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Community college of Rhode IslandCHEMICAL HYGIENE PLANSECTION 1 INTRODUCTION AND OVERVIEW
1.1 INTRODUCTION The Occupational Safety and Health Administration (OSHA) laboratory health standard (Occupational Exposures to Hazardous Chemicals in Laboratories (CFR 1910.1450)) requires employers of laboratory employees to implement exposure control programs and convey chemical health and safety information to laboratory employees working with hazardous materials. The Community College of Rhode Island comes under the jurisdiction of the Rhode Island Department of Labor, which has essentially the same provisions as OSHA. Specific provisions of the standard require: (1) chemical fume hood evaluations; (2) establishment of standard operating procedures for routine and "high hazard" laboratory operations; (3) research protocol safety reviews; (4) employee exposure assessments; (5) medical consultations/exams; (6) employee training; (7) labeling of chemical containers; and (8) the management of chemical safety information sheets (Material Safety Data Sheets) and other safety reference materials. The standard's intent is to ensure that laboratory employees are apprised of the hazards of chemicals in their work area, and that appropriate work practices and procedures are in place to protect laboratory employees from chemical health and safety hazards. The standard operating procedures (laboratory practices and engineering controls) recommended in this manual identify the safeguards to be taken when working with hazardous materials. These safeguards will protect laboratory workers and students from unsafe conditions in the vast majority of situations. There are instances, however, when the physical and chemical properties, the proposed use, the quantity used for a particular purpose or the toxicity of a substance will be such that either additional, or fewer, controls might be appropriate to protect the laboratory worker. Professional judgment is essential in the interpretation of these standard operating procedures, and individual laboratories may modify these procedures to meet their specific uses and operational needs. This document outlines how the Community College of Rhode Island is complying with each of the elements of OSHA's Laboratory Standard. Copies of the Chemical Hygiene Plan are located in all laboratories, in the offices of the Department of Security and Safety and Campus Police and in the Learning Resource Centers at all Campuses. 1.2 CHEMICAL HYGIENE RESPONSIBILITIES Responsibility for chemical health and safety rests at all levels including the: The Dean of Administration, who has ultimate responsibility for chemical hygiene within the College and must, along with other officials, provide continuing support for chemical safety. Laboratory Safety Committee, which reviews and recommends policies that provide for the safe conduct of work involving hazardous chemicals and develops guidelines for reviewing and approving the use of high risk substances in laboratories. Department Chairs, who are responsible for chemical hygiene in each department and who have the primary responsibility for chemical hygiene in the laboratory. Each Chair is responsible for:
Laboratory Faculty and Laboratory Paraprofessionals, who are responsible for:
The laboratory paraprofessionals and faculty share responsibility for collecting, labeling and storing chemical hazardous waste properly as outlined in CCRI's Hazardous Waste Management Program, as well as informing visitors entering their laboratory of the potential hazards and the safety rules and precautions. Chemical Safety Coordinator, who must:
1.3 DEFINITIONS 1.3.1 Laboratory Definition For the purposes of this OSHA standard a laboratory is defined as a facility in which hazardous chemicals (defined below) are handled or manipulated in reactions, transfers, etc. in small quantities (containers that are easily manipulated by one person) on a nonproduction basis. Typically multiple chemical procedures are used. 1.3.2 Hazardous Chemical Definition The OSHA Laboratory Health Standard defines a hazardous chemical as any element, chemical compound, or mixture of elements and/or compounds which is a physical hazard or a health hazard. The standard applies to all hazardous chemicals regardless of the quantity. A chemical is a physical hazard if there is scientifically valid evidence that it is a combustible liquid, a compressed gas, an explosive, an organic peroxide, an oxidizer or pyrophoric, flammable, or reactive. A chemical is a health hazard if 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. Classes of health hazards include:
A chemical is considered a carcinogen or potential carcinogen if it is listed in any of the following publications (OSHA uses the term "select" carcinogen):
A chemical is considered hazardous according to the OSHA standard, if it is listed in any of the following:
Over 600,000 chemicals are considered hazardous by the OSHA definition. In most cases, the chemical container's original label will indicate if the chemical is hazardous. Look for key words like caution, hazardous, toxic, dangerous, corrosive, irritant, carcinogen, etc. Containers of hazardous chemicals acquired or manufactured before 1985 may not contain appropriate hazard warnings. If you are not sure a chemical you are using is hazardous, review the Material Safety Data Sheet for the substance. 1.4 HAZARD IDENTIFICATION Some laboratories may synthesize or develop new chemical substances on occasion, for instance, as part of a student's laboratory project. If the composition of the substance is known and will be used exclusively in the laboratory, the laboratory worker must label the substance and determine, to the best of his/her abilities, the hazardous properties (e.g.. corrosive, flammable, reactive, toxic, etc.) of the substance. This can often be done by comparing the structure of the new substance with the structure of similar materials with known hazardous properties. If the chemical produced is of unknown composition, it must be assumed to be hazardous and appropriate precautions taken. 1.5 TRAINING & INFORMATION 1.5.1 Chemical Safety Training All employees or students, exposed, or potentially exposed, to hazardous chemicals while performing their laboratory duties must receive information and training regarding the standard, the Chemical Hygiene Plan and laboratory safety. Our training consists of several one-hour seminars presented by the Chemical Safety Coordinator covering the four parts of the Community College of Rhode Island Chemical Hygiene Plan. The seminars will include oral presentations, slides, audio-visual presentations, and question and answer periods. The training program is broken down as follows: Part 1: Overview of the Chemical Hygiene Plan of the Community College of Rhode Island and the Rhode Island Hazardous Substance Right-To-Know Act. Part 2: Standard Operating Procedures for Working with Chemicals. Part 3: Specific Health and Safety Information for Working with Chemicals. Part 4: Chemical Toxicology. The training and information will be provided when an employee is initially assigned to a laboratory where hazardous chemicals are present, and also prior to assignments involving new hazardous chemicals and/or new laboratory work procedures. The training and information program will describe the: (1) physical and health hazards of various classes of laboratory chemicals handled; (2) methods/procedures for safely handling and detecting the presence or release of hazardous chemicals present in the laboratory; (3) appropriate response in the event of a chemical emergency (spill, overexposure, etc); (4) chemical safety policies; and (5) applicable details of the Chemical Hygiene Plan (such as the standard operating procedures for using chemicals). When an employee is to perform a non-routine task presenting hazards for which he or she has not already been trained, the employee's supervisor will be responsible for discussing with the employee the hazards of the task and any special measures (e.g. personal protective equipment or engineering controls) that should be used to protect the employee. Every laboratory worker should know the location and proper use of available protective clothing and equipment, and emergency equipment/procedures. Information on protective clothing and equipment is contained in Section 2.3 of this manual. 1.5.2 Chemical Safety Information Sources There are numerous sources of chemical safety information. These sources include: (1) special health and safety reference literature available in the Learning Resource Center at each campus; (2) the labels found on containers of hazardous chemicals; (3) the substance's Material Safety Data Sheet; and (4) laboratory signs. Each of these sources is now discussed in greater detail. 1.5.2.1. Safety Reference Literature The Learning Resource Center at each campus maintains reference materials addressing chemical health and safety issues under the designation Chemical Hygiene Plan Reference Literature. The references include chemical workplace exposure standards, OSHA'S Laboratory Safety Standard, Rhode Island Chapter 28-21, the Hazardous Substance Right-To-Know Act and other laboratory safety references. Material safety data sheets received from suppliers are available in the security offices at the Knight, Flanagan, Providence and Newport Campuses, and also in the MSDS Stations mounted on the walls outside of rooms where the chemicals are being used. 1.5.2.2 Container Labeling All containers of chemicals, which could pose a physical or health hazard to an exposed employee or student, must have a label attached. Labels on purchased hazardous chemicals must include: (1) the common name of the chemical; (2) the name, address and emergency phone number of the company responsible for the product; and (3) an appropriate hazard warning. The warning may be a single word-"danger", "warning" and "caution" - or may identify the primary hazard, both physical (i.e., water reactive, flammable, or explosive) and health ( i.e., carcinogen, corrosive, or irritant). Most labels will provide you with additional safety information to help you protect yourself while working with this substance. This includes protective measures to be used when handling the material, clothing that should be worn, first aid instructions, storage information and procedures to follow in the event of a fire, leak or spill. If you find a container with no label, report it to your laboratory paraprofessional. You should also report labels that are torn or illegible so that the label can be replaced immediately. Existing labels on new containers of hazardous chemicals should never be removed or defaced, except when empty! If you use secondary working containers that will take more than one work shift or laboratory period to empty, or if there is a chance that someone else will handle the container before you finish it, you must label it. This is part of your responsibility to help protect co-workers and students. Read the label each time you use a newly purchased chemical. It is possible the manufacturer may have added new hazard information or reformulated the product since your last purchase, and thus altered the potential hazards you face while working with the product. All employees involved in unpacking chemicals are responsible for inspecting each incoming container to insure that it is labeled with the information outlined above. The Chemical Safety Coordinator or Laboratory Paraprofessional must be notified if containers do not have proper labels. 1.5.2.3 Material Safety Data Sheets A Material Safety Data Sheet, often referred to by its acronym MSDS, is a detailed informational document prepared by the manufacturer or importer of a hazardous chemical which describes the physical and chemical properties of the product. Information included in a Material Safety Data Sheet aids in the selection of safe products, helps employers, employees and students understand the potential health and physical hazards of a chemical and describes how to respond effectively to exposure situations. The format of a Material Safety Data Sheet may vary but there is specific information that must be included in each sheet. It is useful to review this information to increase your ability to use a Material Safety Data Sheet. All Material Safety Data Sheets should include the following information: Section I of the MSDS lists information identifying the manufacturer and the product.
