.), when subject to the labeling requirements of that Act and labeling regulations issued under that Act by the Environmental Protection Agency; ..1910.1200(b)(5)(iii) 1910.1200(b)(5)(iii) Any food, food additive, color additive, drug, cosmetic, or medical or veterinary device or product, including materials intended for use as ingredients in such products (e.g. flavors and fragrances), as such terms are defined in the Federal Food, Drug, and Cosmetic Act (21 U.S.C. 301 et seq.) or the Virus-Serum-Toxin Act of 1913 (21 U.S.C. 151 et seq.), and regulations issued under those Acts, when they are subject to the labeling requirements under those Acts by either the Food and Drug Administration or the Department of Agriculture;

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1910.1200(b)(5)(iv) Any distilled spirits (beverage alcohols), wine, or malt beverage intended for non-industrial use, as such terms are defined in the Federal Alcohol Administration Act (27 U.S.C. 201 et seq.) and regulations issued under that Act, when subject to the labeling requirements of that Act and labeling regulations issued under that Act by the Bureau of Alcohol, Tobacco, and Firearms; 1910.1200(b)(5)(v) Any consumer product or hazardous substance as those terms are defined in the Consumer Product Safety Act (15 U.S.C. 2051 et seq.) and Federal Hazardous Substances Act (15 U.S.C. 1261 et seq.) respectively, when subject to a consumer product safety standard or labeling requirement of those Acts, or regulations issued under those Acts by the Consumer Product Safety Commission; and, 1910.1200(b)(5)(vi) Agricultural or vegetable seed treated with pesticides and labeled in accordance with the Federal Seed Act (7 U.S.C. 1551 et seq.) and the labeling regulations issued under that Act by the Department of Agriculture. ..1910.1200(b)(6) 1910.1200(b)(6) This section does not apply to: 1910.1200(b)(6)(i) Any hazardous waste as such term is defined by the Solid Waste Disposal Act, as amended by the Resource Conservation and Recovery Act of 1976, as amended (42 U.S.C. 6901 et seq.), when subject to regulations issued under that Act by the Environmental Protection Agency; 1910.1200(b)(6)(ii) Any hazardous substance as such term is defined by the Comprehensive Environmental Response, Compensation and Liability ACT (CERCLA) (42 U.S.C. 9601 et seq.) when the hazardous substance is the focus of remedial or removal action being conducted under CERCLA in accordance with the Environmental Protection Agency regulations. 1910.1200(b)(6)(iii) Tobacco or tobacco products; 1910.1200(b)(6)(iv) Wood or wood products, including lumber which will not be processed, where the chemical manufacturer or importer can establish that the only hazard they pose to employees is the potential for flammability or combustibility (wood or wood products which have been treated

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with a hazardous chemical covered by this standard, and wood which may be subsequently sawed or cut, generating dust, are not exempted); 1910.1200(b)(6)(v) Articles (as that term is defined in paragraph (c) of this section); 1910.1200(b)(6)(vi) Food or alcoholic beverages which are sold, used, or prepared in a retail establishment (such as a grocery store, restaurant, or drinking place), and foods intended for personal consumption by employees while in the workplace; ..1910.1200(b)(6)(vii) 1910.1200(b)(6)(vii) Any drug, as that term is defined in the Federal Food, Drug, and Cosmetic Act (21 U.S.C. 301 et seq.), when it is in solid, final form for direct administration to the patient (e.g., tablets or pills); drugs which are packaged by the chemical manufacturer for sale to consumers in a retail establishment (e.g., over-the-counter drugs); and drugs intended for personal consumption by employees while in the workplace (e.g., first aid supplies); 1910.1200(b)(6)(viii) Cosmetics which are packaged for sale to consumers in a retail establishment, and cosmetics intended for personal consumption by employees while in the workplace; 1910.1200(b)(6)(ix) Any consumer product or hazardous substance, as those terms are defined in the Consumer Product Safety Act (15 U.S.C. 2051 et seq.) and Federal Hazardous Substances Act (15 U.S.C. 1261 et seq.) respectively, where the employer can show that it is used in the workplace for the purpose intended by the chemical manufacturer or importer of the product, and the use results in a duration and frequency of exposure which is not greater than the range of exposures that could reasonably be experienced by consumers when used for the purpose intended; 1910.1200(b)(6)(x) Nuisance particulates where the chemical manufacturer or importer can establish that they do not pose any physical or health hazard covered under this section; 1910.1200(b)(6)(xi) Ionizing and non-ionizing radiation; and, 1910.1200(b)(6)(xii) Biological hazards.

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1910.1200(c) "Definitions." "Article" means a manufactured item other than a fluid or particle: (i) which is formed to a specific shape or design during manufacture; (ii) which has end use function(s) dependent in whole or in part upon its shape or design during end use; and (iii) which under normal conditions of use does not release more than very small quantities, e.g., minute or trace amounts of a hazardous chemical (as determined under paragraph (d) of this section), and does not pose a physical hazard or health risk to employees. "Assistant Secretary" means the Assistant Secretary of Labor for Occupational Safety and Health, U.S. Department of Labor, or designee. "Chemical" means any element, chemical compound or mixture of elements and/or compounds. "Chemical manufacturer" means an employer with a workplace where chemical(s) are produced for use or distribution. "Chemical name" means the scientific designation of a chemical in accordance with the nomenclature system developed by the International Union of Pure and Applied Chemistry (IUPAC) or the Chemical Abstracts Service (CAS) rules of nomenclature, or a name which will clearly identify the chemical for the purpose of conducting a hazard evaluation. "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. "Commercial account" means an arrangement whereby a retail distributor sells hazardous chemicals to an employer, generally in large quantities over time and/or at costs that are below the regular retail price. "Common name" means any designation or identification such as code name, code number, trade name, brand name or generic name used to identify a chemical other than by its chemical name. "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 deg. C) as determined by ASTM D-323-72. "Container" means any bag, barrel, bottle, box, can, cylinder, drum, reaction vessel, storage tank, or the like that contains a hazardous chemical. For purposes of this section, pipes or piping

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systems, and engines, fuel tanks, or other operating systems in a vehicle, are not considered to be containers. "Designated representative" means any individual or organization to which an employee gives written authorization to exercise such employee's rights under this section. A recognized or certified collective bargaining agent shall be treated automatically as a designated representative without regard to written employee authorization. "Director" means the Director, National Institute for Occupational Safety and Health, U.S. Department of Health and Human Services, or designee. "Distributor" means a business, other than a chemical manufacturer or importer, which supplies hazardous chemicals to other distributors or to employers. "Employee" means a worker who may be exposed to hazardous chemicals under normal operating conditions or in foreseeable emergencies. Workers such as office workers or bank tellers who encounter hazardous chemicals only in non-routine, isolated instances are not covered. "Employer" means a person engaged in a business where chemicals are either used, distributed, or are produced for use or distribution, including a contractor or subcontractor. "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. "Exposure or exposed" means that an employee is subjected in the course of employment to a chemical that is a physical or health hazard, and includes potential (e.g. accidental or possible) exposure. "Subjected" in terms of health hazards includes any route of entry (e.g. inhalation, ingestion, skin contact or absorption.) "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 projection 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 thirteen (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 twelve (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. F (37.8 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

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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 Flash Point 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. "Foreseeable emergency" means any potential occurrence such as, but not limited to, equipment failure, rupture of containers, or failure of control equipment which could result in an uncontrolled release of a hazardous chemical into the workplace. "Hazardous chemical" means any chemical which is a physical hazard or a health hazard. "Hazard warning" means any words, pictures, symbols, or combination thereof appearing on a label or other appropriate form of warning which convey the specific physical and health hazard(s), including target organ effects, of the chemical(s) in the container(s). (See the definitions for "physical hazard" and "health hazard" to determine the hazards which must be covered.) "Health hazard" 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, hepatotoxins, nephrotoxins, and neurotoxins, agents which act on the hematopoietic system, and agents which damage the lungs, skin, eyes, or mucous membranes. Appendix A provides further definitions and explanations of the scope of health hazards covered by this section, and Appendix B describes the criteria to be used to determine whether or not a chemical is to be considered hazardous for purposes of this standard. "Identity" means any chemical or common name which is indicated on the material safety data sheet (MSDS) for the chemical. The identity used shall permit cross-references to be made among the required list of hazardous chemicals, the label and the MSDS.

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"Immediate use" means that the hazardous chemical will be under the control of and used only by the person who transfers it from a labeled container and only within the work shift in which it is transferred. "Importer" means the first business with employees within the Customs Territory of the United States which receives hazardous chemicals produced in other countries for the purpose of supplying them to distributors or employers within the United States. "Label" means any written, printed, or graphic material displayed on or affixed to containers of hazardous chemicals. "Material safety data sheet (MSDS)" means written or printed material concerning a hazardous chemical which is prepared in accordance with paragraph (g) of this section. "Mixture" means any combination of two or more chemicals if the combination is not, in whole or in part, the result of a chemical reaction. "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 that it is a combustible liquid, a compressed gas, explosive, flammable, an organic peroxide, an oxidizer, pyrophoric, unstable (reactive) or water-reactive. "Produce" means to manufacture, process, formulate, blend, extract, generate, emit, or repackage. "Pyrophoric" means a chemical that will ignite spontaneously in air at a temperature of 130 deg. F (54.4 deg. C) or below. "Responsible party" means someone who can provide additional information on the hazardous chemical and appropriate emergency procedures, if necessary. "Specific chemical identity" means the chemical name, Chemical Abstracts Service (CAS) Registry Number, or any other information that reveals the precise chemical designation of the substance. "Trade secret" means any confidential formula, pattern, process, device, information or compilation of information that is used in an employer's business, and that gives the employer an opportunity to obtain an advantage over competitors who do not know or use it. Appendix D sets out the criteria to be used in evaluating trade secrets. "Unstable (reactive)" means a chemical which in 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.

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"Use" means to package, handle, react, emit, extract, generate as a byproduct, or transfer. "Water-reactive" means a chemical that reacts with water to release a gas that is either flammable or presents a health hazard. "Work area" means a room or defined space in a workplace where hazardous chemicals are produced or used, and where employees are present. "Workplace" means an establishment, job site, or project, at one geographical location containing one or more work areas. ..1910.1200(d) 1910.1200(d) "Hazard determination." 1910.1200(d)(1) Chemical manufacturers and importers shall evaluate chemicals produced in their workplaces or imported by them to determine if they are hazardous. Employers are not required to evaluate chemicals unless they choose not to rely on the evaluation performed by the chemical manufacturer or importer for the chemical to satisfy this requirement. 1910.1200(d)(2) Chemical manufacturers, importers or employers evaluating chemicals shall identify and consider the available scientific evidence concerning such hazards. For health hazards, evidence which is statistically significant and which is based on at least one positive study conducted in accordance with established scientific principles is considered to be sufficient to establish a hazardous effect if the results of the study meet the definitions of health hazards in this section. Appendix A shall be consulted for the scope of health hazards covered, and Appendix B shall be consulted for the criteria to be followed with respect to the completeness of the evaluation, and the data to be reported. 1910.1200(d)(3) The chemical manufacturer, importer or employer evaluating chemicals shall treat the following sources as establishing that the chemicals listed in them are hazardous: 1910.1200(d)(3)(i) 29 CFR part 1910, subpart Z, Toxic and Hazardous Substances, Occupational Safety and Health Administration (OSHA); or, ..1910.1200(d)(3)(ii) 1910.1200(d)(3)(ii)

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"Threshold Limit Values for Chemical Substances and Physical Agents in the Work Environment," American Conference of Governmental Industrial Hygienists (ACGIH) (latest edition). The chemical manufacturer, importer, or employer is still responsible for evaluating the hazards associated with the chemicals in these source lists in accordance with the requirements of this standard. 1910.1200(d)(4) Chemical manufacturers, importers and employers evaluating chemicals shall treat the following sources as establishing that a chemical is a carcinogen or potential carcinogen for hazard communication purposes: 1910.1200(d)(4)(i) National Toxicology Program (NTP), "Annual Report on Carcinogens" (latest edition); 1910.1200(d)(4)(ii) International Agency for Research on Cancer (IARC) "Monographs" (latest editions); or 1910.1200(d)(4)(iii) 29 CFR part 1910, subpart Z, Toxic and Hazardous Substances, Occupational Safety and Health Administration. Note: The "Registry of Toxic Effects of Chemical Substances" published by the National Institute for Occupational Safety and Health indicates whether a chemical has been found by NTP or IARC to be a potential carcinogen. 1910.1200(d)(5) The chemical manufacturer, importer or employer shall determine the hazards of mixtures of chemicals as follows: 1910.1200(d)(5)(i) If a mixture has been tested as a whole to determine its hazards, the results of such testing shall be used to determine whether the mixture is hazardous; ..1910.1200(d)(5)(ii) 1910.1200(d)(5)(ii) If a mixture has not been tested as a whole to determine whether the mixture is a health hazard, the mixture shall be assumed to present the same health hazards as do the components which comprise one percent (by weight or volume) or greater of the mixture, except that the mixture shall be assumed to present a carcinogenic hazard if it contains a component in concentrations of 0.1 percent or greater which is considered to be a carcinogen under paragraph (d)(4) of this section;

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1910.1200(d)(5)(iii) If a mixture has not been tested as a whole to determine whether the mixture is a physical hazard, the chemical manufacturer, importer, or employer may use whatever scientifically valid data is available to evaluate the physical hazard potential of the mixture; and, 1910.1200(d)(5)(iv) If the chemical manufacturer, importer, or employer has evidence to indicate that a component present in the mixture in concentrations of less than one percent (or in the case of carcinogens, less than 0.1 percent) could be released in concentrations which would exceed an established OSHA permissible exposure limit or ACGIH Threshold Limit Value, or could present a health risk to employees in those concentrations, the mixture shall be assumed to present the same hazard. 1910.1200(d)(6) Chemical manufacturers, importers, or employers evaluating chemicals shall describe in writing the procedures they use to determine the hazards of the chemical they evaluate. The written procedures are to be made available, upon request, to employees, their designated representatives, the Assistant Secretary and the Director. The written description may be incorporated into the written hazard communication program required under paragraph (e) of this section. ..1910.1200(e) 1910.1200(e) "Written hazard communication program." 1910.1200(e)(1) Employers shall develop, implement, and maintain at each workplace, a written hazard communication program which at least describes how the criteria specified in paragraphs (f), (g), and (h) of this section for labels and other forms of warning, material safety data sheets, and employee information and training will be met, and which also includes the following: 1910.1200(e)(1)(i) A list of the hazardous chemicals known to be present using an identity that is referenced on the appropriate material safety data sheet (the list may be compiled for the workplace as a whole or for individual work areas); and, 1910.1200(e)(1)(ii) The methods the employer will use to inform employees of the hazards of non-routine tasks (for example, the cleaning of reactor vessels), and the hazards associated with chemicals contained in unlabeled pipes in their work areas. 1910.1200(e)(2)

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"Multi-employer workplaces." Employers who produce, use, or store hazardous chemicals at a workplace in such a way that the employees of other employer(s) may be exposed (for example, employees of a construction contractor working on-site) shall additionally ensure that the hazard communication programs developed and implemented under this paragraph (e) include the following: 1910.1200(e)(2)(i) The methods the employer will use to provide the other employer(s) on-site access to material safety data sheets for each hazardous chemical the other employer(s)' employees may be exposed to while working; ..1910.1200(e)(2)(ii) 1910.1200(e)(2)(ii) The methods the employer will use to inform the other employer(s) of any precautionary measures that need to be taken to protect employees during the workplace's normal operating conditions and in foreseeable emergencies; and, 1910.1200(e)(2)(iii) The methods the employer will use to inform the other employer(s) of the labeling system used in the workplace. 1910.1200(e)(3) The employer may rely on an existing hazard communication program to comply with these requirements, provided that it meets the criteria established in this paragraph (e). 1910.1200(e)(4) The employer shall make the written hazard communication program available, upon request, to employees, their designated representatives, the Assistant Secretary and the Director, in accordance with the requirements of 29 CFR 1910.1020 (e). 1910.1200(e)(5) Where employees must travel between workplaces during a work shift, i.e., their work is carried out at more than one geographical location, the written hazard communication program may be kept at the primary workplace facility. 1910.1200(f) "Labels and other forms of warning." 1910.1200(f)(1)

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The chemical manufacturer, importer, or distributor shall ensure that each container of hazardous chemicals leaving the workplace is labeled, tagged or marked with the following information: ..1910.1200(f)(1)(i) 1910.1200(f)(1)(i) Identity of the hazardous chemical(s); 1910.1200(f)(1)(ii) Appropriate hazard warnings; and 1910.1200(f)(1)(iii) Name and address of the chemical manufacturer, importer, or other responsible party. 1910.1200(f)(2) 1910.1200(f)(2)(i) For solid metal (such as a steel beam or a metal casting), solid wood, or plastic items that are not exempted as articles due to their downstream use, or shipments of whole grain, the required label may be transmitted to the customer at the time of the initial shipment, and need not be included with subsequent shipments to the same employer unless the information on the label changes; 1910.1200(f)(2)(ii) The label may be transmitted with the initial shipment itself, or with the material safety data sheet that is to be provided prior to or at the time of the first shipment; and, 1910.1200(f)(2)(iii) This exception to requiring labels on every container of hazardous chemicals is only for the solid material itself, and does not apply to hazardous chemicals used in conjunction with, or known to be present with, the material and to which employees handling the items in transit may be exposed (for example, cutting fluids or pesticides in grains). ..1910.1200(f)(3) 1910.1200(f)(3) Chemical manufacturers, importers, or distributors shall ensure that each container of hazardous chemicals leaving the workplace is labeled, tagged, or marked in accordance with this section in a manner which does not conflict with the requirements of the Hazardous Materials Transportation Act (49 U.S.C. 1801 et seq.) and regulations issued under that Act by the Department of Transportation. 1910.1200(f)(4)

