CLARKSON UNIVERSITY CHEMICAL HYGIENE PLAN
Revised 03/04/2010 Revised 09/23/2010 Revised 08/19/2013
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TABLE OF CONTENTS 1.0 Policies, Roles and Responsibilities 1.1 Policy, Purpose and Scope 1.2 Definitions 1.3 Roles and Responsibilities 1.3.1 All persons who work in chemical laboratories 1.3.2 Chemical Hygiene Officer 1.3.3 Environmental Health and Safety Manager 1.3.4 Environmental Health and Safety Committee 1.3.5 Department Chairs 1.3.6 Principal Investigators 1.3.7 Custodial and Maintenance Staff 1.3.8 All laboratory workers including graduate students, teaching assistants, undergraduate students, laboratory staff, and volunteers 1.4 Moving a Laboratory 1.5 Reproductive Hazards Policy (Pregnancy and lab work) 2.0 Chemical Inventory Management 3.0 University Wide “Standard Operating Procedures” 3.1 Ultimate Responsibility 3.2 Personal Behavior in Laboratories 3.3 Security 3.4 Housekeeping 3.5 Unattended Use of Equipment or Services 3.6 After-hours Activities 3.7 General Safety Practices 3.8 Use of Special Laboratory Equipment 3.8.1 Systems Under Pressure 3.8.2 Systems Under a Vacuum 3.8.3 Centrifuges 3.9 Use of Electrical and Mechanical Equipment 3.10 Use of Compressed Gas Cylinders 3.10.1 Ordering new Cylinders 3.10.2 Disposing Old Cylinders 3.11 General Chemical Handling Procedures 3.12 Safe Chemical Storage 3.13 Handling Specific Types of Chemicals 3.13.1 Flammable Chemicals 3.13.2 Corrosive Chemicals 3.14 Toxic Materials 3.14.1 Specific Toxic Substances 3.14.2 Toxic and/or Flammable Gases 3.14.3 Highly reactive and explosive materials 3.14.4 Peroxide Forming Chemicals 3.15 Chemical Carcinogens, Reproductive Toxins, Acutely and Extremely Toxic Chemicals (CCs, RTs, A/ETs) 3.16 Working with Unknown Chemicals 3.17 Prior Approval for use of Chemicals that have Special Handling or Disposal 3.17.1 Chemicals requiring prior approval
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3.17.2 Other materials requiring prior approval 3.17.3 Approval Procedure for high hazard agents and processes (HHAPs) 3.17.4 Working Safely with HHAPs 3.18 Format to Prepare Laboratory Specific Procedures 3.18.1 Sample of a Laboratory Specific Procedure 4.0 Controlling Chemical Exposures 4.1 Hazard Communication 4.1.1 Material Safety Data Sheets 4.1.2 Chemical Labeling 4.1.3 Training 4.2 Routes of Exposure 4.2.1 Inhalation 4.2.2 Skin and Eye Contact 4.2.3 Ingestion 4.2.4 Injection 4.3 Engineering Controls 4.3.1 Use of Chemical Fume Hoods and Examples 4.3.2 Perchloric Acid Chemical Fume Hoods 4.3.3 Biosafety Cabinets 4.4 Administrative Controls 4.5 Personal Protection Equipment (PPE) 4.5.1 Clothing 4.5.2 Glove Types 4.5.3 Eye Protection 4.5.4 Respirators 5.0 Chemical Hazards 5.1 Flammability 5.1.1 Pyrophoric Materials 5.2 Odor Threshold and Warning Properties 5.3 Irritating or Corrosive Gases and Vapors 5.3.1 Lung Irritation and Damage 5.3.2 Eye Irritation and Damage 5.3.3 Skin Irritation and Damage 5.4 Sensitizers (Allergens) 5.5 Asphyxiate Gases and Vapors 5.5.1 Types of Asphyxiates 5.6 Central Nervous System (CNS) Depressants 5.7 Poisons 5.8 Systemic Toxins 5.9 Carcinogens 5.10 Reproductive Toxins (Teratogens) 5.11 Chemicals that Damage the Lungs 6.0 Waste Stream Management 6.1 Planning and Purchasing of Chemicals 6.2 Recovery and Recycling 6.3 Hazardous Waste Identification and Determination 6.4 Drain Disposal Procedures 6.4.1 Materials that can be disposed of in the sanitary sewer
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6.4.2 Examples of materials that cannot be disposed in the sanitary sewer 6.4.3 Sink disposal procedure 6.5 Disposal and Collection of Hazardous Waste 6.6 Disposal of Other Materials 6.7 Non-Hazardous Solid Waste Disposal 7.0 Emergency Response 7.1 Injuries and Accidents 7.2 Chemical Spills 7.3 Fires and Explosions 7.4 First Aid Procedure Guidelines 8.0 Medical Consultation and Recordkeeping 8.1 Medical Consultation and Examinations 8.2 Recordkeeping 8.2.1 Access 8.2.2 Exposure Records 8.2.3 Medical Records 8.2.4 Analyses Using Exposure or Medical Records 8.2.5 Employee Information 8.2.6 Retention of Records 9.0 Training Program Appendix A: Minors in Educational Research Labs Appendix B: EPA P-Listed Waste Appendix C: Safety Chemical Storage Guide Appendix D: Common Peroxides and Maximum Retention Times Appendix E: Particularly Hazardous Chemicals Approval Form Appendix F: Chemical Carcinogens Appendix G: Laboratory Health and Safety Resources Appendix H: 29CFR 1910.1450: Occupational Exposure to Hazardous Chemicals in Laboratories Appendix I: Laboratory Specific Procedures Appendix J: Record Of Laboratory Specific Training Appendix K: Hazard Assessment Tool
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1.0 Policies, Roles, and Responsibilities 1.1 Mission, Purpose, and Scope Clarkson’s Environmental Health and Safety Program Mission: To facilitate University compliance with environmental and occupational health regulations and the continuous improvement of campus environmental health and safety activities. Policy: It is the policy of Clarkson University to ensure that all laboratory hazards are identified and information about these hazards is transmitted to employees to provide for their safety and health protection. “Employees” under this policy are defined as including all custodial and maintenance staff, faculty and paid assistants (graduate and undergraduate) who work in science or engineering laboratories. This policy is implemented through the administration of this EHS Laboratory Health and Safety Policy and Chemical Hygiene Plan per to 29 CFR 1910.1450, “Occupational Exposures to Hazardous Chemicals in Laboratories, Final Rule,” published January 31, 1990. Purpose: The purpose of this Chemical Hygiene Plan (CHP) is to define prudent work practices and procedures to help ensure that faculty, staff, student workers, and the environment are protected from the hazards associated with the handling, storage, and use of chemicals in laboratories. Occupational Safety and Health Administration (OSHA) Regulations (29 CFR 1910.1450) require all employers engaged in the laboratory use of hazardous chemicals to develop and carry out the provisions of a Chemical Hygiene Plan that is capable of protecting employees from health hazards associated with hazardous chemicals and capable of keeping exposures below Permissible Exposure Limits (PELs). This CHP applies to all laboratories at Clarkson University, including but not limited to those in the departments of biology and psychology, chemistry, physics, health sciences, mechanical engineering, civil and environmental engineering, chemical engineering, and electrical engineering. OSHA defines a laboratory as “a workplace where relatively small quantities of hazardous chemicals are used on a non-production basis.” Laboratories involve a greater variety of possible hazards than most work places, and some hazards call for precautions not ordinarily encountered. All labs at Clarkson have some type of hazards that need to be managed to minimize the risk to occupants. This CHP applies to all laboratory workers. An example of a laboratory worker would be a university teaching assistant or faculty member instructing an academic lab. Clarkson also has the special responsibility of administering instructional labs with relatively inexperienced students who must be introduced to the safety procedures necessary to conduct various laboratory operations. The students that are in the academic laboratory are not considered laboratory workers unless they are employed by the university. All students involved in laboratory operations, however, must be included in safety programs and Page 5 of 99
training. Safety policies and practices should be a regular part of the curriculum. A brief discussion on the first day of lab is not enough. The Chemical Hygiene Officer and the Environmental Health & Safety Committee will review the CHP annually. Scope of the CHP: This plan applies to, but is not limited to, all research laboratories, teaching laboratories, SPEED team areas and labs, students projects, and club activities. 1.2 Definitions Action level - The concentration designated by OSHA 29 CFR 1910 for a specific substance, calculated as an 8-hour time-weighted average, which initiates certain required activities such as exposure monitoring and medical surveillance. Chemical - Any element, chemical compound, mixture, or substance of elements and/or compounds. Chemical Hygiene Plan - A written program developed and implemented by the laboratory, which sets forth procedures, equipment, personal protective equipment and work practices that are capable of protecting employees from the health hazards associated with the chemicals used in the laboratory. Chemical Hygiene Officer - An employee who is designated by the employer, and is qualified by training or experience, to provide technical guidance in the development and implementation of the provisions of the Chemical Hygiene Plan. Environmental Health & Safety Committee - A committee consisting of qualified and knowledgeable representatives from the university who review safety and health issues throughout the University, including laboratory and chemical safety. This committee reports into the University compliance committee. Explosive means a chemical that causes a sudden, almost instantaneous release of pressure, gas, and heat when subjected to sudden shock, pressure, or high temperature. Flammable means a chemical that falls into one of the following categories: (i) Aerosol, flammable means an aerosol that, when tested by the method described in 16 CFR 1500.45, yields a flame protection exceeding 18 inches at full valve opening, or a flashback (a flame extending back to the valve) at any degree of valve opening; (ii) Gas, flammable means: (A) A gas that, at ambient temperature and pressure, forms a flammable mixture with air at a concentration of 13 percent by volume or less; or (B) A gas that, at ambient temperature and pressure, forms a range of flammable mixtures with air wider than 12 percent by volume, regardless of the lower limit. (iii) Liquid, flammable means any liquid having a flashpoint below 100 deg F (37.8 deg. C), except any mixture having components with flashpoints of 100 deg. C) or higher, the Page 6 of 99
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. Hazardous chemical/agent means a chemical for which there is scientific 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. Health hazard - A chemical that has been shown to cause acute or chronic health effects. 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. Medical consultation means a consultation which takes place between an employee and a licensed physician for the purpose of determining what medical examinations or procedures, if any, are appropriate in cases where a significant exposure to a hazardous chemical may have taken place. Organic peroxide means an organic compound that contains the bivalent -O-O- structure and which may be considered to be a structural derivative of hydrogen peroxide where one or both of the hydrogen atoms has been replaced by an organic radical. Oxidizer means a chemical other than a blasting agent or explosive as defined in § 1910.109(a), that initiates or promotes combustion in other materials, thereby causing fire either of itself or through the release of oxygen or other gases. Permissible Exposure Limit (PEL) - The greatest concentration designated by OSHA, for a specific chemical, which nearly all personnel may be repeatedly exposed to during their 8hour work-shift without adverse effects. 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. Protective Laboratory Practices and Equipment - Laboratory procedures, practices, and equipment accepted by laboratory health and safety experts as effective, or that the employer Page 7 of 99
can show to be effective, in minimizing the potential for exposure to hazardous chemicals. Reproductive toxins 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) It is regulated by OSHA as a carcinogen; or (ii) It is listed under the category, "known to be carcinogens," in the Annual Report on Carcinogens published by the National Toxicology Program (NTP)(latest edition); or (iii) It is listed under Group 1 ("carcinogenic to humans") by the International Agency for research on Cancer Monographs (IARC)(latest editions); or (iv) It is listed in either Group 2A or 2B by IARC or under the category, "reasonably anticipated to be carcinogens" by NTP, and causes statistically significant tumor incidence in experimental animals in accordance with any of the following criteria: (A) After inhalation exposure of 6-7 hours per day, 5 days per week, for a significant portion of a lifetime to dosages of less than 10 mg/m(3); (B) After repeated skin application of less than 300 (mg/kg of body weight) per week; or (C) After oral dosages of less than 50 mg/kg of body weight per day. Threshold Limit Value (TLV) - The greatest concentration, designated by the American Conference of Governmental Industrial Hygienists (ACGIH) for a specific chemical, to which nearly all personnel may be repeatedly exposed to during their 8-hour work-shift without adverse effects. This value will be used when it is lower than the OSHA PEL. Unstable (reactive) means a chemical which is the pure state, or as produced or transported, will vigorously polymerize, decompose, condense, or will become self-reactive under conditions of shocks, pressure or temperature. Water-reactive means a chemical that reacts with water to release a gas that is either flammable or presents a health hazard. 1.3 Roles and Responsibilities 1.3.1 All persons who work in chemical laboratories Persons who work in laboratories where chemicals are handled are expected to: Attend a training session on laboratory safety. Follow University wide standard operating procedures and those of the lab in which the person is working. Report damaged or malfunctioning equipment to the person in charge of the laboratory. All persons should be responsible for correcting, and not tolerating, actions of other persons who share the laboratory (e.g. other students) that could endanger anyone in the laboratory or damage university equipment or property. Working Alone: Generally it is not advisable to work alone in laboratories. However, it is recognized that may be necessary to work after normal work hours. The level of Page 8 of 99
precaution will be defined by the degree of risk involved with the experiment. For some experiments it will be mandatory for a second person in the lab. However, undergraduate research assistants must be supervised by graduate students or faculty members. It is the responsibility of the principle investigator to identify all hazardous procedures in his/her lab and establish requirements for working/ not working alone during such procedures. New York State’s Department of Labor restricts those younger than 18 years of age from completing certain work requirements. Please see Appendix A for Clarkson’s Minors in the Lab Policy. 1.3.2
Chemical Hygiene Officer Provides technical guidance in the development and the implementation of the University Chemical Hygiene Plan and departmental standard operating procedures. Consultant to Environmental Compliance Committee, supplying technical information and assisting with project safety reviews upon request. Reviews accident and incident reports and assists with investigations as needed.
1.3.3
Environmental Health and Safety Manager (EHS Manager) Participates in health and safety audits; if this responsibility is delegated, the Environmental Health and Safety Manager will review the audits and take appropriate action when emergency situations come up. Coordinate all Lab safety training and retain all official records of EHS audits, investigation and training. Maintains a chemical inventory for the entire university. To do this, each laboratory must develop and update annually a chemical inventory. Assists Faculty members with laboratory safety compliance. Faculty who have questions on compliance should contact the EHS Manager, who will meet with Faculty members to provide guidance.
1.3.4
Environmental Health & Safety Committee Meets periodically throughout the year; additional meetings may be needed to handle emerging problem or changes on campus. The Committee is composed of the University Safety Officer, Director of Facilities, other Facilities and Services Representatives as needed, the Environmental Health and Safety Manager, the Risk Management Director, the Director of Campus Safety, and the Associate Dean of Students. Develops and enhances as needed monthly and annual health, safety and housekeeping audits. Reviews health and safety audits results; set and implement corrective actions as needed.
1.3.5
Department Chairs Support the CHO and EHS Manager in maintaining awareness and compliance with the CHP and other laboratory policies and procedures. Page 9 of 99
Ensure all audit findings in their area are corrected by Faculty under their responsibility. Prepare budget requests for health and safety improvements.
1.3.6
Principal Investigators Develop an inventory of all chemicals, hazardous agents and hazardous operations within their laboratories. Inventory must be submitted to EHS on an annual basis on July 1 of each year. Responsible for implementing health, safety and housekeeping procedures for laboratory employees and students. Develop and implement written specific laboratory procedures for hazardous chemicals, operations and equipment used in their laboratory or by their undergraduate and graduate students and staff. Ensure that their graduate students and staff attend training programs developed by the University as required by the Chemical Hygiene Plan. Responsible for providing additional training to all students and staff working in their laboratory regarding specific environmental health and safety hazards in their laboratory to ensure compliance with environmental and safety regulations. Enforce Standard Operating Procedures in their laboratory. These include applicable University, Departmental, Building and specific laboratory procedures. Oversee work in their laboratories to ensure all chemical and safety policies and procedures are being followed. Ensure all Hazardous Waste is appropriately stored and labeled within the laboratory. In addition the PI must arrange for all hazardous waste to be transported from their laboratory to the University storage building on a routine basis. The Faculty is responsible for ensuring student researchers, post-doctorate researchers, fellows, and other staff appropriately label and/or dispose of materials prior to permanently leaving the University Will correct all audit findings and returning all documentation of corrections to EHS Manager. Responsible for appropriately decommissioning any laboratory they vacate. Decommissioning includes, but is not limited to appropriately disposing and handling of waste, chemicals, and laboratory equipment.
1.3.7
Custodial and Maintenance Staff Will carry out usual cleaning or maintenance activities in laboratories, but in the process will not (and will not be expected to) handle or move chemical containers, sweep or mop up laboratory chemical spills, or touch waste baskets which contain loose chemical or chemical containers. Will report to the Principal Investigator or EHS Manager chemical spills or chemicals which have been thrown into waste baskets. Will report to their supervisor concerns about their own health or safety working in specific laboratories. These should be conveyed from their supervisor to the EHS Manager or the Chemical Hygiene Officer.
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1.3.8
Accidental chemical releases (e.g. accidental breaking of a bottle of chemical) will be immediately reported to the Principal Investigator, graduate student, EHS Manager or other person who can assess the hazard. Attend a laboratory health, safety and housekeeping program on a routine basis. Apply appropriate Standard Operating Procedures while working in laboratories.
All laboratory Workers (including teaching assistants, graduate students, undergraduate students, laboratory staff, and volunteers) Teaching Assistants Attend a special training seminar on implementing and enforcing health, safety and housekeeping rules in instructional laboratories. Establish health and safety rules and procedures for students in their laboratory. Enforce safety rules, and monitor student activity, stopping activities which may be or become hazardous. Have the responsibility of removing from the laboratory students who create safety or health hazards. In accordance with the PI's directions, student assistants establish and oversee general laboratory housekeeping. They check the condition of the laboratory at the end of each period; if students haven't cleaned the laboratory as requested, the teaching assistant will do so. Shall be knowledgeable about the health and safety hazards of the chemicals used in the laboratory and transmit this information to the students; will ensure that students handle toxic and hazardous chemicals appropriately. Graduate students, undergraduate students, and volunteers Undergraduate Students and volunteers are not permitted to work in research/instructional laboratories without the supervision of a Principle Investigator, or Teaching Assistant. The following procedures also apply to graduate students, undergraduate students, and volunteers: Follow applicable University wide and departmental procedures. Discusses accidents and incidents with their Principal Investigator and prepare appropriate descriptive reports when required. Reports broken equipment and other laboratory hazards to the PI; adopt a safety first attitude. Graduate and undergraduate student researchers are responsible for appropriately labeling and disposing of materials prior to graduation, end of research appointment, or permanently leaving the University, whichever comes first.
1.4 Moving a Laboratory Moving a Laboratory, if not properly executed, can present a host of potential health and safety issues. To minimize these issues, University personnel must follow the proper Page 11 of 99
procedures when vacating laboratories to ensure all chemical, radioactive and biological materials, sharps, etc. are removed and disposed of properly. The decommissioning process assists in protecting the health and safety of those (cleaning staff, contractors and new occupants, etc.) entering the spaces after the area is vacated. For detailed guidance consult the Clarkson Laboratory Decommissioning Procedure. As graduate and undergraduate students prepare to leave the university, steps should be taken to ensure the following are completed prior to concluding work in that lab: All chemical containers are labeled according to the procedures outlined in 4.1.2 All waste materials are disposed of according to the waste procedures outlined in Section 6.0 All equipment is returned to the rightful owner, including gas cylinders (returned to the vendor). Lab benchtops, fume hoods, and equipment are decontaminated and clean Information regarding any processes and experiments remaining are given to Faculty member in order to continue the research. 1.5 Reproductive Hazards Policy (pregnancy and lab work) Clarkson University strives to make the laboratory experience safe. However, there is always some inherent danger in working with chemicals. Many chemicals, especially organic and biochemical compounds, can be toxic, carcinogenic or mutagenic. As part of the University’s safety program, we strongly advise pregnant women to check with their physicians as to the advisability of working with chemicals and other hazardous materials. Your advisor or teaching assistance can provide you with the chemical inventory for your laboratory so you may discuss this issue with your physician. We urge you to follow your physicians advice in this matter. Your safety and that of your unborn child is our prime concern. EHS Manager can review your work space and provide recommendations to reduce your risk of exposure to chemicals and hazards in the laboratory. This may include, but is not limited to, installing engineering controls, substituting chemicals or materials, or restricting activities or usage of specific chemicals or materials. Refer to Clarkson’s Medical Surveillance Program for more information. 2.0 Chemical Inventory Management The management and control of chemicals is the responsibility of everyone involved in the acquisition, use, and disposal of them. Clarkson University has a responsibility to comply with all federal, state, and local regulations covering chemical purchase, use, transportation, storage, emergency planning, security and disposal. To satisfy this obligation, Clarkson has implemented a chemical management system that includes up to date inventories of our laboratory chemicals. Chemicals enter the University from multiple different locations, as there is no central purchasing system. It is the responsibility of the user (Principal Investigator, graduate student, Page 12 of 99
etc.) to maintain copies of the Safety Data Sheets (SDSs) in your laboratory, ensure adequate training of the staff regarding the information on the SDSs, and to provide a copy of the SDS to the Main SDS Collection, located in the basement of the Student Center. All laboratories are required to maintain a chemical inventory and update the inventory annually. An electronic copy of the inventory must be provided to the EHS Manager annually. 3.0 University Wide “Standard Operating Procedures” The Clarkson University Standard Operating Procedures presented herein apply to personnel in all University laboratories. Individual laboratories may wish to develop stricter and/or additional procedures; if so the laboratory specific procedures should be kept in a binder in your laboratory. These procedures are expected to change over time resulting in a final product that best meets laboratory good work practices and Clarkson University needs. Suggestions about additions and changes in this program are encouraged; call or write the EHS Manager to provide input. The safety practices provided below form the base of training programs which should be attended by all students at least once, (prior to taking their first laboratory class) and laboratory staff. 3.1
Ultimate Responsibility All laboratories are under the authority of a principal investigator; designation may change from time to time if several investigators share a laboratory. The designated principal investigator is charged with these responsibilities: Informing students and employees of the hazards of equipment, procedures and chemicals used in the laboratory; information will be provided orally and/or as written Laboratory Specific Procedures (provided in your lab). Oversee the cleanliness and orderliness of the laboratory meeting criteria set by themselves, and which meet the approval of their Dean and Department Chair. Provide instructions for the appropriate disposal of laboratory waste materials. Contact appropriate individuals in case of a safety incident or chemical spill. Maintain an appropriate spill kit for the chemicals in your laboratory. A chemical spill kit should include absorbent pads, neutralizing agents for acids, bases, and solvents, safety glasses, nitrile or neoprene gloves, hazardous waste labels, plastic bags for spill material disposal, and forceps for picking up broken glass. Maintain an appropriate first aid kit for your laboratory. A first aid kit should contain antiseptic wipes, sterile gauze pads, adhesive bandages, medical tape, antibiotic ointment, burn cream, roller bandage, scissors, a breathing barrier, and latex or nitrile gloves. The above responsibilities are in part met by ensuring that students and technicians: Have attended laboratory health and safety training programs. Have read and understand the Laboratory Safety Manual (Chemical Hygiene Plan), and other policies and procedures determined to be applicable to the laboratory. Page 13 of 99
Are reprimanded (with possible dismissal or rejection from laboratory courses) if they repeatedly break laboratory or University procedures.