Section II describes the various hazardous ingredients contained in the product, the percentages, and exposure limits when appropriate. All hazardous chemicals which comprise 1% or greater of the mixture will be identified. Carcinogens will be listed if their concentrations are 0.1% or greater. If a component is not listed, it has been judged to be non-hazardous or is considered proprietary information by the manufacturer. The types of components that might be listed include:
Section III describes the physical properties of the material: Melting Point, Boiling Point, Vapor Pressure, Vapor Density, Solubility in Water, Specific Gravity, Per Cent Volatile, Evaporation Rate, Appearance and Odor. Section IV describes the fire and explosion hazard data for the material. Based on the flash point and other fire and explosion data, the appropriate extinguishing agent for fires involving the material will be listed. Special procedures may also be listed.
Section V describes the known health hazards associated with the material, applicable exposure limits and symptoms/health effects associated with overexposure. This information will help the user and medical personnel recognize if an overexposure has occurred.
Section VI describes reactivity data; that is, the material's ability to react and release energy or heat under certain conditions or when it comes in contact with certain substances.
Section VII tells the steps to be taken in case of an accidental release or spill. Information is included on containment, evacuation procedures and waste disposal as appropriate. The statements on the Material Safety Data Sheet are very general; more specific information is available from your laboratory paraprofessional.
Section VIII describes the protective equipment for the individual who might have to work with the substance. This section normally describes worst case conditions; therefore, the extent to which personal protective equipment is required is task dependent. Contact your supervisor or Chemical Safety Coordinator for specific instructions, if you are unsure.
Section IX describes handling and storage procedures to be taken with the material. Information may include statements, such as: keep container closed, store in a cool, dry, well ventilated area; keep refrigerated (caution: flammable solvents require a "flammables storage refrigerator"); avoid exposure to sunlight; etc. Section X describes special precautions or miscellaneous information regarding the material. Manufacturers may withhold certain information as proprietary (such as hazardous ingredients) on a Material Safety Data Sheet if the information is considered a trade secret. The Chemical Safety Coordinator has a legal right to obtain this information from the manufacturer to evaluate the potential health risk if potential overexposure or adverse health effects are suspected. 1.5.2.4 Laboratory Signs Prominent signs of the following types should be posted in each laboratory:
1.6 CHEMICAL EXPOSURE ASSESSMENT Regular environmental or employee exposure monitoring of airborne concentrations is not usually warranted or practical in laboratories because chemicals are typically used for relatively short time periods and in small quantities. However sampling may be appropriate when a highly toxic substance is used regularly (three or more separate handling sessions per week), used for an extended period of time (greater than 3 to 4 hours at a time) or used in especially large quantities. Notify the Chemical Safety Coordinator if you are using a highly toxic substance in this manner. The exposures to laboratory employees who suspect and report that they have been over overexposed to a toxic chemical in the laboratory, or are displaying symptoms of overexposure to toxic chemicals, will also be assessed. The assessment will initially be qualitative and, based upon the professional judgment of the Chemical Safety Coordinator, may be followed up by specific quantitative monitoring. A memo, or report, documenting the assessment will be sent to the employees involved and their supervisors or Department Chairs within fifteen days of receipt of the results. A copy will be stored in a central exposure records file maintained by the Department of Security and Safety and Campus Police. Individual concerns about excessive exposures occurring in the laboratory should be brought to the attention of your supervisor, Department Chair, or the Chemical Safety Coordinator immediately. 1.7 MEDICAL CONSULTATION AND EXAMINATION The College will provide employees who work with hazardous chemicals an opportunity to receive medical attention, including any follow-up examinations which the examining physician determines to be necessary, whenever an employee:
Individuals with life threatening emergencies should call the Campus Security Office to have an ambulance summoned. Security can be reached at 825-2109 (Knight Campus), 333-7035 (Flanagan Campus), 455-6050 (Providence Campus) or 851-1620 (Newport Campus). All accidents resulting in injuries which require medical treatment (including first aid) should be reported immediately to Security. The injured employee may seek treatment at a emergency room, at the Pawtucket or Warwick location of OH + R or at his/her own physician. Where medical consultations or examinations are provided the examining physician shall be provided with the following information: (1) the identity of the hazardous chemical(s) to which the employee may have been exposed; (2) the exposure conditions; and (3) the signs and symptoms of exposure the laboratory employee is experiencing, if any. 1.8 CHEMICAL FUME HOOD EVALUATION Every laboratory ventilation hood used for the control of air contaminants shall be tested twice yearly to assure that adequate airflow is being maintained to provide continued protection against employee over-exposure. The Maintenance Departments, under the direction of the College Engineer, is responsible for performing this testing. Laboratory hood airflow shall be considered adequate when the average face velocity equals 100 feet/minute (±20%) with the hood sash at a working height (15 to 20 inches). Other local exhaust ventilation, such as instrument vents, will also be tested. 1.9 RESPIRATORY PROTECTION PROGRAM The College attempts to minimize employee and student respiratory exposure to potentially hazardous chemical substances through engineering methods (such as local exhaust ventilation) or administrative control. It is recognized, however, that for certain situations or operations, the use of these controls may not be feasible or practical. Under these circumstances or while such controls are being instituted, or in emergency situations, the use of personal respiratory protective equipment may be necessary. A sound and effective program is essential to assure that the personnel using such equipment are adequately protected. The College has adopted a written Respiratory Protection Program for using respirators. This plan outlines organizational responsibilities for the following respirator program components: exposure assessment; respirator selection; medical approval and surveillance; fit testing; user training; inspection/repair; cleaning/disinfection; and storage. Each of these program components is required by OSHA's respiratory protection standard (29 CFR 1910.134) in all situations where respirators are used. If you are using a respirator and are not included in the respirator protection program, or have questions concerning the use of respirators or any of the program components; contact your supervisor or the Chemical Safety Coordinator. 1.10
RECORDKEEPING All exposure assessments and occupational medical consultation/examination reports will be confidential and maintained by the Personnel Department a secure area in accordance with OSHA's medical records rule (29 CFR 1910.20). Individuals may obtain copies or read their reports contacting the Personnel Office. 1.11
PROTOCOL SAFETY REVIEW Under some circumstances, a particular chemical substance and associated laboratory operation, procedure or activity may be considered sufficiently hazardous to require prior approval from the Chemical Safety Coordinator before work begins. This approval process will ensure that safeguards are properly set up and that personnel and students are adequately trained in the procedure. The chemical substances listed in Appendix A require prior approval before beginning work. Carefully read the label before using a chemical. The manufacturer's or supplier's Material Safety Data Sheet (MSDS) will provide special handling information. Be aware of the potential hazards existing in the laboratory and the appropriate safety precautions. Know the location and proper use of emergency equipment, the appropriate procedures for responding to emergencies, and the proper methods for storage, transport and disposal of chemicals within the facility. Students and student helpers may never work alone in a laboratory. Faculty and Laboratory Paraprofessionals should not work alone in the laboratory unless absolutely necessary. If you must work alone or in the evening, let someone else know and have them periodically check on you. Label all secondary chemical containers with appropriate identification and hazardous information (see Section I, Container Labeling). Use only those chemicals for which you have the appropriate exposure controls (such as a chemical fume hood) and administrative programs/procedures (training, restricted access, etc.). Always use adequate ventilation with chemicals. Operations using large quantities (500 milliliters or more) of volatile substances with workplace standards at or below 50 ppm should be performed in a chemical fume hood. Use hazardous chemicals and all laboratory equipment only as directed or for their intended purpose. Inspect equipment or apparatus for damage before adding a hazardous chemical. Do not use damaged equipment. Inspect personal protective apparel and equipment for integrity or proper functioning before use. Malfunctioning laboratory equipment (hood) should be labeled or tagged "out of service" so that others will not inadvertently use it before repairs are made. Handle and store laboratory glassware with care. Do not use damaged glassware. Use extra care with Dewar flasks and other evacuated glass apparatus; shield or wrap them to contain chemicals or fragments should implosion occur. Do not dispense more of a hazardous chemical than is needed for immediate use. |
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SECTION 2 STANDARD OPERATING PROCEDURES FOR WORKING WITH
CHEMICALS 2.1 GOOD
WORK PRACTICES/PROCEDURES FOR HANDLING LABORATORY CHEMICALS 2.1.1
General Guidelines 2.1.2 Personal Hygiene Avoid direct contact with any chemical. Keep chemicals off your hands, face and clothing, including shoes. Never smell, inhale or taste a hazardous chemical. Wash thoroughly with soap and water after handling any chemical. Smoking is not allowed in any CCRI building. Smoking, drinking, eating and the application of cosmetics is forbidden in laboratories where hazardous chemicals are used. Never pipet by mouth. Use a pipet bulb or other mechanical pipet filling device. Remove contaminated clothing and gloves before leaving laboratory. 2.1.3