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If the hazardous chemical is regulated by OSHA in a substance-specific health standard, the chemical manufacturer, importer, distributor or employer shall ensure that the labels or other forms of warning used are in accordance with the requirements of that standard. 1910.1200(f)(5) Except as provided in paragraphs (f)(6) and (f)(7) of this section, the employer shall ensure that each container of hazardous chemicals in the workplace is labeled, tagged or marked with the following information: 1910.1200(f)(5)(i) Identity of the hazardous chemical(s) contained therein; and, 1910.1200(f)(5)(ii) Appropriate hazard warnings, or alternatively, words, pictures, symbols, or combination thereof, which provide at least general information regarding the hazards of the chemicals, and which, in conjunction with the other information immediately available to employees under the hazard communication program, will provide employees with the specific information regarding the physical and health hazards of the hazardous chemical. ..1910.1200(f)(6) 1910.1200(f)(6) The employer may use signs, placards, process sheets, batch tickets, operating procedures, or other such written materials in lieu of affixing labels to individual stationary process containers, as long as the alternative method identifies the containers to which it is applicable and conveys the information required by paragraph (f)(5) of this section to be on a label. The written materials shall be readily accessible to the employees in their work area throughout each work shift. 1910.1200(f)(7) The employer is not required to label portable containers into which hazardous chemicals are transferred from labeled containers, and which are intended only for the immediate use of the employee who performs the transfer. For purposes of this section, drugs which are dispensed by a pharmacy to a health care provider for direct administration to a patient are exempted from labeling. 1910.1200(f)(8) The employer shall not remove or deface existing labels on incoming containers of hazardous chemicals, unless the container is immediately marked with the required information. 1910.1200(f)(9) The employer shall ensure that labels or other forms of warning are legible, in English, and prominently displayed on the container, or readily available in the work area throughout each

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work shift. Employers having employees who speak other languages may add the information in their language to the material presented, as long as the information is presented in English as well. 1910.1200(f)(10) The chemical manufacturer, importer, distributor or employer need not affix new labels to comply with this section if existing labels already convey the required information. ..1910.1200(f)(11) 1910.1200(f)(11) Chemical manufacturers, importers, distributors, or employers who become newly aware of any significant information regarding the hazards of a chemical shall revise the labels for the chemical within three months of becoming aware of the new information. Labels on containers of hazardous chemicals shipped after that time shall contain the new information. If the chemical is not currently produced or imported, the chemical manufacturer, importers, distributor, or employer shall add the information to the label before the chemical is shipped or introduced into the workplace again. 1910.1200(g) "Material safety data sheets." 1910.1200(g)(1) Chemical manufacturers and importers shall obtain or develop a material safety data sheet for each hazardous chemical they produce or import. Employers shall have a material safety data sheet in the workplace for each hazardous chemical which they use. 1910.1200(g)(2) Each material safety data sheet shall be in English (although the employer may maintain copies in other languages as well), and shall contain at least the following information: 1910.1200(g)(2)(i) The identity used on the label, and, except as provided for in paragraph (i) of this section on trade secrets: 1910.1200(g)(2)(i)(A) If the hazardous chemical is a single substance, its chemical and common name(s); 1910.1200(g)(2)(i)(B)

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If the hazardous chemical is a mixture which has been tested as a whole to determine its hazards, the chemical and common name(s) of the ingredients which contribute to these known hazards, and the common name(s) of the mixture itself; or, 1910.1200(g)(2)(i)(C) If the hazardous chemical is a mixture which has not been tested as a whole: ..1910.1200(g)(2)(i)(C)(1) 1910.1200(g)(2)(i)(C)(1) The chemical and common name(s) of all ingredients which have been determined to be health hazards, and which comprise 1% or greater of the composition, except that chemicals identified as carcinogens under paragraph (d) of this section shall be listed if the concentrations are 0.1% or greater; and, 1910.1200(g)(2)(i)(C)(2) The chemical and common name(s) of all ingredients which have been determined to be health hazards, and which comprise less than 1% (0.1% for carcinogens) of the mixture, if there is evidence that the ingredient(s) could be released from the mixture in concentrations which would exceed an established OSHA permissible exposure limit or ACGIH Threshold Limit Value, or could present a health risk to employees; and, 1910.1200(g)(2)(i)(C)(3) The chemical and common name(s) of all ingredients which have been determined to present a physical hazard when present in the mixture; 1910.1200(g)(2)(ii) Physical and chemical characteristics of the hazardous chemical (such as vapor pressure, flash point); 1910.1200(g)(2)(iii) The physical hazards of the hazardous chemical, including the potential for fire, explosion, and reactivity; 1910.1200(g)(2)(iv) The health hazards of the hazardous chemical, including signs and symptoms of exposure, and any medical conditions which are generally recognized as being aggravated by exposure to the chemical; 1910.1200(g)(2)(v) The primary route(s) of entry;

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..1910.1200(g)(2)(vi) 1910.1200(g)(2)(vi) The OSHA permissible exposure limit, ACGIH Threshold Limit Value, and any other exposure limit used or recommended by the chemical manufacturer, importer, or employer preparing the material safety data sheet, where available; 1910.1200(g)(2)(vii) Whether the hazardous chemical is listed in the National Toxicology Program (NTP) Annual Report on Carcinogens (latest edition) or has been found to be a potential carcinogen in the International Agency for Research on Cancer (IARC) Monographs (latest editions), or by OSHA; 1910.1200(g)(2)(viii) Any generally applicable precautions for safe handling and use which are known to the chemical manufacturer, importer or employer preparing the material safety data sheet, including appropriate hygienic practices, protective measures during repair and maintenance of contaminated equipment, and procedures for clean-up of spills and leaks; 1910.1200(g)(2)(ix) Any generally applicable control measures which are known to the chemical manufacturer, importer or employer preparing the material safety data sheet, such as appropriate engineering controls, work practices, or personal protective equipment; 1910.1200(g)(2)(x) Emergency and first aid procedures; 1910.1200(g)(2)(xi) The date of preparation of the material safety data sheet or the last change to it; and, ..1910.1200(g)(2)(xii) 1910.1200(g)(2)(xii) The name, address and telephone number of the chemical manufacturer, importer, employer or other responsible party preparing or distributing the material safety data sheet, who can provide additional information on the hazardous chemical and appropriate emergency procedures, if necessary. 1910.1200(g)(3) If no relevant information is found for any given category on the material safety data sheet, the chemical manufacturer, importer or employer preparing the material safety data sheet shall mark it to indicate that no applicable information was found.

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1910.1200(g)(4) Where complex mixtures have similar hazards and contents (i.e. the chemical ingredients are essentially the same, but the specific composition varies from mixture to mixture), the chemical manufacturer, importer or employer may prepare one material safety data sheet to apply to all of these similar mixtures. 1910.1200(g)(5) The chemical manufacturer, importer or employer preparing the material safety data sheet shall ensure that the information recorded accurately reflects the scientific evidence used in making the hazard determination. If the chemical manufacturer, importer or employer preparing the material safety data sheet becomes newly aware of any significant information regarding the hazards of a chemical, or ways to protect against the hazards, this new information shall be added to the material safety data sheet within three months. If the chemical is not currently being produced or imported the chemical manufacturer or importer shall add the information to the material safety data sheet before the chemical is introduced into the workplace again. ..1910.1200(g)(6) 1910.1200(g)(6) 1910.1200(g)(6)(i) Chemical manufacturers or importers shall ensure that distributors and employers are provided an appropriate material safety data sheet with their initial shipment, and with the first shipment after a material safety data sheet is updated; 1910.1200(g)(6)(ii) The chemical manufacturer or importer shall either provide material safety data sheets with the shipped containers or send them to the distributor or employer prior to or at the time of the shipment; 1910.1200(g)(6)(iii) If the material safety data sheet is not provided with a shipment that has been labeled as a hazardous chemical, the distributor or employer shall obtain one from the chemical manufacturer or importer as soon as possible; and, 1910.1200(g)(6)(iv) The chemical manufacturer or importer shall also provide distributors or employers with a material safety data sheet upon request. 1910.1200(g)(7) 1910.1200(g)(7)(i)

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Distributors shall ensure that material safety data sheets, and updated information, are provided to other distributors and employers with their initial shipment and with the first shipment after a material safety data sheet is updated; 1910.1200(g)(7)(ii) The distributor shall either provide material safety data sheets with the shipped containers, or send them to the other distributor or employer prior to or at the time of the shipment; ..1910.1200(g)(7)(iii) 1910.1200(g)(7)(iii) Retail distributors selling hazardous chemicals to employers having a commercial account shall provide a material safety data sheet to such employers upon request, and shall post a sign or otherwise inform them that a material safety data sheet is available; 1910.1200(g)(7)(iv) Wholesale distributors selling hazardous chemicals to employers over-the-counter may also provide material safety data sheets upon the request of the employer at the time of the over-thecounter purchase, and shall post a sign or otherwise inform such employers that a material safety data sheet is available; 1910.1200(g)(7)(v) If an employer without a commercial account purchases a hazardous chemical from a retail distributor not required to have material safety data sheets on file (i.e., the retail distributor does not have commercial accounts and does not use the materials), the retail distributor shall provide the employer, upon request, with the name, address, and telephone number of the chemical manufacturer, importer, or distributor from which a material safety data sheet can be obtained; 1910.1200(g)(7)(vi) Wholesale distributors shall also provide material safety data sheets to employers or other distributors upon request; and, 1910.1200(g)(7)(vii) Chemical manufacturers, importers, and distributors need not provide material safety data sheets to retail distributors that have informed them that the retail distributor does not sell the product to commercial accounts or open the sealed container to use it in their own workplaces. ..1910.1200(g)(8) 1910.1200(g)(8) The employer shall maintain in the workplace copies of the required material safety data sheets for each hazardous chemical, and shall ensure that they are readily accessible during each work

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shift to employees when they are in their work area(s). (Electronic access, microfiche, and other alternatives to maintaining paper copies of the material safety data sheets are permitted as long as no barriers to immediate employee access in each workplace are created by such options.) 1910.1200(g)(9) Where employees must travel between workplaces during a work shift, i.e., their work is carried out at more than one geographical location, the material safety data sheets may be kept at the primary workplace facility. In this situation, the employer shall ensure that employees can immediately obtain the required information in an emergency. 1910.1200(g)(10) Material safety data sheets may be kept in any form, including operating procedures, and may be designed to cover groups of hazardous chemicals in a work area where it may be more appropriate to address the hazards of a process rather than individual hazardous chemicals. However, the employer shall ensure that in all cases the required information is provided for each hazardous chemical, and is readily accessible during each work shift to employees when they are in their work area(s). 1910.1200(g)(11) Material safety data sheets shall also be made readily available, upon request, to designated representatives and to the Assistant Secretary, in accordance with the requirements of 29 CFR 1910.1020(e). The Director shall also be given access to material safety data sheets in the same manner. ..1910.1200(h) 1910.1200(h) "Employee information and training." 1910.1200(h)(1) Employers shall provide employees with effective information and training on hazardous chemicals in their work area at the time of their initial assignment, and whenever a new physical or health hazard the employees have not previously been trained about is introduced into their work area. Information and training may be designed to cover categories of hazards (e.g., flammability, carcinogenicity) or specific chemicals. Chemical-specific information must always be available through labels and material safety data sheets. 1910.1200(h)(2) "Information." Employees shall be informed of: 1910.1200(h)(2)(i) The requirements of this section;

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1910.1200(h)(2)(ii) Any operations in their work area where hazardous chemicals are present; and, 1910.1200(h)(2)(iii) The location and availability of the written hazard communication program, including the required list(s) of hazardous chemicals, and material safety data sheets required by this section. 1910.1200(h)(3) "Training." Employee training shall include at least: 1910.1200(h)(3)(i) Methods and observations that may be used to detect the presence or release of a hazardous chemical in the work area (such as monitoring conducted by the employer, continuous monitoring devices, visual appearance or odor of hazardous chemicals when being released, etc.); 1910.1200(h)(3)(ii) The physical and health hazards of the chemicals in the work area; ..1910.1200(h)(3)(iii) 1910.1200(h)(3)(iii) 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; and, 1910.1200(h)(3)(iv) The details of the hazard communication program developed by the employer, including an explanation of the labeling system and the material safety data sheet, and how employees can obtain and use the appropriate hazard information. 1910.1200(i) "Trade secrets." 1910.1200(i)(1) The chemical manufacturer, importer, or employer may withhold the specific chemical identity, including the chemical name and other specific identification of a hazardous chemical, from the material safety data sheet, provided that: 1910.1200(i)(1)(i)

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The claim that the information withheld is a trade secret can be supported; 1910.1200(i)(1)(ii) Information contained in the material safety data sheet concerning the properties and effects of the hazardous chemical is disclosed; 1910.1200(i)(1)(iii) The material safety data sheet indicates that the specific chemical identity is being withheld as a trade secret; and, 1910.1200(i)(1)(iv) The specific chemical identity is made available to health professionals, employees, and designated representatives in accordance with the applicable provisions of this paragraph. ..1910.1200(i)(2) 1910.1200(i)(2) Where a treating physician or nurse determines that a medical emergency exists and the specific chemical identity of a hazardous chemical is necessary for emergency or first-aid treatment, the chemical manufacturer, importer, or employer shall immediately disclose the specific chemical identity of a trade secret chemical to that treating physician or nurse, regardless of the existence of a written statement of need or a confidentiality agreement. The chemical manufacturer, importer, or employer may require a written statement of need and confidentiality agreement, in accordance with the provisions of paragraphs (i)(3) and (4) of this section, as soon as circumstances permit. 1910.1200(i)(3) In non-emergency situations, a chemical manufacturer, importer, or employer shall, upon request, disclose a specific chemical identity, otherwise permitted to be withheld under paragraph (i)(1) of this section, to a health professional (i.e. physician, industrial hygienist, toxicologist, epidemiologist, or occupational health nurse) providing medical or other occupational health services to exposed employee(s), and to employees or designated representatives, if: 1910.1200(i)(3)(i) The request is in writing; 1910.1200(i)(3)(ii) The request describes with reasonable detail one or more of the following occupational health needs for the information: 1910.1200(i)(3)(ii)(A)

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To assess the hazards of the chemicals to which employees will be exposed; 1910.1200(i)(3)(ii)(B) To conduct or assess sampling of the workplace atmosphere to determine employee exposure levels; 1910.1200(i)(3)(ii)(C) To conduct pre-assignment or periodic medical surveillance of exposed employees; 1910.1200(i)(3)(ii)(D) To provide medical treatment to exposed employees; ..1910.1200(i)(3)(ii)(E) 1910.1200(i)(3)(ii)(E) To select or assess appropriate personal protective equipment for exposed employees; 1910.1200(i)(3)(ii)(F) To design or assess engineering controls or other protective measures for exposed employees; and, 1910.1200(i)(3)(ii)(G) To conduct studies to determine the health effects of exposure. 1910.1200(i)(3)(iii) The request explains in detail why the disclosure of the specific chemical identity is essential and that, in lieu thereof, the disclosure of the following information to the health professional, employee, or designated representative, would not satisfy the purposes described in paragraph (i) (3)(ii) of this section: 1910.1200(i)(3)(iii)(A) The properties and effects of the chemical; 1910.1200(i)(3)(iii)(B) Measures for controlling workers' exposure to the chemical; 1910.1200(i)(3)(iii)(C) Methods of monitoring and analyzing worker exposure to the chemical; and,

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1910.1200(i)(3)(iii)(D) Methods of diagnosing and treating harmful exposures to the chemical; 1910.1200(i)(3)(iv) The request includes a description of the procedures to be used to maintain the confidentiality of the disclosed information; and, ..1910.1200(i)(3)(v) 1910.1200(i)(3)(v) The health professional, and the employer or contractor of the services of the health professional (i.e. downstream employer, labor organization, or individual employee), employee, or designated representative, agree in a written confidentiality agreement that the health professional, employee, or designated representative, will not use the trade secret information for any purpose other than the health need(s) asserted and agree not to release the information under any circumstances other than to OSHA, as provided in paragraph (i)(6) of this section, except as authorized by the terms of the agreement or by the chemical manufacturer, importer, or employer. 1910.1200(i)(4) The confidentiality agreement authorized by paragraph (i)(3)(iv) of this section: 1910.1200(i)(4)(i) May restrict the use of the information to the health purposes indicated in the written statement of need; 1910.1200(i)(4)(ii) May provide for appropriate legal remedies in the event of a breach of the agreement, including stipulation of a reasonable pre-estimate of likely damages; and, 1910.1200(i)(4)(iii) May not include requirements for the posting of a penalty bond. 1910.1200(i)(5) Nothing in this standard is meant to preclude the parties from pursuing non-contractual remedies to the extent permitted by law. 1910.1200(i)(6) If the health professional, employee, or designated representative receiving the trade secret information decides that there is a need to disclose it to OSHA, the chemical manufacturer,