3.2
Personal Behavior in Laboratories Inappropriate personal behavior and irresponsible extracurricular experiments will not be tolerated. Smoking is prohibited in any building on campus. Learn about the hazards of the chemicals you handle; in beginning courses TA's will provide this information; in advanced classes, look this material up in resource materials available in the department or the library. Know the location of first aid kits, spill kits, fire extinguisher, safety shower, eye wash station, fire blanket, etc. Don't block access to this equipment. Label chemical storage containers with your name, contents and generation date. Wear gloves and other protective equipment to keep chemicals off the skin. − Check gloves for wear and tear before using. − Discard worn or torn gloves. All personnel should wash their hands immediately after working with chemicals as well as before leaving the laboratory area. This will prevent any injury resulting from residual chemical, as well as prevent contamination to other areas in and out of the work area. Don't store food and beverages in refrigerators meant for chemical storage. Don't use laboratory glass and plastic ware as beverage or food containers. It is good laboratory practice to refrain from eating and drinking in laboratories; these activities should occur in offices or break areas in the vicinity of the laboratory. Clean your work area daily to the standard of the person in charge of the laboratory. Wear shoes and shirt, slacks, or skirt in the lab. No open toed shoes, shorts, or short skirts are permitted in labs where chemicals are present. Procedures should be performed in such a way as to minimize splash. Personal protective equipment should be used when working with hazardous materials. Dispose of waste chemicals correctly; don't assume they can be thrown in the sink or garbage can. If you don't know the disposal procedure, ask. (See waste disposal section.) Children are not permitted in research and instructional laboratories except by permission of the Department Head. Laboratories are potentially dangerous places for children, and must be "child-proofed" before allowing children to enter. Pets are not permitted in research and instructional laboratories.
3.3
Security All laboratories will be locked when unattended and not in use to protect employees, students, equipment, supplies, and the public. Locked storage cabinets will be utilized for expensive, hazardous, or sensitive items. All suspicious persons or actions will be reported to Campus Safety & Security immediately (x6666). Page 14 of 99
3.4
Housekeeping In the laboratory and elsewhere, keeping things clean and neat generally leads to a safer environment. When housekeeping standards fail, safety performance inevitably deteriorates. Therefore, as a best practices guideline: Work areas will be kept clean and free from obstructions. Keep isles free of chairs, boxes, equipment, and waste receptacles. Lab benches and floors will be cleaned regularly and kept free of clutter and chemical residue. No hazardous chemicals should be stored on the floor or above eye level. Access to emergency equipment, exits, control panels, and outlets will be kept clear at all times. Drawers and cabinets will be closed when not in use. Full hazardous waste collection containers will be removed from the laboratory. Unneeded or unwanted reagents will be returned to the Chemistry Stockroom, as applicable. Spilled chemicals will be cleaned up immediately and disposed of properly.
3.5
Unattended Use of Equipment or Services Avoid leaving equipment running after hours if loss of service (electrical, water, vacuum) may result in hazardous conditions. If equipment must be left running after hours provide experiment shut down information to security staff. All beakers, flasks, and containers containing a chemical (hazardous or not) must be labeled with the full chemical name and primary hazard. To prevent water damage when water must be left running: − Ensure sink and drain are clear, pipes don't leak and tubing is secured with hose clamps. − Know where local shut-off valves are located. − Ensure that sink drains fast enough to accommodate water flow. Leave a note on the lab door stating the water is on and providing an emergency numbers and shut-down instructions in case of a leak or loss of water to the building.
3.6
After-hours Activities The principal investigator has listed laboratory-specific hazardous procedures in Appendix I. Do not conduct these procedures after-hours (evenings, weekends and during university vacations) without specific consent from the principal investigator. If a hazardous procedure is to be carried out after-hours: Prepare an emergency plan and have it approved by the principal investigator before starting the experiment. Make arrangements with others in the building to look in on you; or, tell security you are in the building and ask them to check in with you.
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3.7
General Safety Practices Wear appropriate eye wear all times in all laboratories; wear goggles when handling corrosive chemicals. Keep laboratory doors open when working alone. Keep doorways, halls, entrances and stairways clear; remove delivered or discarded goods from entrances at once. Keep floors dry; clean up water spills immediately. In general do not suspend or drape extension cords, rope, rubber tubing, etc. in areas and at heights which interfere with normal traffic. If this must be done flag the object. Do not lift or move heavy articles without help. Use correct lifting methods and use a hand truck to move them any distance. Avoid operating power tools when working alone. If they must be used, ask another person in the building to be on call in case of an accident.
3.8
Use of Special Laboratory Equipment 3.8.1 Systems Under Pressure Reactions under pressure will be carried out in an apparatus that is designed to withstand the full pressure of the system. All pressurized apparatus will have appropriate pressure relief devices. 3.8.2 System under a vacuum Use approved glassware for vacuum procedures. Do not apply a vacuum to glassware with flat surfaces except for desiccators and filter flasks. Use a metal safety shield or cloth wrapping when applying a vacuum to a desiccator. Wear safety goggles when doing vacuum distillations and freeze-drying; place a safety shield in front of the apparatus. 3.8.3 Centrifuge Place samples in centrifuge such that proper balance is achieved. Never open a centrifuge cover until spinning has stopped.
3.9
Use of Electrical and Mechanical Equipment When performing electrical work on equipment remove fuses (using fuse puller for cartridge fuses) and tag the switch box. Only the person who tags the switch may remove the tag. Disconnect the power supply to motors before adjusting belts or pulleys. Do not wear loose clothing (e.g. unbuttoned shirt sleeves, ties) when working around rotating equipment. Rotating shafts and couplings and exposed belts are hazardous; they should be covered with a guard whenever possible. Confine long hair in a net or pony tail when working with rotating equipment to prevent scalping. Avoid contact with electrical wiring or other fittings; electrical hazards greatly increase when any part of the body is grounded (e.g. in contact with piping or damp floors). Death has been caused by 110 volts to the grounded body. Page 16 of 99
3.10
Properly ground portable equipment; pay special attention to grounding when working in or around damp floors or pipes. Examine extension cords and leads before use. Do not use damaged cords (repair cords when necessary) or two wire cords. Discard two wire extension cords.
Use of Compressed Gas Cylinders IMPORTANT: If a compressed gas cylinder neck breaks, the cylinder becomes a torpedo and will instantaneously blast its way out of the building, through layers of cement block. This can be prevented by keeping cylinders chained in place, by keeping caps on cylinders, and taking the time to transport them correctly. Full, partial and empty cylinders must be used and stored vertically either in a cylinder holder or attached to walls or benches. Strap or chain cylinders in place. Keep valve protection caps on cylinders when not in service. Do not move a cylinder that has a regulator attached. When moving cylinders avoid dragging, rolling and/or sliding them. Use a hand truck even for moving cylinders short distances. Do not heat cylinders higher than 125 F (52 C). Do not let a flame come into contact with any part of a compressed gas cylinder. Do not refill one cylinder from another. Use gas cylinders containing toxic gases in a fume hood. Remove regulator, close valve and affix cap when taking a cylinder out of service; if empty, attach an "EMPTY" tag. 3.10.1 Ordering new Cylinders Cylinders are ordered and delivered by Air Gas. The user ensures that cylinders are chained as soon as received. If the cylinders must be moved more than several feet, a cylinder hand truck must be available. 3.10.2 Disposing Old Cylinders Contact Air Gas to request a cylinder pick-up. Cylinder pick-up will take place when deliveries are made.
3.11
General Chemical Handling Procedures NO MOUTH PIPETING!! Use a suction bulb or automatic pipet; use rubber tubing and a suction bulb to start a siphon. Containers of volatile liquids which have been warmed (e.g. by the sun) may be pressurized and thus splash when opened. Use a towel over the stopper or lid to catch the splash. Use insulated gloves when handling hot objects. Regard all chemical reagents and solvents as poisonous unless you have specific information to the contrary. Label storage and waste containers with the chemical name (or solution contents), your name and generation date.
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Attempt to identify the contents of unlabeled containers; if identification is impossible contact the EHS office for instructions. Store hazardous chemicals on low shelves. This includes, but is not limited to corrosive, toxic, and flammable materials. Remove chemicals from upper shelves using stool or step ladder in good repair. Report ladder or stool maintenance problems to the departmental safety officer. Do not pour chemicals into a bathroom sink or toilet. Do not use toxic solvents such as carbon tetrachloride and benzene as general purpose solvents outside the lab hood, whenever possible. Triple rinse inside and wash the outside of empty chemical containers before throwing into a waste container. Listed bottles should not be triple rinsed and cannot be thrown in the trash. (See Appendix B for EPA P-listed waste)
3.12
Safe Chemical Storage Every chemical container in the laboratory will have a definite storage place. It must be returned to that location after each use. Containers will not be left on the bench tops overnight. Do not store chemicals on desks, bench tops, or in hoods that are used for chemical manipulations. Storage trays or secondary containment will be used to minimize the spread of liquid material should a container break or leak. Chemicals will be stored by hazard class, not alphabetically. Incompatible materials should not be stored near each other, and preferably in different cabinets. At the very least acid will be separated from bases and flammables will be separated from oxidizers. For guidance on chemical storage, refer to Appendix C. Chemical containers will be inspected periodically. Worn or faded labels will be replaced. Unneeded or unwanted items will be returned to the department stock room or donated to the surplus chemical inventory (via EHS Manager). Deteriorated or unusable chemicals will be properly disposed by EHS. Chemical containers need to be dated when opened.
3.13
Handling and Storage of Specific Types of Chemicals 3.13.1 Flammable Chemicals All large quantities of flammables must be stored in a solvent storage room or vented "flammable" cabinet. o Definition of Flammability Class: Class I A : Liquids having a flash point below 73 F and have a boiling point below
o
100 F. Class I B: Liquids having a flash point below 73 F and have a boiling point at or above 100 F. Class I C: Liquids having a flash point at or above 73 F below 100 F.
Definition of Combustible Class:
Class II: Liquids having a closed cup flash point at or above 100F and below 140F Class III A: Liquids having a closed cup flash point at or above 140F and below 200F Class III B: Liquids having a closed cup flash point at or above 200F
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Maximum Quantity of flammables and combustibles allowed in labs (unsprinklered labs) In use and in storage Class of Flammable Liquid Class I A Class I B Class I C Class II Class III A Class III B
Liquid Gallons 30 60 90 120 330 13,200
Flammables needing refrigeration must be stored in an explosion-proof refrigerator marked with a label such as the following: “FLAMMABLES – KEEP FIRE AWAY” Flammables cannot be stored in a temperature controlled roomed. No flames or sparking materials should be in use when working with flammables. Flammable materials should never be heated or handled near hot surfaces or ordinary electrical equipment. Vapors produced from highly flammable materials may cause fire or explosion if contact is made. All equipment (ie. tools, motors) involved with the use of flammable materials MUST be spark-free. Any flammable chemical that emits harmful vapors MUST be used in a chemical fume hood to avoid respiratory irritation and injury. Keep work areas free of incompatible substances that may cause violent reactions with the material. These incompatibilities are listed on the MSDS's. Store only one days worth (or one gallon, whichever is less) of flammable materials in the laboratory.
3.13.2 Corrosive Chemicals Transport large bottles of concentrated acids from the stockroom to the laboratory in rubber carriers. When handling corrosive chemicals such as acids, and under the following conditions, wear goggles and a faceshield: − cutting/breaking alkali metals or solid caustics. − cutting yellow phosphorous. − handling strong acids or alkalis. − washing glassware with cleaning solution. − working with explosives, e.g. chlorates and perchlorates. − performing vacuum distillations. − working with dimethyl sulphate. − performing any work which may cause eye damage. Use appropriate gloves and acid aprons when handling strong acids or alkalis. Check gloves for holes before putting them on. Wash exterior of gloves before removing them. Page 19 of 99
3.14
To avoid violent reaction and splattering while diluting solutions, always pour the concentrated solution into the less concentrated solution while stirring (e.g. acid poured into water, not reverse). When diluting acid use a container which will not break due to the temperature rise which occurs during the mixing process. Skin and clothing contamination: immediately get into the drench shower, removing clothing as needed. Eye contact: rinse with gentle stream of running water (preferably at an eye wash station) for 15 minutes to clean and cool the eye. Skin contact: wash with soap and water; don't use burn ointment. In case of skin contact with fuming sulfuric acid quickly wipe off excess chemical if possible before washing with water. Any corrosive chemical that emits harmful vapors must be used in a chemical fume hood to avoid respiratory irritation and injury. Corrosive materials should never be heated or handled in fragile containers without providing a receptacle to catch the contents in case of collapse. Keep work area free of incompatible substances which may cause violent reactions with the material. Also work areas should be neat to provide comfortable, safe movements.
Toxic Substances Chemicals known to be highly toxic will be stored in well-ventilated areas in chemically resistant secondary containers. Only minimum working quantities will be present in the work area. Work with the substance in a fume hood. Containers of suspected carcinogens or acutely toxic chemicals will carry a label such as the following: “CAUTION – CARCINOGEN, CAUTION – HIGHLY TOXIC” and/or carcinogen label/icon affixed.
3.14.1 Specific Toxic Substances Mercury: Return used mercury to the stockroom; if mercury spills use powdered sulfur to convert small drops to mercury sulfide, or use the mercury spill kit if available. Bromine and/or Phenol: Prior to handling bromine or phenol, prepare a 50 percent ethylisopropyl alcohol solution to use if skin contact occurs. Use this solution to rinse and pack the burned area. Hydrofluoric Acid: Prior to handling hydrofluoric acid obtain a bottle of milk of magnesia [Mg(OH)2]; use this to rinse HF off the skin. HF burns are very serious, and damage done is long lasting and severe; burns must be treated immediately. NOTE: CALCIUM GLUONATE, the anecdote to hydrofluoric acid, should and must be available in the area when hydrofluoric acid is being used. Storage in plastic containers only.
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3.14.2 Toxic and/or Flammable Gases Store and use small cylinders (lecture bottles) in fumehoods; use fumehood precautions listed above. Do not remove health effect warning tags even if you believe the cylinder is empty. Do not remain in the vicinity of a toxic gas release unless you have the proper clothing and respiratory equipment 3.14.3 Highly reactive and explosive materials Examples of highly reactive materials includes: nitric acid, nitrates, permanganates, chromic acid cleaning solutions, peroxides, chlorites, chlorates, perchlorates, and perchloric acid.
Handle reactive, unstable and explosive chemicals carefully. Don't open containers which may contain explosive materials (e.g. picric acid) because the friction caused by turning the cap could cause an explosion. Oxidizers such as chlorates, chlorites and perchlorates form explosive mixtures with carbon sources such as sugar, charcoal, sawdust, shellac, and also with sulfuric acid, phosphorous, antimony and potassium cyanide. Heat, shock or friction (e.g. due to grinding) may set off an explosion. If explosive materials must be prepared prepare the smallest amount practicable. The misuse of reducing agents such as alkali metal hydrides, LiALH4, Raney nickel and Grignard reagent can cause explosion and fire hazards. Do not dispose of this type of material; leave disposal to someone who knows the hazards and regulations involved. Destroy small amounts of scrap sodium and potassium in a fume hood by dissolving in excess 95 percent ethyl alcohol in an oversize beaker. Ethers react with oxygen in air to form unstable peroxides which may detonate when concentrated by evaporation or distillation; when combined with other compounds; or when heated, shocked or subjected to friction. Use perchloric acid in a dedicated fume hood. Perchloric acid hoods should have have a wash down mechanism to clean the hood after each use. Contact EHS Manager prior to working with perchloric acid in a fume hood. Explosives, Peroxidizable Compounds, Extremely Flammable: No flames or sparking materials should be in use when working with flammable/reactive compounds. Flammable/reactive materials should never be heated or handled near hot surfaces or ordinary electrical equipment. Vapors produced from highly flammable materials may cause fire or explosion if contact is made. All equipment (ie. tools, motors) involved with the use of flammable/reactive materials MUST be spark-free, or intrinsically safe. Any flammable/reactive chemical that emits harmful vapors MUST be used in a chemical fume hood to avoid respiratory irritation and injury. Keep work area free of incompatible substances which may cause violent reactions with the material. These incompatibilities are listed on the MSDS's. Page 21 of 99
Due to the sensitivity to mechanical shock of most of these materials, they should not be used on vibrating surfaces and must always be handled with extreme care. Oxidizers: Store oxidizers away from organic materials. Air Reactive: Materials that are air reactive MUST be handled in atmosphere containing inert gases, with no oxygen. Water Reactive: Keep water reactive compounds away from water. Polymerizing Compounds: These materials must be kept under low temperatures 3.14.4 Peroxide Forming Chemicals Specific chemicals that can form dangerous concentrations of peroxides on exposure to air include cyclohexane, cyclooctene, decalin (decahydronaphthalene), pdioxane, ethyl ether anhydrous, diisopropyl ether, and tetrahydrofuran. A more extensive list of chemicals is located in Appendix D. Store peroxides away from organic materials. The quantity of peroxide forming chemicals purchased will be limited to the minimum quantity required. Unused material will not be returned to the original container. Containers of peroxide forming chemicals will be dated when opened, tested after 6 months, and disposed of before their expiration date. o A laboratory may keep their peroxide forming chemicals only if they laboratory performs weekly testing of the bottle for peroxides and documents each test on the container. o The following label can be obtained from EHS for your peroxides
o Laboratory has the ability and knowledge to stabilize the peroxide formation if the level exceeds 5 ppm and performs the stabilization. Peroxide forming chemicals will be stored at the lowest possible temperature consistent with their freezing point to prevent decomposition, but will not be allowed to freeze. Page 22 of 99
Laboratories who do not appropriately handle time-sensitive chemicals will be charged for disposal costs of untested and expired peroxide forming chemicals.
3.15 Chemical Carcinogens, Reproductive Toxins, Acutely And Extremely Toxic Chemicals (CCs, RTs, A/ETs) To the degree possible, glass pipettes or other sharp objects likely to become contaminated should not be used with CC's, RT's, or A/ET's. All personnel should wash their hands immediately after working with CC's, RT's, or A/ET's as well as before leaving the laboratory area. Keep work area free of incompatible substances which may cause violent reactions with the material. Also, area should be neat to provide comfortable, safe movements. These substances must be used and stored only in areas of restricted access. Use of these materials must be in a designated area, which is defined as a hood, glove box, portion of a laboratory, or an entire laboratory designated as the only area where work can be done with these chemicals. Any procedure involving the use of a volatile CC, RT, or A/ET or one whose manipulation is likely to generate an aerosol (solid or liquid) must never be done on the open laboratory bench. A designated area must be clearly posted with signs warning that a specific, extremely hazardous material is in use and that only those trained to work with it are allowed to enter the area while procedures using it are being done. The boundaries of the designated area must be clearly defined. Signage should read: CAUTION-POTENTIAL CANCER (REPRODUCTIVE) HAZARD AUTHORIZED PERSONNEL ONLY Maintenance or emergency personnel should be apprised of potential hazards in the laboratory before they enter the room. Please note: A designated area may be posted with a removable sign if work with extremely hazardous agents is not continuous in the laboratory.
Vapors or aerosols of CC's, RT's, or A/ET's produced by analytical instruments should be captured at the site of production by local exhaust ventilation or be vented through a chemical fume hood. Spill procedures must be developed and posted in the designated area. Staff should be familiar with and have available materials which will inactivate the extremely hazardous chemical. All surfaces on which CC's, RT's, or A/ET's are used or stored should be covered with an impervious material, e.g. stainless steel or plastic trays, or plastic-backed paper. The designated area must always be decontaminated when work is completed. Solid waste must be disposed of in hazardous chemical waste bags labeled with the name of the chemical used. Liquid wastes must be put into screw-top containers which are compatible with the chemical; the container must be labeled with the chemical name, and laboratory using it. Page 23 of 99
Overtly contaminated analytical equipment should be labeled as such and should not be used until decontamination has been effected. Any equipment requiring maintenance or repair work should be decontaminated first. The smallest amount of chemical that is required by the procedure should be used or stored; purchase orders must not be based on financial savings. Whenever possible, the required material should be ordered in amounts equal to that required in a given procedure, so that no weighing is necessary. Housekeeping procedures should be limited to those which suppress aerosol formation, such as wet mops or special vacuum cleaners supplied with a high efficiency particulate air (HEPA) filter on the exhaust. Dry sweeping or dry mopping must not be done. All vacuum services, including water aspirators, should be protected with an absorbent or liquid trap and a HEPA filter to prevent entry of any CC into the system. If a volatile CC, RT, or A/ET is used, a separate vacuum pump, placed in a chemical fume hood, should be used.