Housekeeping Keep floors clean and dry. Keep all aisles, hallways, and stairs clear of all chemicals. Stairways and hallways should not be used as storage areas. Keep all work areas, and especially work benches, clear of clutter and obstructions. All working surfaces should be cleaned regularly. Access to emergency equipment, utility controls, showers, eyewashes and exits should never be blocked. Wastes should be kept in the appropriate, properly labeled containers according to the guidelines in CCRI's Hazardous Waste Management Program. 2.2 WHEN NOT TO PROCEED WITHOUT REVIEWING SAFETY PROCEDURES Sometimes laboratory workers should not proceed with what seems to be a familiar task. Hazards may exist that are not fully recognized. Certain indicators (procedural changes) should cause the employee to stop and review the safety aspects of their procedure. These indicators include:
The occurrence of any of these conditions should cause the laboratory employee to pause, evaluate the safety implications of these changes or results, make changes as necessary and proceed cautiously. 2.3 PROTECTIVE CLOTHING AND LABORATORY SAFETY EQUIPMENT2.3.1 General Consideration - Personal Protective Clothing [Equipment] Personal protective clothing and equipment should be selected carefully and used in situations where engineering and administrative controls cannot be used or while such controls are being established. CCRI has a Respiratory Protection Program that specifically addresses the problem of respiratory hazards. Respirators and dust masks in particular are viewed as less protective than other controls because they rely heavily on each employee's work practices and training to be effective. The engineering and administrative controls, which should always be, considered first when reducing or eliminating exposures to hazardous chemicals include:
The Material Safety Data Sheet (MSDS) will list the personal protective equipment recommended for use with the chemical. The MSDS addresses worst case conditions. Therefore, all the equipment shown may not be necessary for the specific laboratory scale task. Other sections of this manual or the Chemical Safety Coordinator can assist you in determining which personal protective devices are required for each task. Remember that there is no harm in being overprotective. Appropriate personal protective equipment will be provided to employees. 2.3.2. Protection of Skin and BodySkin and body protection involves wearing protective clothing over all parts of the body, which could become contaminated with hazardous chemicals. Personal protective equipment (PPE) should be selected on a task basis, and checked to insure it is in good condition prior to use. 2.3.2.1 Normal clothing worn in the laboratoryWhere there is no immediate danger to the skin from contact with a hazardous chemical it is still prudent to select clothing to minimize exposed skin surfaces. Faculty, paraprofessionals and students should wear long sleeved/long legged clothing and avoid short sleeved shirts, short trousers or skirts. A laboratory coat should be worn over street clothes and be laundered regularly. Laboratory coats are intended to prevent contact with dirt, chemical dusts and minor chemical splashes or spills. If it becomes contaminated, it should be removed immediately and affected skin surface washed thoroughly. Shoes should be worn in the laboratory at all times. Sandals and perforated shoes are not appropriate. In addition, long hair and loose clothing should be confined. 2.3.2.2 Protective clothing Additional protective clothing may be required for some procedures or with specific substances (such as when carcinogens or large quantities of corrosives, oxidizing agents or organic solvents are handled). This clothing may include impermeable aprons and gloves as well as plastic coated coveralls, shoe covers, and arm sleeves. Protective sleeves should always be considered when wearing an apron. These garments can either be washable or disposable. They should never be worn outside the laboratory. The choice of garment depends on the degree of protection required and the areas of the body which may become contaminated. Rubberized aprons, plastic coated coveralls, shoe covers, and sleeves offer much greater resistance to permeation by chemicals than laboratory coats and provide additional time to react (remove the garment and wash affected area) if contaminated.
Chemical resistant gloves should be worn whenever the potential for contact with corrosive or toxic substances and substances of unknown toxicity exists. However, because of the potential for severe, even life-threatening allergic reactions to latex rubber, the college no longer permits the purchase and use of natural latex gloves on its premises. Gloves should be selected on the basis of the materials being handled, the particular hazard involved, and their suitability for the operation being conducted. Before each use, gloves should be checked for integrity. Gloves should be washed prior to removal whenever possible to prevent skin contamination. Non-disposable gloves should be replaced periodically, depending on frequency of use and their resistance to the substances handled. Protective garments are not equally effective for every hazardous chemical. Some chemicals will "break through" the garment in a very short time. Therefore, garment and glove selection is based on chemical resistance. However, natural latex gloves are not allowed even if they are resistant to the chemical being used. GLOVE TYPE SELECTION GUIDE
‡ NO LONGER RECOMMENDED FOR ANY USE AT CCRI Contact the Chemical Hygiene Officer with any personal protective equipment questions. Complete information about latex rubber use at CCRI may be read in CCRI's Latex Product Safety Policy which is available in the Learning Resource centers, form laboratory department chairs, from the Chemical Safety Coordinator or on CCRI's EHS WebPage by clicking on Latex Product Safety Policy. 2.3.3
Protection of the Eyes Eye protection is required for all personnel and any visitors present in locations where chemicals are handled and a chemical splash hazard exists. Chemical splash goggles or other protective eyewear be worn in the laboratory based upon the physical state, the operation or the level of toxicity of the chemical used. Safety glasses effectively protect the eye from solid materials (dust and flying objects) but are not effective at protecting the eyes from chemical splash to the face. Splash Goggles should be worn in situations where bulk quantities of chemicals are handled and chemical splashes to the face are possible. Splash Goggles form a liquid proof seal around the eyes, protecting them from a splash. When handling highly reactive substances or large quantities of hazardous chemicals, corrosives, poisons, and hot chemicals, goggles with face shield should be worn. When a lower level of hazard exists, other appropriate protective eyewear may be worn. Contact lenses can increase the risk of eye injury if worn in the laboratory-particularly if they are of the gas permeable variety. Gases and vapors can be concentrated under such lenses and cause permanent eye damage. Chemical splashes to the eye can get behind all types of lenses. Once behind a lens the chemical is difficult to remove by flushing. For these reasons it is recommended that contact lenses not be worn in laboratories. Eye and face injuries are prevented by the use of the following: COMPARISON
CHART--EYE PROTECTION DEVICES
Source: ANSI Z87.1(1979) Occupational and Educational Eye and Face Protection, available from American National Standards Institute, Inc., 1430 Broadway, New York, N.Y. 10018 Protection of the Respiratory System Inhalation hazards can be controlled using ventilation or respiratory protection. Check the label and MSDS for information on a substance's inhalation hazard and special ventilation requirements. When a potential inhalation hazard exists a substance's label or MSDS contains warnings such as:
Take
appropriate precautions before using these substances. Controlling inhalation exposures via engineering controls
(ventilation) is always the preferred method (See Section 2.3.5.1). As
with other personal protective equipment, respiratory protection relies
heavily on employee work practices and training to be effective. Respirators are designed to protect against specific types of substances in limited concentration ranges. Respirators must be selected based on the specific type of hazard (toxic chemical, oxygen deficiency, etc.), the contaminant's anticipated airborne concentration, and required protection factors. The College has implemented a Respiratory Protection Program. Respirators are not to be used except in conjunction with a complete respiratory protection program as required by OSHA. If your work requires the use of a respirator or if you believe that it might, contact your supervisor or the Chemical Safety Coordinator. See Section 1.9 for additional information. 2.3.5.1 Chemical Fume Hoods In the laboratory the chemical fume hood is the primary means of controlling inhalation exposures. Hoods are designed to retain vapors and gases released within them, protecting the laboratory employee's breathing zone from the contaminant. This protection is accomplished by having a curtain of air (approximately 100 linear feet per minute) move constantly through the face (open sash) of the hood. Chemical fume hoods can also be used to isolate apparatus or chemicals that may present physical hazards to employees. The closed sash on a hood serves as an effective barrier to fires, flying objects, chemical splashes or spattering and small implosions and explosions. Hoods can also effectively contain spills which might occur during dispensing procedures particularly if trays are placed in the bottoms of the hoods. When using a chemical fume hood keep the following principles of safe operation in mind: Keep all chemicals and apparatus at least six inches inside the hood (behind sash). Hoods are not intended for storage of chemicals. Materials stored in them should be kept to a minimum. Stored chemicals should not block vents or alter airflow patterns. Keep the hood sash at a minimum height (4 to 6 inches) when not manipulating chemicals or adjusting apparatus within the hood. When working in front of a fume hood, make sure the sash opening is appropriate. This can be achieved by lining up to arrows placed on the sash door and hood frame. This sash opening will ensure an adequate air velocity through the face of the hood. Do not allow objects such as paper to enter the exhaust ducts. This can clog ducts and adversely affect their operation. Follow the chemical manufacturers or supplier's specific instructions for controlling inhalation exposures with ventilation (chemical fume hood) when using their products. These instructions are located on the products MSDS and/or label. However, it should be noted that these ventilation recommendations are often intended for non-laboratory work environments and must be adapted to suit the laboratory environment as well as the specific procedure or process. If
specific guidance is not available from chemical manufacturer or
supplier, or if the guidance is inappropriate for the laboratory
environment, contact the Chemical Safety Officer and/or review the hood
use guidelines in the table below. These guidelines are based on information readily available on a
chemical's MSDS: (1) applicable workplace exposure standards (Threshold
Limit Values (TLV) or Permissible Exposure Limits (PEL)); (2) acute and
chronic toxicity data (LD50 and specific organ toxicity); and (3)
potential for generating airborne concentrations (vapor pressure).