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importer, or employer who provided the information shall be informed by the health professional, employee, or designated representative prior to, or at the same time as, such disclosure. ..1910.1200(i)(7) 1910.1200(i)(7) If the chemical manufacturer, importer, or employer denies a written request for disclosure of a specific chemical identity, the denial must: 1910.1200(i)(7)(i) Be provided to the health professional, employee, or designated representative, within thirty days of the request; 1910.1200(i)(7)(ii) Be in writing; 1910.1200(i)(7)(iii) Include evidence to support the claim that the specific chemical identity is a trade secret; 1910.1200(i)(7)(iv) State the specific reasons why the request is being denied; and, 1910.1200(i)(7)(v) Explain in detail how alternative information may satisfy the specific medical or occupational health need without revealing the specific chemical identity. 1910.1200(i)(8) The health professional, employee, or designated representative whose request for information is denied under paragraph (i)(3) of this section may refer the request and the written denial of the request to OSHA for consideration. 1910.1200(i)(9) When a health professional, employee, or designated representative refers the denial to OSHA under paragraph (i)(8) of this section, OSHA shall consider the evidence to determine if: ..1910.1200(i)(9)(i) 1910.1200(i)(9)(i) The chemical manufacturer, importer, or employer has supported the claim that the specific chemical identity is a trade secret;
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1910.1200(i)(9)(ii) The health professional, employee, or designated representative has supported the claim that there is a medical or occupational health need for the information; and, 1910.1200(i)(9)(iii) The health professional, employee or designated representative has demonstrated adequate means to protect the confidentiality. 1910.1200(i)(10) 1910.1200(i)(10)(i) If OSHA determines that the specific chemical identity requested under paragraph (i)(3) of this section is not a "bona fide" trade secret, or that it is a trade secret, but the requesting health professional, employee, or designated representative has a legitimate medical or occupational health need for the information, has executed a written confidentiality agreement, and has shown adequate means to protect the confidentiality of the information, the chemical manufacturer, importer, or employer will be subject to citation by OSHA. ..1910.1200(i)(10)(ii) 1910.1200(i)(10)(ii) If a chemical manufacturer, importer, or employer demonstrates to OSHA that the execution of a confidentiality agreement would not provide sufficient protection against the potential harm from the unauthorized disclosure of a trade secret specific chemical identity, the Assistant Secretary may issue such orders or impose such additional limitations or conditions upon the disclosure of the requested chemical information as may be appropriate to assure that the occupational health services are provided without an undue risk of harm to the chemical manufacturer, importer, or employer. 1910.1200(i)(11) If a citation for a failure to release specific chemical identity information is contested by the chemical manufacturer, importer, or employer, the matter will be adjudicated before the Occupational Safety and Health Review Commission in accordance with the Act's enforcement scheme and the applicable Commission rules of procedure. In accordance with the Commission rules, when a chemical manufacturer, importer, or employer continues to withhold the information during the contest, the Administrative Law Judge may review the citation and supporting documentation "in camera" or issue appropriate orders to protect the confidentiality of such matters. 1910.1200(i)(12) Notwithstanding the existence of a trade secret claim, a chemical manufacturer, importer, or employer shall, upon request, disclose to the Assistant Secretary any information which this section requires the chemical manufacturer, importer, or employer to make available. Where there

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is a trade secret claim, such claim shall be made no later than at the time the information is provided to the Assistant Secretary so that suitable determinations of trade secret status can be made and the necessary protections can be implemented. 1910.1200(i)(13) Nothing in this paragraph shall be construed as requiring the disclosure under any circumstances of process or percentage of mixture information which is a trade secret. ..1910.1200(j) 1910.1200(j) "Effective dates." Chemical manufacturers, importers, distributors, and employers shall be in compliance with all provisions of this section by March 11, 1994. Note: The effective date of the clarification that the exemption of wood and wood products from the Hazard Communication standard in paragraph (b)(6)(iv) only applies to wood and wood products including lumber which will not be processed, where the manufacturer or importer can establish that the only hazard they pose to employees is the potential for flammability or combustibility, and that the exemption does not apply to wood or wood products which have been treated with a hazardous chemical covered by this standard, and wood which may be subsequently sawed or cut generating dust has been stayed from March 11, 1994 to August 11, 1994. [59 FR 17479, April 13, 1994; 59 FR 65947, Dec. 22, 1994; 61 FR 5507, Feb. 13, 1996]

APPENDIX A OF 29 CFR 1910.1200

Although safety hazards related to the physical characteristics of a chemical can be objectively defined in terms of testing requirements (e.g. flammability), health hazard definitions are less precise and more subjective. Health hazards may cause measurable changes in the body - such as decreased pulmonary function. These changes are generally indicated by the occurrence of signs and symptoms in the exposed employees - such as shortness of breath, a non-measurable, subjective feeling. Employees exposed to such hazards must be apprised of both the change in body function and the signs and symptoms that may occur to signal that change. The determination of occupational health hazards is complicated by the fact that many of the effects or signs and symptoms occur commonly in non-occupationally exposed populations, so that effects of exposure are difficult to separate from normally occurring illnesses. Occasionally, a substance causes an effect that is rarely seen in the population at large, such as angiosarcomas caused by vinyl chloride exposure, thus making it easier to ascertain that the occupational exposure was the primary causative factor. More often, however, the effects are common, such as lung cancer. The situation is further complicated by the fact that most chemicals have not been adequately tested to determine their health hazard potential, and data do not exist to substantiate these effects.

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There have been many attempts to categorize effects and to define them in various ways. Generally, the terms "acute" and "chronic" are used to delineate between effects on the basis of severity or duration. "Acute" effects usually occur rapidly as a result of short-term exposures, and are of short duration. "Chronic" effects generally occur as a result of long-term exposure, and are of long duration. The acute effects referred to most frequently are those defined by the American National Standards Institute (ANSI) standard for Precautionary Labeling of Hazardous Industrial Chemicals (Z129.1-1988) - irritation, corrosivity, sensitization and lethal dose. Although these are important health effects, they do not adequately cover the considerable range of acute effects which may occur as a result of occupational exposure, such as, for example, narcosis. Similarly, the term chronic effect is often used to cover only carcinogenicity, teratogenicity, and mutagenicity. These effects are obviously a concern in the workplace, but again, do not adequately cover the area of chronic effects, excluding, for example, blood dyscrasias (such as anemia), chronic bronchitis and liver atrophy. The goal of defining precisely, in measurable terms, every possible health effect that may occur in the workplace as a result of chemical exposures cannot realistically be accomplished. This does not negate the need for employees to be informed of such effects and protected from them. Appendix B, which is also mandatory, outlines the principles and procedures of hazard assessment. For purposes of this section, any chemicals which meet any of the following definitions, as determined by the criteria set forth in Appendix B are health hazards. However, this is not intended to be an exclusive categorization scheme. If there are available scientific data that involve other animal species or test methods, they must also be evaluated to determine the applicability of the HCS. 1. "Carcinogen:" A chemical is considered to be a carcinogen if: (a) It has been evaluated by the International Agency for Research on Cancer (IARC), and found to be a carcinogen or potential carcinogen; or (b) It is listed as a carcinogen or potential carcinogen in the Annual Report on Carcinogens published by the National Toxicology Program (NTP) (latest edition); or, (c) It is regulated by OSHA as a carcinogen. 2. "Corrosive:" A chemical that causes visible destruction of, or irreversible alterations in, living tissue by chemical action at the site of contact. For example, a chemical is considered to be corrosive if, when tested on the intact skin of albino rabbits by the method described by the U.S. Department of Transportation in appendix A to 49 CFR part 173, it destroys or changes irreversibly the structure of the tissue at the site of contact following an exposure period of four hours. This term shall not refer to action on inanimate surfaces. 3. "Highly toxic:" A chemical falling within any of the following categories: (a) A chemical that has a median lethal dose (LD(50)) of 50 milligrams or less per kilogram of body weight when administered orally to albino rats weighing between 200 and 300 grams each.
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(b) A chemical that has a median lethal dose (LD(50)) of 200 milligrams or less per kilogram of body weight when administered by continuous contact for 24 hours (or less if death occurs within 24 hours) with the bare skin of albino rabbits weighing between two and three kilograms each. (c) A chemical that has a median lethal concentration (LC(50)) 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 (or less if death occurs within one hour) to albino rats weighing between 200 and 300 grams each. 4. "Irritant:" A chemical, which is not corrosive, but which causes a reversible inflammatory effect on living tissue by chemical action at the site of contact. A chemical is a skin irritant if, when tested on the intact skin of albino rabbits by the methods of 16 CFR 1500.41 for four hours exposure or by other appropriate techniques, it results in an empirical score of five or more. A chemical is an eye irritant if so determined under the procedure listed in 16 CFR 1500.42 or other appropriate techniques. 5. "Sensitizer:" A chemical that causes a substantial proportion of exposed people or animals to develop an allergic reaction in normal tissue after repeated exposure to the chemical. 6. "Toxic." A chemical falling within any of the following categories: (a) A chemical that has a median lethal dose (LD(50)) of more than 50 milligrams per kilogram but not more than 500 milligrams per kilogram of body weight when administered orally to albino rats weighing between 200 and 300 grams each. (b) A chemical that has a median lethal dose (LD(50)) of more than 200 milligrams per kilogram but not more than 1,000 milligrams per kilogram of body weight when administered by continuous contact for 24 hours (or less if death occurs within 24 hours) with the bare skin of albino rabbits weighing between two and three kilograms each. (c) A chemical that has a median lethal concentration (LC(50)) in air of more than 200 parts per million but not more than 2,000 parts per million by volume of gas or vapor, or more than two milligrams per liter but not more than 20 milligrams per liter of mist, fume, or dust, when administered by continuous inhalation for one hour (or less if death occurs within one hour) to albino rats weighing between 200 and 300 grams each. 7. "Target organ effects." The following is a target organ categorization of effects which may occur, including examples of signs and symptoms and chemicals which have been found to cause such effects. These examples are presented to illustrate the range and diversity of effects and hazards found in the workplace, and the broad scope employers must consider in this area, but are not intended to be all-inclusive. 1. Hepatotoxins: Chemicals which produce liver damage Signs & Symptoms: Jaundice; liver enlargement Chemicals: Carbon tetrachloride; nitrosamines 2. Nephrotoxins: Chemicals which produce kidney damage Signs & Symptoms: Edema; proteinuria Chemicals: Halogenated hydrocarbons; uranium
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3. Neurotoxins: Chemicals which produce their primary toxic effects on the nervous system Signs & Symptoms: Narcosis; behavioral changes; decrease in motor functions Chemicals: Mercury; carbon disulfide 4. Agents which act on the blood or hemato-poietic system: Decrease hemoglobin function; deprive the body tissues of oxygen Signs & Symptoms: Cyanosis; loss of consciousness Chemicals: Carbon monoxide; cyanides 5. Agents which damage the lung: Chemicals which irritate or damage pulmonary tissue Signs & Symptoms: Cough; tightness in chest; shortness of breath Chemicals: Silica; asbestos 6. Reproductive toxins: Chemicals which affect the reproductive capabilities including chromosomal damage (mutations) and effects on fetuses (teratogenesis) Signs & Symptoms: Birth defects; sterility Chemicals: Lead; DBCP 7. Cutaneous hazards: Chemicals which affect the dermal layer of the body Signs & Symptoms: Defatting of the skin; rashes; irritation Chemicals: Ketones; chlorinated compounds 8. Eye hazards: Chemicals which affect the eye or visual capacity Signs & Symptoms: Conjunctivitis; corneal damage Chemicals: Organic solvents; acids

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APPENDIX C MIOSHA STANDARD: HAZARDOUS WORK IN LABORATORIES R 325.70101-325.70114

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APPENDIX D MIOSHA STANDARD: HAZARDOUS WASTE OPERATIONS EMERGENCY RESPONSE PLAN R 325.52101 - R 325.52137

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APPENDIX E LABORATORY INSPECTION FORM

LABORATORY INSPECTION Room Number __________________ LSSU Crawford Science Hall Inspection Date __________________ Rate each item according to the following scheme: 1. Satisfactory (readily accessible, clearly visible, good condition, not applicable to this lab) 2. Unsatisfactory (not readily accessible, needs attention, poor condition) 3. Poses imminent health / safety risk 1 2 3 General Comments: Housekeeping, general cleanliness Aisles not cluttered, egress paths free of obstructions Laboratory authority list on door Discipline specific laboratory safety policies posted Appropriate hazard and warning signs posted Location signs for safety/emergency equipment Food not stored in laboratory refrigerators, food warnings on door Condition of equipment, general facilities, lab hoods Emergency phone numbers posted, access to emergency phone Fire Safety Fire extinguisher(s) accessible, fully charged Fire blanket(s) accessible Flammables maintained at minimal levels in laboratory Stored flammables are in flammable material storage cabinets Flammables not stored along egress path Flammables stored in explosion-proof refrigerators or cold room Other Safety Devices Emergency eyewash fountain Emergency deluge shower Emergency first aid supplies Protective equipment (goggles, face masks, gloves, aprons, etc.) Evacuation route marked Master utility cutoffs (check if present) Gas Water Smoke Detector (storage areas) Chemical Handling Stored chemicals organized according to compatibility Ethers identified by date of receipt and latest date for disposal All chemical containers clearly labeled with contents

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 Only chemicals for current experiments accessible to students Chemicals stored at safe levels, in cabinets or on stable shelving Containers present for used chemicals, and wastes Chemical wastes labeled properly and segregated prior to disposal Gas cylinders strapped firmly in place, stored cylinders capped Work generating toxic and hazardous fumes done in hoods Vessels used under vacuum are taped or of appropriate construction Ventilation Laboratory at negative pressure with respect to corridors Hoods located in low-traffic, draft-free areas Hood face velocity (60-100 fpm) ___________ sash height _________ Low-velocity warning alarms on hoods Fume-generating apparatus at least 20 cm behind face of hoods Fume hoods used for designated purposes Hoods suitable for frequency and type of use required Electrical All electrical circuits grounded No circuits overloaded Circuit breakers properly labeled Electrical apparatus grounded or double insulated Motors in labs with flammable vapors are non-sparking Lighting adequate, lights in hoods protected from vapors Other cc: Departmental Chairs

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APPENDIX F HOOD INSPECTION FORM

Building: _________________

Department: _________________ Date: _________________ Hood # __________ Room #__________ Dimensions: W______ H______ D______ Face Velocity Readings:_____ _____ _____ _____ Average Face Velocity: _____ fpm at 14" opening above air foil P F Sash Operation P F Lights Functioning P F

Hood # __________ Room #__________ Dimensions: W______ H______ D______ Face Velocity Readings:_____ _____ _____ _____ Average Face Velocity: _____ fpm at 14" opening above air foil P F Sash Operation P F Lights Functioning P F

Hood # __________ Room #__________ Dimensions: W______ H______ D______ Face Velocity Readings:_____ _____ _____ _____ Average Face Velocity: _____ fpm at 14" opening above air foil P F Sash Operation P F Lights Functioning P F Room #: _________ Room #: _________ Work Order Sent?