3.16
Working with Unknown Chemicals NEVER WORK WITH A CHEMICAL THAT IS NOT POSITIVELY IDENTIFIED. Since the properties as well as the material itself is unknown, the addition of any substance may cause a potentially dangerous reaction.
3.17
Prior Approval for the use of chemicals that have special handling or disposal The extreme hazards of some chemicals demand that special handling and disposal techniques be used. Before beginning any laboratory operation, the supervisor or instructor must review MSDSs for each chemical that they are unfamiliar with to determine precautions, waste disposal implications and methods. The use of this select group of chemicals will require prior approval of the EHS Manager before they are introduced and/or utilized in the laboratory setting. This will ensure that: The chemical and physical hazards associated with these chemicals are adequately assessed. Sufficient hazard/exposure control strategies and equipment are available for safe use of chemicals. Certain administrative procedures, such as the generation of hazardous wastes within the specified small quantity generator thresholds are maintained.
3.17.1 Chemicals Requiring Prior Approval They will be referred to as high hazard agents and processes (HHAP), and include but is not limited to acutely toxic materials, phyrophoric materials, air reactive materials, explosive materials, and high hazard processes. 3.17.2 Other materials requiring prior approval Lab supervisors/researchers may wish to employ activities, not specifically covered by the CHP, which may require prior approval from University offices. These activities include: The use of live animals: contact the Chair of the Animal Care & Use Committee. The uses of radiation generating equipment or radioisotopes: contact the Radiation Safety Officer. Use of radioactive materials or radiation generating Page 24 of 99
equipment must be in accordance with Clarkson’s license and the New York State Department of Health Regulations. Biological agents (pathogens), including select agents: contact the Biosafety Officer or Chair of the Biosafety Committee. Controlled Substances (including Iodine): contact the Chemical Hygiene Officer. 3.17.3 Approval Procedure for high hazard agents and process. If chemicals are very hazardous or the material is used in large quantities then special approval is required. Laboratory workers planning to use a HHAP must first receive explicit written approval from their Principal Investigator and EHS Manager. The following steps must be taken: 1. Laboratory workers must complete a High Hazard Agents and Process Approval form, which is located in Appendix E. Information required on the form includes: Identity, physical characteristics, and health hazards of the substances involved Consideration of exposure controls such as fume hoods, glove boxes and personal protective equipment Designation of an area (hood, glove box, portion of lab, entire lab) specifically for experimental procedures with the substances involved Plans for storage and secondary containment Procedures for safe removal of contaminated waste Decontamination procedures 2. The laboratory worker submits the form to the EHS Manager for review and approval. 3. The area where the HHAP will be used should be posted as a designated area. Signs for this purpose are available through EHS or may be made by the department or laboratory worker, as long as it includes the following information: DANGER DESIGNATED AREA for ______________________________ AUTHORIZED PERSONNEL ONLY 4. The laboratory worker proceeds with the experiment, following the practices outlined in the High Hazard Agents and Process Approval form, as well as the appropriate work practices outlined in this manual and written in the laboratoryspecific procedures. All work is conducted within the Designated Area. 5. The laboratory worker decontaminates all equipment and disposes of waste promptly, as outlined in the High Hazard Agents and Process Approval form. 3.17.4 Working Safely with HHAPs The increased hazard risk associated with HHAPs calls for more strict operating procedures in the laboratory: Work Habits Page 25 of 99
Principal Investigators PI must ensure that the research staff fully understand how to complete the procedure or process, including going over the hazards of the material or process and emergency procedures. There should be no eating, drinking, smoking, chewing of gum or tobacco, application of cosmetics or storage of utensils, food or food containers in laboratory areas where high hazard agents are used or stored. All personnel should wash their hands and arms immediately after the completion of any procedure in which a high hazard agent has been used and when they leave the laboratory. Each procedure should be conducted with the minimum amount of the substance, consistent with the requirements of the work. The laboratory worker should keep records of the amounts of each highly hazardous material used, the dates of use and the names of the users. Work surfaces, including fume hoods, should be fitted with a removable liner of absorbent plastic-backed paper to help contain spilled materials and to simplify subsequent cleanup and disposal.
Personal Protective Equipment HHAPs may require more stringent use of personal protective equipment. For substances, check the MSDS for information on proper gloves, lab clothing and respiratory protection. Proper personal protective equipment must be worn at all times when handling the high hazard agent or performing the high hazard process. Lab clothing that protects street clothing, such as a fully fastened lab coat or a disposable jumpsuit, should be worn when HHAPs are being used/performed. Laboratory clothing used while manipulating high hazard agents should not be worn outside the laboratory area. When methods for decontaminating clothing are unknown or not applicable, disposable protective clothing should be worn. Disposable gloves should be discarded after each use and immediately after overt contact with a high hazard agent. Ventilation/Isolation Most high hazard agent work should be performed in a fume hood, glove box, or other form of ventilation. If the chemical may produce vapors, mists or fumes, or if the procedure may cause generation of aerosols, use of a fume hood is required. A fume hood used for high hazard agents must have an average face velocity of between 95 and 125 feet per minute. This measurement is noted on the hood survey sticker. If the hood has not been inspected within the past year, contact EHS at 8-5294 for re-inspection before using the hood. A glove box should be used if protection from atmospheric moisture or oxygen is needed or when a fume hood may not provide adequate protection from exposure to the substance; e.g., a protection factor of 10,000 or more is needed. Highly toxic gases must be used and stored in a vented gas cabinet connected to a laboratory exhaust system. Gas feed lines operating above atmospheric pressure must use coaxial tubing.
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Storage and Transportation Stock quantities of high hazard agents should be stored in a designated storage area or cabinet with limited access. Additional storage precautions (i.e., a refrigerator, a hood, a flammable liquid storage cabinet) may be required for certain compounds based upon other properties. Containers must be clearly labeled. Double containment should also be considered. Double containment means that the container will be placed inside another container that is capable of holding the contents in the event of a leak and provides a protective outer covering in the event of contamination of the primary container. Containers should be stored on trays or pans made of polyethylene or other chemically resistant material. Persons transporting high hazard agetns from one location to another should use double containment to protect against spills and breakage. Vacuum Lines and Services Each vacuum service, including water aspirators, should be protected with an absorbent or liquid trap to prevent entry of any high hazard agent into the system. When using volatile high hazard agents, a separate vacuum pump should be used. The procedure should be performed inside a fume hood. Decontamination and Disposal Contaminated materials should either be decontaminated by procedures that decompose the high hazard agent to produce a safe product or be removed for subsequent disposal. All work surfaces must be decontaminated at the end of the procedure or work day, whichever is sooner. Prior to the start of any laboratory activity involving a high hazard agent, plans for the handling and ultimate disposal of contaminated wastes and surplus amounts of the high hazard agent should be completed. EHS can assist in selecting the best methods available for disposal. 3.18
Format To Prepare Laboratory Specific Procedures The principle investigator should develop laboratory specific procedures for operations performed in their laboratory. If the operation is common to other labs it is requested that a copy of the specific procedure(s) be forwarded to the Environmental Health and Safety Office, Box 5563. Laboratory Specific Procedures should be included in Appendix I of this manual.
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3.18.1 Example of a Laboratory Specific Procedure NAME OF LABORATORY TO WHICH THIS APPLIES: Biology Lab, Room 412 Science Center NAME OF HAZARDOUS ITEM:
syringes, needles, scalpels, sharps. This includes gas chromatography syringes.
DESCRIPTION OF HAZARD:
needle sticks, cuts and scratches can cause and spread infection such as staph, hepatitis and AIDS.
SPECIAL INSTRUCTIONS: Do not re-sheath needles. Handle sharps carefully such that you or others are not stuck or scratched. When ready to dispose of sharps, DO NOT RESHEATH; DO NOT THROW INTO GENERAL WASTE! Always dispose of sharps in special "sharps" containers which should be present in the lab. When the container appears close to full, inform the laboratory director so that new containers can be ordered.
RESTRICTIONS ON USE OF ITEM: All orders for syringes must be placed with the Syringe Officer, the name of whom can be provided by the Industrial Hygiene and Radiation Safety Office. DO NOT remove syringes from the laboratory even for use in another laboratory. Each laboratory that uses syringes should order their own, through the Syringe Officer, so that use of syringes can be tracked.
PREPARED BY:
Alan Rossner, PI
DATE: January. 2010
4.0 Controlling Chemical Exposures 4.1 Hazard Communication (further information can be found in Clarkson’s Hazard Communication Program) 4.1.1 Material Safety Data Sheets Material Safety Data Sheets(MSDS) must be available to all employees upon request per 29CFR1910.1200 OSHA Hazard Communication Standard. A complete inventory of MSDSs for all materials on campus is maintained at the Physical Plant Building. Each lab must have a binder containing MSDSs of the chemicals and materials in that laboratory and made available to the workers in that lab. Each lab should establish a procedure and ensure all people working in the lab are adequately informed of the location of the MSDSs as well as the information provided on them.
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Do not wait until a chemical spills to obtain an MSDS, if the lab is using a new material then MSDS should be obtained and reviewed with people who will be handling the material! The following is a list of locations where MSDSs can be obtained. Online access: Several addresses are listed below and additional addresses can be found on the world wide web (WWW) o SIRI MSDS Index: www.siri.org o List of Toxic Chemical Resources: http://consumerlawpage.com/resource/toxicr.shtml o List of MSDS Resources: http://uuhsc.utah.edu/pharmacy/rxweblinks/rxlink27.html Physical Plant Original copies: Buildings and Equipment Maintenance x 6439 Labs in the Science Center: o Science Center Room 131 – MSDS File Cabinet. The Chemistry Department and Chemistry T.A.s have keys to this room. o Chemistry Stock Room located on the Second Floor of the Science Center, Room 240. Please attempt to obtain an MSDS from the other listed sources before requesting them from the Chemistry stock room. Emergency Access After Hours: Contact Security to request an MSDS after hours. 4.1.2 Chemical Labeling It is the responsibility of each laboratory supervisor to ensure that laboratory workers label all chemical containers. Most incoming containers are labeled by the manufacturer. However containers, such as transfer containers, need to be labeled appropriately by the user. It is the responsibility of all workers in the laboratory to ensure the label remains legible. If a label becomes difficult to read, the laboratory worker must re-label the container. Each container must be labeled with the identity of the substance and the appropriate hazard warning. Containers that need to be labeled included, but is not limited to: Transfer containers Beakers Flasks Experiments left running without supervision, including during lunch break, when leaving to go to class or a meeting, or left running overnight (any container of liquid or solid) Any container not used during the work shift Once a container is emptied, the label should be removed prior to disposal of the container or reuse of the container. If a container is left unlabeled and a chemical determination cannot be made, EHS will contract a hazardous waste company to test and dispose of the material at a cost to the Faculty member of that laboratory. Page 29 of 99
4.1.3 Training All researchers must complete laboratory safety orientation prior to commencement of work with hazardous materials. All researchers, no matter what material handling, must complete a training course that includes, but is not limited, to Hazard Communication, Fire Safety, and Emergency Response. The Orientation course is provided by the Environmental Health & Safety Manager, however it is not the only training that should be completed by the researcher. Faculty should ensure further training is completed in the laboratory on laboratory specific hazards and procedures. A record of those trainings should be recorded in Appendix J. 4.2 Routes of Exposure The basic routes for a chemical to enter the body in a laboratory setting are: inhalation, skin and eye contact, ingestion, and injection. The prevention of entry by one of these routes can be accomplished by control mechanisms such as engineering controls, personal protective equipment, and administrative controls. Each route can be minimized by a variety of control measures depending on the hazard and operation. 4.2.1 Inhalation Inhalation of hazardous chemicals is the most common route of entry to the body in laboratory operations. There are permissible exposure limits (PELs) set-forth by the OSHA (http://www.osha.gov/pls/oshaweb/owadisp.show_document?p_table=STANDARDS &p_id=9992). The American Conference of Governmental Industrial Hygienists (ACGIH) publishes annual lists of Threshold Limit Values (TLVs) and Short Term Exposure Limits (STELs) for common chemicals and biological agents used in the laboratory. These values are guides, not legal standards that are more current, and are defined as follows: TLV: Time-weighted average concentration for a normal 8-hour workday to which nearly all workers may be repeatedly exposed without adverse effects. STEL: Maximum airborne concentration to which workers can be exposed for periods of up to 15 minutes. Such exposures should be limited to no more than four per day with at least 60 minutes between exposures; and the total timeweighted average should not exceed the TLV value. To avoid significant inhalation exposures and to limit exposure to concentrations above TLVs or OSHA’s PELs values, there are a number of control measures that can be used. Substituting a less toxic or less volatile chemical is the most desirable measure. If substitution is not practical, ventilation will be used to reduce exposure. All hazardous chemicals should be used in a properly functioning chemical fume hood. For extremely toxic substances, such as those classified as poison inhalation hazards by the Department of Transportation, the use of closed systems such as a glove box may be required. See also Section 4.3 on engineering controls. If necessary, respiratory protection will be worn to limit chemical exposures, however, airborne concentration must be determined. The EHS Manager must be Page 30 of 99
contacted prior to any use of a respirator or dust mask. Respirators will not be worn without first meeting the requirements of the OSHA Respirator Standard 29 CFR 1910.134. See Clarkson’s Respiratory Protection Program for more information. 4.2.2 Skin and Eye Contact Contact with the skin is a frequent mode of chemical injury. To reduce the risk of chemicals entering the body via skin or eye contact, controls include substitution and ventilation as described above. If this does not control the exposure the next step is wearing personal protective equipment such as gloves, eye protection, lab coats, aprons, appropriate shoes, and special protective equipment as required by the specific hazard present. The laboratory supervisor should consult reference to determine the proper protective material for the chemicals being used. Administrative controls to reduce skin/eye contact exposure include: Establishing hazardous and non-hazardous areas in the laboratory. Enforcing sound chemical hygiene procedures such as no eating or drinking in the lab and washing hands and face after handling chemicals. 4.2.3 Ingestion Most of the chemicals used in the laboratory are toxic if they enter the body via ingestion. The relative toxicity of a chemical can be determined by its LD50, which is the quantity of material that a single does will cause the death of 50% of the test animals. It is usually expressed in grams or milligrams per kilogram of bodyweight. Ingestion should not be a route of exposure in a laboratory setting. The best way to eliminate exposure by ingestions is to limit actual contact with all chemicals. Wear gloves and practice good hygiene measures. Food and drink will not be stored or consumed in areas where chemicals are being used or stored. Label all chemical containers, and replace worn or faded labels as-soon-as-possible. Liquid chemicals will not be pipetted or siphoned by mouth. The appropriate apparatus will be used to perform this function. 4.2.4 Injection Exposure to chemicals by injection seldom occurs in the chemical laboratory. Attention to detail and adherence to general standard operating procedures will provide control against accidental injection exposure. Red sharps containers will be used to collect all used needles and syringes. Separate collection containers will be used to collect broken glass. Label the containers, “CAUTION – Broken Glass.” Upon request, the CHO will assist with exposure evaluations for any suspected exposures to substances used in the laboratory. Records of exposure evaluations and exposure monitoring will be maintained at the Environmental Health and Safety Office.
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4.3 Engineering Controls If special engineering controls are required for special tasks in your laboratory all employees shall be trained on how to use the controls properly and all equipment shall be evaluated to ensure it is controlling the hazard. Please document the engineering controls, including: Performance Criteria Test Methods and Frequency List of Safety Equipment Audit Criteria and Frequency 4.3.1 Use of Chemical Fume Hoods and Examples Laboratory operations involving toxic, hazardous or odoriferous materials must be conducted within the hood. Air flow into the hood mixes with emitted contaminants and carries them out the duct. Successful containment minimizes fugitive emissions from the hood. This protects the lab worker and keeps background levels of contaminants in the lab to acceptable concentrations. Some hoods have been designated for special purposes, such as, radioisotope hoods or perchloric acid hoods. Specific design and procedures for perchloric acid hoods are required due to the potential danger related to the possible accumulation of perchlorates. No hood provides perfect containment of materials emitted within the hood. It is always possible to improve hood performance, but perfection is not possible. Therefore, people working in laboratories will be exposed to materials they handle and use. The goal is to minimize that exposure, given constraints of technical and financial feasibility. A fume hood must be utilized whenever flammable, toxic or offensive vapors are a hazard. The best ventilating efficiency is attained with the hood sash closed far enough so as to obtain an air velocity of 120 linear feet per minute. Keeping all items six inches behind the sash line and minimizing the quantity of equipment within the hood area will greatly improve the exhaust effect. The operating condition of a hood should be determined before the hood is put to use. 1. Use for operations which use or release toxic chemical vapor or dust, or which have fire or explosion potential. 2. Don't use for long-term chemical storage. 3. As a rule of thumb: handle chemicals with a PEL less than 50 ppm in a hood. 4. Confirm adequate hood ventilation before starting the experiment using a paper flag or smoke stick. 5. Keep hood closed or with a 2" opening (according to the building ventilation requirements) except when making adjustments in the hood. 6. Place bulky equipment on platforms inside hood to allow flow of air underneath; this provides for smooth flow of air in the hood. 7. Remove unneeded equipment and chemicals to ensure smooth air flow. 8. Report malfunctioning hoods to lab instructor or supervisor. Page 32 of 99
9. In some buildings hoods must be left on at all times because they are part of the building ventilation system. In other buildings hoods can be turned off, but only if they do not contain chemicals. 10. Sash must be at an equivalent height as the person using it. Head should never be entered inside of the hood. Face Velocity Several governmental and industry organizations have adopted fume hood safety standards. These standards are designed to measure a fume hood’s ability to contain fumes. They are based on a measurement of the speed at which laboratory air enters a fume hood's face opening, i.e. face velocity. The intent of these standards is to designate face velocities that are high enough to contain fumes but not so high as to cause air turbulence between a hood's face and a worker. Below is a list of some standards organizations and the face velocities they require: OSHA: "...airflow into and within the hood should not be excessively turbulent...; hood face velocity should be adequate (typically 60-100 feet per minute)..." National Research Council: Recommends face velocities between 80 and 100fpm. 120fpm is recommended for substances with very high toxicity or where outside influences adversely influence hood performance. Face velocities approaching or exceeding 150fpm should not be used. NFPA (National Fire and Protection Agency): Section 6-4.5 states, "Face velocities of 0.4 m/sec to 0.6 m/sec (80 fpm to 120 fpm) generally provide containment if the hood location requirements and laboratory ventilation criteria of this standard are met." Typical Testing Procedure 1. Position the sash so that the fume hood opening is 18 inches. 2. Puff smoke around the opening of the hood by using the Ventilation Smoke Tubes. No smoke should come out of the hood. 3. Divide the fume hood opening into nine squares. 4. Turn the Alnor thermoanemometer to the Temperature position to check the battery. The reading must be 1, if 0, recharge the battery. Turn the Alnor now to the Velocity position. 5. Measure the velocity of the air at the center of each of the nine squares. This is accomplished by placing the probe of the Alnor at the center of the square. 6. Put the sash at a six inch open position. 7. Divide the fume hood opening into three squares. 8. Follow step 5 above for the three measurements.
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Determining Whether to Pass a Hood The following three conditions must all be met in order for the hood to pass: 1. The average face velocity with the sash at an opening of 18 inches must be a minimum of 100 fpm. 2. The average face velocity with the sash at an opening of six inches cannot be greater than 300 fpm. 3. Smoke cannot come out of the hood. Clarkson Maintenance staff performs fume hood inspections on an annual basis. All conventional hoods and specialty hoods are inspected individually. After initial postinstallation checks, the Maintenance Department will annually inspect fume hoods for the following: average face velocity of the hood with the sash fully opened Average face velocity of the hood with the sash half open smoke test to determine air flow patterns and leakage placement of airflow indicators in hood survey hood condition for spills, airflow blockage, and disabled sash stops If the fume hood is not functioning properly, the Maintenance Supervisor is informed for an immediate assessment. 4.3.2 Perchloric Acid Chemical Fume Hoods Perchloric acid is a very strong oxidizer. If it is used to digest organic materials or heated above ambient temperature, perchloric acid vapors may be produced. These vapors can condense to form explosive perchlorates in the hood, duct work or fan. For this reason, perchloric acid chemical must be used in a chemical fume hood dedicated to this chemical. 1. NFPA 45 Laboratory Ventilation Systems and Hood Requirements. This standard requires that if perchloric acid is heated above ambient temperature and the vapors are not scrubbed or trapped before entering the lab hood or it is exhaust system, a separate hood will be provided, designed for use with perchloric acid only. The lab hood will be labeled “Perchloric Acid Operations Only”. 2. Organic will not be used in the designated lab hood. 3. The lab hood and exhaust system will be tested for perchlorates prior to maintenance operations. 4. A water spray system will be provided for wash down of the exhaust system. The wash down should be performed following each use or at the end of the day. Cold water wash down sprinklers can be dispersed throughout the system to provide adequate wash down. 4.3.3 Biosafety Cabinets (Tissue Culture Hood) A conventional fume hood should not be used for work with viable biological agents. A biosafety cabinet is specially designed and constructed to offer protection to both the worker and the biological materials. Similarly, a biosafety cabinet should generally not be used for work with hazardous chemicals. Most biosafety cabinets exhaust the contaminated air through high Page 34 of 99
efficiency particulate air (HEPA) filters back into the laboratory. This type of filter will not contain most hazardous materials, particularly gases, fumes or vapors. Even when connected to the building exhaust system, a ducted biosafety cabinet may not achieve a face velocity of 95 - 125 feet per minute, making it inappropriate for use with hazardous chemicals. Biosafety Cabinets are inspected annually by an outside contractor. 4.4 Administrative Controls Employing administrative controls is the most desirable method for controlling chemical exposures and must be used whenever plausible. Administrative controls include but are not limited to: Hazard information and education. Substitution of non-hazardous or less hazardous chemicals, procedures, or equipment. Reducing the volumes of experiments or quantities used. Control and minimize individual exposure times. Rotate responsibilities. Restrict access to an area where a hazardous chemical is in use. Conduct operations that produce nuisance odors outside of typical hours. Place proper signs on doors to indicate the hazards within and the name and phone numbers of appropriate individuals to contact in an emergency. 4.5 Personal Protection Equipment (PPE) The Environmental Health & Safety Department (ext. 6640) provides information to employees on appropriate protective equipment from hazardous and/or toxic substances per OSHA’s personal protective equipment standard, 29 CFR 1910.132. The use of PPE alone should not be relied on to provide protection against hazards. Engineering and administrative controls described above shall be used in place of PPE whenever possible to eliminate or reduce hazards. If potential hazards still exist after all feasible engineering and administrative controls are in place, PPE shall be used in conjunction with engineering and administrative controls to protect employees. 4.5.1 Hazard Assessment OSHA requires that a hazard assessment for PPE be conducted before assignment. A template to use when conducting the lab hazard assessment can be found in Appendix K: Hazard Assessment Tool. The purpose of a hazard assessment is to determine whether hazards are present or likely to be present in the workplace which would require the use of PPE. If such hazards are present, or are likely to be present, Clarkson University shall: 1. Select the appropriate type of PPE that will protect employees from the hazards identified. 2. Communicate PPE selection decisions to each affected employee. 3. Provide PPE that properly fits each affected employee. 4. Conduct and document appropriate employee training in the use and limitations of the equipment provided.