These terms are defined in the glossary at the back of this
manual. The guidelines
outlined in the table below should not be considered as necessary or
appropriate in every case, but as reasonable "rules of thumb". Guidelines
for Chemical Fume Hood Use
Whenever chemicals have the possibility of damaging the skin or eyes, an emergency supply of water must be available. All laboratories in which bulk quantities of hazardous chemicals are handled and could contact the eyes or skin resulting in injury should have access to eyewash stations and safety showers. As with any safety equipment, these can only be useful if they are accessible. Therefore:
Showers should be checked monthly to assure that access is not restricted and that the start chain is within reach. The flow through the safety showers should be tested periodically to ensure sufficient flow (approximately 60 gallons per minute). 2.3.5.3 Fire Safety Equipment Fire safety equipment easily accessible to the laboratory must include a fire extinguisher (type ABC) and may include fire hoses, fire blankets, and automatic extinguishing systems. 2.4 CHEMICAL PROCUREMENT, DISTRIBUTION, AND STORAGE 2.4.1 Procurement Before a new substance that is known or suspected to be hazardous is received, information on proper handling, storage, and disposal should be known to those who will handle it. It is the responsibility of the department chair to ensure that the laboratory facilities in which the substance will be handled are adequate and that those who will handle the substance have received proper training. The necessary information on proper handling of hazardous substances can be obtained from the Material Safety Data Sheets which are provided by the vendor. Because storage in laboratories is restricted to small containers, order small-container lots to avoid hazards associated with repackaging. No container should be accepted without an adequate identifying label as outlined in Section 1.5.2.2 of this manual. 2.4.2 Distribution When hand carrying open containers of hazardous chemicals or unopened containers with corrosive or highly, acutely or chronically toxic chemicals, place the container in a secondary container or a bucket. Rubberized buckets are commercially available and provide both secondary containment as well as "bump" protection. If several bottles must be moved at once, the bottles should be transported on a small cart with a substantial rim to prevent slippage from the cart. Call the Department of Security and Safety and Campus Police for an escort and use an elevator to transport chemicals from one floor to another. 2.4.3 Chemical Storage in the Laboratory Carefully read the label before storing a hazardous chemical. The MSDS will provide any special storage information as well as information on incompatibilities. Do not store unsegregated chemicals in alphabetical order. Do not store incompatible chemicals in close proximity to each other. Separate hazardous chemicals in storage into twelve categories as follows:
Once separated into the above hazard classes, chemicals may be stored alphabetically. Use approved storage containers and safety cans for flammable liquids. It is preferable to store flammable chemicals in flammable storage cabinets. Flammable chemicals requiring refrigeration should be stored only in the refrigerators and freezers specifically designed for flammable storage. A good place to store hazardous chemicals is a vented cabinet under the hood. Chemicals of different chemical classes can be segregated by placing them in trays. Do not store chemicals on bench tops or in hoods. Liquids (particularly corrosives or solvents) must not be stored above eye level.Use secondary containers (one inside the other) for especially hazardous chemicals (carcinogens, etc.). Use spill trays under containers of strong reagents. Avoid exposure of chemicals while in storage to heat sources (especially open flames), radiators, hotplates and direct sunlight. Conduct
periodic inventories of chemicals stored in the laboratory (annually)
and dispose of old or unwanted chemicals promptly in accordance with
CCRI's Hazardous Waste
Management Program. Insure all containers are properly labeled.
2.4.3.1 Chemical Storage--Chemical Stability Stability refers to the susceptibility of a chemical to dangerous decomposition. The label and MSDS will indicate if a chemical is unstable. Special note: Peroxide Formers - Ethers, liquid paraffins, and olefins form peroxides on exposure to air and light. Peroxides are extremely sensitive to shock, sparks, or other forms of accidental ignition (even more sensitive than primary explosives such as TNT). Since these chemicals are packaged in the air atmosphere, peroxides can form even though the containers have not been opened. Sealed containers of ethers must be discarded before the expiration date on the label. Hazardous waste disposal companies are forbidden by law to transport ether containers that have gone beyond their expiration date. CCRI is then forced to call the Rhode Island DEM or the State Fire Marshal's office to have the potentially explosive materials removed from College premises. Opened containers of ethers must be discarded at the end of each semester. All ether containers should be dated upon receipt and upon opening. See Section 3.2, Highly Reactive Chemicals and High Energy Oxidizers for additional information and examples of materials which may form explosive peroxides. For additional information on chemical stability, contact your supervisor or the Chemical Safety Coordinator. 2.4.3.2 Chemical Storage - Incompatible Chemicals Certain
hazardous chemicals should not be mixed or stored with other chemicals
because a severe reaction can take place or an extremely toxic
reaction product can result. The label and MSDS will contain
information on incompatibilities. The following table, taken
from
2.5.1 Prevention The best approach to handling chemical spills is to avoid them in the first place. Try to anticipate them and remove those conditions that can lead to spills. · Avoid storage of large amounts of materials, either in containers larger than you need or in multiple containers of the same chemical. The Chemical Safety Coordinator can help you to dispose of excess inventory. · Use secondary containment such as plastic trays for particularly hazardous substances such as flammable solvents or concentrated acids. · Review your handling procedures of chemicals whose spillage might cause a severe problem and revise your handling procedures. 2.5.2
Cleaning Up Chemical Spills
Chemical
spills should only be cleaned up by knowledgeable and trained personnel. · Obtain the necessary equipment ahead of time (spill kits and personal protective equipment) to respond to a minor spill. · Learn how to clean up minor spills of the chemicals you use regularly safely. A MSDS contains special spill clean-up information and should also be consulted. · If the spill is too large for you to handle, is a threat to laboratory personnel or the public, or involves a highly toxic, or reactive chemical, call the Department of Security and Safety and Campus Police for assistance immediately.
2.5.3 Minor Chemical Spill If
you are cleaning up a small spill yourself, make sure that you are aware
of the hazards associated with the materials spilled, have adequate
ventilation (open windows, chemical fume hood on) and proper personal
protective equipment (minimum - gloves, protective eyewear, and lab coat). Consider all residual chemical and cleanup materials (absorbent,
gloves, etc.) as hazardous waste. Place
these materials in a sealed container (plastic bags) and store in a
chemical fume hood. Contact
the Chemical Safety Coordinator for disposal assistance.
Use appropriate kit to neutralize and absorb inorganic acids and bases. Collect residue, place in container, and dispose as hazardous chemical waste. For other chemicals, use appropriate kit or absorb spill with vermiculite, dry sand, diatomaceous earth or paper towels. Collect residue, place in container, and dispose as chemical waste. Clean spill area with paper towels and the appropriate solvent (water or small amount of an organic solvent when appropriate). Put the paper towels in plastic bags and label the as hazardous waste. 2.5.4
Major Chemical Spill If the spill is too large for you to handle, is a threat to laboratory personnel or the public, or involves a highly toxic, irritating or reactive chemical, call the Department of Security and Safety and Campus Police for assistance immediately.
Follow the procedures outlined in CCRI’s Hazardous Substance Release Emergency Response Plan. That is, do not attempt to clean up anything but the most minor spill yourself. Security staff are trained in emergency response and will make the decision to call one or more of the following:
After
calling Security, attend to injured or contaminated persons and remove
them from exposure. If
spilled material is flammable, turn off ignition and heat sources. Place other device (plastic bag) over spilled material to keep
substance from volatilizing. Close doors to affected area. Have a person with knowledge of the incident and laboratory available to answer questions from responding emergency personnel. Security
will then notify the following according to the procedures specified in
sections 2.5.2, 2.5.3, and 2.5.4 of this Plan
and in CCRI's Hazard Substance
Release Emergency Response Plan The following five vendors are authorized under the new state Master Price Agreement to provide cleanup services for hazardous waste and petroleum-related emergencies at CCRI. Only the Department of Security and Safety and Campus Police and the Chemical Safety Coordinator are authorized to call them for assistance.