Hood # __________ Room #__________ Dimensions: W______ H______ D______ Face Velocity Readings:_____ _____ _____ _____ Average Face Velocity: _____ fpm at 14" opening above air foil P F Sash Operation P F Lights Functioning P F P P F F

Differential Pressure of Lab: _________inches w g Differential Pressure of Lab: _________inches w g Yes _____ N/A _____

Comments: _____________________________________________________________________________ _______________________________________________________________________________________ _______________________________________________________________________________________

Inspector: _____________________________________________________

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APPENDIX G EMPLOYEE TRAINING PROGRAM

I. METHODS AND OBSERVATIONS THAT MY BE USED TO DETECT THE PRESENCE OR RELEASE OF A HAZARDOUS CHEMICAL II. MEASURES EMPLOYEES CAN TAKE TO PROTECT THEMSELVES FROM HAZARDS III. PHYSICAL AND HEALTH HAZARDS IN THE WORK AREA IV. MATERIAL SAFETY DATA SHEETS V. SPILLS AND EMERGENCIES IN THE LABORATORY VI. CHEMICAL HYGIENE PLAN The following program is designed to provide a complete employee training program under the lab rule. It covers all topics required by the lab rule. Where the program is expected to provide general health and safety training, the complete text of the training is provided. Where site-specific information is required the program introduces the topic and explains what must be inserted. There is no specific requirement under the lab rule for number of hours or format of training, but lab rule training is expected to be analogous to hazard communication training and that usually involves one to three hours of classroom-type lecture. Instructors Guide The following pages are a manual that you may use as a guide for your employee training manual. You may use the manual as it is or you may modify it to meet the needs of your unique setting. The manual contains all of the information necessary to meet the requirements of the general health and safety training requirements of the lab rule. OSHAs intention is not that you can go over each specific chemical in the lab, but that you can train your employees on categories of chemicals, such as flammables, corrosives, and carcinogens. The training must cover the chemical hygiene plan, and must indicate some of the specific hazards in the lab, so these portions must be developed and added to this program. This training program has been developed to meet the needs of audiences with varying backgrounds and academic training. It was designed to meet the requirements of the rule in a straight-forward and simple way, rather than being technically complex. In our experience this approach has worked well, because it is not uncommon for individuals with even advanced degrees to be unfamiliar with occupational health and safety training. In planning how specific to be with your training, there are some guidelines OSHA officials have indicated should be considered in deciding which chemical substances should be included individually in training. These are: 1. The most hazardous chemicals used in the lab 2. The chemicals to which the greatest number of employees are exposed

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3. The chemicals which have the highest volume use 4. The chemicals or operations in which the greatest exposure occurs 5. Any chemicals that are producing symptoms in employees What follows is an outline of the basic training program that uses headings required by OSHA and develops each topic in a program created for this system. It is meant to be fully complaint with the rule, while relevant and practical for lab employees. An asterisk indicates where site specific information must be inserted by the instructor. Employee Training Program: Occupational Exposure to Hazardous Chemicals in Laboratories I. Methods and Observations that may be used to detect the presence or release of hazardous chemical. A. Recognizing Hazards in the laboratory- what makes a work situation dangerous: 1. The chemical in itself is extremely hazardous-Although many lab chemicals are fairly hazardous and present a high degree of risk under almost any conditions of use. Cyanide salts and hydrogen sulfide are examples of extremely hazardous chemicals. 2. The chemical is used in large amounts- Relatively low hazard chemicals can cause serious health effects when used in amounts large enough to cause high level exposures. Pathology residents at a Boston Hospital lab experienced an epidemic of heartbeat irregularities from very high levels of Freon generated by doing frozen sections. 3. The chemical used over a long period of time- Some chemicals that may be extreme hazards, and are not used in large amounts, can still cause serious hazards when exposure occurs repeatedly over many years. This type of exposure occurs in workers who remain at the same kind of job over a prolonged period of time. Workers have developed partial paralysis from long-term repeated exposure to acryl amide. 4. The work involves processes that change the properties or form of the chemical- Chemical reactions are, of course, the main purpose of the lab. In most cases, the person carrying out the reaction is familiar with what will occur. Runaway reactions, unplanned reactions, or formation of byproducts all occur, however, and can cause fire, explosion, or release of toxic substances. Such reactions can also occur in the lab when using chemical-containing products for non-lab purposes such as cleaning and maintenance, i.e. If a maintenance worker attempts to remove a polymerized residue of an isocyanate product with floor wax stripper that contained ammonia, the resulting isocyanate vapors could cause significant respiratory problems in that worker. 5. The worker has little or no control over exposure- In most workplace situations, if you begin to experience adverse effects from chemical exposure, you can take steps to stop the exposure or remove yourself from the area. When outside circumstances limit your control, the chances of a serious incident become higher. These might include working in a confined space, such as removing a cylinder of gas in a basement storage closet with no ventilation, an uncontrolled release such as a spill or leak, or even working under time pressures and deadlines, when normal safety instincts are overridden. B. Recognizing exposure in the laboratory- how you can tell if you are being exposed.

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1. The chemical is visible and open to the air- All liquids will produce at least traces of vapor, and of course man will produce large amounts it they are open to the room air. Solids, when they are handled, rarely fail to generate at least slight amounts of dust. In general, it is safest to assume that slight exposure is occurring any time a chemical is handled in the open. 2. The chemical that has escaped from its container and is visible in the airAlthough it is not a quantitative measure of exposure levels, the visible presence of dust, mist, fumes or vapor is clear-cut indication that exposure is occurring at more than a trace level. 3. You experience a symptom of any kind- The intent of the lab rule as well as all health and safety regulations is to ensure that employees do not suffer adverse health effects as a result of workplace exposures. If you are having irritation, dizziness, headaches, or other minor health problems as a result of chemical exposure, you are being over-exposed. 4. A warning system has been activated or an incident has occurred- In some labs, there are warning devices to warn of chemical release. If there are any such devices in your lab, it is important to know exactly which alarms signify what types of releases, and to be aware of what you should be in the event an alarm does go off. How you can tell if exposure has happened: 5. OSHA illness and injury log- All employers must post a record, once a year during the month of February, of all injuries and illnesses related to work that resulted in lost time. In addition, the log must be maintained, and employees given access to it, throughout the year. (This log need only be maintained for the business or institution as a whole; a separate posting need not be done for the lab). Inspection of this document can reveal a pattern of illness that demonstrates that a hazardous chemical exposure is occurring. 6. More than one person in the same area experiences similar health problems at the same time- It is very unlikely that two or more people who work in the same place would develop the same type of health problem at the same time by coincidence. If you or your coworkers discover that several of you have had similar health problems during the same time period, it may be an indication that chemical over-exposure is occurring, and certainly warrants further investigation. C. Measuring Exposure 1. Bulk Sampling- Simply taking some of the unknown material and sending it to a lab for identification is called bulk sampling. 2. Industrial Hygiene Monitoring-This is collecting air and checking for the amount of chemical present in it. a. Area Sample- samples are collected at the point where the chemical is coming out of the container or general room air is sampled. b. Personal Sample- the employees personal breathing air is sampled. There are several different ways to collect a sample: a. Grab Sample- sampling is done for a few seconds to determine exposure at that moment b. Continuous Sample- sampling is done over a longer period of time. c. Wipe Sample- picking up dust or residue off of a surface with a wipe and then analyzing it. Results of Sampling Most industrial hygiene results are reported in parts per million (ppm) for gases and vapors. PPM refers to parts of a substance per million parts of air, i.e.

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10 ppm of acetic acid would mean that out of a million parts of air, 10 of them are acetic acid. Solids are reported in milligrams per cubic meter (mg/m3). This refers to milligrams of a substance per cubic meter of air. Various experts have determined safe exposure limits which can then be compared to the results of the sample. 3. Biological monitoring- This type of monitoring tests the worker for the chemical in their body (it sometimes tests for the effects of the chemical in the body). The worker undergoes medical tests with the results showing if overexposure has occurred. When this kind of testing is done, workers have a right to results of the tests. II. Measures employees can take to protect themselves from hazards A. Controlling Exposure in laboratory- There are many possible methods that can be used to control exposure in the lab ranging from simple room ventilation, eye protection, and a lab coat, up to glove boxes and respirators. The control measures that provide the necessary protection, with the least expense and inconvenience for the person working with it, will vary widely with the chemicals involved and the type of process carried out. Control measures can be divided into three broad categories: 1. At the source- Controlling chemical at the source refers to those methods where the exposure is stopped before it exists at all. There are several ways to do this: a. Substituting a safer chemical for a hazardous one. If a reaction is being run with a particularly hazardous chemical, it may be possible to find a less hazardous alternative. Benzene, for instance, is used as a standard in gas chromatography, but if another aromatic to a human carcinogen at the source by substitution. b. Enclosing the container or process where the chemical is used, such as a glove box can prevent exposure. c. Isolating the process to another area of the facility, such as a designated area will control the exposure for some employees who do not have to be there. It means, of course, that the employees who do work there will need additional protection. d. Process change. Sometimes a reaction to test or produce is carried out under conditions that create hazards. It may be possible to design an alternative reaction to test or produce the same result that eliminates the hazard, i.e. running a reaction at a high temperature that causes high vapor levels, may create exposures that could be controlled if a catalyst was used and the reaction was run at room temperature. 2. Along the path- This is controlling the chemical in the air between its container and the worker. Methods of along the path control include: a. Local exhaust ventilation (hood) b. General ventilation (fans, windows, normal building ventilation) c. Careful housekeeping (wiping up spills, dusts) d. Special work methods If properly used, these methods can keep down the level of chemicals in the air very effectively, as long as exposures are not excessive. 3. At the worker- If the chemical is not controlled at the source or along the path, it will reach the individual carrying out the process. At that point, if exposure levels are hazardous, illness and injury can only be avoided by personal protective equipment (PPE). PPE should be used only when there is no other alternative, because this method allows dangerous levels of chemicals to reach the personal environment or the worker. If you are going to use PPE, you must

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be properly trained, fitted and the equipment must be the right type for the hazard it is protecting against. Improper PPE can be worse than none at all. In the lab, gloves and eye protection are both mainstays of control measures and are very appropriate for many situations. Details about specific types of PPE are described below. B. Specific information about Controls in this Laboratory Standard operating procedures (SOPs) for this lab can be found in the Chemical Hygiene Plan (CHP). These SOPs will be reviewed during this training. These SOPs include the types of PPE to use when working with specific chemicals and for emergency procedures. The CHP developed for this facility also include section son fume hoods and other controls in use. C. PPE 1. What is Personal Protective Equipment? Personal protective equipment, or PPE, is a term used for a variety of products worn by lab worker which are designed to protect them from safety and health hazards. 2. When is PPE needed? PPE is needed anytime there is a possibility that you may be exposed to hazardous materials. 3. What type of PPE will I use? The level of protection you are required to wear depends on the specific hazards of the chemicals you are working with. The three most common types of PPE in use are: a. Eye/ Face Protection b. Gloves c. Apron/ Protective Clothing If you are required to use a respirator, you will need several hours of classroom and hands-on training. It will also require proper fitting and testing instruction. If anyone in you lab uses a respirator, your employer is required to develop a full respirator program under OSHA standards. Even if one is present in your work area, respirators should never be used without proper training. Because certain respirators and their cartridges provide protection against only certain substances, improper use of a respirator may provide no protection or cause more harm than no respirator at all. 4. Limitations of PPE a. Without proper fitting and selection, PPE is ineffective -If gloves are too large, they may hinder your ability to obtain a good grasp. Too loose cuffs on gloves may allow irritating material to get into the gloves and be held next to the skin. If the chemical penetrates the glove, there will be repeat exposure every time the glove is reused. -There is no single glove or clothing material that protects against all chemicals. -Gloves and aprons are made of certain materials to protect against certain hazards. -Gloves and aprons used to protect against alcohols may not protect against acids. -Make sure you have protective clothing made out of the proper material to protect against the hazard you are working with.

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-Data is usually provided by the manufacturer about the type of hazards the glove or apron is made to protect against. If this information is not available on the package, ask your supervisor to call the manufacturer. -Eye or face protection may only protect against splashing, not irritating vapors. b. PPE may be uncomfortable c. PPE may restrict sight, hearing, touch, and movement -Take note of the effect PPE has on your senses before using it in a work situation. Make sure the gloves you wear do not prevent you from keeping a grip on glass test tubes, beakers, and other containers where chemicals are placed. Make sure that goggles or face shields do not restrict you sight. d. PPE may become ineffective with use if not maintained properly. e. Protective clothing has a limited lifetime -The actual life of clothing will depend on use, condition, length of contact with chemicals, temperature, concentration of chemicals, and physical wear and tear. After a certain amount of exposure some protective clothing materials deteriorate and develop small cracks which allow breakthrough. 5. Care and maintenance of PPE The manufacturers instructions for care and maintenance of PPE should be followed. However, there are also some basic guidelines to help keep PPE maintained. a. Protective clothing made of different materials should be stored separately, because it is often impossible to tell materials apart. Because there is not just one material that is impervious to all chemicals, selecting protective clothing made out of the wrong material for the hazard could result in and illness or injury due to exposure. b. Do not fold gloves or aprons in an unnatural way. If possible, store them laying flat. Folding causes stress to the folded areas, weakening them and making them more susceptible to breakthrough. c. Periodic cleaning, depending on the frequency of use, to remove chemical buildup will lengthen the life of the PPE. d. Gloves with a rough finish require a more thorough cleaning because the surface traps solutions which may cause deterioration. e. If protective clothing swells, they should be taken out of use to permit chemicals to evaporate and the original shape restored. f. Defective PPE should be immediately scrapped and replaced. You should inform your supervisor immediately if PPE is defective, or hinders your ability to perform a task. g. PPE should be inspected before and after use for wear or holes. 6. Standard Inspection Procedures for protective clothing Before use: a. Determine that the clothing material is correct for the hazard it is to be used against.

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b. Visually inspect for: imperfect seams, non-uniform coatings, tears, malfunctioning closures c. Hold it up to the light to check for pinholes d. Flex the clothing: observe fro cracks and other signs of deterioration e. If the clothing has been used before, check for signs of chemical attack: discoloration, swelling, stiffness While working, periodically check for signs of any of this happening in the area that you are working in. 7. Glove Inspection- Before use: Pressurize gloves for pin holes, even if they are brand new! This can be done by inflating the gloves and holding them under water. No air should escape. You should wash your hands and face thoroughly with skin cleanser after use of PPE to ensure that the skin is free from any substance that may have permeated the protective clothing. III The Physical and Health Hazards in the Work Area There are tens of thousands of commercially available hazardous chemicals and many labs routinely use hundreds or more of these. It is not possible to discuss each one individually, so chemicals are usually grouped into categories of hazards. There are many ways to do this. The system used below divides all potential hazards into two broad groups: physical and health. Each group is then further divided into specific hazards based on how they are likely to occur or be experienced by the employee. A. Physical/Safety Hazards 1. FIRE- The biggest fire hazard in most labs comes from the ignition of vapors, from a flammable liquid, by a spark or flame. Under the definition of flammable used in the lab rule, a flammable liquid is one that can give off sufficient vapor, at a temperature under 100 degrees Fahrenheit, to ignite from a spark or a flame. The amount of vapor a flammable liquid is likely to produce and where vapor will travel to, can help identify the extent of the hazard. -Important Definitions: Vapor Pressure- is a measure of how readily a liquid or a solid mixes with air at its surface. A higher vapor pressure indicates a higher concentration of the substance in the air and therefore increases the likelihood of breathing it in. Vapor Density- how heavy the vapor given off by a chemical is compared to the air and thus, whether it will rise or fall when it is given off. Air has a vapor density of 1.00. The higher the vapor density about 1.0, the more likely it is that the chemical vapor will sink to the floor. Flash Point- is the temperature at which a liquid or solid gives off vapor that can form flammable mixture with the air. In labs, ethers are one common source of fires. Ethyl ether, for instance, has a flash point of -27 degrees of Celsius, a vapor pressure of 442 mm Hg, and vapor density of 2.56. Thus ether readily gives off vapors capable of creating a flammable mixture with the air at even low temperatures, and the vapor tents to sink, or creep along the top of a lab bench. Igniting a Bunsen burner can then make the flame flash back along the vapor to the container of ether and start a fire. 2. Reactivity and Explosion- All lab employees are familiar with chemical reactivity. However, recognizing reactive hazards may involve a slightly different perspective than you usually use, in that a side reaction that maybe of o consequence to the procedure you are doing may have more serious implications in terms of hazards. It is also important to be alert to reactions that may occur that are not part of the procedure you are doing, but are accidental. Finally, many

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people working in labs may not be fully aware of all classes of reactivity, either because the focus of the lab does not involve using that chemistry knowledge every day, or because their own training was not in that area. -Reactive Hazards: Oxidizers are chemicals that can act as a supply of oxygen to other chemicals when mixed. When an oxidizer comes in contact with a substance that can accept the oxygen it gives off, a reducer, a tremendous amount of heat can be produced. Oxidizers, like bleach and peroxides, will react violently when mixed with reducers. They may self-ignite or explode. They should never be stored next to each other, or allowed to combine, except under controlled conditions. Explosives- are materials which are capable of detonation, explosive decomposition or reaction at normal temperatures and pressures. Polymerization- Some substances will form long chains of single molecules (polymerize) when catalyzed into doing so. When done slowly, this is a safe, useful reaction. Some compounds can polymerize on their own, and do this so rapidly that they cause a fire or explosion. Incompatibility- Some chemicals will catch fire, explode or give off toxic byproducts when combined with certain other specific chemicals. For example, sodium metal will catch fire on contact with water. Ammonia compounds can react with chlorine compounds to produce chloramine gas which is highly toxic. B. Heath Hazards 1. How do chemicals affect the body? To answer this question several factors have to be considered. a. Dose (how much?)- This means simply how much of the chemical gets to the part of the body where it has its effect. For example, if you handed someone 2 aspirin tablets, the dose would be how many milligrams of aspirin they swallowed and kept down. b. Duration (How long?)- This refers to the length of time you received a certain dose of a chemical. A person taking a dose of 2 aspirin every 4 hours for a week is going to have a lot more aspirin in their body than someone who takes 3 aspirins at a single time. c. Route of Entry (How do the chemicals get there?)- Chemicals can affect you by four different paths: i. Breathing- Any chemical that is in the air will be inhaled into your lungs. Once there, many will pass into your bloodstream. ii. Skin- Some chemicals are able to pass straight through the skin, usually without you feeling it, and directly into the bloodstream. Chemicals like this can be dangerous, because there is no way to measure exposure and the employee will not know he/she is being exposed. iii. Swallowing- Any dust or residue that is in the workplace can settle on your hands, face, food, cigarette, or drink. In all these cases the chemical may then get into your mouth and be swallowed. Even if you eat in a place separate from where you work, the residue may remain on your hands or face and could get into your mouth and be swallowed. iv. Direct Contact- Some substances do direct damage to any tissue they touch. For example, some chemicals burn the skin on contact, without ever entering the body. 2. Types of Exposure and Effect

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a. Exposure i. If you walked into a room where there was leaking chlorine gas, you would have acute exposure ii. If you worked around formaldehyde and gradually developed an allergy over several weeks, you would have had chronic exposure. b. Effect i. If you got a sudden bout of trouble breathing and wheezing from the formaldehyde, that lung allergy reaction would be an acute effect. ii. If there was enough chlorine gas to cause scarring of the lungs so that years later you still had trouble breathing, you would have suffered a chronic effect. The main thing to remember is that acute effects will be felt quickly, and chronic effect last for a long time and are usually gradual, but that both types of effects can come from either short, quick (acute) exposures or long slow (chronic) exposures 3. Five Types of Health Hazards a. Irritation- Some substances cause damage on contact with human tissue. These substances are called irritants. If the damage is very quick and severe, leading to permanent damage, the substance is called a corrosive. -It is important to remember that even if the sensation you feel is mild, there is a chance that if the contact with the chemical continues, a more severe reaction could occur. If you breathe a strong irritant, you may start coughing and develop tightness in your chest, and in severe cases, even pain and trouble breathing. Severe irritation of the lungs can cause a serious reaction much like internal swelling. The fluid build-up, called pulmonary edema, can be fatal. -Prevention- The best way to protect yourself from the effects of irritants will vary with the chemical. If you are working with small quantities of nitric acid in the lab, goggles and special gloves may be necessary. If you are working around vapors of a highly irritating substance, full respirator protection will be required. b. Poisons- Chemicals which shut down the functions of the body necessary for life (heartbeat, breathing, brain function, etc.). Poisons usually enter the body without warning (many are not irritating) and begin to work in a very short time. In toxicology chemicals may be classified as: i. Asphyxiants- prevent oxygen from entering cell metabolism ii. Central nervous system depressants- inhibit brain cell activity. In any case, if you are exposed to enough poison, death can be almost instant. At lower than fatal levels, you may experience the following symptoms: Lightheadedness, dizziness, weakness, trouble breathing, trouble concentrating, nausea, confusion. -If you experience these symptoms, it may be that you just need some fresh air, but if there is any chance there could be an unknown chemical in the area, or if you are being exposed to a chemical at high levels, you should leave the area immediately and notify someone.