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Clarkson University laboratory managers/supervisors are responsible for conducting Hazard Assessments in their designated areas with assistance provided by the Environmental Health and Safety Department when needed. Each of the basic hazards will be reviewed and a determination made as to the type, level of risk, and seriousness of potential injury. Consideration will be given to the possibility of exposure to several hazards at once. The general procedure for determining appropriate protective equipment is to: 1. Identify the potential hazards and the type of protective equipment that is available, and what protection it provides (i.e., splash protection, impact protection, etc.). 2. Compare the capabilities and limitations of various types of PPE with the hazards associated with the environment (e.g., sharp or rough materials, vibration, projectiles, radiation intensities). 3. Select the PPE which provides a level of protection greater than the minimum required to protect employees from the hazards. 4. Select PPE that will fit each employee properly and provides protection from the hazard. Hazard Assessment Hazard Type
Examples of Hazard
Common Related Tasks
Impact
Chipping, grinding, machining, masonry Flying objects such as large work, wood working, sawing, drilling, chips, fragments, particles, chiseling, powered fastening, riveting and sand and dirt. sanding.
Heat
Anything emitting extreme heat.
Furnace operations, pouring, casting, hot dipping, and welding.
Chemicals
Splash, fumes, vapors and irritating mists.
Acid and chemical handling, degreasing, plating and working with blood.
Harmful dust.
Woodworking, buffing and general dusty conditions.
Radiant energy, glare and intense light.
Welding, torch-cutting, brazing, soldering and laser work.
Dust Optical Radiation
Reference: http://www.osha.gov/SLTC/etools/eyeandface/ppe/selection.html
4.5.2 Clothing An employee's appearance and dress should be appropriate to the work setting and specific departmental operations. Employees who work in a laboratory setting must:
Most PPE is designed to protect against a specific type of hazard (e.g., chemical permeation, particulate filtration), and will not protect against other types of hazards Page 36 of 99
that may be present in a work environment. For this reason, it is important to always be aware of all hazards that may be encountered and know the types of protective equipment available, its limitations and how to properly use it for each job. If you have questions about the type of protective clothing required for your work, please consult with the applicable Safety Data Sheets (SDSs) or contact the Environmental Health and Safety Department at ext. 6640. Wear laboratory coats at all times when conducting research or working in a research area where there is the potential for the skin to be exposed to chemicals and/or other hazards in the laboratory. Similarly, appropriate gloves and eye and face protection must be worn for the hazards present in each laboratory. Protective clothing, such as rubber aprons and sleeve covers, must be worn when working with highly hazardous and/or toxic or corrosive materials. When working with flammable materials, a flame-resistant lab coat should be worn. It is recommended that synthetic materials not be worn when flammable materials are in use. When infectious materials are present, closed lab coats and gloves are essential. Shorts and other above-the-knee summer apparel are not permitted. Additionally, if you are working with hazardous chemicals, you should dress in a manner that reduces the risk of skin injuries on legs. Shoes must provide safe and secure footing and offer protection from hazards. Flipflops, sandals, open-toed and open-weave shoes are not permitted because of the danger of spillage of corrosive or irritating chemicals. Low-rise shoes with fully enclosed uppers, ankle collars and toe box are recommended. Confine long hair, loose clothing and dangling accessories that could get caught in laboratory machinery or interfere with experiments (e.g., ties, strings, wide sleeves). Finger rings or other tight jewelry which is not easily removed should be avoided because of the danger of corrosive or irritating liquids getting underneath the piece and producing irritation. Carefully inspect all protective equipment before use to ensure that the equipment provides a safe level of protection. Do not use defective equipment. Do not wear laboratory coats, gloves and/or other protective equipment in lunch rooms, conference rooms or break rooms. Do not wear gloves in elevators.
4.5.3 Hand Protection Employees shall wear appropriate gloves to protect their hands from chemicals which may be absorbed through or damage the skin, objects which may cut or puncture the skin, biological agents, human or animal tissues, radioactive materials, or any other hazard which may cause illness, injury, or impairment. There is no one glove that will protect against all workplace hazards. Gloves should be chosen according to the nature of the hazard(s) and the type of work performed. Always wash your hands between changing gloves and after completing work.
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Glove Selection and Permeability Gloves used for handling chemicals and liquids should be chosen based on the resistance to the specific solvents or compounds being used. It is also important to remember that permeation of glove materials is dependent upon glove thickness and the duration and extent of exposure. Test gloves for leaks before working with allergenic, sensitizing or hazardous and/or toxic chemicals. It’s also important to realize that the permeation resistance of chemical resistant gloves may be compromised by exposure to heat or cold, periods of long storage, minute punctures cause by handling rough or sharp items, etc. Nitrile rubber
Polyvinyl Alcohol (PVA)
Polyvinyl Chloride (PVC)
Neoprene
Natural rubber or latex
Permeated by some common solvents, such as acetone, acetonitrile, dioxane, ethyl acetate, and methylene chloride. Permeated by chloroform and phenol. Permeated by corrosives such as nitric and sulfuric acids. Permeated by nitrogen containing materials such as anilines, amines, nitrates, and nitrites. Permeated rapidly by chemicals containing a hydroxyl group (–OH) such as phenol, alcohols, glycols, ammonium hydroxide, and water. Resists many chlorinated hydrocarbons such as methylene chloride, and aromatic hydrocarbons such as toluene and xylene. Permeated by nearly all chlorinated hydrocarbons, including methylene chloride, chloroform, and carbon tetrachloride. Provides some resistance against corrosive materials. Permeated by nearly all chlorinated hydrocarbons, including methylene chloride, chloroform, and carbon tetrachloride. Permeated by xylene, dioxane, and tetrahydrofuran. Offers the best barrier protection for moderate to high-risk instances when exposure to blood or body fluids is a concern. Protect against chemicals like methanol and acetone and cleaning products like bleach and ammonia. Must be mindful of possible latex-allergy concerns.
Butyl rubber
Offers the highest degree of protection to most organic solvents. Permeated by hexane, methylene chloride, tetrahydrofuran, and toluene within 30 minutes.
Viton
Offers a greater degree of protection to hexane, methylene chloride, and toluene than butyl rubber.
For more information about selecting an appropriate glove type, refer to the Safety Data Sheet (SDS), a chemical resistant and permeation chart such as the one provided by Best Glove (http://www.bestglove.com) or Ansell (http://www.ansellpro.com/download/Ansell_7thEditionChemicalResistanceGuide.pdf) or contact the Environmental Health and Safety Department at ext. 6640. Page 38 of 99
Thermal Protection Thermally insulated gloves are designed to protect the hands from intense heat (e.g. glass washing) or cold (cryogenics), and should not be assumed to offer any protection against chemical permeation. Other Hand Protection Gloves used when dealing with sharp objects should be cut and puncture resistant. Abrasion resistance gloves may be desirable for certain tasks. Many glove charts include this information. 4.5.4 Eye and Face Protection Appropriate eye and/or face protection is required whenever there is a potential for hazardous materials to come in contact with the eye and/or face from flying particles, molten metal, liquid chemicals, acids or caustic liquids, chemical gases or vapors, or potentially injurious light radiation. Examples of such include safety glasses, goggles and face shields. All protective eye and face devices must comply with the requirements set forth in the American National Standard for Occupational and Educational Eye and Face Protection (ANSI) Z87.1 standard. This applies not only to persons who work continuously in these areas, but also to persons who may be in the area only temporarily, such as maintenance or clerical personnel. Safety Glasses At minimum, ANSI-approved safety glasses and/or goggles are required to be worn when working with any hazardous materials, or when there is a risk of splashing, irritating mists, vapors, fumes, or flying projectiles. Ordinary prescription glasses are not designed to provide adequate protection against occupational hazards. Prescription safety glasses are recommended for employees who must routinely wear safety glasses in lieu of fitting safety glasses over their personal glasses. Clarkson University will absorb one third the cost of prescription safety glasses for any permanent employee whose job duties make the wearing of prescription safety glasses advisable. Employees are permitted to purchase one pair every two years. Employees need to ensure that the frames and lens meet ANSI-Z87 standards. Please consult with your optician prior to purchasing the glasses to make sure they will qualify as prescription safety glasses and meet the ANSI Z87.1-1989 standard. Proof of this will be necessary in order for the University to reimburse an employee. Please bring proof of purchase and proof of ANSI-Z87 compliance to the Human Resources Department. Safety Goggles Safety goggles will provide a greater degree of protection than safety glasses by providing a tighter fit against the face. Safety goggles or face shields should be worn whenever there is an elevated risk of a chemical splash or flying projectiles. Laser Safety Goggles When working in designated laser areas, proper eye protection suitable for the specific laser type involved is necessary. The correct choice of optical density and color is based on the wavelength and power of the specific laser being used. Refer to the Clarkson University Laser Safety Program for guidance. Page 39 of 99
When working in areas that will produce intense ultraviolet light, goggles or a face shield with filter plates or tinted glass must be worn. These operations include, but are not limited to, arc welding, arc cutting, and laser use. Glasses with suitable filter lenses can be used in less intense applications, such as light gas welding operations, torch brazing, and inspection. Face Shield When working with a corrosive liquid, dispensing liquefied nitrogen, or where appropriate, a face shield shall be worn to protect the chin, neck, face and ears. Face shields will supply added protection from flying particles and liquid splash. To gain maximum protection against chemical splash, a face shield should be used in conjunction with safety glasses. Welding Shield Welding shields protect an individual’s eyes from burns caused by infrared or intense radiant light as well as protect the face and eyes from flying sparks, metal spatter, and slag chips produced during welding, brazing, soldering, and cutting. The shield is typically constructed of vulcanized fiber or fiberglass and fitted with a filtered lens. General Ordinary prescription glasses are not designed to provide adequate protection against occupational hazards. Prescription safety glasses that meet ANSI Z87.1 are recommended for employees who must routinely wear safety glasses in lieu of fitting safety glasses over their personal glasses. All safety glasses should have side shields. At minimum, approved safety glasses and/or goggles shall be worn when working with hazardous materials. Wearing of contact lenses is discouraged when working with hazardous materials. Persons who wear contact lenses are at greater risk for prolonged exposure and potentially permanent eye injury in the event of a chemical splash, since some chemicals can be absorbed into the contact lens and make it harder to remove. Using contaminated fingers to remove contacts in a stressful splash situation represents further exposure risk. If contact lenses are worn when working with hazardous materials, safety glasses (at a minimum) must be worn to protect the eyes, and safety goggles are encouraged. 4.5.5 Respirators Whenever exposure to airborne material or concentrations of gases and vapors by inhalation is likely to exceed the action level or threshold limits described in corresponding material safety data sheets (MSDSs) and safety data sheets (SDSs), work must be conducted in a chemical fume hood, glove box, or similar local exhaust ventilation. When these measures are not feasible or insufficient in establishing a safe work environment, appropriate respirators should be worn by workers. Consult with the Environmental Health & Safety Department before using a respirator. All employees who wear respirators must comply with and be included in the Clarkson University Respiratory Protection Program, which includes requirements for medical clearance, fit testing, and training prior to wearing any airpurifying respirator per the OSHA Respiratory Protection standard, 29 CFR 1910.134. 4.5.6 Radiation Protection
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Refer to the Clarkson University Radiation Safety Program for information on types of PPE to protect against radiation. 4.5.7 Maintenance and Disposal of PPE Some types of PPE offer indicators of when they are reaching the end of their effectiveness, but many do not. Hazardous environments are not always indicated by an odor or by visible particulates, so it is important that end of service indicators, or lack thereof, are understood for each item of PPE worn. Before wearing any item of PPE, it should be inspected for defects or signs of wear. Massproduced chemical resistant gloves may have defect rates of up to ten percent, so it is important to always inspect gloves closely before donning them. Most chemical resistant gloves (aside from thicker gloves used for larger scale operations) should be considered to be disposable, and only worn once. PPE that is potentially contaminated with infectious biological material must be disposed of in biohazardous waste containers and certain types may require disposal as hazardous waste. For example, air-purifying respirator cartridges used to protect against environments containing lead or cadmium dusts may require such disposal. Consult with the Environmental Health and Safety Department (x6640) for PPE disposal questions. 4.5.8 Training Once the proper PPE for each process/equipment has been selected, employees must be trained on the PPE. At a minimum, each employee using PPE must know: 1. 2. 3. 4. 5. 6. 7. 8.
The nature and extent of hazard(s) present for each process the employee operates When PPE should be worn What PPE is necessary Use and limitations of the PPE How to properly inspect, don, doff, adjust and wear the PPE How to determine if PPE is no longer effective or is damaged How to get replacement PPE How to properly care for, maintain, store, and dispose of the PPE
Retraining of employees is required whenever: 1. Changes in the workplace render the previous training obsolete 2. Changes in the type of PPE render previous training obsolete 3. Employer observed inadequacies in an employees' knowledge or use of assigned PPE indicates that an employee has not retained the necessary understanding or skill Failure to comply with Clarkson University’s PPE requirements can result in employee injury, injury of others nearby and/or OSHA citations and fines. Thus, anyone who does not comply with this program will be disciplined for noncompliance according to the following schedule: 1. First offense: Verbal warning (documented in personnel file) Page 41 of 99
2. Second offense: First written warning (documented in personnel file) 3. Third offense: Final written warning (documented in personnel file) and 3-day suspension without pay 4. Last resort: Discharge 5.0 Chemical Hazards This Section contains a description of the physical and/or toxic hazards commonly encountered in laboratory chemicals. For each class some examples are provided. The examples provided are not a complete listing of chemicals that fall within that hazard class. To use this section, obtain information on specific chemicals of interest (using MSDS's, compendia of information, etc.) to determine which hazard classes apply; then refer to this Section for a description of that hazard class. 5.1 Flammability Certain physical characteristics are used to describe the flammability characteristics of chemicals. The flash point is the temperature at which there is enough vapor above the liquid to ignite in the presence of a spark, and the auto ignition temperature is the temperature which the material will ignite without a spark source. The boiling point is the temperature at which the vapor pressure above liquid is equal to atmospheric pressure and the vapor pressure is the partial pressure of chemical vapor at a stated temperature, often 25 C. The lower the flash point, lower the auto ignition temperature, lower the boiling point, and higher the vapor pressure, the greater the flammability hazard. Lower and upper explosion or flammability limits are also used to characterize the flammability of chemicals. The LEL (or LFL), lower explosive (flammable) limit, and UEL (or UFL), upper explosive (flammable) limit define the lower and upper ends of the explosive or flammable range. Air and solvent mixtures (expressed as percent solvent vapor) within the flammable range will burn; below the LEL or above the UEL the mixture is too lean (not enough fuel) or too rich (too much fuel), respectively, to burn. 5.1.1 Pyrophoric Materials Pyrophoric materials react with air, or with moisture in air. Typical reactions that occur are oxidation and hydrolysis, and the heat generated by the reactions may ignite the chemical. In some cases, these reactions liberate flammable gases, which make ignition a certainty and explosion a real possibility. 5.2 Odor Threshold and Warning Properties Warning properties include odor, irritation, and color--chemical properties that warn you the chemical is in the area. Chemicals with good warning properties don't sneak up on you; you can smell, see or feel them, so you know to look for the source or leave the area. Chemicals with poor warning properties don't warn you of their presence, so are potentially more dangerous. People often link "strong smell" with "dangerous", and ignore the fact that some dangerous chemicals lack odor (carbon monoxide).
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Chemicals with good warning properties can be smelled, felt or seen at safe exposure levels; this table compares a selection of "odor thresholds" with safe 8 hour exposure levels, TLVs. TLV's are developed by the American Committee of Governmental Industrial Hygienists (ACGIH), a standard setting organization. COMPARISON OF TLV AND ODOR THRESHOLDS FOR A SELECTION OF CHEMICALS CHEMICAL NAME TLV (ppm) ODOR THRESHOLD (ppm) acrolein 0.1 0.61 acrylic acid 2.0 0.1 arsine 0.05 0.2-0.6 diborane 0.1 2.5 ethylene dichloride 10 40 formic acid 5.0 49 methyl acrylonitrile 1.0 7.0 methyl formate 100 73 methyl isocyanate 0.02 2.1 phosgene 0.1 0.1-1.0 Note: these are not 100 percent odor recognition values; such values would be much higher, for instance for methyl formate 100 percent recognition = 2,000 ppm. __________________________________________________________ A table of odor thresholds published in "The Safe Handling of Chemicals In Industry" by P. A. Carson and C. J. Mumford, Volume 1, 1988.
5.3 Irritating or Corrosive Gases and Vapors 5.3.1 Lung Irritation And Damage Intense exposure (prolonged exposure to irritants or brief exposure to corrosives) causes lung tissue to swell and seep fluid, a condition called chemical pneumonitis; lungs may be damaged enough to cause death. Methyl isocyanate caused chemical pneumonitis in the Bhopol India tragedy. Chemical pneumonitis survivors may have permanent lung damage with symptoms similar to emphysema and a form of asthma in which airways constrict when exposed to quite low levels of irritating chemicals. 5.3.2
Eye Irritation And Damage Irritating and corrosive gases may cause intense pain and temporary eye damage which can take several weeks to heal. During exposure the eyes are usually tightly shut--which opens the victim up to the hazards of temporary blindness. Direct eye contact with irritants and corrosive liquids or powders can cause (at best) short term irritation and swelling to (worst case) permanent blindness. Quick and correct actions can reduce symptoms and prevent blindness. Prevention is the best approach to prevent eye damage; wear goggles and face shield when handling corrosive materials. However, if contact does occur, wash chemical out of eyes immediately and continue rinsing with a gentle stream of water for 15 minutes. Page 43 of 99
5.3.3 Skin Irritation And Damage Corrosive chemicals cause severe burns which will form scars unless treated properly. Wash contaminated skin with soap and water (or special solvent in several notable cases--bromine, phenol, hydrogen fluoride) immediately. Irritating chemicals cause a wide range of skin effects including burns, blisters, redness, itching, dryness, cracks (e.g. between fingers), roughness and a variety of skin problems termed dermatitis (skin inflammation). In general irritant effects are not severe, but are at least, annoying; and at worst, temporarily or permanently debilitating (e.g. when an irritant effect turns into an allergy). 5.4 Sensitizers (Allergens) Some chemicals cause allergies; an allergy (or sensitivity) is an abnormal response to low exposure levels of chemicals which don't elicit a similar response in the majority of people. The allergic response can be quite serious. Once an allergy develops it usually does not go away. If the symptoms are serious, the person must not be allowed to work where the chemical is used or generated. Allergic responses vary from life threatening (anaphylactic "bee sting" type reactions which can cause death by asphyxiation within minutes of exposure); to moderate (dermatitis, severe headache, head or chest cold or flu symptoms); to slight (rash, dry skin, itching nose or eyes). 5.5 Asphyxiate Gases and Vapors Animals require a constant supply of oxygen to survive, and asphyxiates reduce or eliminate this supply. Low levels of exposure to asphyxiates (or chronic exposure to less powerful ones) generally cause headaches, fatigue and confusion. High levels (or low levels of very toxic ones) will cause coma and, if the victim is not rescued, death. Asphyxiates can act quickly. One breath of pure nitrogen causes immediate collapse and unconsciousness--leaving no time to recognize and respond to the danger. 5.5.1
Types of Asphyxiates Chemical asphyxiates cause asphyxiation by reacting inside the body; generally small amounts can cause illness or death. For example, hydrogen sulfide interferes with nerve cell function, putting certain nerves to sleep, including olfactory (smell) nerves and the ones necessary for breathing. Moderate exposure levels eliminate our ability to smell--so right at the beginning of exposure we smell the characteristic rotten egg odor--and then it appears to go away. The odor is not gone; the ability to perceive it is gone. At higher concentrations or after prolonged breathing this chemical causes loss of consciousness and loss of the breathing mechanism. Several minutes in this state result in death. ppm H2S Symptoms 0.2 Detectable odor 20-150 Eye irritation Page 44 of 99
150 Loss of smell (olfactory paralysis) 250 Severe lung irritation 500 Severe systemic effects *1000 Collapse, respiration may stop soon 5000 Fatal *1000 ppm = 0.1% contaminant in air. Certain amines, nitrites and carbon monoxide produce asphyxia by reacting with blood hemoglobin, reducing its capacity to carry oxygen. This table shows the correlation of symptoms with the percent of hemoglobin carrying carbon monoxide (which is normally less than 1% in nonsmokers and less than 5% in smokers). % HbCO in blood Symptoms 0-10% No symptoms (PEL=10 ppm) 10-20% Yawning, flushed skin, headache 20-30% Headache, dizziness 30-40% Severe headache, weakness, dizziness, nausea, possibly collapse 40-50% Severe headache, weakness, dizziness, nausea, increased respiration, probable collapse 60-70% Fainting, coma 70-80% Respiratory failure, death 90% Prompt cardiac arrest Simple asphyxiates are not toxic, but can cause serious problems in confined spaces. Simple asphyxiates reduce oxygen levels from the usual 21% to lower levels by simple displacement. For example methane may seep into an underground electrical vault and displace most of the air dropping the oxygen concentration to 5%, not enough to survive in. Physiological effects become more severe as the oxygen level decreases, as shown below: % Oxygen in air Symptoms 16-21% No noticeable effect 19.50% OSHA standard 12-16% Possible headache; reduced coordination and ability to think clearly 10-12% Loss of ability to think clearly 6-10% Loss of consciousness, death. Asphyxiating conditions can be set up in confined spaces when vessels or pipes are flushed with nitrogen; when CO2 fire extinguishers are used in confined areas; due to generation or leakage of gas from cryogenic or welding processes; due to the formation of rust in closed (or very large) pipes or vessels; and in tanks, in the presence of high levels of microorganisms which use oxygen in metabolic reactions. Page 45 of 99
Corrosive Chemical Asphyxiation: breathing certain chemicals can cause severe lung burns resulting in lung damage, swelling and loss of function--thereby affecting the amount of oxygen available to the body (thus meeting the definition of asphyxiation). However this type of "asphyxia" is generally viewed as a corrosive effect rather than true asphyxia. 5.6 Central Nervous System (CNS) Depressants Anesthetic or narcotic materials depress the central nervous system (CNS, the brain and spinal cord) causing sleepiness, dizziness, drunk behavior, headache and often nausea and vomiting. Many organic solvents, alcohols, ethers, ketones, esters, etc. are CNS depressants. CNS effects generally occur within a few minutes of overexposure and may last quite awhile, until the chemical has been detoxified by the liver. Chlorinated hydrocarbon solvents (methylene chloride, methyl chloroform, carbon tetrachloride, etc.) have a peculiar and dangerous effect at high exposure levels (inhalation or direct skin contact): they cause changes in heart function (similar to a heart attack) which can cause death in minutes. The exposure situation is usually use of these materials in a confined area, where extremely high exposure levels can rapidly develop. Deaths in "glue sniffing" may also be due to this type of heart effect. One of the most dangerous symptoms of overexposure to CNS depressants is inebriation (drunk behavior) because victims are more likely to make mistakes, to fall or trip, and are less likely to follow or hear instructions or see imminent danger. They are dangerous to themselves and others. Watch for signs of inebriation due to overexposure to chemicals, both in your coworkers and yourself. Many chemicals (especially solvents) can enter the body through the skin, and entry by this route is often more toxic than by oral or inhalation routes. (Propylamine is ten times as toxic via skin than via mouth). Some areas of skin are more easily penetrated by chemicals than others: the scrotum is very easily penetrated (which makes contaminated slacks particularly hazardous); the scalp and forehead are quite easily penetrated, and the palm of the hand is the least easily penetrated. OSHA and ACGIH workplace standards regulate permissible air levels of chemicals; if chemicals can also get into the body via skin, then these organizations give them an "S" or "skin" notation, which means that skin contact must be controlled as well. Chemicals denoted "skin" by ACGIH and OSHA are listed in the following table. 5.7 Poisons Certain chemicals are acutely toxic at very low levels and can cause serious, life-threatening damage in amounts readily ingested, inhaled or absorbed through the skin.