2.6.2 Chemicals Spills on the Body Quickly remove all contaminated clothing and footwear. Immediately flood the affected body area in cold water for at least 15 minutes. Remove jewelry to facilitate removal of any residual material. Wash off chemical with water only. Do not use neutralizing chemicals, unguents, creams, lotions or salves. Get medical attention promptly. It should be noted that some chemicals (phenol, aniline,) are rapidly absorbed through the skin. If a large enough area of skin is contaminated an adverse health effect (systemic toxicological reaction) may occur immediately to several hours after initial exposure depending on the chemical. If more than 9 square inches of skin area has been exposed to a hazardous chemical, seek medical attention after washing the material off the skin. If the incident involves hydrofluoric acid (HF), seek immediate medical attention. Provide the physician with the chemical name. 2.6.3
Chemical Splash in the Eye Irrigate the eyeball and inner surface of eyelid with plenty of cool water for at least 15 minutes. Use eyewash or other water source. Forcibly hold eyelid open to ensure effective wash.
2.6.4 Ingestion of Hazardous Chemicals
Provide the ambulance crew and physician with the chemical name and any other relevant information. If possible send the container, MSDS or the label with the victim. Anyone overcome with smoke or chemical vapors or fumes should be removed to uncontaminated air and treated for shock. Do not enter the area if you expect that a life threatening condition still exists-oxygen depletion, explosive vapors or highly toxic gases (cyanide gas, hydrogen sulfide, nitrogen oxides, carbon monoxide). Persons
who are CPR certified follow standard CPR protocols or immediately seek
the assistance of someone who is trained and certified in CPR. 2.6.6 Burning Chemicals on Clothing Extinguish
burning clothing by using the drop-and-roll technique or by dousing with
cold water, or use of emergency shower if
it is immediately available. Actions to be Avoided During Emergencies There are some actions which must not be taken when handling emergencies. These include: If you discover a fire or fire-related emergency such as abnormal heating of material, a flammable gas leak, a flammable liquid spill, smoke, or odor of burning, immediately follow these procedures: Notify the Fire Department by dialing Security: Knight Campus 825-2109; Flanagan Campus 333-7035; Providence Campus 455-6050; Newport Campus 851-1620. Activate the building alarm (fire pull station). If the alarm is not available or operational, verbally notify people in the building. Isolate the area by closing windows and doors and evacuate the building. Shut down equipment in the immediate area, if possible. Use a portable fire extinguisher to:
Provide the fire/police teams with the details of the problem upon their arrival. Special hazard information you might know is essential for the safety of the emergency responders. If the fire alarms are ringing in your building:
2.8 CHEMICAL WASTE DISPOSAL PROGRAM Laboratory chemical waste must be disposed of in accordance with local, state, and federal requirements. These waste management practices are designed to ensure maintenance of a safe and healthful environment for laboratory employees and the surrounding community without adversely affecting the environment. This is accomplished through regular removal of chemical waste and disposal of these wastes in compliance with all regulations and policies. Specific guidance on how to identify, handle, collect, segregate, store and dispose of chemical waste is available from your supervisor or the Chemical Safety Coordinator. Remember:
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SECTION
3
HEALTH
AND SAFETY INFORMATION FOR WORKING WITH CHEMICALS OF SPECIFIC HAZARD
CLASSES 3.1 FLAMMABLE LIQUIDS 3.1.1 General Information Flammable
liquids are among the most common of the hazardous materials found in
laboratories. They are
usually highly volatile (have high vapor pressures at room temperature)
and their vapors, mixed with air at the appropriate ratio, can ignite
and burn. By definition,
the lowest temperature at which they can form an ignitable vapor/air
mixture (the flash point) is less than 37.8'C (100'F) and for several
common laboratory solvents (ether, acetone, toluene, acetaldehyde) the
flash point is well below that. As
with all solvents, their vapor pressure increases with temperature and,
therefore, as temperatures increase they become more hazardous. For a fire to occur, three distinct conditions must exist simultaneously: (1) the concentration of the vapor must be between the upper and lower flammable limits of the substance (the right fuel/air mix); (2) an oxidizing atmosphere, usually air, must be available; and (3) a source of ignition must be present. Removal of any of these three conditions will prevent the start of a fire. Flammable liquids may form flammable mixtures in either open or closed containers or spaces (such as refrigerators), when leaks or spills occur in the laboratory, and when heated. Control strategies for preventing ignition of flammable vapors include removing all sources of ignition or maintaining the concentration of flammable vapors below the lower flammability limit by using local exhaust ventilation such as a hood. The former strategy is more difficult because of the numerous ignition sources in laboratories. Ignition sources include: open flames, hot surfaces, operation of electrical equipment, and static electricity. The concentrated vapors of flammable liquids are denser than air and can travel away from a source a considerable distance (across laboratories, into hallways, down elevator shafts or stairways). If the vapors reach a source of ignition a flame can result that may flash back to a source of the vapor. The danger of fire and explosion presented by flammable liquids can usually be eliminated or minimized by strict observance of safe handling, dispensing, and storing procedures. 3.1.2 Special Handling Procedures While working with flammable liquids you should wear gloves, protective glasses, and long sleeved lab coats. Wear goggles if dispensing solvents or performing an operation which could result in a splash to the face. Large quantities of flammable liquids should be handled in a chemical fume hood or under some other type of local exhaust ventilation. Five-gallon containers must be dispensed to smaller containers in a hood or under local exhaust ventilation. When dispensing flammable solvents into small storage containers, use metal or plastic containers or safety cans (avoid glass containers). Make sure that metal surfaces or containers through which flammable substances are flowing are properly grounded, discharging static electricity. Free flowing liquids generate static electricity which can produce a spark and ignite the solvent. Large quantities of flammable liquids must be handled in areas free of ignition sources (including spark emitting motors and equipment) using non-sparking tools. Remember that vapors are heavier than air and can travel to a distant source of ignition. Never heat flammable substances with an open flame. Instead use any of the following heat sources: steam baths, water baths, oil baths, heating mantles or hot air baths. Do not distill flammable substances under reduced pressure. Store flammable substances away from ignition sources. The preferred storage location is in flammable storage cabinets. If no flammable storage cabinet is available store these substances in a cabinet under the hood or bench. Five-gallon containers should only be stored in flammable storage cabinets. You can also keep small amounts of flammable liquids inside the hood for a short period of time. Storage in chemical fume hoods is not preferred because it reduces hood performance by obstructing airflow. The volume of flammable liquids dispensed in small containers (not including safety cans) in the open areas of laboratories should not exceed one gallon. Never store glass containers of flammable liquids on the floor. Oxidizing and corrosive materials should not be stored in close proximity to flammable liquids. Flammable liquids should not be stored or chilled in domestic refrigerators and freezers but in units specifically designed for this purpose. If flammable liquids will be placed in ovens make sure the ovens are appropriately designed for flammable liquids (no internal ignition sources and/or vented mechanically).
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3.2 HIGHLY REACTIVE CHEMICALS & HIGH ENERGY OXIDIZERS
3.2.1 General Information
Highly reactive chemicals include those which are inherently unstable and susceptible to rapid decomposition as well as chemicals which, under specific conditions, can react alone, or with other substances in a violent uncontrolled manner, liberating heat, toxic gases, or leading to an explosion. Reaction rates almost always increase dramatically as the temperature increases. Therefore, if heat evolved from a reaction is not dissipated, the reaction can accelerate out of control and possibly result in injuries or costly accidents.
Air, light, heat, mechanical shock (when struck, vibrated or otherwise agitated), water, and certain catalysts can cause decomposition of some highly reactive chemicals, and initiate an explosive reaction. Hydrogen and chlorine react explosively in the presence of light. Alkali metals, such as sodium, potassium and lithium, react violently with water liberating hydrogen gas. Examples of shock sensitive materials include acetylides, azides, organic nitrates, nitro compounds, and peroxides.
Organic peroxides are a special class of compounds that have unusual stability problems, making them among the most hazardous substances normally handled in the laboratories. As a class, organic peroxides are low powered explosives. Organic peroxides are extremely sensitive to light, heat, shock, sparks, and other forms of accidental ignition; as well as to strong oxidizing and reducing materials. All organic peroxides are highly flammable.
Peroxide formers can form peroxides during storage and especially after exposure to the air (once opened). Peroxide forming substances include: aldehydes, ethers (especially cyclic ethers such as dioxane or tetrahydrofuran), compounds containing benzylic hydrogen - atoms, compounds containing the allylic structure (including most alkenes), vinyl and vinylidine compounds.