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-Most of the time it will not be serious, but every year thousands die of chemical poisoning. In many of these cases people thought they were just getting a little dizzy and kept working. i. Preventions- Keeping exposure levels low is the only prevention. The most important thing you can do is take these risks seriously and stay informed about the hazards of these chemicals you are working with and around. c. Organ Damage Over Time- Some chemicals are damaging to just one particular part of the body. This is usually called the target organ. These kinds of chemicals usually take a long time to do damage and the worker usually feels fine. By the time symptoms appear and the organ no longer works right, the damage is usually permanent. i. Prevention- Keeping exposure levels low is the only prevention. Most chemicals that can cause this kind of damage have legal exposure levels which should protect workers from the long term effects of these chemicals. d. Allergy- Allergy causing chemicals, also called allergens and sensitizers, produce allergic reactions in people who have developed a hypersensitivity to them. Allergies always develop after the first exposure, but symptoms can occur at any time after that. In the process, exposure to an allergen leads to the formation of antibodies within the cells being sensitized. The antibodies cause no symptoms, but do mean that sensitization ahs occurred. On any subsequent exposure, histamine and other substances are released which cause the symptoms of allergy. -Allergies cause 4 kinds of problems: i. Skin Allergy- causes rashes that itch (i.e. poison ivy) the longer the exposure the worse the reaction. If the worker is always from the chemical for a while it may get better. ii. Lung Allergy- causes asthma attacks, with shortness of breath, tightness in the chest, wheezing and coughing. Asthma also has other etiologies. Chemical asthma can be very serious. iii. Nose and Eye Allergies- These allergic symptoms include: itching, sneezing, watering eyes, etc. similar to those symptoms caused by hay fever. iv. Systemic Reaction- This is a general overall body reaction. This includes anaphylaxis, a complete collapse of the circulatory system. You can easily and rapidly die from this. Workplace chemicals usually dont cause this kind of reaction but in rare cases they might. v. Prevention- If you have any of the above symptoms, check the MSDS of the chemicals you work with to see if they can cause allergies. You should also check with your doctor. If you have become allergic to a chemical, you will probably need to work in a new job assignment. Chemical allergies usually dont go away, but get worse with time. Once you have become allergic, even small amounts of chemical can trigger symptoms. e. Abnormal Cell Reproduction- Chemical mutagens cause alterations in DNA. Mutations can cause three results: i. mutations with no noticeable change ii. cancer iii. birth defects

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Carcinogens- are chemicals that cause cell changes that lead to cancer Teratogens- are substances that cause mutations in a developing fetus that lead to a birth defect. -Prevention- There is no safe or unsafe level of exposure to carcinogens, mutagens, or teratogens. The only way to deal with this kind of risk is to keep it as low as possible. IV. Material Safety Data Sheets (MSDS) A. What is an MSDS? -An MSDS is an information bulletin provided by the manufacturer of a chemical. MSDS tell you the hazardous ingredients of the product and its particular characteristics. The Lab Rule lists MSDS as one possible reference for all the hazards, safe handling, storage, and disposal of hazardous chemicals found in the lab. OSHA requires that employers maintain any copies of the MSDS accompanying a shipment of a chemical. When new and significant information becomes available about a product, chemical manufacturers must update their MSDS within 3 months. Employers must inform lab workers of the locations and availability of MSDS. This information is part of your Employee information materials. B. Contents: Every MSDS should contain the following information: 1. Product Identification- The identification on the MSDS should match exactly with the name the container of the substance is labeled with. 2. Ingredients- This section should list the components of the substance, their Chemical Abstract Services Number (CAS#), and the percentages of each component in the substance. 3. Physical Characteristics- This section should include boiling points, vapor density, vapor pressure, appearance, odor, etc. 4. Chemical Reactivity Characteristics- This section will include what conditions under which the substance is unstable, how it reacts when mixed with certain types of substances, incompatible materials, etc. 5. Fire and Explosion Hazards- This section will contain flashpoints, fire fighting procedures, unusual fire hazards, etc. 6. Health Hazards- This section will include routes of exposure, symptoms, PELs, TLVs, first aid procedures, etc. 7. Personal Protection/ Workplace Control- This section includes PPE, engineering controls, work practices, storage, handling, etc. 8. Spill and Leak Procedures- This section includes steps to be taken if the material is released or spilled, methods of disposal, etc. V. Spills and Emergencies in the Lab This section must be based on site specific information about the physical description of the facility along with existing policies on who is to handle emergency spills and leaks and additional training that may be necessary for these individuals. VI. Chemical Hygiene Plan (CHP) A. The CHP must be readily available to all employees, employee representatives and, upon request, to OSHA. B. The CHP must contain all the following elements: 1. SOPs 2. Control measures 3. Fume hood requirements 4. Medical consultation and exams

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5. Prior approval programs 6. Designation of personnel 7. Additional employee protection

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APPENDIX H INCOMPATIBILITY OF COMMON LABORATORY CHEMICALS

When certain hazardous chemicals are stored or mixed together, violent reactions may occur because the chemicals are incompatible or unsuitable for mixing. Classes of incompatible chemicals should be segregated from each other during storage, according to hazard class. Use the following general guidelines for hazard class storage: Flammable/Combustible Liquids and Organic Acids Flammable Solids Mineral Acids Caustics Oxidizers Perchloric Acid Compressed Gases Before mixing any chemicals, refer to this partial list, the chemicals' MSDS or Mary St. Antoine. CHEMICAL Acetic acid Acetylene Acetone Alkali and alkaline earth metals Ammonia Ammonium nitrate Aniline Azides Bromine Calcium oxide Carbon (activated) Carbon tetrachloride Chlorates Chromic acid Chromium trioxide Chlorine Chlorine dioxide Copper INCOMPATIBLE CHEMICAL(S) aldehyde, bases, carbonates, hydroxides, metals, oxidizers, peroxides, phosphates, xylene halogens (chlorine, fluorine, etc.), mercury, potassium, oxidizers, silver acids, amines, oxidizers, plastics acids, chromium, ethylene, halogens, hydrogen, mercury, nitrogen, oxidizers, plastics, sodium chloride, sulfur acids, aldehydes, amides, halogens, heavy metals, oxidizers, plastics, sulfur acids, alkalis, chloride salts, combustible materials, metals, organic materials, phosphorous, reducing agents, urea acids, aluminum, dibenzoyl peroxide, oxidizers, plastics acids, heavy metals, oxidizers acetaldehyde, alcohol's, alkalis, amines, combustible materials, ethylene, fluorine, hydrogen, ketones (acetone, carbonyls, etc.), metals, sulfur acids, ethanol, fluorine, organic materials alkali metals, calcium hypochlorite, halogens, oxidizers benzoyl peroxide, ethylene, fluorine, metals, oxygen, plastics, silanes powdered metals, sulfur, finely divided organic or combustible materials acetone, alcohol's, alkalis, ammonia, bases, benzene, combustible materials, hydrocarbons, metals, organic materials, phosphorous, plastics alcohol's, ammonia, benzene, combustible materials, flammable compounds (hydrazine), hydrocarbons (acetylene, ethylene, etc.), hydrogen peroxide, iodine, metals, nitrogen, oxygen, sodium hydroxide hydrogen, mercury, organic materials, phosphorous, potassium hydroxide, sulfur calcium, hydrocarbons, oxidizers

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Hydroperoxide Cyanides Flammable liquids Fluorine Hydrocarbons Hydrofluoric acid Hydrogen peroxide Hydrogen sulfide Hypochlorites Iodine Mercury Nitrates Nitric acid Oxalic acid Oxygen Perchloric acid Peroxides, organic Phosphorus (white) Potassium Potassium chlorate Potassium perchlorate Potassium permanganate Silver Sodium Sodium nitrate Sodium peroxide Sulfides Sulfuric acid

reducing agents acids, alkaloids, aluminum, iodine, oxidizers, strong bases ammonium nitrate, chromic acid, hydrogen peroxide, nitric acid, sodium peroxide, halogens alcohol's, aldehydes, ammonia, combustible materials, halocarbons, halogens, hydrocarbons, ketones, metals, organic acids acids, bases, oxidizers, plastics metals, organic materials, plastics, silica (glass) acetylaldehyde, acetic acid, acetone, alcohol's carboxylic acid, combustible materials, metals, nitric acid, organic compounds, phosphorous, sulfuric acid, sodium, aniline acetylaldehyde, metals, oxidizers, sodium acids, activated carbon acetylaldehyde, acetylene, ammonia, metals, sodium acetylene, aluminum, amines, ammonia, calcium, fulminic acid, lithium, oxidizers, sodium acids, nitrites, metals, sulfur, sulfuric acid acetic acid, acetonitrile, alcohol's, amines, (concentrated) ammonia, aniline, bases, benzene, cumene, formic acid, ketones, metals, organic materials, plastics, sodium, toluene oxidizers, silver, sodium chlorite acetaldehyde, secondary alcohol's, alkalis and alkalines, ammonia, carbon monoxide, combustible materials, ethers, flammable materials, hydrocarbons, metals, phosphorous, polymers acetic acid, alcohol's, aniline, combustible materials, dehydrating agents, ethyl benzene, hydriotic acid, hydrochloric acid, iodides, ketones, organic material, oxidizers, pyridine acids (organic or mineral) oxygen (pure and in air), alkalis acetylene, acids, alcohol's, halogens, hydrazine, mercury, oxidizers, selenium, sulfur acids, ammonia, combustible materials, fluorine, hydrocarbons, metals, organic materials, sugars alcohol's, combustible materials, fluorine, hydrazine, metals, (also see chlorates)organic matter, reducing agents, sulfuric acid benzaldehyde, ethylene glycol, glycerol, sulfuric acid Silver acetylene, ammonia, oxidizers, ozonides, peroxyformic acid Sodium acids, hydrazine, metals, oxidizers, water Sodium nitrate acetic anhydride, acids, metals, organic matter, peroxyformic acid, reducing agents acetic acid, benzene, hydrogen sulfide metals, oxidizers, peroxyformic acid, phosphorous, reducers, sugars, water acids potassium chlorates, potassium perchlorate, potassium permanganate

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This area reserved for EPA chem. Compat. chart

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APPENDIX I GLOVE RESISTANCE TO VARIOUS CHEMICALS

E = Excellent. G = Good, F = Fair, Natural Rubber G E G P G F F P F G P P P P P G F P P F F F F F F P G P P G G P = Poor

Chemical Acetaldehyde Acetic acid Acetone Acrylonitrile Ammonium hydroxide (conc.) Aniline Benzaldehyde Benzene Benzyl Chloride (a) Bromine Butane Butyraldehyde Calcium hypochlorite Carbon disulfide Carbon tetrachloride Chlorine Chloroacetone Chloroform (a) Chromic acid Cyclohexane Dibenzyl ether Dibutyl phthalate Diethanolamine Diethyl ether Dimethyl Sulfoxide (b) Ethyl acetate Ethylene dichloride (a) Ethylene glycol Ethylene trichloride (a) Ethylene trichloride (a) Fluorine Formaldehyde

Neoprene G E G G E G F F P G E P G P F G E F P E G F E G G F G P P G E

Nitrile E E G E E E G G G G G G P E G G E E

Vinyl G E F F E F G F P G P G G F F G P P E P P E P P F P E P P G E

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Formic acid Glycerol Hexane Hydrobromic acid (40%) Hydrochloric acid (conc.) Hydrofluoric acid (30%) Hydrogen peroxide Iodine Methylamine Methyl cellosolve Methyl chloride (a) Methylene chloride (a) Methyl ethyl ketone Monoethanolamine Morpholine Naphthalene (a) Nitric acid (conc.) Perchloric acid Phenol Phosphoric acid Potassium hydroxide (sat.) Propylene dichloride Sodium hydroxide Sodium hypochlorite Sulfuric acid (conc.) Toluene (a) Trichloroethylene (a) Tricresyl phosphate Triethanolamine Trinitrotoluene

G G P G G G G G G F P F F F F G P F G G G P G G G P P P F P

E G E E G G G G G E E F G E E G P G E E G F G P G F F F E E

E E G G G E G G E P F G G F F G G E -

E E P E E E E G E P P F P E E G G E E E E P E G G F F F E P

(a) Aromatic and halogenated hydrocarbons will attack all types of natural and synthetic glove material. Should swelling occur, the user should change to fresh gloves and allow the swollen gloves to dry and return to normal. (b) No data on the resistance to dimethyl sulfoxide of natural rubber, neoprene, nitrile rubber, or vinyl materials are available; the manufacturer of the substance recommends the use of butyl rubber gloves.

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APPENDIX J COMMON LABORATORY FLAMMABLE AND COMBUSTIBLE CHEMICALS

Flammable and combustible chemicals are the most commonly used hazardous chemicals. The hazard of a flammable or combustible chemical is based on its flash point, and, in the case of a flammable chemical, its boiling point as well. The National Fire Protection Association (NFPA) has identified flammability classes from the flash point and boiling point data of chemicals. The following table lists some common flammable and combustible chemicals, their flash points and boiling points, and associated NFPA flammability classes: Flashpoin t (F) -38 -36 -49 -20 -57 -157 12 -22 -4 55 -7 53 52 16 68 6 40 20 80 82 88 75 81-90 103 118 156 100 100-140 145 154 170 190 160 Flashpoin t (C) -39 -38 -45 -29 -49 -105 -11 -30 -20 13 -22 12 11 -9 20 -14 4 -7 27 28 31 24 27-32 39 48 69 38 38-60 63 68 77 88 71 Boiling Point (F) 69 99 95 55 97 -44 176 115 179 173 156 180 149 176 239-241 153 231 193 185-187 270 239-243 248 280-291 244 307-316 213 263 300-400 352 322 316 412 406 Boiling Point (C) 21 37 35 13 36 -42 80 46 81 78 69 82 65 80 116 67 111 89 85-86 132 115-117 120 138-144 48 153-158 101 128 150-200 178 161 158 211 208 NFPA Class IA IA IA IA IA IA IB IB IB IB IB IB IB IB IB IB IB IB IC IC IC IC IC II II II II II IIIA IIIA IIIA IIIA IIIA

Chemical Acetaldehyde Dimethyl sulfide Ethyl ether Ethylene oxide Pentane Propane Benzene Carbon disulfide Cyclohexane Ethyl alcohol n-Hexane Isopropyl alcohol Methyl alcohol Methyl ethyl ketone Pyridine Tetrahydrofuran Toluene Triethylamine tert Butyl isocyanate Chlorobenzene Epichlorohydrin 2-Nitropropane Xylene Acetic Acid, glacial Bromobenzene Formic Acid Morpholine Stoddard Solvent Benzaldehyde Cyclohexanol Methacrylic Acid Nitrobenzene Tetrahydronaphthalene

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Benzyl Alcohol Caproic Acid Ethylene Glycol Phenyl Ether Stearic Acid

213 215 232 239 385

101 102 111 115 196

401 400 388 498 726

205 204 198 258 386

IIIB IIIB IIIB IIIB IIIB

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APPENDIX K FLAMMABLE LIQUID STORAGE LIMITS FOR LABORATORIES

Maximum Quantities of Flammable and Combustible Liquids in Sprinklered Laboratory Units Outside of Flammable Liquid Inside Liquid Storage Areas
Laboratory Unit Fire Hazardous Class A B C D Maximum Quantity per 100 ft2 of Laboratory Unit (gals) 10 20 5 10 2 4 1.1 1.1 Maximum Quantity per Laboratory Unit (gals) 600 800 300 400 150 200 75 75 Maximum Quantity per 100 ft2 of Laboratory Unit (gals) 20 40 10 20 4 8 2 2 Maximum Quantity per Laboratory Unit (gals) 1200 1600 600 800 300 400 150 150

Flammable or Combustible Liquid Class I I, II, IIIA I I, II, IIIA I I I, II, IIIA I I I, II, IIIA I

Maximum Quantities of Flammable and Combustible Liquids in Non-sprinklered Laboratory Units Outside of Flammable Liquid Inside Liquid Storage Areas
Laboratory Unit Fire Hazardous Class A B C D Maximum Quantity per 100 ft2 of Laboratory Unit (gals) 10 20 5 10 2 4 1.1 1.1 Maximum Quantity per Laboratory Unit (gals) 300 400 150 200 75 100 37 37 Maximum Quantity per 100 ft2 of Laboratory Unit (gals) 20 40 10 20 4 8 2 2 Maximum Quantity per Laboratory Unit (gals) 600 800 300 400 150 200 75 75

Flammable or Combustible Liquid Class I I, II, IIIA I I, II, IIIA I I I, II, IIIA I I I, II, IIIA I

Laboratories listed as Class A shall be considered high hazard laboratories and shall not be used as instructional laboratories. Laboratories listed as Class B shall be considered intermediate hazard laboratories. Laboratories listed as Class C shall be considered low hazard laboratories. Laboratories listed as Class D shall be considered minimal fire hazard laboratories.