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5.8 Systemic Toxins Systemic toxins damage tissues at sites other than the point of contact. They enter the body through the skin, mouth or lungs, spread via blood, and damage one or more internal organs such as the liver, kidneys, blood forming tissue, reproductive system, brain or nerves. Systemic damage is usually caused by long term exposure (years) to relatively low levels of chemicals, an exposure pattern often found in industry. Short term exposure to high levels of chemicals (acute exposure) is less likely to cause systemic toxic effects. We learn about systemic toxicity from human experience (e.g., occupational overexposure) and animal research. Some chemicals have many target organs, some just one. The target organ depends on the material and route and pattern of exposure. It is best to treat systemic toxins as possibly harmful to all organs, since the complete toxicity profile is usually not known. Examples: 5.9 Carcinogens (Cancer Causing Materials) A number of chemicals are known or suspected as causing or helping to cause cancer. A few chemicals are known human carcinogens (such as asbestos and cigarette smoke). Most are known or suspected animal carcinogens. Chemicals known to cause cancer in animals are considered potential human carcinogens. Current evidence (e.g. for cigarette smoke and asbestos) indicates a 10 to 20 year delay between onset of exposure and onset of cancer; and, for most known human carcinogens, there was a high level, long term exposure pattern. Can long or short term exposure to low levels of asbestos or side stream smoke (or other carcinogens) cause cancer? No one knows. However for regulatory purposes human carcinogens are considered carcinogenic whatever the exposure amount or pattern--thus exposure must by law be kept to a minimum. Refer to Appendix H for a list of known human carcinogens and reasonably anticipated to be human carcinogens. Mutagens are chemicals which damage DNA, and DNA damage is believed to play an important role in initiating cancer. Thus mutagens are viewed as "potential suspected animal carcinogens" even in the light of evidence to the contrary. 5.11 Reproductive Toxins (Teratogens) Chemicals which are linked to reproductive damage of various types include: abnormal sperm and/or low sperm count infertility reduced libido and/or impotence altered menstrual cycles or no ovulation spontaneous abortions damaged eggs DNA changes in egg or sperm (mutations)
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Reproductive effects are, by definition, damaging to parents and not the conceptus (fetus or embryo); fetal and embryonic damage is called TERATOGENESIS. 5.12 Chemicals That Damage the Lungs The damaging effects of inhaled corrosive materials have already been presented, and are not included in this section. There are other chemicals, less obviously corrosive, but still irritating and damaging to delicate lung tissues. In general lung damage is caused by the long term moderate exposure level pattern found in the workplace, though short term high exposure levels have caused severe, permanent damage. Again, in the usual case, the damage occurs over an extended period of time and is not discovered until the victim is debilitated by the damage. 6.0 Waste Stream Management Some materials, by law, cannot be discarded in the sink or in garbage cans. Clarkson University abides by environmental laws for both legal and ethical reasons. Therefore, before throwing chemicals away, be sure you know the correct way to dispose of the material. If the information below does not answer your question, ask your instructor or advisor, the CHO, or EHS Manager. 6.1 Planning and Purchasing of Chemicals It is your responsibility as generators of hazardous waste to make every attempt possible to minimize the amount produced. To the extent that chemicals can be recovered, recycled, or reused safely there is obvious economic incentive to do so. In addition, materials that are recovered, recycled, or reused do not become a liability problem or a problem for the environment. The planning of every purchase must include the consideration of the disposal of leftover starting materials and of the products and by-products that may be generated as a result of usage of a hazardous material. Questions to be considered include the following: Can any material be recovered, reused, or recycled? Will the experiment produce an acutely hazardous waste? Can any unusual disposal problem be anticipated? Are materials being acquired in only the quantities needed? Are any of the materials already on site? (in another location) Is there the possibility of replacing a hazardous material or solvent with one with is less hazardous or more easily disposed of? Hazardous materials should be purchased in the smallest possible volumes to reduce the amount of unused chemicals that could end up as wastes. As the cost of chemicals and disposal continues to climb, any reduction in volume of chemicals purchased will offer benefits. Keep in mind that the perceived economy of buying in bulk is more than offset by disposal costs for the package and its residues.
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6.2 Recovery and Recycling The recycling process is exempt from hazardous waste regulation except that waste accumulated prior to recycling must be managed according to accumulation requirements. Distillation is an example of a viable recovery option. All residues such as still bottoms from the recycling process are regulated and must be managed as hazardous waste. Other candidates for recycling include batteries, precious metals, scrap metals, waste oil, and mercury. Every effort must be made to determine if other materials can be reused, recovered, or recycled. 6.3 Hazardous Waste Identification and Determination The first step in hazardous waste management comes when the two following questions must be answered: Is this material a waste? A waste is any solid, liquid, or contained gaseous material that is discarded by beinging disposed of, burned or incinerated, or recycled. There are some exceptions for recycled materials. The waste can be a by-product of a laboratory operation or process or a commercial reagent or product that is no longer wanted or needed. Is this waste a regulated hazardous waste? Regulated waste can either be: 1. EPA listed waste (http://frwebgate.access.gpo.gov/cgi-bin/getcfr.cgi?TITLE=40&PART=261&SECTION=31&TYPE=TEXT) 2. If your waste is not listed, it still may be hazardous if it meets one or more of the following characteristics: Ignitable, Reactive, Toxic, or Corrosive The hazardous waste regulations apply to materials only when they become a waste and only if they are deemed hazardous under specific evaluation criteria. Once you determine that a chemical material is a waste, it must be evaluated to determine if it is a hazardous waste. Hazardous wastes are defined by the New York State Department of Environmental Conservation (NYDEC) following Environmental Protection Agency (EPA) regulations. Wastes can be hazardous in one of two ways: they are either wastes and spent materials that are hazardous by definition and contained in specific lists, or they exhibit one of four hazardous characteristics: ignitability, corrosivity, reactivity, or toxicity. Listed Wastes Wastes that are hazardous because they appear on one of four lists are called "listed hazardous wastes". The four lists are categorized as wastes from specific sources (K-list), wastes from non-specific sources (F-list), certain discarded commercial products (U-list), and "acutely hazardous" commercial chemical products (P-list). The F and K lists apply to general processes, while the U and P lists are for reagent chemicals. The P-list category which contains wastes such as cyanides is more rigorously regulated. As a SQG, Colgate cannot generate more than 1 kg/month or store more than 1 kg of waste from the P-list. Generation of acutely hazardous waste must be closely monitored. Mixtures of hazardous
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and non-hazardous waste are regulated as hazardous waste. So please segregate hazardous and non-hazardous materials whenever possible. Characteristic Wastes If a waste is not on one of the lists of hazardous wastes , you must determine if the waste possesses one or more of four hazardous characteristics defined below: ignitability, corrosivity, reactivity, or toxicity. Such wastes are called "characteristic hazardous wastes". A generator may use his knowledge based on the materials or processes used or may test the waste to determine if it possesses one of the four characteristics. Personnel who generate chemical waste should have enough general knowledge of the hazardous characteristics of their waste to classify it. Ignitability a liquid, other than an aqueous solution containing less than 24 percent alcohol by volume, with a flash point below 140 degrees F (60 C). a non-liquid, which under standard conditions is capable of causing fire through friction, absorption of moisture, or spontaneous chemical changes and when ignited, burns in a manner that creates a hazard an ignitible compressed gas, which includes gases that form flammable mixtures at a concentration of 13 percent or less in air an oxidizer, such as permanganate, inorganic peroxide, or nitrate, that readily stimulates combustion of organic materials. Reactivity normally unstable and readily undergoes violent change without detonation. reacts violently with water. forms potentially explosive mixtures with water generates, when mixed with water, toxic gases, vapors, or fumes in a quantity sufficient to present a danger. is a cyanide or sulfide bearing waste that generated toxic gases, vapors, or fumes at a pH between 2 and 12.5. is capable of detonation or explosive reaction when subject to a strong initiating source or heated in confinement is readily capable of detonation, explosive decomposition, or reaction at standard temperature and pressure. is an explosive Corrosivity is aqueous and has a pH less than or equal to 2 or greater than or equal to 12.5. is a liquid that corrodes steel at a rate greater than 6.35 mm per year at a test temperature of 130 degrees F (55 C). Toxicity tested using the Toxicity Characteristic Leaching Procedure (TCLP), which stimulates the leaching of materials in a landfill into the surrounding groundwater. Good sources for assistance in hazard determination are MSDSs, chemical dictionaries, and labels.
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6.4 Drain Disposal Procedures Sinks and most drains on campus are connected to the local sanitary sewer system with the effluent eventually going to Potsdam's Wastewaste Treatment Facility. Materials that cannot be disposed of via the sanitary sewer are materials that interfere with the treatment systems or chemicals that may cause a danger to the system or human health. 6.4.1 Materials that can be disposed of in the sanitary sewer. Aqueous solutions of non-hazardous chemicals Elementary neutralization of acids and bases (pH - 5.5 to 9.5) Aqueous radioactive materials (see RSO for daily limit) Aqueous biological materials that have been disinfected 6.4.2 Examples of materials that cannot be disposed in the sanitary sewer. Per Potsdam Village Ordinance, Chapter 138: Sewers. Any substance that alone or by interaction with other substances can cause fire or explosion. Prohibited materials include but are not limited to: o solvents and alcohols, peroxides, oxidizers, sulfides, hydrides, carbides, chlorates, perchlorates, bromates, carbides, ethers, gasoline, kerosene, benzene, naphtha, fuel oil. Generally this includes wastes that would be characterized as ignitible. Solid or viscous substances in quantities or of such size capable of causing obstruction to the flow in sewers or other interference with the proper operation of the sewage works such as, but not limited to, ashes, cinders, sand mud, straw, shavings, metal glass, rags, feathers, tar, plastics, wood, unground garbage, whole blood, paunch manure, hair and fleshings, agar or other gels or paper. Any water or waste containing fats, wax, grease or oils, whether emulsified or not, in excess of 100 milligrams per liter or containing substances which may solidify or become viscous at temperatures between 32° and 150° F. (0° and 65° C.). Waste having a pH less than 5.5 or greater than 9.5. Wastewater with corrosive properties capable of causing damage or hazard to structures, equipment, or personnel at the treatment plant. Any waters or wastes containing strong-acid iron-pickling wastes or concentrated plating solutions, whether neutralized or not. Any waters or wastes containing toxic or poisonous solids, liquids or gases in sufficient quantity, either singly or by interaction with other wastes, to injure or interfere with any sewage treatment process, constitute a hazard to humans or animals, create a public nuisance, or create any hazard in the receiving waters of the sewage treatment plant. Prohibited materials include but are not limited to: o Cyanides (in excess of 2 mg/L), mercury, heavy metals, carcinogens, mutagens, teratogens, etc. Any waters or wastes containing iron, chromium, copper, zinc and similar objectionable or toxic substances or wastes exerting an excessive chlorine requirement to such degree that any such material received in the composite sewage at the sewage treatment works exceeds the limits established by the Superintendent for such materials. Page 51 of 99
Any waters or wastes containing phenols or other taste- or odor-producing substances in such concentrations exceeding limits which may be established by the Superintendent as necessary, after treatment of the composite sewage, to meet the requirements of the state, federal or other public agencies of jurisdiction for such discharge to the receiving waters. Any noxious or malodorous liquids, gases, or solids. Waste of objectionable color such as dyes or stains. Waste with temperature that inhibits biological activity (exceeding 150o F or 65° C). Unknown or unidentified chemicals Biologicals that have not been disinfected Many of the above requirements are defined in the Village of Potsdam Sewer Ordinance Chapter 138, Article IV & V. If you are unsure whether a material can be disposed of down the drain, label the material as chemical waste and contact the EHS Manager. 6.4.3 Sink Disposal Procedure Drain disposal will be only into a drain that is connected to the Potsdam Wastewater Treatment Plant, never into a storm sewer drain that flows directly to surface water. Flush with at least 100 fold excess of water at the sink. Supervisors must monitor disposal for adherence to guidelines on type, quantity, rate, and flushing procedures. 6.5 Disposal and Collection of Hazardous Waste Laboratory supervisors are responsible for knowing whether the waste streams they generate are regulated and how to appropriately hand each waste stream. The CHO can assist in that determination that must be performed prior to the waste being generated. Refer to Section 6.3 regarding waste determination. Steps to handle waste properly are below. 1. A completed waste label must be on the waste container when the FIRST drop of waste enters the container. Waste labels are provided by the University. Contact the Chemistry Stockroom (x2338) or EHS Manager for labels (see image below of the waste label). Each bottle must be labeled with the following: Principle Investigator: Faculty member Lab Room Number: Where the lab is produced Start Date: When the first drop enters Waste Constituents: All chemicals in the bottle o MUST be full chemical name (no abbreviations) Check the hazard characteristics
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2. Collected liquids and solids can be mixed AFTER determining the mixture is safe (e.g. will not generate toxic gases or explosive products). Organic solvents can be mixed together. Disposing of a mixture of a halogenatal and non-halogenatal solvents is very explosive, DO NOT MIX! If there is a question about the safety of a waste mixture, don't mix. Do not mix solids and liquids, unless the solid is soluble in the liquid Do not put solid waste (paper, glass, etc.) in a liquid waste container. Each time an addition is made to a waste mixture add to the label what was added, and approximately how much. When necessary, dedicate each waste container to a specific waste stream. 3. Ensure that all chemicals that enter a container are compatible with that container. For example, use glass containers for strong acids and bases. However, Hydrofluoric acid must be stored in a polyethylene container. 4. Waste must be stored in a central location in each lab. Do NOT transport waste between labs. It must remain in the lab in which it was produced. Likewise, do not put this material in your car and take it to the stock room. Only one vehicle on campus is approved for transportation of waste chemicals. 5. When reusing chemical containers, ensure that the waste is compatible with the original contents. Deface the original label so that the name and hazard symbols are no longer visible. Adhere and complete a hazardous waste label. 6. Bottles must be kept closed except when adding waste. Remove any funnels and cap the container immediately after transferring waste into the container. If a change in pressure may occur, leave the cap loose but in place. 7. When a toxic and/or hazardous gas is generated attempt to render the gas harmless by bubbling through a reaction mixture. 8. Contaminated solid waste can be placed in a plastic bag or container with a completed hazardous waste labeled adhered to the outside of the bag. Bags must be kept closed except when adding waste and must be sealed prior to disposal.
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9. Chemical waste should be stored in segregated secondary containment, until it can be picked up. Waste should not be stored on the floor, by the sink or other sewer access point, or above eye level. 10. Acutely toxic chemicals (P-List) must be disposed of as chemical waste, regardless of the contents of the bottle. Label with the hazardous waste label and contact Chemistry Stockroom for pickup. See Appendix B for the P-list. 11. If you find unlabeled containers make every attempt to identify contents; it is very expensive to dispose of unknown materials. If a container is unlabeled, EHS will contract with a hazardous waste company to identify and dispose of the material at the expense of the Faculty member. 12. Contact the Chemistry Stockroom (x2338) for waste pickup. 13. Warning: some materials have a limited shelf life. Review your stock of materials periodically to ensure chemicals are disposed of prior to their expiration date. See Appendix D for proper handling and disposal of time sensitive chemicals (peroxide formers). 6.6 Disposal of Other Materials Sharps: Sharps includes but is not limited to all needles, syringes, scalpels, razor blades, pipette tips, Pasteur pipettes, glass vacutainers, capillary tubes, slides and cover slips All sharps must be placed in appropriate sharps container. o Container must be rigid, leak-proof, and puncture-proof; o Single use only; Once the container is ¾ full, close the top of the container. If the sharps are chemically contaminated, place a Hazardous Waste label on the container and complete the label. Cross out the biohazard symbol on the container (if using a red sharps container). Contact the Chemical Stockroom for a hazardous waste pickup. If the sharps are radioactive, cross out the biohazard symbol (if using a red sharps container) and place a radioactive material sticker on the container. Contact the Radiation Safety Officer to request a waste pickup. If the sharps are biohazardous or not contaminated, arrangements should be made with the Environmental Health & Safety Manager to have the waste transported to the CantonPotsdam Hospital. Broken Glass: • Uncontaminated Broken Glass should be disposed in your laboratory broken glass container. If your lab does not have a metal container with a lid for broken glass, please contact your building custodian to request one. • Contaminated Broken Glass should be placed in a rigid, leak-proof container. Label with appropriate hazard waste label (chemical, biological, or radiological). Glass Containers: • Uncontaminated Glass containers: Deface the original label and any other labels that show the chemical name or hazard symbols. Place container in a sturdy box and label the box “Uncontaminated Glass for disposal”. Place box with your regular trash for disposal.