Examples of shock sensitive chemicals, high-energy oxidizers and
substances that can form explosive peroxides are listed at the end of Section 3.
3.2.2 Special Handling Procedures
Before working with a highly reactive material or high-energy oxidizer,
review available reference literature to obtain specific safety
information.
The proposed reactions should be discussed with your supervisor.
Always minimize the amount of material involved in the
experiment; the smallest amount sufficient to achieve the desired result
should be used. Scaleups
should be handled with great care, giving consideration to the reaction
vessel size and cooling, heating, stirring and equilibration rates.
Excessive amounts of highly reactive compounds must not be purchased,
synthesized, or stored in the laboratories.
The key to safely handling reactive chemicals is to keep their
quantities as small as possible and to keep them isolated from the
substances that initiate their violent reactions.
Unused peroxides must not be returned to the original container.
Do not work alone. All operations where highly reactive and explosive chemicals are used should be performed during the normal workday or when other employees are available either in the same laboratory or in the immediate area.
Perform all manipulations of highly reactive or high-energy oxidizers in a chemical fume hood. (Some factors to be considered in judging the adequacy of the hood include its size in relation to the reaction and required equipment, the ability to fully dose the sash, and the composition of the sash.)
Make sure that the reaction equipment is properly secured. Reaction vessels should be supported from beneath with tripods or lab jacks. Use shields or guards which are damped or secured.
If possible use remote controls for controlling the reaction (including cooling, heating and stirring controls). These should be located either outside the hood or at least outside the shield.
Handle shock sensitive substances gently, avoid friction, grinding, and all forms of impact.. Glass containers that have screw cap lids or glass stoppers should not be used. Polyethylene bottles that have screw-cap lids may be used. Handle water-sensitive compounds away from water sources. Light-sensitive chemicals should be used in light-tight containers. Handle highly reactive chemicals away from the direct light, open flames, and other sources of heat. Oxidizing agents should only be heated with fiberglass heating mantles or sand baths.
High-energy oxidizers, such as perchloric add, should only be handled in a wash down hood if the oxidizer will volatilize and potentially condense in the ventilation system. Inorganic oxidizers such as perchloric acid react violently with most organic materials.
When working with highly reactive compounds and high-energy oxidizers always wear the following personal protection equipment: lab coats, gloves and protective goggles. During the reaction, a face shield long enough to give throat protection should be worn.
Labels on peroxide forming substances should contain the date the
container was received, first opened and the initials of the person who
first opened the container.
They should be checked for the presence of peroxides before using, and
quarterly while in storage (peroxide test strips are available).
If peroxides are found, the materials should be decontaminated,
if possible, or disposed of.
The results of any testing should be placed on the container label.
If there is any sign of visible crystal formation around the
bottle cap or at the bottom of a liquid peroxide forming substance, do
not attempt to open the bottle or shake or transport it.
Notify the Chemical Safety Coordinator at once to arrange for
safe disposal of the material. Never distill substances contaminated with peroxides.
Peroxide forming substances that have been opened for more than
one year should be discarded. Never use a metal
spatula with peroxides.
Contamination by metals can lead to explosive decompositions.
Store highly reactive chemicals and high-energy oxidizers in closed cabinets segregated from the materials with which they react and, if possible, in secondary containers. You can also store them in the cabinet under a hood. Do not store these substances above eye level or on open shelves.
Store peroxides and peroxide forming compounds at the lowest possible temperature. If you use a refrigerator make sure it is appropriately designed for the storage of flammable substances. Store light-sensitive compounds in the light-tight containers. Store water-sensitive compounds away from water sources.
Shock sensitive materials should be discarded as hazardous waste after one year if in a sealed container and within six months of opening unless an inhibitor was added by the manufacturer.
3.2.3 List of Shock Sensitive Chemicals
Shock sensitive refers to the susceptibility of a chemical to decompose rapidly or explode when struck, vibrated or otherwise agitated. The following are examples of materials which can be shock sensitive:
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Acetylides of heavy metals |
Hexanite |
Organic nitramines |
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Aluminum ophrite explosive |
Hexanitrodiphenylamine |
Organic peroxides |
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Amatol |
Hexanitrostilbene |
Picramic acid |
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Ammonal |
Hexogen |
Picramide |
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Ammonium nitrate |
Hydrazinium nitrate |
Picratol |
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Ammonium perchlorate |
Hyrazoic acid |
Picric acid |
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Ammonium picrate |
Lead azide |
Picryl chloride |
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Calcium nitrate |
Lead mannite |
Polynitro aliphatic compounds |
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Copper Acetylide |
Lead mononitroresorcinate |
Potassium nitroaminotetrazole |
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Cyanuric triazide |
Lead picrate |
Silver acetylide |
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Cyclotrimethylenetrinitramine |
Lead salts |
Silver azide |
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Dinitroethyleneurea |
Lead styphnate |
Silver styphnate |
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Dinitroglycerine |
Magnesium ophorite |
Silver tetrazene |
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Dinitrophenol |
Mannitol hexanitrate |
Sodatol |
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Dinitrophenolates |
Mercury oxalate |
Sodium amatol |
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Dinitrophenyl hydrazine |
Mercury tartrate |
Sodium dinitro-orthocresolate |
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Dinitrotoluene |
Mononitrotoluene |
Styphnic acid |
| Dipicryl sulfone | Nitrated carbohydrates | Tetrazene |
| Dipicrylamine | Nitrated glucoside | Tetranitrocarbazole |
| Erythritol tetranitrate | Nitrated polyhydric alcohol | Tetrytol |
| Fulminate of mercury | Nitrogen trichloride | Trinitroanisole |
| Fulminate of silver | Nitrogen tri-iodide | Trinitrobenzene |
| Fulminating gold | Nitroglycerin | Trinitrobenzoic acid |
| Fulminating mercury | Nitroglycide | Trinitrocresol |
| Fulminating platinum | Nitroglycol | Trinitro-meta-cresol |
| Fulminating silver | Nitroguanidine | Trinitronaphtalene |
| Gelatinized nitrocellulose |
Nitronium Perchlorate |
Trirtitrophenetol |
| Germane | Nitroparaffins | Trinitrophloroglucinol |
| Guanyl nitrosaminoguanylidene hydrazine | Nitronium Perchlorate | Trinitroresorcinol |
| Guanyl nitrosamino guanyl-tetrazene | Nitrourea | Tritonal |
| Heavy metal azides | Organic amine nitrates | Urea nitrate |
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3.2.4 List of High Energy Oxidizers The following are examples of materials which are powerful oxidizing reagents:
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The following are examples of materials commonly used in laboratories which may form explosive peroxides.
3.3 COMPRESSED GASES 3.3.1 General Information Compressed gases are unique in that they represent both a physical and a potential chemical hazard (depending on the particular gas). Gases contained in cylinders may be from any of the hazard classes described in this section (flammable, reactive, corrosive, or toxic). Because of their physical state (gaseous), concentrations in the laboratory can increase instantaneously if leaks develop at the regulator or piping systems, creating the potential for a toxic chemical exposure or a fire/explosion hazard. Often there is little or no indication that leaks have or are occurring. Finally, the large amount of potential energy resulting from compression of the gas makes a compressed gas cylinder a potential rocket or fragmentation bomb if the tank or valve is physically broken. 3.3.2 Special Handling Procedures The contents of any compressed gas cylinder should be clearly identified. No cylinder should be accepted for use that does not legibly identify its contents by name. Color-coding is not a reliable means of identification and labels on caps have no value as caps are interchangeable. Carefully
read the label before using or storing compressed gas. The MSDS
will provide any special hazard information. 3.3.3
Special Precautions for Hydrogen Hydrogen gas has several unique properties, which make it potentially dangerous to work with. It has an extremely wide flammability range (LEL 4%, UEL 74.5%) making it easier to ignite than most other flammable gases. Unlike most other gases, hydrogen's temperature increases during expansion. If a cylinder valve is opened too quickly the heat or static charge generated by the escaping gas may cause it to ignite. Hydrogen burns with an invisible flame. Caution should therefore be exercised when approaching a suspected hydrogen flame. A piece of paper can be used to tell if the hydrogen is burning. Hydrogen embrittlement can weaken carbon steel. Therefore, cast iron pipes and fittings shall not be used. Those precautions associated with other flammable substances also apply to Hydrogen (see Section 3.1). 3.4.1
General Information The major classes of corrosive chemicals are strong acids and bases, dehydrating agents, and oxidizing agents. These chemicals can erode the skin and the respiratory epithelium and are particularly damaging to the eyes. Inhalation of vapors or mists of these substances can cause severe bronchial irritation. If your skin is exposed to a corrosive, flush the exposed area with water for at least fifteen minutes. Then seek medical treatment. Strong alkalis: The common strong bases used in the labs are potassium hydroxide, sodium hydroxide, and ammonia. Bums from these materials are often less painful than acids. However, damage may be more severe than acid bums because the injured person, feeling little pain, often does not take immediate action and the material is allowed to penetrate into the tissue. Ammonia is a severe bronchial irritant and should always be used in a well-ventilated area, if possible in a hood. Dehydrating agents: This group of chemicals includes concentrated sulfuric acid, sodium hydroxide, phosphorous pentoxide, and calcium oxide. Because much heat is evolved on mixing these substances with water, mixing should always be done be adding the agent to water, and not the reverse, to avoid violent reaction and spattering. Because of their affinity for water, these substances cause severe burns on contact with skin. Affected areas should be washed promptly with large volumes of water. Oxidizing agents: In addition to their corrosive properties, powerful oxidizing agents such as perchloric and chromic acids (sometimes used as cleaning solutions), present fire and explosion hazards on contact with organic compounds and other oxidizable substances. The hazards associated with the use of perchloric acid are especially severe. It should be handled only after thorough familiarization with recommended operating procedures (see section on reactives and high-energy oxidizers).