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Flammable Liquid Container Size Limits

Only approved containers authorized by NFPA (National Fire Protection Association) 30 shall be used to store flammable liquids.
Container Glass Metal or Approved Plastic Safety Cans Metal Drums Polyethylene Flammable Class IA IB 1 pt* 1 qt* 1.1 gal 5 gal 2.6 gal 5 gal not allowed 5 gal 1.1 gal 5 gal IC 1.1 gal 5 gal 5 gal 5 gal 5 gal Combustible Class II III 1.1 gal 5 gal 5 gal 5 gal 5 gal 5 gal 60 gal 60 gal 60 gal 60 gal

*Class IA and IB liquids may be stored up to one gallon in glass containers if liquid purity would be affected by storage in metal containers or if metal containers could undergo excessive corrosion by the contained liquid.

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APPENDIX L COMMON LABORATORY CORROSIVES

ORGANIC ACIDS Formic Acid Acetic Acid (Glacial) Propionic Acid Butyric Acid Chloroacetic Acid Trichloroacetic Acid Acetyl Chloride Acetyl Bromide Chloroacetyl Chloride Oxalic Acid Propionyl Chloride Propionyl Bromide Acetic Anhydride Methyl Chloroformate Dimethyl Sulfate Chlorotrimethylsilane Dichlorodimethylsilane Phenol Benzoyl Chloride Benzoyl Bromide Benzyl Chloride Benzyl Bromide Salicylic Acid INORGANIC ACIDS Hydrofluoric Acid Hydrochloric Acid Hydrobromic Acid Hydriodic Acid Sulfuric Acid Chromerge No-Chromix Chlorosulfonic Acid Sulfuryl Chloride Bromine Pentafluoride Thionyl Chloride Tin Chloride Tin Bromide Titanium Tetrachloride Perchloric Acid Nitric Acid Phosphoric Acid Phosphorus Trichloride Phosphorus Tribromide Phosphorus Pentachloride Phosphorus Pentoxide ORGANIC BASES Ethylenediamine Ethylimine Tetramethylethylenediamine Hexamethylenediamine Trimethylamine aq. soln. Triethylamine Phenylhydrazine Piperazine Hydroxylamine Tetramethylammonium Hydroxide

INORGANIC BASES Ammonium Hydroxide Calcium Hydroxide Sodium Hydroxide Potassium Hydroxide Calcium Hydride Sodium Hydride Hydrazine Ammonium Sulfide Calcium Oxide

ELEMENTS Fluorine (gas) Chlorine (gas) Bromine (liquid) Iodine (crystal) Phosphorus

ACID SALTS Aluminum Trichloride Antimony Trichloride Ammonium Bifluoride Calcium Fluoride Ferric Chloride Sodium Bisulfate Sodium Fluoride

References : The Foundations of Laboratory Safety, S.. R. Rayburn, 1990. Prudent Practices for Handling Hazardous Chemicals in Laboratories, National Research Council, 1981. Improving Safety in the Chemical Laboratory, 2nd Ed., J. A. Young, 1991. Material Safety Data Sheets, various chemical companies.

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APPENDIX M COMMON LABORATORY OXIDIZERS

Oxidizers react with other chemicals by giving off electrons and undergoing reduction. Uncontrolled reactions of oxidizers may result in a fire or an explosion, causing severe property damage or personal injury. Use oxidizers with extreme care and caution and follow all safe handling guidelines specified in the MSDS. Bleach Bromates Bromine Butadiene Chlorates Chloric Acid Chlorine Chlorite Chromates Chromic Acid Dichromates Fluorine Haloate Halogens Hydrogen Peroxide Hypochlorites Iodates Sodium Borate Mineral Acid Nitrates Nitric Acid Nitrites Nitrous oxide Ozanates Oxides Oxygen Oxygen difluoride Ozone Peracetic Acid Perhaloate Perborates Percarbonates Perchlorates Perchloric Acid Permanganates Peroxides Persulfate Perhydrate Sulfuric Acid

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APPENDIX N CLASSES OF PEROXIDIZABLE CHEMICALS

A. Chemicals that form explosive levels of peroxides without concentration Butadienea Isopropyl ether a Chloroprene Tetrafluoroethylenea Divinylacetylene Vinylidene chloride B. Chemicals that form explosive levels of peroxides on concentration Acetal 2-Hexanol Acetaldehyde Methylacetylene Benzyl alcohol 3-Methyl-1-butanol 2-Butanol Methylcyclopentane Cumene Methyl isobutyl ketone Cyclohexanol 4-Methyl-2-pentanol 2-Cyclohexen-1-ol 2-Penten-1-ol Cyclohexene 4-Penten-1-ol Decahydronaphthalene 1-Phenylethanol Diacetylene 2-Phenylethanol Dicyclopentadiene 2-Propanol Diethyl ether Tetrahydroforan Diethylene glycol dimethyl ether (diglyme) Tetrahydronaphthalene Dioxanes Vinyl ethers Ethylene glycol dimethyl ether (glyme) Other secondary alcohols 4-Heptanol C. Chemicals that may autopolymerize as a result of peroxide accumulation Acrylic acidb Tetrafluoroethylenec Acrylonitrileb Vinyl acetate Butadienec Vinylacetylene c Chloroprene Vinyl chloride Chlorotrifluoroethylene Vinylpyridine b Methyl methacrylate Vinyladiene chloride Styrene D. Chemicals that may form peroxides but cannot clearly be placed in sections A-C Acrolein 1,3-Dioxepaned Allyl etherd Di(1-propynyl) etherf Allyl ethyl ether Di(2-propynyl) ether Allyl phenyl ether Di-n-propoxymethaned p-(n-Amyloxy)benzoyl chloride 1,2-Epoxy-3-isopropoxypropaned n-Amyl ether 1,2-Epoxy-3-phenoxypropane

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Benzyl n-butyl etherd Benzyl etherd Benzyl ethyl etherd Benzyl methyl ether Benzyl 1-naphthyl etherd 1,2-Bis(2-chloroethoxy)ethane Bis(2-ethoxyethyl) ether Bis(2-(methoxyethoxy)ethyl) ether Bis(2-chloroethyl) ether Bis(2-ethoxyethyl) adipate Bis(2-ethoxyethyl) phthalate Bis(2-methoxyethyl) carbonate Bis(2-methoxyethyl) ether Bis(2-methoxyethyl)phthalate Bis(2-methoxymethyl) adipate Bis(2-n-butoxyethyl) phthalate Bis(2-phenoxyethyl) ether Bis(4-chlorobutyl) ether Bis(chloromethyl) ethere 2-Bromomethyl ethyl ether -Bromophenetole o-Bromophenetole p-Bromophenetole 3-Bromopropyl phenyl ether 1,3-Butadiyne Buten-3-yne tert-Butyl ethyl ether tert-Butyl methyl ether n-Butyl phenyl ether n-Butyl vinyl ether Chloroacetaldehyde diethylacetald 2-Chlorobutadiene 1-(2-Chloroethoxy)-2-phen-oxyethane Chloroethylene Chloromethyl methyl ethere -Chlorophenetole o-Chlorophenetole p-Chlorophenetole Cyclooctened Cyclopropyl methyl ether Diallyl etherd p-Di-n-butoxybenzene 1,2-Dibenzyloxyethaned p-Dibenzyloxybenzened 1,2-Dichloroethyl ethyl ether

Ethoxyacetophenone 1-(2-Ethoxyethoxy)ethyl acetate 2-Ethoxyethyl acetate (2-Ethoxyethyl)-o-benzoyl benzoate 1-Ethoxynaphthalene o,p-Ethoxyphenyl isocyanate 1-Ethoxy-2-propyne 3-Ethoxyopropionitrile 2-Ethylacrylaldehyde oxime 2-Ethylbutanol Ethyl -ethoxypropionate 2-Ethylhexanal Ethyl vinyl ether Furan 2,5-Hexadiyn-1-ol 4,5-Hexadien-2-yn-1-ol n-Hexyl ether o,p-Iodophenetole Isoamyl benzyl etherd Isoamyl etherd Isobutyl vinyl ether Isophoroned p-Isopropoxypropionitriled Isopropyl 2,4,5-trichlorophenoxy-acetate Limonene 1,5-p-Methadiene Methyl p-(n-amyloxy)benzoate 4-Methyl-2-pentanone n-Methylphenetole 2-Methyltetrahydrofuran 3-Methoxy-1-butyl acetate 2-Methoxyethanol 3-Methoxyethyl acetate 2-Methoxyethyl vinyl ether Methoxy-1,3,5,7-cycloocta tetraene -Methoxypropionitrile m-Nitrophenetole 1-Octene Oxybis(2-ethyl acetate) Oxybis(2-ethyl benzoate) ,-Oxydipropionitrile 1-Pentene Phenoxyacetyl chloride -Phenoxypropionyl chloride Phenyl o-propyl ether

138

2,4-Dichlorophenetole Diethoxymethaned 2,2-Diethoxypropane Diethyl ethoxymethylenemalonate Diethyl fumarated Diethyl acetald Diethylketenef m,o,p-Diethoxybenzene 1,2-Diethoxyethane Dimethoxymethaned 1,1-Dimethoxyethaned Dimethylketenef 3,3-Dimethoxypropene 2,4-Dinitrophenetole

p-Phenylphenetone n-Propylether n-Propyl isopropyl ether Sodium 8,11,14-eicosa tetraenoate Sodium ethoxyacetylidef Tetrahydropyran Triethylene glycol diacetate Triethylene glycol dipropionate 1,3,3-Trimethoxypropened 1,1,2,3-Tetrachloro-1,3-butadiene 4-Vinyl cyclohexene Vinylenecarbonate Vinylidene chiorided

a b c

d e f

When stored as a liquid monomer Although these chemicals form peroxides, no explosions involving these monomers When stored in liquid form, these chemicals form explosive levels of peroxides without concentration. They may also be stored as a gas in gas cylinders. When stored as a gas, these chemicals may auto-polymerize as a result of peroxide accumulation. These chemicals easily form peroxides and should probably be considered under part B. OSHA-regulated carcinogen Extremely reactive and unstable compound.

Safe Storage Period for Peroxide Forming Chemicals Description Unopened chemicals from manufacturer Opened containers Chemicals in Part A Chemicals in Parts B and D Uninhibited chemicals in Part C Inhibited chemicals in Part C
a

Period 18 months 3 months 12 months 24 hours 12 monthsa

Do not store under inert atmosphere, oxygen required for inhibitor to function.

Sources: Kelly, Richard J., Chemical Health & Safety, American Chemical Society, 1996, Sept, 28-36

139

APPENDIX O SHOCK SENSITIVE AND EXPLOSIVE CHEMICALS

Shock sensitive refers to the susceptibility of a chemical to rapidly decompose or explode when struck, vibrated or otherwise agitated. Explosive chemicals are those chemicals which have a higher propensity to explode under a given set of circumstances than other chemicals (extreme heat, pressure, mixture with an incompatible chemical, etc.). The label and MSDS will indicate if a chemical is shock sensitive or explosive . The chemicals listed below may be shock sensitive or explode under a given number of circumstances and are listed only as a guide to some shock sensitive or explosive chemicals. Follow these guidelines: Write the date received and date opened on all containers of shock sensitive chemicals. Some chemicals become increasingly shock sensitive with age. Unless an inhibitor was added by the manufacturer, closed containers of shock sensitive materials should be discarded after 1 year. Wear appropriate personal protective equipment when handling shock sensitive chemicals.
acetylene acetylides of heavy metal amatex amatol ammonal ammonium nitrate ammonium perchlorate ammonium picrate azides of heavy metals baratol calcium nitrate chlorate copper acetylide cyanuric triazide cyclotrimethylenetrinitramine dinitrophenol dinitrophenyl hydrazine dinitrotoluene ednatol erythritol tetranitrate Mixtures: germanium hexanitrodiphenyamine hexanitrostilbene hexogen hydrazoic acid lead azide lead mononitroresorcinate lead styphnate mannitol hexanitrate sodium picramate tetranitrocarbazole fulminate of mercury fulminate of silver ethylene oxide ethyl-tetryl organic fulminating gold fulminating mercury fulminating platinum fulminating silver gelatinized nitrocellulose guanyl guanyl nitrosamino guanyltetrazene hydrazine nitrated carbohydrate nitrated glucoside nitrogen triiodide nitrogen trichloride nitroglycerin nitroglycide nitroglycol tetracene tetrytol trimethylolethane trimonite trinitroanisole trinitrobenzene trinitrobenzoic acid trinitrocresol trinitroresorcinol tritonal urea nitrate nitroguanidine nitroparaffins nitrourea nitramines ozonides pentolite perchlorates of heavy metals peroxides picramic acid picramide picratol picric acid picryl sulphonic acid silver acetylide silver azide tetranitromethane

140

APPENDIX P CARCINOGENS
The list below is a compilation of substances classified as carcinogens by either the Michigan Occupational Safety and Health Administration (MIOSHA), the International Agency for Research on Cancer (IARC) and the National Toxicology Program (NTP). Some of these substances are classified as Select Carcinogens and require special work practices. See List of Acronyms and Abbreviations for the definition of Select Carcinogen Chemical Name Acetaldehyde Acetamide 2-Acetylaminofluorene Acrylamide Acrylonitrile Adriamycin AF-2 (2-(2-Furyl)-3-(5-nitro-2-furyl)acrylamide) Aflatoxin M1 Aflatoxins, naturally occurring A--C (2-amino-9H-pyrido[2,3-b]indole) 2-Aminoanthraquinone p-Aminoazobenzene o-Aminoazotoluene 4-Aminobiphenyl 1-Amino-2-methylanthraquinone 2-Amino-5-(5-nitro-2-furyl)-1,3,4-thiadiazole Amitrole Amsacrine Analgesic mixtures containing phenacetin Androgenic (anabolic) steroid o-Anisidine o-Anisidine hydrochloride Antimony trioxide Aramite Arsenic and compounds Asbestos Asbestos, actinolite Asbestos, anthophylite Asbestos, tremolite Auramine (technical-grade) Azacitidine Azaserine Azathioprine Benzal chloride Benz[a]anthracene Benzene Benzidine MIOSHAa Class A CH 2A 2B 2A 2B 2B 1 2B 2B 2B 1 2B 2B 2B 1 2A 2B 2B 2B 1 1 IARCb 2B 2B NTPc 2 2 2 2 2 1 2 Class A 2 1 2 2 1 2 CH CH CH CH CH 1 1

CH Class A

2B 2A 2B 1 2A 2A 1 1

2 1 2 1 1

141

Benzidine-based dyes Benzo[a]pyrene Benzo[b]fluoranthene Benzo[j]fluoranthene Benzo[k]fluoranthene Benzofuran Benzotrichloride Benzoyl chloride Benzyl chloride Benzyl violet 4B 2,2-Bis(bromomethyl)propane-1,3-diol Beryllium and certain compounds Betel quid with tobacco N,N-Bis(2-chloroethyl)-2-naphthylamine (chlornaphazine) Bis(chloromethyl)ether (technical grade) Bischloroethyl nitrosourea (BCNU) Bleomycins Bracken fern Bromodichloromethane 1,3-Butadiene 1,4-Butanediol dimethanesulfonate (Busulphan Myleran) Butylated hydroxyanisole (BHA) -Butyrolactone C.I. Acid Red 114 C.I. Basic Red 9 C.I. Direct Blue 15 C.I. Citrus Red no. 2 Cadmium and compounds Caffeic acid Captafol Carbon tetrachloride Catechol Ceramic Fibres (respirable size) Carbon-black Carrageenan, degraded Chlorambucil Chloramphenicol Chlordane Chlordecone (Kepone) Chlorendic acid Para-Chloroaniline Chlorinated paraffins (C12 60% Chlorine) -Chlorinated toluenes 1-(2-Chloroethyl)-3-cyclohexyl-1-nitrosourea (CCNU) 1-(2-Chloroethyl)-3-(4-methylcyclohexyl)-1nitrosourea (Methyl-CCNU; Semustine) Chloroform Chloromethyl methyl ether (technical-grade) 1-Chloro-2-methylpropene 3-Chloro-2-methylpropene

Class A

CH

2A 2A 2B 2B 2B 2B 2A 2A 2A 2B 2B 1 1 1 1 2A 2B 2B 2B 2A 1 2B 2B 2B 2B 2B 2B 1 2B 2A 2B 2B 2B 2B 2B 1 2A 2B 2B 2B 2B 2B 2A 2A 1 2B 1 2B