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•
Contaminated glass containers: You must rinse the container prior to disposal. If container contained hazardous material (ex: cyanides, carcinogens, etc), the rinse material must be collected as hazardous waste. If the contamination is a P-Listed waste (See Appendix B), dispose of empty bottle as hazardous waste. For rinsed containers, deface the original label and any other labels that show the chemical name or hazard symbols. Place container in a sturdy box and label the box “Uncontaminated Glass for disposal”. Place box with your regular trash for disposal. Used Oil: • Is not hazardous, but cannot go to trash. Do not mix the oil with other materials. Collect the used oil in a sealable container and label it “Used Oil”. Contact Phil Dennicort for pickup (x2338). Gas Cylinders: • Can be returned to the vendor. Please contact Facilities Stockroom for pickup (x2325). Controlled Drugs: • Must be disposed according to DEA regulations. Contact the CHO for information on proper disposal. Universal Waste: • Universal waste includes batteries, mercury bulbs, and other mercury containing items. Label the item as “universal waste” and contact your building custodian for pickup 6.7 Non-hazardous solid waste Disposal Non-hazardous solids can be disposed of in the trash (no liquid wastes are allowed in the landfill). As mentioned before, the decision to use the trash must be made after careful consideration of the consequences. Non-hazardous materials will create a hazard if solid particles are inhaled or reach the eyes. A custodian may come in contact with it when he or she empties the trash. Our grounds grew could be exposed to the material when they handle the trash and compact it in the truck. All of our solid waste goes to a transfer station and then onto a landfill, where it will be essentially forever. Do not dispose of chemicals loosely in the trash. Minimize potential for exposure by encasing non-hazardous chemicals in bags, boxes, or containers. Never dispose of large amounts of non-hazardous chemicals in the trash. Broken glass should be collected in puncture resistant containers and disposed of in such a way as to protect custodians and the grounds crew. Empty containers that once held a hazardous material will be rinsed clean to remove any residue. All residues containing hazardous waste will be managed as such. Substances known to be toxic will not be disposed of in the trash even if they are not regulated as hazardous waste. 7.0 Spills and Emergency Procedures 7.1 Injuries and Accidents Do not trade lives! If there is a serious incident (fire, toxic gas release) evacuate the building immediately! Do not enter the building to save anyone--entry requires special equipment, which is not readily available. Page 55 of 99
Telephone number lists are posted outside of the laboratory and next to the laboratory telephones. They contain the contact for the lab and also the NFPA rating for the lab. These must be kept up to date in order to assist emergency personnel. Everyone must be familiar with Clarkson’s Emergency Response procedures, which are located in the front of the University Directories as well as on the website (http://www.clarkson.edu/emergency/emergency_procedures/index.html). Know where emergency equipment is located including but not limited to emergency showers, emergency eye washes, fire extinguishers, fire alarm pull stations and spill kits. If you are working with hazardous materials or equipment plan an emergency response before you start the experiment. Know what to do if an accident or injury occurs. 1. Do not move an injured person unless they are in further danger. Do not expose yourself to potential injury or exposure. If clothing is on fire, knock the person on the ground and roll them around to smother the flames or douse them under a safety shower. A fire blanket should only be used as a last resort. 2. If safe to do so, administer first aid such as washing in a safety shower or special first aid (such as the use of calcium gluconate for hydrofluoric acid exposure). 3. Warn personnel in adjacent areas of potential hazards to their safety. 4. Extinguish small fires by using the portable fire extinguisher located in the lab. Use the pass method (Pull pin, Aim, Squeeze, Sweeping motion at base of fire). 5. Turn off nearby apparatus and remove flammable materials from the area. 6. Call Campus Safety & Security for assistance (x6666). If it is a life threatening medical emergency, call 911. If possible, notify a supervisor. 7. ALL ACCIDENTS MUST BE REPORTED; the period for reporting depends on the seriousness of the accident. Serious personal injury or building damage must be reported to the principal investigator, Environmental Health and Safety officer, or another faculty member immediately. Less serious injury or small fires or small equipment damage can wait until the next business day if the accident occurred in the evening or on the weekend. 4. Written reports must be prepared for all accidents or incidents causing (or nearly causing) personal injury or property damage. Additional reports should be prepared by the instructor, TA and/or witnesses for serious accidents. 5. More information on accident reporting and report forms can be found on the Department of Risk Management’s website (www.clarkson.edu/risk_ehs). 7.2 Chemical Spills The time to prepare to handle a spill is long before it occurs. Appropriate precautions and the proper equipment will alleviate many of the potential complications associated with the spill of a hazardous material. The following principles will decrease the likelihood of a spill:
Substitute a less hazardous chemical, procedure, or piece of equipment, such as alcohol thermometers instead of mercury thermometers. Always store chemical containers with closed caps. Page 56 of 99
Use secondary containment whenever possible. Trays and wash basins work well. Use of coated safety bottles is preferred. Do not store chemicals on the floors, desks, or counter tops. Check shelving; watch for overloading or overcrowding. Practice good housekeeping. Clutter increases the likelihood of a spill or accident. Minimize chemical storage in the laboratory. Purchase only the amount needed.
Anticipate chemical spills by having appropriate cleanup and safety equipment on hand. These cleanup supplies should be consistent with the hazards and quantities of substances used. Clean-up kits are available in some locations and have absorbents, neutralizers, and protective equipment, but these kits may not cover everything used in a particular lab. If you have a chemical with a specific hazard, you must provide the appropriate spill and first aid equipment (where applicable) for your laboratory. This includes, but is not limited to mercury amalgamate powder and calcium gluconate for hydrofluoric acid exposure. In case of liquid chemical spill: If there is any risk to your health or safety, evacuate the area and close door; Do not attempt to stop or contain the spill. GENERAL PROCEDURES: 1. Remove contaminated clothing immediately. Go to the nearest emergency shower and take a shower. 2. Alert personnel in adjacent areas. 3. Get medical attention for injured personnel: a. For minor injuries of students, go to the Student Health Center (ERC). Staff should go to the Emergency Room or their physician. b. For all other injuries, call Campus Safety & Security at x6666 for an ambulance. 4. Confine the spill, and evacuate nonessential personnel from spill area. 5. If spill material is flammable, extinguish flames and all other sources of ignition. Also, when a flammable material is spilled do not trip any switches that could create a spark; do turn off pilot lights and other flames in the area 6. Secure the appropriate clean-up supplies and wear the appropriate protective clothing. 7. In climate controlled rooms, respiratory protection is required. Call Campus Safety & Security (x6666). 8. Remove glass using forceps. 9. Attempt to stop any release into the environment (ex: floor drains, etc) 10. Notify Campus Safety (x6666). 11. Collect spilled chemical and absorbent material in a container, label it with the hazardous waste label contact the Chemistry Stockroom for pick-up (x2338). When the nature of the spill constitutes a more serious hazard or involves the release of gas or fumes, the following procedures should be followed: 1. Activate the emergency alarm system. 2. Rescue injured personnel, if possible. Do Not put yourself in harms way. Only rescue when safe to do so. Page 57 of 99
3. Evacuate the building; move to the assembly area. 4. Notify Campus Safety (x6666) with the details of the situation. In case of compressed toxic/corrosive gas release: If the leak cannot be remedied by tightening a valve gland or a packing nut, emergency action procedures should be activated. When the nature of the spill constitutes a more serious hazard or involves the release of gas or fumes, the following procedures should be followed: If a leak is suspected, do not use a flame for detection; instead use a flammable-gas leak detector or soapy water. Activate the building’s emergency alarm system. Alert other people in the building. Send someone to call Campus Security immediately x6666 call 911 from a telephone in other building. Evacuate the building; move to the assembly area, which is usually the parking lot away from the main door of the building. Help evacuate people with disabilities. Notify Campus Security with the details of the situation. University personnel should never attempt to repair a leak at the valve threads or safety device; rather, they should consult with the supplier for instructions. In case of power failure: During a power failure, if there is no sunlight or emergency lighting then REMAIN STILL. Do not attempt to exit in sudden darkness. When vision is possible, TURN OFF all electrical apparatus, particularly computers, heaters, AV equipment, and coffee makers. If necessary, EXIT the building calmly. BE AWARE to avoid obstacles that may trip or impact your body. WAIT for further instructions from emergency coordinators or other management. 7.3 Fires and Explosions 1. Know how to use the fire alarm and extinguisher; turn in a fire alarm if there is any doubt that you may fail to put out the fire. Turn in a fire alarm for any serious emergency such as toxic gas release or an explosion. 2. Use laboratory fire extinguisher on incipient fires. Use the pass method (Pull pin, Aim, Squeeze, Sweeping motion at base of fire). 3. Take an extinguisher with you to check out an area where there may be a fire. 4. After using a fire extinguisher contact Facilities and Services for a replacement. 5. If you hear a fire alarm in your building leave the building--don't look for the fire. Preventing Laboratory Fires 1. Do not use open flames or open electrical heating elements near flammable materials. Use steam baths or heating mantles to heat flammable materials. 2. Don't use spark creating equipment (e.g. most switches and electrical outlets) inside hoods because explosive conditions may prevail. Disconnects and switches should be outside of the hood. Page 58 of 99
3. Store flammable liquids only in refrigerators designed for flammable material storage. 4. Attach rubber hoses securely to gas outlets to ensure they do not leak. Turn outlets off at source when they are not in use. 5. Do not leave gas flames burning unattended overnight or for lengthy periods. 6. If there is a release of flammable vapor or gas do not make or break electrical contacts in the area; if equipment can be turned off from outside of the room, do so. 7. If clothing is on fire, knock the person on the ground and roll them around to smother the flames or douse them under a safety shower. A fire blanket should only be used as a last resort. 7.4 First Aid Procedure Guidelines Vigorously wash injury with soap and water for several Minor cuts and punctures minutes. If the person is bleeding profusely, Call 911. Major cuts and abrasions Keep victim lying down and raise the bleeding part higher than the rest of the body if the cut is severe. DO NOT REMOVE THE OBJECT. Seek medical attention Impalement by foreign immediately. object Using an emergency eye wash, immediately flush eye with Splash in eye water continuously for 15 minutes. Hold the eyelid open. Contamination to the body Using an emergency shower, immediately remove contaminated clothing and drench skin with water. Flush area for 15 minutes. Conventional showers may be used in available areas. If skin is unbroken, submerge the burned area in clean water. Thermal burns Do not break any blisters, or use any medication. Do not induce vomiting. Poisoning by ingestion Supply the Material Safety Data Sheet (MSDS) for emergency personnel. IF THE VICTIM IS UNCONSCIOUS, Call 911. Poisoning by inhalation Do not become a victim yourself by exposure to the same poison while rescuing the victim. Call 911. Where possible, transport victim to uncontaminated air immediately. IF THE VICTIM IS UNCONSCIOUS, Call 911.
Clothing fire
Immediately DROP TO THE FLOOR AND ROLL. If someone else’s clothing catches fire, knock that person to the floor and roll them around to smother the flames. A person may panic if his/her clothing catches fire and may run. This can result in more severe burn injuries.
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8.0 Medical Consultation and Recordkeeping 8.1 Medical Consultations And Examinations Under certain conditions it may be necessary for employees to seek medical consultation to determine the need for treatment or further medical examination. Medical examinations will be provided without loss of pay and at reasonable times and places. Clarkson University will pay for these services under the following conditions: 1. If air monitoring data indicated that an employee is exposed to greater than the action level for a substance which has an action level and is regulated by an OSHA health standard which requires medical surveillance. 2. Whenever an employee develops signs or symptoms associated with a hazardous chemical to which the employee may have been exposed in the laboratory. 3. Whenever a spill, leak, explosion or other event results in the likelihood of hazardous exposure. The following information will be provided to the physician: 1. Qualitative and quantitative information. 2. Conditions of exposure. 3. Signs and symptoms at exposure and later. The physician will prepare for the University a written opinion which includes: 1. Medical examination and test results. 2. Recommendations for follow-up. 3. Medical conditions which place the employee at increased risk due to exposure to laboratory chemicals. The physician reports to the employee either in writing or in person the following information. 1. 1,2, and 3 above. 2. Medical conditions discovered in the examination which are unrelated to occupation exposure. (Note that this information is not transmitted to the University). 8.2 Recordkeeping OSHA’s Access to recordkeeping rule supplements the Hazard Communication standard and its informational benefits for employees by adding information on exposure and medical effects. Both standards together give employees and employers the information they need to help avoid, reduce or eliminate work place hazards. 8.2.1
Access “Access” for the purpose of the standard, means the right and opportunity to examine and copy. Access to employee medical and exposure records must be provided in a reasonable manner and place. If access cannot be provided within 15 days after the employee’s request, the employer must state the reason for the delay and the earliest date when the records will be made available Page 60 of 99
8.2.2 Exposure Records Upon request, the employer must provide the employee, or employee’s designated representative access to employee exposure records. If no records exist, the employer must provide records of other employees with job duties similar to those of the employee. Access to these records does not require the written consent of the other employees. 8.2.3 Medical Records The employer also must provide employees and their designated representatives’ access to medical records relevant to the employee. Access to the medical records of another employee may be provided only with the specific written consent of that employee. The standard provides a suitable sample authorization letter for this purpose. Prior to employee access to medical records, physicians, on behalf of employers, are encouraged to discuss with employees the contents of their medical records; physicians also may recommend ways of disclosing medical records other than by direct employee access. Where appropriate, a physician representing the employer can elect to disclose information on specific diagnoses of terminal illness or psychiatric conditions only to an employee’s designated representative, and not directly to the employee. In addition, a physician, nurse, or other responsible health care person who maintains medical records may delete from requested medical records the names of persons who provided confidential information concerning an employee’s health status. 8.2.4 Analyses using exposure or medical records The standard assures that an employee (or designate representative), as well as OSHA, can have access to analyses that were developed using information from exposure or medical records about the employee’s working conditions or workplaces. Personal identities, such as names, addresses, social security and payroll numbers, age, race, and sex, must be removed from the data analyses prior to access. 8.2.5 Employee information At the time of initial employment and at least annually thereafter, employees must be told of the existence, location, and availability of their medical and exposure records. The employer also must inform each employee of his or her rights under the access standard and make copies of the standard available. Employees also must be told who is responsible for maintaining and providing access to records. 8.2.6 Retention of Records Each employer must preserve and maintain accurate medical and exposure records for each employee. The access standard imposes no obligation to create records but does apply to any medical or exposure records created by the employer in compliance with other OSHA rules or at his or her own volition. Exposure records and data analyses based on them are to be kept for 30 years. Medical records are to be kept for at least the duration of employment plus 30 years. Page 61 of 99
Background data for exposure records such as laboratory reports and work sheets need be kept only for 1 year. Records of employees who have worked for less than 1 year need not be retained after employment, but the employer must provide these records of one-time treatment need not be retained for any specified period. OSHA does not mandate the form, manner, or process by which an employer preserves a record, except that chest X-ray films must be preserved in their original state. Three months before disposing of records, employers must notify the Director of NIOSH. 9.0 TRAINING PROGRAMS 9.1 All employees working in laboratories that may be exposed to hazardous materials must attend training: Upon initial assignment If hazards change in the laboratory If new hazards are introduced into lab At the frequency specified in specific regulations such as handling radioactive material, biological hazards, etc. 9.2 Training will include, but is not limited to: Background information about the OSHA Lab Standard Review of laboratory incidents Hazard Communication o Routes of Exposure o MSDS locations o Labeling of chemicals Safety Handling of Chemicals o Chemical storage o Transportation and shipping o Other special handling procedures
How to protect yourself o Engineering controls o Personal protective equipment Waste Disposal o Sanitary Sewer disposal o Hazardous Waste disposal o Other materials for disposal Emergency Response Procedures o Accidents o Fire o Spills
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APPENDIX A Minors Working in Educational Research Labs PURPOSE: The purpose of this policy is to outline the necessary training, allowable work, and level of supervision for a minor working or volunteering in a Clarkson University laboratory. SCOPE: This policy covers all laboratories, including chemical, biological, and instrumentation labs. “Minor” is defined as a person under the age of 18 from the date of employment or volunteer start date. POLICY: 1. No person under 14 years of age may work in a laboratory at Clarkson University. 2. Researchers under 18 years of age cannot work with human blood, body fluids, or unfixed tissues. Minors cannot sign a consent form for post exposure prophylaxis. Even if parental consent could be obtained, there is the problem that the antiretroviral drugs recommended by the CDC for post-exposure prophylaxis have not been evaluated for prophylactic use in adolescents. 3. Clarkson University does not allow minors to work directly with radioactive materials. Minors who will be working in a laboratory where radioactive materials are present must provide parental/guardian consent to the Radiation Safety Office. Consultation with the Radiation Safety Office to review applicable safety practices is required. 4. Minors are not allowed to work with Class 3b or 4 lasers. 5. In accordance with New York State Child Labor Laws (NYSCLL), persons under the age of 18 cannot operate machinery such as circular saws, band saws, and guillotine shears. NYSCLL also bans the use of power-driven woodworking, metal-forming, metalpunching, and metal-shearing machines as well as power-driven hoisting apparatus. Therefore minors are prohibited from working in the Machine Shops. 6. Also, NYSCLL and Clarkson University prohibit minors from cleaning, oiling, or wiping machinery and adjusting belts on machinery. 7. Clarkson University and NYSCLL prohibit minors from preparing any composition in which dangerous or poisonous acids are used. Dangerous or poisonous acids include, but are not limited to, hydrofluoric acid, perchloric acid, solutions with concentrations of sulfuric acid greater than ten percent (10%), and solutions with concentrations of nitric acid greater than ten percent (10%). Page 63 of 99
8. Appropriate supervision must be provided in the laboratory since minors may not have sufficient experience to deal with unanticipated problems. 9. Everyone working in a laboratory must attend Laboratory Safety Training with the Environmental Health & Safety Manager. This training will include, but is not limited to the proper use of personal protective equipment. The Principal Investigator/Faculty member (PI) for each laboratory must conduct hazard specific training with minors and other personnel in their labs. As part of the laboratory specific training provided by the PI, the minor must be informed and shown which materials and equipment are prohibited. 10. Everyone working in a laboratory must complete and return the WAIVER, CONSENT AND ASSUMPTION OF RISK FOR MINORS WORKING IN LABORATORIES (attached)
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WAIVER, CONSENT AND ASSUMPTION OF RISK FOR MINORS WORKING IN LABORATORIES We, _____________________________________ (“Minor”) and his/her parent(s)/guardian(s) (such parent(s) or guardian(s) acting both in their individual capacities and, to the extent required by law, on behalf of Minor), understand, acknowledge, consent and agree as follows: 1. Minor has been offered the opportunity to work (either paid or unpaid) in a research laboratory at Clarkson University. 2. We understand that laboratories are specialized environments involving the use of scientific instrumentation, chemicals, radiation and biological materials, which must be used with care and which even under ideal laboratory conditions may involve risk from chemical, biological, and radioactive material exposure, instrumentation, and needle sticks. These risks, which may include injury and property damage, including possibly short-term and long-term disability, and even death, can come from causes which are many and varied, may not be presently foreseeable, and may include negligent or intentional acts or omissions of others. 3. Minor will be required to attend a laboratory safety instruction course and will be taught and supervised in the proper handling of instrumentation and materials to minimize risk. 4. It is Clarkson University policy that Minor cannot work directly with human blood, body fluids, or unfixed tissues. However, these materials may be present in the research laboratory. 5. Clarkson does not allow Minor to handle radioactive materials. However, Minor may work in a laboratory where radioactive materials are present. 6. Minor is not allowed to work with Class 3b or 4 lasers. However, Minor may work in a laboratory where Class 3b or 4 lasers are present. 7. In accordance with New York State Child Labor Laws (NYSCLL), persons under the age of 18 cannot operate machinery such as circular saws, band saws, and guillotine shears. NYSCLL also bans the use of power-driven woodworking, metal-forming, metal-punching, and metal-shearing machines as well as power-driven hoisting apparatus. Therefore, Minor is prohibited from working in the Machine Shops. 8. Also, NYSCLL and Clarkson University prohibits Minor from cleaning, oiling, or wiping machinery and adjusting belts on machinery. 9. Clarkson University and NYSCLL prohibits Minor from preparing any composition in which dangerous or poisonous acids are used. Dangerous or poisonous acids include, but are not limited to hydrofluoric acid, perchloric acid, solutions with concentrations of sulfuric acid greater than ten percent (10%), and solutions with concentrations of nitric acid greater than ten percent (10%). 10. It is Clarkson University policy that appropriate supervision will be provided at all times in the laboratory. As such, Minor will not attempt any work in a laboratory unless a qualified supervising Clarkson University employee is present and consents to the work. 11. Minor shall follow the instructions of Clarkson University staff and shall comply with all applicable University policies and procedures in his/her work, and shall at all times exercise care and caution in the laboratory. 12. Knowing the circumstances and risks described above, and in consideration of permission for Minor to work in the above-referenced laboratory, we agree to Minor’s working in a Clarkson University laboratory. We voluntarily acknowledge, accept and assume all risks of such work, whether or not described above or otherwise presently foreseeable and whether or not caused by the negligent or intentional acts or omissions of others. On behalf of ourselves and our respective heirs, personal representatives and assigns, we release Clarkson University and its trustees, officers, employees, agents, and representatives from any and all claims, causes of action and damages (collectively, “Claims”) each of us may have in the future, waive all such Claims, and agree not to sue the University or its trustees, officers, employees, agents and representatives for
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any such Claims, which may arise out of the Minor’s presence in the laboratory, including without limitation Claims resulting from the University’s own negligence. 13. We grant permission to Clarkson University to provide such emergency care and treatments, as in its judgment may be deemed necessary or advisable in the event that Minor should require emergency care while acting in the course of his/her work at the University. 14. This Agreement is to be as broad and inclusive as is permitted by the laws of the State of New York. Accordingly, if any portion of this Agreement is held invalid, the remaining terms shall continue in full force and effect.
Minor printed name_________________________________________________ Signed (Minor) ____________________________________________________ Date_____________ Parent/Guardian printed name_________________________________________ Signed (parent/guardian) _____________________________________________Date_____________ Parent/Guardian printed name_________________________________________ Signed (parent/guardian) _____________________________________________Date_____________
Medical Emergency Contact Information Person(s) to contact first and second: Backup contact (relative or friend) First Contact:
Second Contact:
Name(s): _______________________
Name(s): __________________________
Relation to Student: ______________
Relation to Student: __________________
Daytime phone: _________________
Daytime Phone: _____________________
Evening phone __________________
Evening Phone: _____________________
SUBMIT COMPLETED FORM TO ENVIRONMENTAL HEALTH AND SAFETY, BOX 5542.