Corrosive chemicals should be used in the chemical fume hood, or over plastic trays when handled in bulk quantities (>1 liter) and when dispensing. When working with bulk quantities of corrosives wear gloves, face shields, laboratory coats, and rubber aprons. Store corrosives in cabinets, under the hood or on low shelves, preferably in the impervious trays to separate them physically from other groups of chemicals. Keep containers not in use in storage areas and off bench tops. If it is necessary to move bulk quantities from one laboratory to another or from the stockroom use a safety carrier (rubber bucket for secondary containment and protection of the container). 3.5 CHEMICALS OF HIGH ACUTE AND CHRONIC TOXICITY 3.5.1 General Information Substances that possess the characteristic of high acute toxicity can cause damage after a single or short-term exposure. The immediate toxic effects to human health range from irritation to illness and death. Hydrogen cyanide, phosgene, and nitrogen dioxide are examples of substances with high acute toxicity. The lethal oral dose for an average human adult for highly toxic substances range from one ounce to a few drops. The following procedures should be used when the oral LD, of a substance in the rat or mouse is less than 50 milligrams per kilogram body weight for solid materials or non-volatile liquids and 500 mg/kg body weight for volatile liquids or gases. Oral LD50 data for the rat or mouse is listed in the substance's MSDS. The LD50 toxicity test is usually the first toxicological test performed and is a good indicator of a substance's acute toxicity. Substances that possess the characteristic of high chronic toxicity cause damage after repeated exposure or exposure over long periods of time. Health effects often do not become evident until after a long latency period - twenty to thirty years. Substances that are of high chronic toxicity may be toxic to specific organ systems - hepatotoxins, nephrotoxins, neurotoxins, toxic agents to the hematopoietic system and pulmonary tissue or carcinogens, reproductive toxins, mutagens, teratogens or sensitizers. The definition of each of these categories of toxic substances, and examples of substances, which fall into each of these different categories, can be found in Section 4 of this manual. Specific acute and chronic toxicity information on the substances used in your laboratory can be found on the MSDS's of these substances. See Section 1.5.2.1 for information on how to obtain/locate MSDS's. If you have additional questions contact the Chemical Safety Coordinator. 3.5.2 Special Handling Procedures Avoid or minimize contact with these chemicals be any route of exposure. Protect the hands and forearms by wearing gloves appropriate to the job and a laboratory coat rinse gloves prior to removing them. Use these chemicals in a chemical fume hood or other appropriate containment device if the material is volatile or the procedure may generate aerosols (See guidelines for chemical fume hood use in Section 2.3.5.1). If a chemical fume hood is used it should be evaluated to confirm that it is performing adequately (a face velocity of at least 100 linear feet per minute (±20%)) with the sash at the operating height. Store volatile chemicals of high acute or chronic toxicity in the cabinet under the hood or other vented area. Volatile chemicals should be stored in unbreakable primary or secondary containers or placed in chemically resistant trays (to contain spins). Nonvolatile chemicals should be stored in cabinets or in drawers. Do not store these chemicals on open shelves or counters. Decontaminate working surfaces with wet paper towels after completing procedures. Place the towels in plastic bags and secure. Dispose of them in the normal trash unless they are obviously contaminated. Volatile chemicals should be transported between laboratories in durable outer containers. Vacuum pumps used in procedures should be protected from contamination with scrubbers or filters. If one or more of these substances are used in large quantities, on a regular basis (three or more separate handling sessions per week), or for long periods of time (4-6 hours) a qualitative and potentially quantitative exposure assessment should be performed. Lab personnel of childbearing age should be informed of any known male or female reproductive toxins used in the laboratory. An employee who is pregnant, or planning to become pregnant, and who is working with potential reproductive toxins that might affect the fetus, should contact the Chemical Safety Coordinator to evaluate her exposure and should inform her personal physician. The Chemical Safety Coordinator can assess potential exposures and work with the employee and laboratory supervisor, if necessary, to adjust work practices to minimize the potential risk.
3.6
REGULATED CHEMICALS & PARTICULARLY HAZARDOUS CHEMICALS 3.6.1
General Information This section establishes supplemental work procedures to control the handling of substances that are known to exhibit unusual acute or long-term chronic health hazards (carcinogens, reproductive toxins and highly acutely toxic substances). These unusually hazardous chemicals are listed as follow: Others may be added to the list as necessary.
UNUSUALLY
HAZARDOUS CHEMICALS 3.6.2
Special Handling Procedures Volatile chemicals should be stored in a vented storage area in an unbreakable, primary or secondary container or placed in a chemically resistant tray (to contain spills). Nonvolatile chemicals should be stored in cabinets or in drawers. Do not store these chemicals on open shelves or counters. Access to all of these chemicals should be restricted. Volatile chemicals should be transported between laboratories in durable outer containers. All procedures with these chemicals should be performed in designated areas. Other employees working in the area should be informed of the particular hazards associated with these substances and the appropriate precautions that are necessary for preventing exposures. All designated areas should be posted with a sign, which reads:
Vacuum pumps used in procedures should be protected from contamination with scrubbers or filters. Analytical instruments or other laboratory equipment generating vapors and/or aerosols during their operation, should be locally exhausted or vented in a chemical fume hood. Skin surfaces which might be exposed to these substances during routine operations or foreseeable accidents should be covered with appropriate protective clothing. Gloves should be worn whenever transferring or handling these substances. Consider using full body protection (disposable coveralls) if the potential for extensive personal contamination exists. All protective equipment should be removed when leaving the designated area and decontaminated (washed) or, if disposable, placed in a plastic bag and secured. Call the Chemical Safety Coordinator for disposal instructions. Skin surfaces - hands, forearms, face and neck - should be washed immediately. Work surfaces on which these substances will be handled should be covered with an easily decontaminated surface (such as stainless steel) or protected from contamination with plastic trays or plastic backed paper. Call the Chemical Safety Coordinator for decontamination and disposal procedures; these will be substance specific. Materials that will be disposed of should be placed in plastic bags and secured. Chemical wastes from procedures using these substances should be placed in containers and disposed of as hazardous chemical waste. The wastes should be stored in the designated area (defined above) until picked up. If it is possible to safely chemically decontaminate all toxic substances to nontoxic materials during or at the end of the procedure this should be done. Normal laboratory work should not be conducted in a designated area until it has been decontaminated or determined to be safe e by the laboratory supervisor or Chemical Safety Coordinator. If one or more of these substances are used in large quantities, on a regular basis (three or more separate handling sessions per week), or for long periods of time (4-6 hours) a qualitative and potentially quantitative exposure assessment should be performed. Contact the Chemical Safety Coordinator to have this assessment performed. The Chemical Safety Coordinator in conjunction with the Department Chairman will determine if is appropriate to establish an ongoing medical surveillance program. Lab personnel of childbearing age should be informed of any known male and female reproductive toxins used in the laboratory. An employee who is pregnant, or planning to become pregnant, and who is working with potential reproductive toxins that might affect the fetus, should contact the Chemical Safety Coordinator to evaluate her exposure and inform her personal physician. The Chemical Safety Coordinator can assess potential exposures and work with the employee and laboratory supervisor, if necessary, to adjust work practices to minimize the potential risk. SECTION 4 CHEMICAL TOXICOLOGY 4.1
CHEMICAL TOXICOLOGY OVERVIEW Toxicology is the study of the nature and action of poisons. Toxicity is the ability of a chemical substance or compound to produce injury once it reaches a susceptible site in, or on, the body. A
material's hazard potential is
the probability that injury will occur after consideration of the
conditions under which the substance is used.