2 2 2 2 2

2 1 2 2 1 1 2 2 1 2 2 1 2 2 2 2 1 2 1 2

Class A

142

Chlorophenoxy herbicides 4-Chloro-o-phenylenediamine Chloroprene Chlorothalonil p-Choro-o-toluidine and its strong acid salts Chlorozotocin Chromium (VI) compounds Ciclosporin Cisplatin Coal-tar pitches Coal-tars Cobalt and cobalt compounds Coffee (urinary bladder) Conjugated estrogens Creosotes p-Cresidine Cupferron Cycasin Cyclophosphamide Cyclosporin A DDT Dacarbazine Dantron (Chrysazin; 1, 8-Dihydroxyanthraquinone) Daunomycin N,N'-Diacetylbenzidine 2,4-Diaminoanisole 1,4-Diaminoanisole sulfate 4,4'-Diaminodiphenyl ether 2,4-Diaminotoluene Dibenz[a, h]acridine Dibenz[a, h]anthracene Dibenz[a, j]acridine 7H-Dibenzo[c,g]carbazole Dibenzo[a, e]pyrene Dibenzo[a, h]pyrene Dibenzo[a, i]pyrene Dibenzo[a, l]pyrene 1,2-Dibromo-3-chloropropane (DBCP) 2,3-Dibromopropan-1-ol p-Dichlorobenzene 3,3'-Dichlorobenzidene dihydrochloride 3,3'-Dichlorobenzidine 3,3'-Dichloro-4-4'-diaminodiphenyl ether 1,2-Dichloroethane Dichloromethane 2-(2,4-Dichlorophenoxy)propionic acid 1,3-Dichloropropene (technical-grade) Dichlorvos Diepoxybutane Diesel engine exhaust particulates

2B 2B 2B 2B 2A 2A 1 1 2A 1 1 2B 2B 2A 2B 2B 1 2B 2B 2B 2B 2B 2B 2B 2B 2A 2B 2B 2B 2B 2B 2B 2B 2B 2B 2B 2B 2B 2B 2B 2B 2B 2A

2 2 2 2 1 2 1 1 1 2 2 1 1 2 2 2

CH

2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2

Class A

143

Diesel fuel, marine Di(2-ethylhexyl) phthalate 1,2-Diethylhydrazine Diethyl Sulfate Diethylstilbestrol (DES) Diglycidyl resorcinol ether Dihydrosafrole Diisopropyl sulfate 3,3'-Dimethoxybenzidine (o-Dianisidine) 3,3'-Dimethoxybenzidine dihydrochloride 2,6-Dimethylaniline 3,3'-Dimethylbenzidine (o-Tolidine) 1,2-Dimethylhydrazine Dimethyl sulfate p-Dimethylaminoazobenzene Trans-2-[(Dimethylamino)methylimino]-5-[2-(5-nitro-2furyl)vinyl]-1,3,4-oxadiazole Dimethylcarbamoyl Chloride 1,1-Dimethylhydrazine Dimethyl vinyl chloride 3,7-Dinitrofluoranthene 3,9-Dinitrofluoranthene 1,6-Dinitropyrene 1,8-Dinitropyrene 2,4-Dinitrotoluene 2,6-Dinitrotoluene 1,4-Dioxane Direct Black 38 Direct Blue 6 Disperse blue 1 Engine exhaust, gasoline Environmental Tobacco Smoke 1,2-Epoxybutane Epichlorohydrin Erionite Estrogens (not conjugated) estradiol-17 Estrogens (not conjugated) estrone Estrogens (not conjugated) ethinylestradiol Estrogens (not conjugated) mestranol Ethyl acrylate Ethylbenzene Ethylene thiourea Ethylene dibromide Ethylene oxide Ethyleneimine, inhibited Ethyl methanesulfonate N-Ethyl-N-nitrosourea Etoposide Etoposide in combination with cisplatin and bleomycin Formaldehyde (gas)

2B 2 2B 2A 1 2B 2B 2B 2B 2B 2B 2A 2A 2B 2B 2A 2B 2B 2B 2B 2B 2B 2B 2B 2B 2B 2B 2A 1 2 1 2 2 2 2 2 2 2 2 2 2 2 2 1 1 2 1 2 1 2 2 2 2 2 2 1 2 2 2

Class A

CH Class A

2B 2B 2B 2A 1 2B 2A 2A 1 2A

CH

144

2-(2-Formylhydrazino)-4-(5-(5-nitro-2-furyl)thiazole Fowler's solution Fuel oil, residual Furan Gasoline Gasoline engine exhaust fumes Gasoline, unleaded Glass wool (respirable size) Glu-P-1 (2-amino-6-methyldipyrido[1, 2-a:3', 2'd]imidazole) Glu-P-2 (2-aminodipyrido[1, 2-a:3',2'-d]imidazole) Glycidaldehyde Glycidol Griseofulvin HC blue 1 Heptachlor Hexachlorobenzene Hexachlorocyclohexane (all isomers) Hexachloroethane Hexamethylphosphoramide Hydrazine (anhydrous) Hydrazine sulfate Hydrazobenzene Indeno[1, 2, 3-cd]pyrene Inorganic-acid mists, containing sulfuric acid IQ (2-Amino-3-methylimidazo[4,5-f]quinoline) Iron-dextran complex Isoprene Lasiocarpine Lead and lead compounds, inorganic Lead acetate Lead phosphate Lindane Magenta (containing CI basic red 9) MeA-a-C (2-Amino-3-methyl-9H-pyrido[2, 3]indole) Medroxyprogestrone acetate MelQ (2-Amino-3, 4-dimethylimidazol[4, 5f]quinoline MelQx (2-AMino-3, 8-dimethylimidazo[4, 5f]quinoxaline Melphalan Merphalan 5-Methoxypsoralen 8-Methoxysoralen (methoxsalen) plus ultraviolet A radiation 2-Methylaziridine (propyleneimine) Methylazoxymethanol acetate 5-Methylchrysene 4,4'-Methylene bis(2-chloroaniline) (MBOCA) 4,4'-Methylene bis(2-methylaniline) 4,4'-Methylene bis(N,N-dimethylbenzenamine)

2B 1 2B 2B 2B 2B 2B 2B 2B 2B 2B 2A 2B 2B 2B 2B 2B 2B 2B 2B 2B 1 2A 2B 2B 2B 2B

2 2 2 2 2 2 2 2 2 2 2 2 2

2B 2B 2B 2B 2B 1 2B 2A 1 2B 2B 2B 2A 2B 1

1 2 2 2 2

145

4,4'-Methylenedianiline 4,4'-Methylenedianiline dihydrochloride Methyl Mercury Compounds Methyl methanesulfonate 2-Methyl-1-nitroanthraquinone (uncertain purity) N-Methyl-N'-nitro-N-nitrosoguanidine (MNNG) N-Methyl-N-nitrosourea N-Methyl-N-nitrosourethane Methylthiouracil Metronidazole Michler's ketone [4,4-(Dimethylamino)benzophenone] Mineral oils, untreated and mildly-treated Mirex Mitomycin C Mitoxantrone Monocrotaline MOPP and other combined chemotherapy including alkylating agents 5-(Morpholinomethyl)-3-[(5-nitrofurfurylidene)amino]-2oxazolidinone Mustard gas Nafenopi -Naphthylamine 2-Napthylamine Nickel compounds Nickel and certain nickel compounds Nickel metallic, and alloys Niridazole Nitrilotriacetic acid Nitrilotriacetic acid and its salts 5-Nitroacenaphthene 2-Nitroanisole Nitrobenzene 4-Nitrobiphenyl 6-Nitrochrysene Nitrofen, technical-grade 2-Nitrofluorene 1-[(5-Nitrofurfurylidene)amino]-2-imidazolidinone N-[4-(5-Nitro-2-furyl)-2-thiaxolyl]acetamide Nitrogen mustard Nitrogen mustard N-oxide Nitrogen mustard hydrochloride Nitromethane 2-Nitropropane 1-Nitropyrene 4-Nitropyrene N-Nitrosodi-n-butylamine N-Nitrosodi-n-propylamine N-Nitrosodiethanolamine N-Nitrosodiethylamine

CH

2B 2B 2B 2A 2B 2A 2A 2B 2B 2B 1 2B 2B 2B 2B 1 2B 1 2B

2 2 2 2 2 2 2 1 2

1 1 2

Class A Class A

1 1 2B 2B 2B 2B 2B 2B 2B

2 2

Class A 2B 2B 2B 2B 2B 2A 2B 2 2B 2B 2B 2B 2B 2B 2B 2A 2 2 2 2 2 2 2

146

N-Nitrosodimethylamine N-Nitroso-N-ethylurea 3-(N-Nitrosomethylamino)propionitirile 4-(N-Nitrosomethylamino)-1-(3-pyridyl)-butanone (NNK) N-Nitrosomethylethylamine N-Nitroso-N-methylurea N-Nitrosomethylvinylamine N-Nitrosomorpholine N-Nitrosonornicotine N-Nitrosopiperidine N-Nitrosopyrrolidine N-Nitrososarcosine Norethisterone Ochratoxin A Oestrogen-progestogen therapy, post menopausal Oestrogen replacement therapy Oestrogen, nonsteroidal Oestrogen, steroidal Oil orange ss Oral contraceptives, combined Oral contraceptives, sequential Oxazepan 4,4-Oxydianiline Oxymetholone Palygorskite (long fibers, > 5 micrometers) Panfuran S (containing dihydorxymethylfuratrizine) Phenacetin Phenazopyridine hydrochloride Phenobarbital Phenolphthalein Phenoxybenzamine hydrochloride Phenyl glycidyl ether Phenytoin Phlp (2-Amino-1-methyl-6-phenyl-imidazo[4,5b]pyridine) Piperazine estrone sulfate Polybrominated biphenyls Polychlorinated biphenyls (PCBs) Ponceau 3R Ponceau MX Potassium bromate Procarbazine hydroxhloride Progesterone Progestins Progestogen-only contraceptives 1,3-Propane sultone -Propiolactone Propyleneimine Propylene oxide Propylthiouracil

Class A

2A 2A 2B 2B 2B 2A 2B 2B 2B 2B 2B 2B 2B 2B 2B 1 1 1 2B 1 1 2B 2B 2B 2B 2A 2B 2B 2B 2B 2B 2B 2B 2B 2A 2B 2B 2B 2A 2B 2B 2B 2B 2B 2B 2B

2 2 2 2 2 2 2 2 2 2 2 2

2 2 2 2 2 2 2 1 2 2

2 2 2 2 2 2 2

Class A

147

Radon 222 and its decay products Reserpine Rockwool Safrole Selenium sulfide Shale-oils Silica, crystalline cristobalite (respirable size) Silica, crystalline tridymite (respirable size) Silica, crystalline quartz (respirable size) Slagwool Sodium equilin sulfate Sodium estrone sulfate Sodium ortho-phenylphenate Soots Sterigmatocystin Streptozotocin Strong inorganic acid mists containing sulfuric acid Styrene Styrene-7,8-oxide Sulfallate Talc (containing asbestos fibers) Tamoxifen Tars Teniposide 2,3,7,8-Tetrachlorodibenzo-para-dioxin (TCDD) Tetrachloroethylene Tetrafluoroethylene Tetranitromethane Thioacetamide 4,4'-Thiodianiline Thiotepa Thiourea Thorium dioxide Tobacco products, smokeless Tobacco smoke o-Tolidine Toluene diisocyanates o-Toluidine o-Toluidine hydrochloride Toxaphene (Polychlorinated camphenes) Treosulfan Trichlormethine (trimustine hydrochloride) Trichloroethylene 2,4,6-Trichlorophenol 1,2,3-Trichloropropane Tris (2,3-dibromopropyl)phosphate Trp-P-1 (3-Amino-1,4-dimethyl-5H-pyrido[4,3-b] indole) Trp-P-2 (3-Amino-1-methyl-5H-pyrido[4,3-b]indole) Trypan blue Uracil mustard

1 2B 2B 1 1 1 2B 2B 1 2B 2B 2B 2A 2B 1 1 2A 1 2A 2B 2B 2B 2B 1 2B 1 1 2B 2B 2A 2B 1 2B 2A 2A 2A 2B 2B 2B 2B

1 2 2 2 1 1 1 1 1 1 2 1

1 1 1 2 2 2 2 1 2 1 1 1 2 2 2 2 2 2 2 2 2

148

Urethane Vinyl acetate Vinyl bromide Vinyl chloride 4-Vinyl cyclohexene 4-Vinyl-1-cyclohexene diepoxide 4-Vinylcyclohexene diepoxide Vinyl fluoride Welding Fumes 2,6-Xylidine (2,6-Dimethylaniline) Zalcitabine Zidovidine

CSA

2B 2B 2A 1 2B 2B 2A 2B 2B 2B 2B

2 1 2

(a) Michigan Occupational Safety and Health Administration (MIOSHA): Class A: Regulated as a known human carcinogen CSA: listed as a Cancer Suspect Agent CH: listed as a Cancer Hazard (b) International Agency for Research on Cancer (IARC): 1. Carcinogenic to humans with sufficient epidemiological evidence 2A. Probably carcinogenic to humans with (usually) at least limited human evidence 2B. Probably carcinogenic to humans, but having (usually) no human evidence For a complete listing of IARC carcinogens, mixtures and exposure circumstances, see www.iarc.fr (c) National Toxicology Program (NTP): a. Known to be carcinogenic with evidence from human studies b. Reasonably anticipated to be a carcinogen, with limited evidence in humans or sufficient evidence in experimental animals More information on NTP carcinogens can be found at: http://ntp-server.niehs.nih.gov

149

APPENDIX Q NIOSH RECOMMENDED EXPOSURE LIMITS

The following table lists Immediately Dangerous to Life or Health (IDLH) concentrations from the National Institute for Occupational Safety and Health (NIOSH). Data updated as of March 1, 1995. Chemical Acetaldehyde Acetic acid Acetic anhydride Acetone Acetonitrile Acetylene tetrabromide Acrolein Acrylamide Acrylonitrile Aldrin Allyl alcohol Allyl chloride Allyl glycidyl ether 2 Aminopyridine Ammonia Ammonium sulfamate n-Amyl acetate sec-Amyl acetate Aniline o-Anisidine p-Anisidine Antimony compounds (as Sb) ANTU Arsenic (inorganic compounds, as As) Arsine Azinphosmethyl Barium (soluble compounds, as Ba) Benzene Benzoyl peroxide Benzyl chloride Beryllium compounds (as Be) Boron oxide Boron trifluoride Bromine Bromoform 1,3-Butadiene 2-Butanone 2-Butoxyethanol n-Butyl acetate IDLH 2,000 ppm 50 ppm 200 ppm 2,500 ppm [LEL] 500 ppm 8 ppm 2 ppm 60 mg/m3 85 ppm 25 mg/m3 20 ppm 250 ppm 50 ppm 5 ppm 300 ppm 1,500 mg/m3 1,000 ppm 1,000 ppm 100 ppm 50 mg/m3 50 mg/m3 50 mg Sb/m3 100 mg/m3 5 mg As/m3 3 ppm 10 mg/m3 50 mg Ba/m3 500 ppm 1,500 mg/m3 10 ppm 4 mg Be/m3 2,000 mg/m3 25 ppm 3 ppm 850 ppm 2,000 ppm [LEL] 3,000 ppm 700 ppm 1,700 ppm [LEL]

150

sec-Butyl acetate tert-Butyl acetate n-Butyl alcohol sec-Butyl alcohol tert-Butyl alcohol n-Butylamine tert-Butyl chromate n-Butyl glycidyl ether n-Butyl mercaptan p-tert-Butyltoluene Cadmium dust (as Cd) Cadmium fume (as Cd) Calcium arsenate (as As) Calcium oxide Camphor (synthetic) Carbaryl Carbon black Carbon dioxide Carbon disulfide Carbon monoxide Carbon tetrachloride Chlordane Chlorinated camphene Chlorinated diphenyl oxide Chlorine Chlorine dioxide Chlorine trifluoride Chloroacetaldehyde alpha-Chloroacetophenone Chlorobenzene o-Chlorobenzylidene malononitrile Chlorobromomethane Chlorodiphenyl (42% chlorine) Chlorodiphenyl (54% chlorine) Chloroform 1-Chloro-1-nitropropane Chloropicrin beta-Chloroprene Chromic acid and chromates Chromium (II) compounds [as Cr(II)] Chromium (III) compounds [as Cr(III)] Chromium metal (as Cr) Coal tar pitch volatiles Cobalt metal, dust and fume (as Co) Copper (dusts and mists, as Cu) Copper fume (as Cu) Cotton dust (raw) Crag (r) herbicide Cresol (o, m, p isomers) Crotonaldehyde

1,700 ppm [LEL] 1,500 ppm [LEL] 1,400 ppm [LEL] 2,000 ppm 1,600 ppm 300 ppm 15 mg Cr(VI)/m3 250 ppm 500 ppm 100 ppm 9 mg Cd/m3 9 mg Cd/m3 5 mg As/m3 25 mg/m3 200 mg/m3 100 mg/m3 1,750 mg/m3 40,000 ppm 500 ppm 1,200 ppm 200 ppm 100 mg/m3 200 mg/m3 5 mg/m3 10 ppm 5 ppm 20 ppm 45 ppm 15 mg/m3 1,000 ppm 2 mg/m3 2,000 ppm 5 mg/m3 5 mg/m3 500 ppm 100 ppm 2 ppm 300 ppm 15 mg Cr(VI)/m3 250 mg Cr(II)/m3 25 mg Cr(III)/m3 250 mg Cr/m3 80 mg/m3 20 mg Co/m3 100 mg Cu/m3 100 mg Cu/m3 100 mg/m3 500 mg/m3 250 ppm 50 ppm