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STATEMENT FOR MINORS WORKING IN LABORATORIES Name of Minor:_____________________________
Start Date:__________ End Date:__________
Principal Investigator/Faculty:_______________________
Lab Location:____________________
The information below lists the materials that are present in the above listed laboratory. Although these materials may be present, minors are prohibited from handling certain materials (as stated in the “Minors Working In Research Labs Policy”). As part of the laboratory specific training provided by the Principal Investigator/Faculty, the minor must be informed and shown which materials and equipment are prohibited. Hazards present in the lab above include: Biological Hazards Infectious Agents (bacteria, viruses, etc) Non-human Vertebrate Animals and Tissue Human blood, body fluids and/or tissue Chemicals Toxic, flammable, corrosive, irritants Carcinogenic, mutagenic, teratogenic Highly hazardous Metals (mercury, beryllium, cadmium, etc) Dangerous or Poisonous Acids including, hydrofluoric, sulfuric, or nitric acid
Radioactive Materials Open Sources Sealed Sources Radiation Containing Equipment Equipment Lasers Class 3B or 4 Lasers Class 1 to 3a Robotics High voltage electrical systems Other:______________________________ ____________________________________ ____________________________________ ____________________________________ ____________________________________
I have trained the above named person on safety procedures for the above referenced lab and on the Standard Operating Procedures and in the proper handling of materials and equipment that will be used. Principal Investigator/Faculty (print)____________________________________ Principal Investigator/Faculty (signature)________________________________ Date:_____________
I have received safety training from _______________________________ on ____________________. Name of Principal Investigator/Faculty trainer
Date of training
I have read and understand the Laboratory Safety Manual, Chemical Hygiene Plan and the Lab’s Safety Policies and Procedures. I agree to comply with the policies and procedures in the Laboratory Safety Manual, Chemical Hygiene Plan, and the Lab’s Safety Policies and Procedures documents as well as those discussed during the training session. Name_____________________________________________________ Signature__________________________________________________ Date_____________________
SUBMIT COMPLETED FORM TO ENVIRONMENTAL HEALTH AND SAFETY, BOX 5542.
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APPENDIX B EPA P-List Waste The "P" list identifies chemical products that are considered acute hazardous wastes. For any bottle containing a chemical on this list (even if it is empty) you must dispose of the container as hazardous waste. Affix a yellow chemical hazardous waste label to the bottle and contact the Chemistry Stockroom Manager to pick-up the container (x2338). If you have any questions, please contact the Environmental Health & Safety Manager at x6640. The "P" Wastes Sorted by Waste Substance Waste CAS Number By Waste Substance Number P023 P002 P057 P058 P002 P003 P070 P203 P004 P005 P006 P007 P008 P009 P119 P099 P010
107-20-0 591-08-2 640-19-7 62-74-8 591-08-2 107-02-8 116-06-3 1646-88-4 309-00-2 107-18-6 20859-73-8 2763-96-4 504-24-5 131-74-8 7803-55-6 506-61-6 7778-39-4
Acetaldehyde, chloroAcetamide, N (aminothioxomethyl)Acetamide, 2-fluoroAcetic acid, fluoro-, sodium salt 1-Acetyl-2-thiourea Acrolein Aldicarb Aldicarb sulfone Aldrin Allyl alcohol Aluminum phosphide 5-(Aminomethyl)-3-isoxazolol 4-Aminopyridine Ammonium picrate Ammonium vanadate Argentate(1-), bis(cyano-C)-, potassium Arsenic acid H3AsO4
P012
1327-53-3
Arsenic oxide As2O3
P011
1303-28-2
Arsenic oxide As2O5
P011 P012 P038 P036 P054 P067 P013 P024 P077 P028 P042 P046 P014 P127
1303-28-2 1327-53-3 692-42-2 696-28-6 151-56-4 75-55-8 542-62-1 106-47-8 100-01-6 100-44-7 51-43-4 122-09-8 108-98-5 1563-66-2
Arsenic pentoxide Arsenic trioxide Arsine, diethylArsonous dichloride, phenylAziridine Aziridine, 2-methylBarium cyanide Benzenamine, 4-chloroBenzenamine, 4-nitroBenzene, (chloromethyl)1,2-Benzenediol, 4-[1-hydroxy-2-(methylamino)ethyl]-, Benzeneethanamine, alpha, alpha-dimethylBenzenethiol 7-Benzofuranol, 2,3-dihydro-2, 2-dimethyl-, methylcarbamate
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Waste CAS Number By Waste Substance Number P188
57-64-7
P001
*81-81-2
P028 P015 P017 P018 P045 P021 P189
100-44-7 7440-41-7 598-31-2 357-57-3 39196-18-4 592-01-8 55285-14-8
P191 P192 P190 P127 P021
644-64-4 119-38-0 1129-41-5 1563-66-2 592-01-8
P022 P189 P095 P023 P024 P026 P027 P029 P202 P030 P031 P033 P034 P016 P036 P037 P038 P041 P040 P043 P191 P004
75-15-0 55285-14-8 75-44-5 107-20-0 106-47-8 5344-82-1 542-76-7 544-92-3 64-00-6
P060
465-73-6
P037
60-57-1
460-19-5 506-77-4 131-89-5 542-88-1 696-28-6 60-57-1 692-42-2 311-45-5 297-97-2 55-91-4 644-64-4 309-00-2
Benzoic acid, 2-hydroxy-, compd. with (3aS-cis)-1,2,3,3a,8,8a-hexahydro-1,3a,8trimethylpyrrolo[2,3-b]indol-5-yl methylcarbamate ester (1:1) 2H-1-Benzopyran-2-one, 4-hydroxy-3-(3-oxo-1-phenylbutyl)-, & salts, when present at concentrations greater than 0.3% Benzyl chloride Beryllium powder Bromoacetone Brucine 2-Butanone, 3,3-dimethyl-1-(methylthio)-, O-[methylamino)carbonyl] oxime Calcium cyanide Carbamic acid, [(dibutylamino)-thio]methyl-, 2,3-dihydro-2,2- dimethyl- 7-benzofuranyl ester Carbamic acid, dimethyl-, 1-[(dimethyl-amino)carbonyl]- 5 methyl- 1H-pyrazol-3-yl ester Carbamic acid, dimethyl-, 3-methyl-1- (1-methylethyl)-1H- pyrazol-5-yl ester Carbamic acid, methyl-, 3-methylphenyl ester Carbofuran Calcium cyanide Ca(CN)2 Carbon disulfide Carbosulfan Carbonic dichloride Chloroacetaldehyde p-Chloroaniline 1-(o-Chlorophenyl)thiourea 3-Chloropropionitrile Copper cyanide Cu(CN) m-Cumenyl methylcarbamate Cyanides (soluble cyanide salts), not otherwise specified Cyanogen Cyanogen chloride (CN)Cl 2-Cyclohexyl-4,6-dinitrophenol Dichloromethyl ether Dichlorophenylarsine Dieldrin Diethylarsine Diethyl-p-nitrophenyl phosphate O,O-Diethyl O-pyrazinyl phosphorothioate Diisopropylfluorophosphate (DFP) Dimetilan 1,4,5,8-Dimethanonaphthalene, 1,2,3,4,10,10-hexa- chloro-1, 4, 4a, 5, 8, 8a,-hexahydro-, (1alpha, 4alpha, 4abeta, 5alpha, 8alpha, 8abeta)1,4,5,8-Dimethanonaphthalene, 1,2,3,4,10,10-hexa- chloro-1, 4, 4a, 5, 8, 8a-hexahydro,(1alpha, 4alpha, 4abeta, 5beta, 8beta, 8abeta)2,7:3,6-Dimethanonaphth [2,3-b] oxirene, 3,4,5,6,9,9-hexachloro-1a, 2, 2a, 3, 6, 6a, 7, 7a-octahydro-, (1aalpha, 2beta, 2aalpha, 3beta, 6beta, 6aalpha, 7beta, 7aalpha)-
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Waste CAS Number By Waste Substance Number P051
*72-20-8
P044 P046 P047 P048 P020 P085 P111 P039 P049 P185 P050 P088 P051 P051 P042 P031 P194
60-51-5 122-09-8 *534-52-1 51-28-5 88-85-7 152-16-9 107-49-3 298-04-4 541-53-7 26419-73-8 115-29-7 145-73-3 72-20-8 72-20-8 51-43-4 460-19-5 23135-22-0
P066 P101 P054 P097 P056 P057 P058 P198 P197 P065 P059 P062 P116 P068 P063 P063 P096 P060 P192 P202 P007 P196 P196 P092 P065
16752-77-5 107-12-0 151-56-4 52-85-7 7782-41-4 640-19-7 62-74-8 23422-53-9 17702-57-7 628-86-4 76-44-8 757-58-4 79-19-6 60-34-4 74-90-8 74-90-8 7803-51-2 465-73-6 119-38-0 64-00-6 2763-96-4 15339-36-3 15339-36-3 62-38-4 628-86-4
2,7:3,6-Dimethanonaphth [2,3-b]oxirene, 3,4,5,6,9,9-hexachloro-1a,2,2a,3,6,6a,7,7aoctahydro-, (1aalpha,2beta,2abeta,3alpha,6alpha,6abeta,7beta, 7aalpha)-, & metabolites Dimethoate alpha, alpha-Dimethylphenethylamine 4,6-Dinitro-o-cresol, & salts 2,4-Dinitrophenol Dinoseb Diphosphoramide, octamethylDiphosphoric acid, tetraethyl ester Disulfoton Dithiobiuret 1,3-Dithiolane-2-carboxaldehyde, 2,4-dimethyl-, O- [(methylamino) carbonyl]oxime Endosulfan Endothall Endrin Endrin, & metabolites Epinephrine Ethanedinitrile Ethanimidothioc acid, 2-(dimethylamino)-N-[[(methylamino) carbonyl]oxy]-2-oxo-, methyl ester Ethanimidothioic acid, N-[[(methylamino)carbonyl]oxy]-, methyl ester Ethyl cyanide Ethyleneimine Famphur Fluorine Fluoroacetamide Fluoroacetic acid, sodium salt Formetanate hydrochloride Formparanate Fulminic acid, mercury(2+) salt Heptachlor Hexaethyl tetraphosphate Hydrazinecarbothioamide Hydrazine, methylHydrocyanic acid Hydrogen cyanide Hydrogen phosphide Isodrin Isolan 3-Isopropylphenyl N-methylcarbamate 3(2H)-Isoxazolone, 5-(aminomethyl)Manganese, bis (dimethylcarbamodithioatoS,S')Manganese dimethyldithiocarbamate Mercury, (acetato-O)phenylMercury fulminate
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Waste CAS Number By Waste Substance Number P198
23422-53-9
P197 P082 P064 P016 P112 P118 P050
17702-57-7 62-75-9 624-83-9 542-88-1 509-14-8 75-70-7 115-29-7
P059 P199 P066 P068 P064 P069 P071 P190 P128 P072 P073
76-44-8 2032-65-7 16752-77-5 60-34-4 624-83-9 75-86-5 298-00-0 1129-41-5 315-18-4 86-88-4 13463-39-3
Methanimidamide, N,N-dimethyl N'-[3-[[(methylamino) carbonyl]oxy]phenyl]-, monohydrochloride Methanimidamide, N,N-dimethyl N'-[2-methyl-4-[[(methylamino)carbonyl]oxy] phenyl] Methanamine, N-methyl-N-nitrosoMethane, isocyanatoMethane, oxybis[chloroMethane, tetranitroMethanethiol, trichloro6,9-Methano-2,4,3-benzodioxathiepin, 6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9ahexahydro-, 3-oxide 4,7-Methano-1H-indene, 1,4,5,6,7,8,8-heptachloro 3a,4,7,7a-tetrahydroMethiocarb Methomyl Methyl hydrazine Methyl isocyanate 2-Methyllactonitrile Methyl parathion Metolcarb Mexacarbate alpha-Naphthylthiourea Nickel carbonyl Ni(CO)4,
P074
557-19-7
Nickel cyanide Ni(CN)2
P075 P076 P077 P078 P076 P081 P082 P084 P085 P087
*54-11-5 10102-43-9 100-01-6 10102-44-0 10102-43-9 55-63-0 62-75-9 4549-40-0 152-16-9 20816-12-0
Nicotine, & salts Nitric oxide p-Nitroaniline Nitrogen dioxide NO2 Nitrogen oxide NO Nitroglycerine N-Nitrosodimethylamine N-Nitrosomethylvinylamine Octamethylpyrophosphoramide Osmium oxide OsO4,
P087 P088 P194 P089 P034 P128 P199 P048 P047 P202 P201 P020
20816-12-0 145-73-3 23135-22-0 56-38-2 131-89-5 315-18-4 2032-65-7 51-28-5 *534-52-1 64-00-6 2631-37-0 88-85-7
Osmium tetroxide 7-Oxabicyclo[2.2.1]heptane-2,3 dicarboxylic acid Oxamyl Parathion Phenol, 2-cyclohexyl-4,6-dinitroPhenol, 4-(dimethylamino)-3,5 dimethyl-, methylcarbamate (ester) Phenol, (3,5-dimethyl-4 (methylthio)-, methylcarbamate Phenol, 2,4-dinitroPhenol, 2-methyl-4,6-dinitro-, & salts Phenol, 3-(1-methylethyl)-, methyl carbamate Phenol, 3-methyl-5-(1methylethyl)-, methyl carbamate Phenol, 2-(1-methylpropyl)-4,6 dinitro-
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Waste CAS Number By Waste Substance Number P009 P092 P093 P094 P095 P096 P041 P039 P094 P044 P043 P089 P040 P097 P071 P204 P188 P110 P098 P099 P201 P203 P070 P101 P027 P069 P081 P017 P102 P003 P005 P067 P102 P008 P075 P204
131-74-8 62-38-4 103-85-5 298-02-2 75-44-5 7803-51-2 311-45-5 298-04-4 298-02-2 60-51-5 55-91-4 56-38-2 297-97-2 52-85-7 298-00-0 57-47-6 57-64-7 78-00-2 151-50-8 506-61-6 2631-37-0 1646-88-4 116-06-3 107-12-0 542-76-7 75-86-5 55-63-0 598-31-2 107-19-7 107-02-8 107-18-6 75-55-8 107-19-7 504-24-5 *54-11-5 57-47-6
P114 P103 P104 P105 P106 P108 P018 P108
12039-52-0 630-10-4 506-64-9 26628-22-8 143-33-9 *57-24-9 357-57-3 *57-24-9
Phenol, 2,4,6-trinitro-, ammonium salt Phenylmercury acetate Phenylthiourea Phorate Phosgene Phosphine Phosphoric acid, diethyl 4 nitrophenyl ester Phosphorodithioic acid, O,O-diethyl S-[2-(ethylthio)ethyl] ester Phosphorodithioic acid, O,O-diethyl S-[(ethylthio)methyl] ester Phosphorodithioic acid, O,O-dimethyl S-[2-(methylamino)-2 oxoethyl] ester Phosphorofluoridic acid, bis(1-methylethyl) ester Phosphorothioic acid, O,O-diethyl O-(4-nitrophenyl) ester Phosphorothioic acid, O,O-diethyl O-pyrazinyl ester Phosphorothioic acid, O-[4-[(dimethylamino)sulfonyl]phenyl] O,O-dimethyl ester Phosphorothioic acid, O, O,-dimethyl O-(4-nitrophenyl) ester Physostigmine Physostigmine salicylate Plumbane, tetraethylPotassium cyanide K(CN) Potassium silver cyanide Promecarb Propanal, 2-methyl-2-(methyl sulfonyl)-, O [(methylamino)carbonyl] oxime Propanal, 2-methyl-2-(methylthio)-, O [(methylamino)carbonyl]oxime Propanenitrile Propanenitrile, 3-chloroPropanenitrile, 2-hydroxy-2 methyl1,2,3-Propanetriol, trinitrate 2-Propanone, 1-bromoPropargyl alcohol 2-Propenal 2-Propen-1-ol 1,2-Propylenimine 2-Propyn-1-ol 4-Pyridinamine Pyridine, 3-(1-methyl-2-pyrrolidinyl)-, (S)-, & salts Pyrrolo [2,3-b]indol-5-ol, 1,2,3,3a,8,8a-hexahydro 1,3a,8-trimethyl-, methylcarbamate (ester), (3aS-cis) Selenious acid, dithallium (1+) salt Selenourea Silver cyanide Ag (CN) Sodium azide Sodium cyanide Na (CN) Strychnidin-10-one, & salts Strychnidin-10-one, 2,3-dimethoxyStrychnine, & salts
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Waste CAS Number By Waste Substance Number P115 P109 P110 P111 P112 P062 P113 P113
7446-18-6 3689-24-5 78-00-2 107-49-3 509-14-8 757-58-4 1314-32-5 1314-32-5
Sulfuric acid, dithallium (1+) salt Tetraethyldithiopyrophosphate Tetraethyl lead Tetraethyl pyrophosphate Tetranitromethane Tetraphosphoric acid, hexaethyl ester Thallic oxide Thallium oxide Tl2O3
P114 P115 P109 P045 P049
12039-52-0 7446-18-6 3689-24-5 39196-18-4 541-53-7
Thallium(I) selenite Thallium(I) sulfate Thiodiphosphoric acid, tetraethyl ester Thiofanox Thioimidodicarbonic diamide [(H2N)C(S)]2NH
P014 P116 P026 P072 P093 P185 P123 P118 P119 P120
108-98-5 79-19-6 5344-82-1 86-88-4 103-85-5 26419-73-8 8001-35-2 75-70-7 7803-55-6 1314-62-1
Thiophenol Thiosemicarbazide Thiourea, (2-chlorophenyl)Thiourea, 1-naphthalenylThiourea, phenylTirpate Toxaphene Trichloromethanethiol Vanadic acid, ammonium salt Vanadium oxide V2O5
P120 P084 P001 P205 P121 P121
1314-62-1 4549-40-0 *81-81-2 137-30-4 557-21-1 557-21-1
Vanadium pentoxide Vinylamine, N-methyl-N-nitroso Warfarin, & salts, when present at concentrations greater than 0.3% Zinc, bis(dimethylcarbamodithioato-S,S') Zinc cyanide Zinc cyanide Zn (CN)2
P122
1314-84-7
Zinc phosphide Zn3P2, when present at concentrations greater than 10%
P205
137-30-4
Ziram
FOOTNOTE:*CAS Number given for parent compound only.
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APPENDIX C Safe Chemical Storage 1. Acids - Store large bottles of acids on low shelf or in acid cabinets. - Segregate oxidizing acids from organic acids, flammables and combustible materials. - Segregate acids from bases and active metals such as sodium, potassium, etc. - Have spill control pillows or acid neutralizers available in case of spill. - Sulfuric Acid and Nitric Acid must be in their own segregated secondary containment. Strong Oxidizing Acids Chromic acid Hydrobromic Acid Iodic Acid Nitric Acid Perchloric Acid Sulfuric Acid
Organic Acids Acetic Acid Benzoic Acid Phenol Trichloroacetic Acid
2. Bases - Segregate bases from acids. - Store solutions of inorganic hydroxides in polyethylene containers. - Have spill control pillows or caustic neutralizers available for spills. Ammonium Hydroxide Bicarbonates Carbonates
Calcium Hydroxide Potassium Hydroxide Sodium Hydroxide
3. Flammables - Store in approved safety cans or cabinets. - Segregate from oxidizing acids and oxidizers. - Keep away from any source of ignition: flames, heat or sparks. - Know where fire-fighting equipment is stored and how to use it. - Store volatile, flammable liquids in explosion-proof refrigerator. Flammable Solids Benzoyl peroxide Calcium Carbide Flammable Gases Acetylene Ammonia Butane Carbon Monoxide Ethane
Phosphorus, yellow Picric Acids
Ethyl Chloride Ethylene Ethylene Oxide Formaldehyde Hydrogen
Hydrogen Sulfide Methane Propane Propylene
4. Oxidizers - Store in a cool, dry place. - Keep away from flammable and combustible materials, such as paper or wood. - Keep away from reducing agents such as zinc, alkaline metals, formic acid. - DO NOT STORE IN A FLAMMABLE CABINET.
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Oxidizers - Solids Ammonium Dichromate Ammonium Perchlorate Ammonium Persulfate Benzoyl Peroxide Bromates Calcium Hypochlorite Chlorates Chromium Trioxide
Ferric Trioxide Ferric Chloride Iodates Iodine Nitrates Periodic Acid Permanganic Acid Peroxides, Salts of
Potassium Dichromate Potassium Ferricyanide Potassium Permanganate Potassium Persulfate Sodium Chlorite Hypochlorite Sodium Dichromate Sodium Perborate
5. Pyrophoric Substances: These ignite spontaneously on contact with air. - Store in a cool, dry place. Boron Diborane Cadmium Dichloroborane Calcium Furaldehyde Chromium* Iron* Cobalt* Lead* * Finely divided metals form a pyrophoric hazard.
Magnanese* Nickel* Phosphorus, Yellow* Titanium* Zinc*
6. Light Sensitive Chemicals - Avoid exposure to light. - Store in amber bottles in a cool, dry place. Bromine Ethyl Ether Ferric Ammonium Citrate Hydrobromic Acid
Mercuric Salts Oleic Acid Potassium Ferricyanide
Silver salts Sodium Iodide Mercurous Nitrate
7. Carcinogens - Label all containers as Cancer Suspect Agents. - Store according to hazardous nature of chemicals, e.g. flammable, corrosive. - When necessary, store securely. Antimony compounds Arsenic compounds Benzidine Beryllium Cadmium compounds
Chromates, Salts of Beta-Napthylamine Vinyl Chloride Acrylonitrile Benzene
Chloroform Dimethyl Sulfate Dioxane Ethylene Dibromide Hydrazine Nickel Carbonyl
8. Water Reactives -DO NOT STORE UNDER SINK -Store in own secondary containment -Location, substance, and amount must be posted on NFPA sign, or on cabinet. Acetic Anhydride Sulfuric Acid 66
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INCOMPATIBLE CHEMICALS - IN STORAGE AND REACTIONS Care must always be taken to ensure that incompatible chemicals do not come into contact with each other. Such contact could result in an explosion or fire or the liberation of highly toxic vapors. Incompatibilities are listed in Section VI of most Material Safety Data Sheets.