4.1.2
Dose-Response Relationships The potential toxicity (harmful action) inherent in a substance is exhibited only when that substance comes in contact with a living biological system. The potential toxic effect increases as the exposure increases. All chemicals will exhibit a toxic effect given a large enough dose. The toxic potency of a chemical is thus ultimately defined by the dose (the amount) of the chemical that will produce a specific response in a specific biological system. 4.1.3 Routes of Entry into the Body There are three main routes by which hazardous chemicals enter the body: Absorption through the respiratory tract via inhalation. Absorption through the skin via dermal contact. Absorption through the digestive tract via ingestion. (Ingestion can occur through eating or smoking with contaminated hands or in contaminated work areas.) Most exposure standards, such as the Threshold Limit Values (TLV's) and Permissible Exposure Limits (PEL's), are based in the inhalation route of exposure. These limits are normally expressed in terms of either parts per million (ppm) or milligrams per cubic meter (mg/m3) concentration in air. If a significant route of exposure for a substance is through skin contact, the MSDS, PEL, and/or TLV will have a "skin" notation. Examples of substances where skin absorption may be a significant factor include: pesticides, carbon disulfide, carbon tetrachloride, dioxane, mercury, thallium compounds, xylene and hydrogen cyanide. 4.1.4 Types of Effects Acute poisoning is characterized by sudden and severe exposure and rapid absorption of the substance. Normally, a single large exposure is involved. Adverse health effects are often reversible. Examples: carbon monoxide or cyanide poisoning.
Rate of entry and route of exposure; that is, how fast is the toxic dose delivered and by what means. Age of the individual can affect the capacity to repair tissue damage. Previous exposure can lead to tolerance, increased sensitivity or make no difference. State of health, physical condition and life style can affect the toxic response. Pre-existing
disease can result in increased sensitivity. Environmental
factors such as temperature and pressure. Host factors including genetic predisposition and the sex of the exposed individual. 4.1.6 Physical Classifications When considering the toxicity of gases and vapors, the solubility of the substance is a key factor. Highly soluble materials, like ammonia irritate the upper respiratory tract. On the other hand, relatively insoluble materials, like nitrogen dioxide, penetrate deep into the lung. Fat-soluble materials, like pesticides, tend to have longer residence times in the body and be cumulative poisons. An aerosol is composed of microscopic solid or liquid particles dispersed in a gaseous medium. The toxic potential of an aerosol is only partially described by its airborne concentration. For a proper assessment of the toxic hazard, the size of the aerosol's particles must be determined. A particle's size will determine if a particle will be deposited within the respiratory system and the location of deposition. Particles above 10 micrometers tend to deposit in the nose and other areas of the upper respiratory tract. Below 10 micrometers particles enter and are deposited in the lung. Very small particles (<0.2 micrometers) are generally not deposited but exhaled.
Long term exposure to irritants can result in increased mucous secretions and chronic bronchitis.
Chemical asphyxiants reduce the body's ability to absorb, transport, or utilize inhaled oxygen. They are often active at very low concentrations (a few ppm). Examples include Carbon Monoxide and Cyanides. Primary anesthetics have a depressant effect upon the central nervous system, particularly the brain. Examples include: Halogenated Hydrocarbons and Alcohols.
Some
toxic agents act on the
There are toxic agents that produce damage of the pulmonary tissue (lungs) but not by immediate irritant action. Fibrotic changes can be caused by free silica and asbestos. Other dusts can cause a restrictive disease called pneumoconiosis. Examples include:
A carcinogen is an agent that can initiate or increase the proliferation of malignant neoplastic cells or the development of malignant or potentially malignant tumors. Known human carcinogens include:
A mutagen interferes with the proper replication of genetic material (chromosome strands) in exposed cells. If germ cells are involved, the effect may be inherited and become part of the genetic pool passed onto future generations.
A sensitizer is a chemical which can cause an allergic reaction in normal tissue after repeated exposure to the chemical. The reaction may be as mild as a rash (allergic dermatitis) or as serious as anaphylactic shock. Examples include:
4.2 Some Target Organ Effects The
following is a categorization of target organ effects, which may occur
from chemical exposure. Signs
and symptoms of these effects and examples of chemicals, which have been
found to cause such effects, are listed.
4.3 OCCUPATIONAL HEALTH STANDARDS TLV:
The threshold limit
value is a recommended occupational exposure guideline published
by the American Conference of Governmental Industrial Hygienists.
TLV's are expressed as parts of vapor or gas per million
parts of air by volume (ppm) or as approximate milligrams of
particulate per cubic meter or air (mg/m3).
The TLV is the average concentration of a chemical that most
people can be exposed to for a working lifetime with no ill effects.
The TLV is an advisory guideline.
If applicable, a ceiling
concentration (C), which should not be exceeded, or a skin
absorption notation (S) will be indicated with the TLV. PEL: The permissible exposure limit is a legal standard issued by OSHA. Unless specified, the PEL is a time weighted average (TWA). TWA: Most exposure standards are based in time weighted averages. The TWA is the average exposure over an eight-hour workday. Some substances have ceiling (C) limits. Ceiling limits are concentrations that should never be exceeded. The MSDS will list the occupational health standards for the hazardous chemical or each component of a mixture.
SECTION
5 ACGIH - The American Conference of Governmental Industrial Hygienists is a voluntary membership organization of professional industrial hygiene personnel in governmental or educational institutions. The ACGIH develops and publishes recommended occupational exposure limits each year called Threshold Limit Values (TLV's) for hundreds of chemicals, physical agents, and biological exposure indices. ACUTE - Short duration, rapidly changing conditions. ACUTE EXPOSURE - An intense exposure over a relatively short period of time. ANSI - The American National Standards Institute is a voluntary membership organization (run with private funding) that develops consensus standards nationally for a wide variety of devices and procedures. ASPHYXIANT - A chemical (gas or vapor) that can cause death or unconsciousness by suffocation. Simple asphyxiants, such as nitrogen, either remove or displace oxygen in the air. They become especially dangerous in confined or enclosed spaces. Chemical asphyxiants, such as carbon monoxide and hydrogen sulfide, interfere with the body's ability to absorb or transport oxygen to the tissues. BOILING POINT - The temperature at which the vapor pressure of a liquid equals atmospheric pressure or at which the liquid changes to a vapor. The boiling point is usually expressed in degrees Celsius. If a flammable material has a low boiling point, it indicates a special fire hazard. " C" - Degrees, Celsius; the common metric laboratory temperature scale. "C" OR CEILING - A description usually seen in connection with ACGIH exposure limits. It refers to the concentration that should not be exceeded, even for an instant. It may be written as TLV-C or Threshold Limit Value-Ceiling. (See also THRESHOLD LIMIT VALUE). CARCINOGEN - A substance or physical agent that may cause cancer in animals or humans. CAS NUMBER - identifies a particular chemical by the Chemical Abstracts Service, a service of the American Chemical Society that indexes and compiles abstracts of worldwide chemical literature called Chemical Abstracts. cc or CC- Cubic centimeter, a volumetric measurement that is also equal to one milliliter (ml). CHEMICAL - As broadly applied to the chemical industry, an element or a compound produced by chemical reactions on a large scale for either direct industrial and consumer use or for reaction with other chemicals. CHEMICAL REACTION - A change in the arrangement of atoms or molecules to yield substances of different composition and properties. (see REACTIVITY) CHRONIC - Persistent, prolonged or repeated conditions. CHRONIC EXPOSURE - A prolonged exposure occurring over a period of days, weeks, or years. COMBUSTIBLE
- CONCENTRATION - The relative amount of a material in combination with another material. For example, 5 parts of (acetone) per million (parts of air). CORROSIVE - A substance that according to the DOT, causes visible destruction or permanent changes in human skin tissue at the site of contact or is highly corrosive to steel or aluminum. CUBIC METER (m3) - A measure of volume in the metric system. CUTANEOUS - Pertaining to or affecting the skin. DECOMPOSITION - The breakdown of a chemical or substance into different parts or simpler compounds. Decomposition can occur due to heat, chemical reaction, decay, etc. DERMAL - Pertaining to or affecting the skin. DERMATITIS - An inflammation of the skin. DILUTION VENTILATION - See GENERAL VENTILATION. DOT - The United States Department of Transportation is the federal agency that regulates the labeling and transportation of hazardous materials. DYSPNEA - Shortness of breath; difficult or labored breathing. EPA - The Environmental Protection Agency is the governmental agency responsible for administration of laws to control and/or reduce pollution of air, water, and land systems. EPA NUMBER - The number assigned to chemicals regulated by the Environmental Protection Agency (EPA). EPIDEMIOLOGY - The study of disease in human populations. ERYTHEMA - Reddening of the skin. EVAPORATION RATE - The rate at which a material is converted to vapor (evaporates) at a given temperature and pressure when compared to the evaporation rate of a given substance. Health and fire hazard evaluations of materials involve consideration of evaporation rates as one aspect of the evaluation. °F - Degrees Fahrenheit; the common temperature scale used in the U.S. FLAMMABLE LIQUID - According to the DOT and NFPA a flammable liquid is one that has a flash point below 100°F. (See FLASH POINT) Classes
Of Flammable Liquids:
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