151

Cumene Cyanides (as CN) Cyclohexane Cyclohexanol Cyclohexanone Cyclohexene Cyclopentadiene 2,4-D DDT Decaborane Demeton Diacetone alcohol Diazomethane Diborane Dibutyl phosphate Dibutyl phthalate o-Dichlorobenzene p-Dichlorobenzene Dichlorodifluoromethane 1,3-Dichloro 5,5-dimethylhydantoin 1,1-Dichloroethane 1,2-Dichloroethylene Dichloroethyl ether Dichloromonofluoromethane 1,1-Dichloro 1-nitroethane Dichlorotetrafluoroethane Dichlorvos Dieldrin Diethylamine 2-Diethylaminoethanol Difluorodibromomethane Diglycidyl ether Diisobutyl ketone Diisopropylamine Dimethyl acetamide Dimethylamine N,N-Dimethylaniline Dimethyl 1,2-dibromo 2,2-dichlorethyl phosphate Dimethylformamide 1,1-Dimethylhydrazine Dimethylphthalate Dimethyl sulfate Dinitrobenzene (o, m, p isomers) Dinitroocresol Dinitrotoluene Di sec-octyl phthalate Dioxane Diphenyl Dipropylene glycol methyl ether Endrin

900 ppm [LEL] 25 mg/m3 (as CN) 1,300 ppm [LEL] 400 ppm 700 ppm 2,000 ppm 750 ppm 100 mg/m3 500 mg/m3 15 mg/m3 10 mg/m3 1,800 ppm [LEL] 2 ppm 15 ppm 30 ppm 4,000 mg/m3 200 ppm 150 ppm 15,000 ppm 5 mg/m3 3,000 ppm 1,000 ppm 100 ppm 5,000 ppm 25 ppm 15,000 ppm 100 mg/m3 50 mg/m3 200 ppm 100 ppm 2,000 ppm 10 ppm 500 ppm 200 ppm 300 ppm 500 ppm 100 ppm 200 mg/m3 500 ppm 15 ppm 2,000 mg/m3 7 ppm 50 mg/m3 5 mg/m3 50 mg/m3 5,000 mg/m3 500 ppm 100 mg/m3 600 ppm 2 mg/m3

152

Epichlorohydrin EPN Ethanolamine 2-Ethoxyethanol 2-Ethoxyethyl acetate Ethyl acetate Ethyl acrylate Ethyl alcohol Ethylamine Ethyl benzene Ethyl bromide Ethyl butyl ketone Ethyl chloride Ethylene chlorohydrin Ethylenediamine Ethylene dibromide Ethylene dichloride Ethylene glycol dinitrate Ethyleneimine Ethylene oxide Ethyl ether Ethyl formate Ethyl mercaptan N-Ethylmorpholine Ethyl silicate Ferbam Ferrovanadium dust Fluorides (as F) Fluorine Fluorotrichloromethane Formaldehyde Formic acid Furfural Furfuryl alcohol Glycidol Graphite (natural) Hafnium compounds (as Hf) Heptachlor n-Heptane Hexachloroethane Hexachloronaphthalene n-Hexane 2-Hexanone Hexone sec Hexyl acetate Hydrazine Hydrogen bromide Hydrogen chloride Hydrogen cyanide Hydrogen fluoride (as F)

75 ppm 5 mg/m3 30 ppm 500 ppm 500 ppm 2,000 ppm [LEL] 300 ppm 3,300 ppm [LEL] 600 ppm 800 ppm [LEL] 2,000 ppm 1,000 ppm 3,800 ppm [LEL] 7 ppm 1,000 ppm 100 ppm 50 ppm 75 mg/m3 100 ppm 800 ppm 1,900 ppm [LEL] 1,500 ppm 500 ppm 100 ppm 700 ppm 800 mg/m3 500 mg/m3 250 mg F/m3 25 ppm 2,000 ppm 20 ppm 30 ppm 100 ppm 75 ppm 150 ppm 1,250 mg/m3 50 mg Hf/m3 35 mg/m3 750 ppm 300 ppm 2 mg/m3 1,100 ppm [LEL] 1,600 ppm 500 ppm 500 ppm 50 ppm 30 ppm 50 ppm 50 ppm 30 ppm

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Hydrogen peroxide Hydrogen selenide (as Se) Hydrogen sulfide Hydroquinone Iodine Iron oxide dust and fume (as Fe) Isoamyl acetate Isoamyl alcohol (primary and secondary) Isobutyl acetate Isobutyl alcohol Isophorone Isopropyl acetate Isopropyl alcohol Isopropylamine Isopropyl ether Isopropyl glycidyl ether Ketene Lead compounds (as Pb) Lindane Lithium hydride L.P.G. Magnesium oxide fume Malathion Maleic anhydride Manganese compounds (as Mn) Mercury compounds [except (organo) alkyls, as Hg] Mercury (organo) alkyl compounds(as Hg) Mesityl oxide Methoxychlor Methyl acetate Methyl acetylene Methyl acetylenepropadiene mixture Methyl acrylate Methylal Methyl alcohol Methylamine Methyl (namyl) ketone Methyl bromide Methyl Cellosolve (r) Methyl Cellosolve (r) acetate Methyl chloride Methyl chloroform Methylcyclohexane Methylcyclohexanol o-Methylcyclohexanone Methylene bisphenyl isocyanate Methylene chloride Methyl formate 5-Methyl 3-heptanone Methyl hydrazine

75 ppm 1 ppm 100 ppm 50 mg/m3 2 ppm 2,500 mg Fe/m3 1,000 ppm 500 ppm 1,300 ppm [LEL] 1,600 ppm 200 ppm 1,800 ppm 2,000 ppm [LEL] 750 ppm 1,400 ppm [LEL] 400 ppm 5 ppm 100 mg Pb/m3 50 mg/m3 0.5 mg/m3 2,000 ppm [LEL] 750 mg/m3 250 mg/m3 10 mg/m3 500 mg Mn/m3 10 mg Hg/m3 2 mg Hg/m3 1,400 ppm [LEL] 5,000 mg/m3 3,100 ppm [LEL] 1,700 ppm [LEL] 3,400 ppm [LEL] 250 ppm 2,200 ppm [LEL] 6,000 ppm 100 ppm 800 ppm 250 ppm 200 ppm 200 ppm 2,000 ppm 700 ppm 1,200 ppm [LEL] 500 ppm 600 ppm 75 mg/m3 2,300 ppm 4,500 ppm 100 ppm 20 ppm

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Methyl iodide Methyl isobutyl carbinol Methyl isocyanate Methyl mercaptan Methyl methacrylate Methyl styrene Mica Molybdenum (insoluble compounds, as Mo) Molybdenum (soluble compounds, as Mo) Monomethyl aniline Morpholine Naphtha (coal tar) Naphthalene Nickel carbonyl (as Ni) Nickel metal and other compounds (as Ni) Nicotine Nitric acid Nitric oxide p-Nitroaniline Nitrobenzene p-Nitrochlorobenzene Nitroethane Nitrogen dioxide Nitrogen trifluoride Nitroglycerine Nitromethane 1-Nitropropane 2-Nitropropane Nitrotoluene (o, m, p isomers) Octachloronaphthalene Octane Oil mist (mineral) Osmium tetroxide (as Os) Oxalic acid Oxygen difluoride Ozone Paraquat Parathion Pentaborane Pentachloronaphthalene Pentachlorophenol n-Pentane 2-Pentanone Perchloromethyl mercaptan Perchloryl fluoride Petroleum distillates (naphtha) Phenol p-Phenylene diamine Phenyl ether (vapor) Phenyl etherbiphenyl mixture (vapor)

100 ppm 400 ppm 3 ppm 150 ppm 1,000 ppm 700 ppm 1,500 mg/m3 5,000 mg Mo/m3 1,000 mg Mo/m3 100 ppm 1,400 ppm [LEL] 1,000 ppm [LEL] 250 ppm 2 ppm 10 mg Ni/m3 5 mg/m3 25 ppm 100 ppm 300 mg/m3 200 ppm 100 mg/m3 1,000 ppm 20 ppm 1,000 ppm 75 mg/m3 750 ppm 1,000 ppm 100 ppm 200 ppm Unknown 1,000 ppm [LEL] 2,500 mg/m3 1 mg Os/m3 500 mg/m3 0.5 ppm 5 ppm 1 mg/m3 10 mg/m3 1 ppm Unknown 2.5 mg/m3 1,500 ppm [LEL] 1,500 ppm 10 ppm 100 ppm 1,100 ppm [LEL] 250 ppm 25 mg/m3 100 ppm 10 ppm

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Phenyl glycidyl ether Phenylhydrazine Phosdrin Phosgene Phosphine Phosphoric acid Phosphorus (yellow) Phosphorus pentachloride Phosphorus pentasulfide Phosphorus trichloride Phthalic anhydride Picric acid Pindone Platinum (soluble salts, as Pt) Portland cement Propane n-Propyl acetate n-Propyl alcohol Propylene dichloride Propylene imine Propylene oxide n-Propyl nitrate Pyrethrum Pyridine Quinone Rhodium (metal fume and insoluble compounds, as Rh) Rhodium (soluble compounds, as Rh) Ronnel Rotenone Selenium compounds (as Se) Selenium hexafluoride Silica, amorphous Silica, crystalline (respirable dust) cristobalite/tridymite quartz/tripoli Silver (metal dust and soluble compounds, as Ag) Soapstone Sodium fluoroacetate Sodium hydroxide Stibine Stoddard solvent Strychnine Styrene Sulfur dioxide Sulfuric acid Sulfur monochloride Sulfur pentafluoride Sulfuryl fluoride 2,4,5-T 250 mg/m3

100 ppm 15 ppm 4 ppm 2 ppm 50 ppm 1,000 mg/m3 5 mg/m3 70 mg/m3 250 mg/m3 25 ppm 60 mg/m3 75 mg/m3 100 mg/m3 4 mg Pt/m3 5,000 mg/m3 2,100 ppm [LEL] 1,700 ppm 800 ppm 400 ppm 100 ppm 400 ppm 500 ppm 5,000 mg/m3 1,000 ppm 100 mg/m3 100 mg Rh/m3 2 mg Rh/m3 300 mg/m3 2,500 mg/m3 1 mg Se/m3 2 ppm 3,000 mg/m3 25 mg/m3 50 mg/m3 10 mg Ag/m3 3,000 mg/m3 2.5 mg/m3 10 mg/m3 5 ppm 20,000 mg/m3 3 mg/m3 700 ppm 100 ppm 15 mg/m3 5 ppm 1 ppm 200 ppm 250 mg/m3 Talc

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Talc Tantalum (metal and oxide dust, as Ta) TEDP Tellurium compounds (as Te) Tellurium hexafluoride TEPP Terphenyl (o, m, p isomers) 1,1,1,2-Tetrachloro 2,2-difluoroethane 1,1,2,2-Tetrachloro 1,2-difluoroethane 1,1,2,2-Tetrachloroethane Tetrachloroethylene Tetrachloronaphthalene Tetraethyl lead (as Pb) Tetrahydrofuran Tetramethyl lead (as Pb) Tetramethyl succinonitrile Tetranitromethane Tetryl Thallium (soluble compounds, as Tl) Thiram Tin (inorganic compounds, as Sn) Tin (organic compounds, as Sn) Titanium dioxide Toluene Toluene 2,4-diisocyanate o-Toluidine Tributyl phosphate 1,1,2-Trichloroethane Trichloroethylene Trichloronaphthalene 1,2,3-Trichloropropane 1,1,2-Trichloro 1,2,2-trifluoroethane Triethylamine Trifluorobromomethane 2,4,6-Trinitrotoluene Triorthocresyl phosphate Triphenyl phosphate Turpentine Uranium (insoluble compounds, as U) Uranium (soluble compounds, as U) Vanadium dust Vanadium fume Vinyl toluene Warfarin Xylene (o, m, p isomers) Xylidine Yttrium compounds (as Y) Zinc chloride fume Zinc oxide Zirconium compounds (as Zr)

1,000 mg/m3 2,500 mg Ta/m3 10 mg/m3 25 mg Te/m3 1 ppm 5 mg/m3 500 mg/m3 2,000 ppm 2,000 ppm 100 ppm 150 ppm Unknown 40 mg Pb/m3 2,000 ppm [LEL] 40 mg Pb/m3 5 ppm 4 ppm 750 mg/m3 15 mg Tl/m3 100 mg/m3 100 mg Sn/m3 25 mg Sn/m3 5,000 mg/m3 500 ppm 2.5 ppm 50 ppm 30 ppm 100 ppm 1,000 ppm Unknown 100 ppm 2,000 ppm 200 ppm 40,000 ppm 500 mg/m3 40 mg/m3 1,000 mg/m3 800 ppm 10 mg U/m3 10 mg U/m3 35 mg V/m3 35 mg V/m3 400 ppm 100 mg/m3 900 ppm 50 ppm 500 mg Y/m3 50 mg/m3 500 mg/m3 25 mg Zr/m3

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APPENDIX R EXPLANATION OF THE NFPA DIAMOND

Symbolism The four divisions are typically color-coded, with blue indicating level of health hazard, red indicating flammability, yellow (chemical) reactivity, and white containing special codes for unique hazards. Each of health, flammability and reactivity is rated on a scale from 0 (no hazard; normal substance) to 4 (severe risk). Blue/Health

4. Very short exposure could cause death or major residual injury. (e.g., hydrogen cyanide) 3. Short exposure could cause serious temporary or residual injury. (e.g., chlorine gas) 2. Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. (e.g., chloroform) 1. Exposure would cause irritation but only minor residual injury. (e.g., turpentine) 0. Exposure under fire conditions would offer no hazard beyond that of ordinary combustible material. (e.g., sodium chloride)

Red/Flammability

4. Will rapidly or completely vaporize at normal atmospheric pressure and temperature, or is readily dispersed in air and will burn readily. (e.g., propane) Flash point below 23C (73F). 3. Liquids and solids that can be ignited under almost all ambient temperature conditions. (e.g., gasoline) Flash point below 38C (100F) but above 23C (73F). 2. Must be moderately heated or exposed to relatively high ambient temperature before ignition can occur. (e.g. diesel fuel) Flash point between 38C (100F) and 93C (200F). 1. Must be pre-heated before ignition can occur. (e.g., canola oil) Flash point over 93C (200F). 0. Will not burn. (e.g., water)

Yellow/Reactivity

4. Readily capable of detonation or explosive decomposition at normal temperatures and pressures. (e.g., Nitroglycerin) 3. Capable of detonation or explosive decomposition but requires a strong initiating source, must be heated under confinement before initiation, reacts explosively with water, or will detonate if severely shocked. (e.g., fluorine) 2. Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. (e.g., phosphorus) 1. Normally stable, but can become unstable at elevated temperatures and pressures. (e.g., calcium) 0. Normally stable, even under fire exposure conditions, and is not reactive with water. (e.g., liquid nitrogen)

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White/Special The white "banda" area can contain several symbols:

'W' - reacts with water in an unusual or dangerous manner (e.g. cesium, sodium) 'OX' - oxidizer (e.g. potassium perchlorate) 'COR' - corrosive; strong acid or base (e.g. sulfuric acid, potassium hydroxide) o 'ACID' and 'ALK' to be more specific. 'BIO' - Biohazard (e.g. smallpox virus) The radioactive trefoil ( ) - is radioactive (e.g. plutonium) 'CRYO' - Cryogenic

Note: Only 'W' and 'OX' are officially part of the NFPA 704 standard, but other self-explanatory symbols are occasionally used in an unofficial manner.

Taken from http://en.wikipedia.org/wiki/NFPA_704.

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APPENDIX S RESISTANCE OF SELECTED CLOTHING MATERIALS TO VARIOUS CHEMICALS

Properties Chemical Resistance Fair durability Degraded by Cotton acids; binds Resistant to rips and Resistant to tears but less so than most chemicals polyamide fibers; Modacrylic abrasion-resistant but less so than nylon or polyester Materials Strength Flammability Static Properties Comfort Uses Lab coats Lab coats

Special treatment for No static Comfortable, flame problems lightweight In direct flame, fabric Has antistatic Comfortable, soft, and shrinks to resist flame properties resilient; easy to clean; penetration; will not melt has soil release or drip; self-extinguishing; properties rapidly dissipates when source of ignition is removed Exceptionally strong Not water Melts when heated; Static buildup Lightweight Nylon and abrasion absorbent requires flame retardant possible; requires resistant antistatic agent Usually reinforced at Resistant to Can be ignited by Accumulates Lightweight points of strain; will corrosive flammable solvents and considerable Plastic not stick together, chemicals others in event of static charge of static peel, crack, or stiffen discharge electricity Resistant to rips and Excellent High melting point; flame- Good static Lightweight; good tears chemical resistant dissociation permeability; limited Polyolefin resistance; low moisture absorbency; binding for wearer perspiration chemicals may cause discomfort Strong Resistant to Low melting point; Static buildup; Lightweight most chemicals; requires flame retardant requires antistatic Polypropylene oxygen and agent light-sensitive Fairly durable Degraded by Rayon acids; binds some chemicals

Lab coats

Aprons, sleeve protectors, boots

Bouffant caps

Aprons

Lab coats

*Based on manufacturer's claims.

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