________________________________________ Acetaldehyde: acids, bases, phenols, alcohols, strong oxidizers, ammonia, amines, ketones, hydrogen sulfide, hydrogen cyanide. Forms peroxides on contact with air. Acetic Acid: chromic acid, nitric acid, ethylene glycol, perchloric acid, peroxides, permanganates, phosphates Acetone: sulfuric and nitric acids, oxidizers. Acetonitrile: strong oxidizers Acetylene: copper (tubing), fluorine, bromine, chlorine, iodine, silver, mercury and their compounds Acrylamide: strong oxidizers Alkali Metals: (e.g., potassium and sodium) with water, carbon dioxide, carbon tetrachloride, and other chlorinated hydrocarbons. Ammonia, Anhydrous: mercury, halogens, calcium hypochlorite, hydrogen fluoride. Ammonium Nitrate: acids, metal powders, flammable liquids, chlorates, nitrates, sulphur and finely divided organics or combustibles. Aniline: nitric acid, hydrogen peroxide Benzyl Chloride: oxidizers, acids, aluminum, copper, iron, magnesium, zinc. Bleach (sodium hypochlorite): ammonia containing compounds, acids, formaldehyde and other reducing agents Bromine: ammonia, acetylene, butadiene, butane, hydrogen, sodium carbide, turpentine and finely divided metals. Carbon: activated calcium hypochlorate - all oxidizing agents Chlorates: ammonium salts, acids, metal powders, sulphur, finely divided organics or combustibles Chromic Acid: acetic acid, naphthalene, camphor, alcohol, glycerine, turpentine and other flammable liquids Chlorine Dioxide: ammonia, methane, phosphine, hydrogen sulphide Chlorine: ammonia, acetylene, butadiene, and other petroleum fractions, hydrogen, sodium carbide, turpentine and finely divided powdered metals. Copper: acetylene, hydrogen peroxide Cyanides: acids and alkalies Ethanolamine: strong oxidizers, strong acids Ether, ethyl: strong oxidizers; forms peroxides on exposure to air and light Ethyl acetate: nitrates, strong oxidizers, alkalis and acids Ethylene glycol dinitrate: acids, alkalis Flammable liquids: ammonium nitrate, chromic acid, hydrogen peroxide, nitric acid, sodium peroxide, halogens Formaldehyde: strong oxidizers, alkalis and acids (e.g. hydrogen peroxide, hydrochloric acid), phenols, magnesium carbonate, nitromethane, peroxyformic acid Formic Acid: strong oxidizers, strong caustics, concentrated sulfuric acid; corrosive to metals Hexane: strong oxidizers Hydrazine: oxidizers, acids (e.g., hydrogen peroxide, nitric acid) metallic oxides; may ignite on contact with porous organic materials (e.g., cloth, wood). Hydrochloric acid: hydroxides, alkalis, amines; corrosive to most metals Hydrogen Sulfide: fuming nitric acid, oxidizing gases. Hypochlorites: acids, activated carbon. Iodine: acetylene, ammonia (aqueous or anhydrous), hydrogen. Isoamyl alcohol: strong oxidizers Isoprophyl alcohol: strong oxidizers, acids, acetylene, chlorine, ethylene oxide Mercury: acetylene, fulminic acid, copper, chlorine dioxide Nitrates: acids Nitric Acid (concentrated): acetic acid, aniline, chromic acid, hydrocyanic acid, hydrogen sulfide, flammable liquids, flammable gases, copper, brass, any heavy metals.
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Nitrites: acids Nitroparaffins: inorganic bases, amines Oxalic Acids: silver, mercury Oxygen: oils, grease, hydrogen, flammable liquids, solids, or gases Perchloric Acid: acetic anhydride, bismuth and its alloys, alcohol, paper, wood, grease, oils. Peroxides, organic: acids (organic or mineral), avoid friction, store cold Phenol: strong oxidizers, acids, bases, calcium hypochlorite, aluminum chloride, metals (aluminum, magnesium, lead, zinc are attacked by hot phenol) Phosphoric Acid: strong caustics; reacts with most metals to produce hydrogen gas Phosphorous (white): air, oxygen , alkalis, reducing agents. Potassium: carbon tetrachloride, carbon dioxide, water Potassium chlorate: sulfuric and other acids Potassium perchlorate (see also chlorates): sulfuric and other acids. Potassium permanganate: glycerol, ethylene glycol, benzaldehyde, sulfuric acid Propanol: strong oxidizers Silver: acetylene, oxalic acid, tartaric acid, ammonium compounds, fulminic acid. Sodium: carbon tetrachloride, carbon dioxide, water. Sodium Hydroxide: acids, flammable liquids, organic halogens, nitromethane, corrosive to most metals Sodium Nitrite: ammonium nitrate and other ammonium salts. Sodium Peroxide: ethyl or methyl alcohol, glacial, acetic acid, acetic anhydride, benzaldehyde, carbon disulfide, glycerin, ethylene glycol, ethyl acetate, methyl acetate, furfural. Sulfides: acids Sulfuric Acid: organic materials, chlorates, perchlorates, permanganates, carbides, fulminates Toluene: strong oxidizers Triethylamine: strong oxidizers, strong acids Xylenes: strong oxidizers
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APPENDIX D Common Peroxides and Maximum Retention Times EHS recommends that you dispose of peroxide forming chemicals that have been kept longer than their maximum retention times. The maximum retention times begin on the date of opening a manufacturer’s bottle or the date of synthesis in your laboratory. Peroxides form at varying rates depending on the chemical, the length of exposure to air and light and the container type. Peroxides can form in freshly distilled and unstabilized ethers within two weeks, in ethyl ether within eight days, and in tetrahydrofuran within three days. Below are lists of peroxide forming chemicals and their maximum retention times. Follow this guide unless an expiration date is provided by the chemical manufacturer. There are four classes of peroxide-forming chemicals based upon the peroxide formation hazard: Class A – Severe Peroxide Hazard Class B – Concentration Hazard Class C – Shock and Heat Sensitive Class D – Potential Peroxide-Forming Chemicals Peroxide-forming chemicals must be disposed within the timeframes specified in the table below regardless if the container has unopened. Disposal with EHS must occur within the timeframe allowed once the container is received or opened, whichever the earlier of the two dates.
Date Opened Date Received
Class A 3 months 1 year
Class B 6 months 1 year
Class C 6 months 1 year
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Class D Only if peroxide crystals are present.
Peroxide Forming Chemical Lists Class A – Severe Peroxide Hazard Spontaneously decompose and become explosive with exposure to air without concentration. Butadiene (liquid monomer) Chloroprene (liquid monomer) Divinyl acetylene
Isopropyl ether Potassium amide Potassium metal
Sodium amide (sodamide) Tetrafluoroethylene (liquid monomer) Vinylidene chloride
Class B – Concentration Hazard Require external energy for spontaneous decomposition. Form explosive peroxides when distilled, evaporated or otherwise concentrated. Acetal Acetaldehyde Benzyl alcohol 2-Butanol Cumene Cyclohexanol Cyclohexene 2-Cyclohexen-1-ol Decahydronaphthalene Diacetylene Dicyclopentadiene
Diethylene glycol dimethyl ether (diglyme) Diethyl ether Dioxanes Ethylene glycol dimethyl ether (glyme) Furan 4-Heptanol 2-Hexanol Methylacetylene 3-Methyl-1-butanol Methylcyclopentane Methyl isobutyl ketone
4-Methyl-2-pentanol 2-Pentanol 4-Penten-1-ol 1-Phenylethanol 2-Phenylethanol 2-Propanol Tetrahydrofuran Tetrahydronaphthalene Vinyl ethers Other secondary alcohols
Class C – Shock and Heat Sensitive Highly reactive and can auto-polymerize as a result of internal peroxide accumulation. The peroxides formed in these reactions are extremely shock and heat sensitive. Acrylic acid Acrylonitrile Butadiene (gas) Chloroprene
Chlorotrifluoroethylene Methyl methacrylate Styrene Vinylpyridine Tetrafluoroethylene (gas)
Vinyl acetate Vinylacetylene (gas) Vinyladiene chloride Vinyl chloride (gas)
Class D – Potential Peroxide Forming Chemicals May form peroxides but cannot be clearly categorized in Class A, B, or C. Acrolein Allyl ether Allyl ethyl ether Allyl phenyl ether p-(n-Amyloxy)benzoyl chloride n-Amyl ether Benzyl n-butyl ether Benzyl ether Benzyl ethyl ether
p-Chlorophenetole Cyclooctene Cyclopropyl methyl ether Diallyl ether p-Di-n-butoxybenzene 1,2-Dibenzyloxyethane p-Dibenzyloxybenzene 1,2-Dichloroethyl ethyl ether 2,4-Dichlorophenetole
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4,5-Hexadien-2-yn-1-ol n-Hexyl ether o.p-Iodophenetole Isoamyl benzyl ether Isoamyl ether Isobutyl vinyl ether Isophorone b-Isopropoxypropionitrile Isopropyl-2,4,5-trichlorophenoxy acetate
Benzyl methyl ether Benzyl-1-napthyl ether 1,2-Bis(2-chloroethoxyl)ethane Bis(2-ethoxyethyl)ether Bis(2-(methoxyethoxy)ethyl) ether Bis(2-chloroethyl) ether Bis(2-ethoxyethyl) adipate 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) ether 2-Bromomethyl ethyl ether beta-Bromophenetole o-Bromophenetole p-Bromophenetole 3-Bromopropyl phenyl ether tert-Butyl methyl ether n-Butyl phenyl ether n-Butyl vinyl ether Chloroacetaldehyde diethylacetal 2-Chlorobutadiene 1-(2-Chloroethoxy)-2-phenoxyethane Chloroethylene Chloromethyl methyl ether beta-Chlorophenetole o-Chorophenol
Diethoxymethane 2,2-Diethoxypropane Diethyl ethoxymethylenemalonate Diethyl fumarate Diethyl acetal Diethylketene Diethoxybenzene (m-,o-,p-) 1,2-Diethoxyethane Dimethoxymethane 1,1-Dimethoxyethane Di(1-propynl) ether Di(2-propynl) ether Di-n-propoxymethane 1,2-Epoxy-3-isopropoxypropane 1,2-Epoxy-3-phenoxypropane p-Ethoxyacetophenone 1-(2-Ethoxyethoxy)ethyl acetate 2-Ethoxyethyl acetate (2-Ethoxyethyl)-a-benzoyl benzoate 1-Ethoxynaphthalene o,p-Ethoxyphenyl isocyanate 1-Ethoxy-2-propyne 3-Ethoxypropionitrile 2-Ethylacrylaldehyde oxime 2-Ethylbutanol Ethyl-b-ethoxypropionate Ethylene glycol monomethyl ether 2-Ethylhexanal Ethyl vinyl ether 2,5-Hexadiyn-1-ol
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n-Methylphenetole 2-Methyltetrahydrofuran 3-Methoxy-1-butyl acetate 2-Methoxyethanol 3-Methoxyethyl acetate 2-Methoxyethyl vinyl ether Methoxy-1,3,5,7-cyclooctatetraene b-Methoxypropionitrile m-Nitrophenetole 1-Octene Oxybis(2-ethyl acetate) Oxybis(2-ethyl benzoate) b,b-Oxydipropionitrile 1-Pentene Phenoxyacetyl chloride a-Phenoxypropionyl chloride Phenyl-o-propyl ether p-Phenylphenetone n-Propyl ether n-Propyl isopropyl ether Sodium 8-11-14-eicosatetraenoate Sodium ethoxyacetylide Tetrahydropyran Triethylene glycol diacetate Triethylene glycol dipropionate 1,3,3-Trimethoxypropene 1,1,2,3-Tetrachloro-1,3-butadiene 4-Vinyl cyclohexene Vinylene carbonate
APPENDIX E Particularly Hazardous Substance Use Approval Form Before using any particularly hazardous substance, please complete this form and have it approved by the EHS Manager. See the back of this form for more complete definitions of a particularly hazardous substances and instructions for completing this form.
Name_____________________________ Phone _____________ Building ______________ Supervisor _________________________ Lab Group ________________________________
1. Substance Information A. Chemical name ___________________________________ CAS number _______________ B. Primary Hazards (eg. Acutely toxic, pyrophoric, high hazard processes) _________________________________________________________________ C. Estimated Rate of Use (e.g., grams/month) _______________________ D. MSDS reviewed and readily available
□ Yes □ No
2. Hazards Physical Hazards A. Flammable □ Yes C. Reactive
□ Yes
□ No □ No
□ Yes □ No D. Temperature sensitive □ Yes □ No B. Corrosive
E. Stability (e.g., decomposes, forms peroxides, polymerizes, shelf-life concerns)
□ Stable □ Unstable F. Known incompatibilities ___________________________________________________________________ Health Hazards G. Significant Route(s) of Exposure Inhalation Hazard □ Yes □ No Skin Absorption H. Sensitizer
□ Yes □ No
□ Yes □ No I. Medical Consultation Needed
3. Procedure A. Briefly describe how the material will be used
B. Vacuum system used □ Yes □ No C. If yes, describe method for trapping effluents Page 81 of 99
□ Yes □ No
4. Exposure Controls Ventilation/Isolation A. Hood required □ Yes
□ No
See hood sticker for the following information
If yes, hood currently operates at 95 - 125 feet per minute face velocity Lab Hood number ________________ B. Glove box required
□ Yes □ No
C. Vented gas cabinet required
□ Yes □ No
□ Yes □ No
D. Personal Protective Equipment (PPE) (Check all that apply) □ Safety glasses □ Chemical splash goggles □ Face shield
□ Gloves ( type _________) □ Lab coat □ Respirator
□ Apron
□Other, please describe _________________________________
5. Location/Designated Area A. Building ________________________________ B. Room _________________________ C. Describe below the area where substance(s) will be used and the method of posting as a designated area.
D. Location where substances will be stored _________________________________________ E. Storage Method/Precautions □ refrigerator/freezer
□ double containment □ flammable liquid storage cabinet
□ hood □ vented cabinet □ other, describe ___________________________
6. Spills and Decontamination A. Spill control materials readily available
□ Yes □ No
B. Special personal protective equipment needed (e.g., respirator) Describe _________________
□ Yes □ No
C. Decontamination method ______________________________________________________
7. Waste Disposal
□ Yes □ No C. Dispose as hazardous waste □ Yes □ No A. In-lab neutralization
B. Deactivation
□ Yes □ No
8. Authorization This individual has demonstrated an understanding of the hazards of the listed substance and plans to handle the substance in a manner that minimizes risk to health and property. He/she is authorized to use the substance in the manner described. Page 82 of 99
____________________________ Principal Investigator/Supervisor
____________________________ EHS Manager
Please submit this form to ______________. Do not use the substance until approval is granted.
KEY TO FORM* Using this form For purposes of this form, a particularly hazardous substance (PHS) includes known or suspected human carcinogens, reproductive toxins, and substances with acute toxicity above certain thresholds. A more complete definition is included in the Clarkson Chemical Hygiene Plan. Each individual planning to use a PHS must complete this form and have it approved by their Principal Investigator or supervisor and the EHS Manager prior to their initial use. Responsibility for determining whether a chemical is a PHS and completing this form rests jointly with the supervisor and the individual seeking use approval. To simplify the approval process, EHS has developed a list of the more commonly used PHSs; however, this list is not exhaustive. For help in determining whether a substance meets the PHS criteria, call EHS at x6640.
1. Substance Information A. Enter name and CAS (Chemical Abstract Service) number of the PHS. B. Carcinogen: if on IARC, OSHA or NTP list Reproductive toxin: mutagens, teratogens, embryotoxins High Acute Toxicity: oral LD50 ≤ 50 mg/kg, skin LD50 ≤ 200 mg, air LC50 ≤ 200 ppm or ≤ 2 mg/l. See Chemical Hygiene Plan for more information. C. Self-explanatory D. MSDS may be available in hard copy or via the internet.
2. Hazards Refer to Physical Properties section of MSDS A. Flammable liquid: flashpoint ≤ 100° F Flammable solid: liable to cause fire through friction, absorption of moisture, spontaneous chemical change, or which can be ignited readily and when ignited burns vigorously B. Corrosive: Causes visible destruction of, or irreversible alterations in, living tissue by chemical action at the site of contact.
C. Reactive: May become unstable or contact with water produces flammable or toxic gas. D. Temperature Sensitive: Must be kept within a certain temperature range to ensure stability. E. Unstable: substance will vigorously polymerize, decompose, condense, or will become self-reactive under conditions of shock, or high or elevated pressure or temperature. Also includes timesensitive materials, particularly those that produce peroxides over time. F. List chemicals or materials that might cause instability or adverse conditions if mixed with the particularly hazardous substance(s). G. Inhalation: inhalation of the substance may cause adverse health effects. Skin exposure: substance is readily absorbed through the skin or can cause significant damage to skin upon contact. H. Certain chemicals are known to effect the immune system, causing a person to experience allergic reactions, up to and including anaphylactic shock, upon exposure to the chemical, after the initial sensitization. I. Some chemicals can accumulate in body tissues and may require initial or periodic medical surveillance. Contact EHS or the Student Health Center for more information.
3. Procedure A. Briefly describe the part of the experimental procedure that involves the substance, with particular attention to how the chemical will be manipulated. B. Vacuum systems include central vacuum systems and vacuum pumps within the lab. C. Describe what will be done to ensure that the substance is not accidentally drawn into the vacuum system. Cold traps or filters are some examples of such measures.
4. Exposure Controls A. A fume hood should be used for chemicals that may produce vapors, mists, or fumes, or if the procedure may cause generation of aerosols. The hood must have an average face velocity of between 95 and 125 feet per minute. This measurement is noted on the hood survey sticker. If
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the hood has not been inspected within the past year, contact EHS at 8-5294 for re-inspection before using the hood. The EHS hood number is noted on the top of the fume hood inspection sticker. B. A glove box should be used if protection from atmospheric moisture or oxygen is needed or when a fume hood may not provide adequate protection from exposure to the substance; e.g., a protection factor of 10,000 or more is needed. C. Highly toxic gases must be used and stored in a vented gas cabinet connected to a laboratory exhaust system. Gas feed lines operating above atmospheric pressure must use coaxial tubing. D. Safety glasses protect from flying particles and minor chemical splashes, for instance, from opening a centrifuge tube. Chemical splash goggles should be worn when there is a possibility of a significant chemical splash. Most chemical manipulations, particularly where pressure is involved, warrant chemical splash goggles. Face shield, worn with splash goggles, provides full face protection when working with large volumes of chemicals. Gloves should be worn when working with any particularly hazardous substance. Since not all gloves offer significant protection from every chemical, it is important to choose the glove that offers the best resistance. See the MSDS or glove manufacturer compatibility charts for more information. Lab coats should be worn when working with hazardous substances. The coat should not be worn outside the laboratory and should be laundered separately from other clothing. Aprons offer chemical resistance and protection from splashes and can be used in conjunction with a lab coat. Respirators offer protection from inhalation of substances when engineering controls are not sufficient. Use of respirators must be approved by
EHS. Contact EHS at x6640 if a respirator is needed.
5. Location/Designated Area A and B. Building and room number where the substance will be used. C. Describe where in this room the substance will be used. For example, in a hood, on a specific benchtop, in several areas of the laboratory, etc. This room or area must be posted with a Designated Area sticker. D. Describe where the substance will be stored. Be specific, e.g, on a shelf, in a refrigerator, in a hood, etc. E. Self-explanatory. Double containment means that the container will be placed inside another container that is capable of holding the contents in the event of a leak and provides a protective outer covering in the event of contamination of the primary container.
6. Spills and Decontamination A and B. Self-explanatory. C. Describe how the work area will be decontaminated after use, in the event of a spill, or upon completion of the work and before removal of the designated area signage.
7. Waste Disposal A. Some corrosive chemicals may be neutralized before disposal via the drain or the hazardous waste program. B. Some materials, such as ethidium bromide, can be chemically deactivated before disposal via the drain or the hazardous waste program. C. See the EHS web page for more information about the hazardous waste program. Particularly hazardous substances must not be poured down the drain without consulting EHS.
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APPENDIX F Chemical Carcinogens OSHA Without establishing PELs, OSHA promulgated standards in 1974 to regulate the industrial use of 13 chemicals identified as potential occupational carcinogens. 2-Acetylaminofluorene 4-Aminodiphenyl Benzidine bis-Chloromethyl ether 3,3'-Dichlorobenzidine 4-Dimethylaminoazobenzene Ethyleneimine Methyl chloromethyl ether alpha-Naphthylamine beta-Naphthylamine 4-Nitrobiphenyl N-Nitrosodimethylamine beta-Propiolactone Exposures of workers to these 13 chemicals are to be controlled through the required use of engineering controls, work practices, and personal protective equipment, including respirators. See 29 CFR 1910.1003-1910.1016 for specific details of these requirements (http://www.osha.gov/pls/oshaweb/owadisp.show_document?p_id=10007&p_table=STANDARDS).
U.S. National Toxicology Program: 11th Report on Carcinogens For many years, government research agencies (including the National Toxicology Program), industries, academia, and other research organizations have studied various substances to identify those that may cause cancer. Much of this information on specific chemicals or occupational exposures has been published in the scientific literature or in publicly available and peer-reviewed technical reports. This literature is a primary source of information for identifying and evaluating substances for listing in the RoC. Many of the listed substances also have been reviewed and evaluated by other organizations, including the International Agency for Research on Cancer (IARC) in Lyon, France, the Environmental Protection Agency of the State of California, and other U.S. Federal and international agencies. The criteria for listing an agent, substance, mixture, or exposure circumstance in the RoC are as follows: Known To Be Human Carcinogen: There is sufficient evidence of carcinogenicity from studies in humans*, which indicates a causal relationship between exposure to the agent, substance, or mixture, and human cancer. Reasonably Anticipated To Be Human Carcinogen: There is limited evidence of carcinogenicity from studies in humans*, which indicates that causal interpretation is credible, but that alternative explanations, such as chance, bias, or confounding factors, could not adequately be excluded, or there is sufficient evidence of carcinogenicity from studies in experimental animals, which indicates there is an increased incidence of malignant and/or a combination of malignant and benign tumors (1) in multiple species or at
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multiple tissue sites, or (2) by multiple routes of exposure, or (3) to an unusual degree with regard to incidence, site, or type of tumor, or age at onset, or there is less than sufficient evidence of carcinogenicity in humans or laboratory animals; however, the agent, substance, or mixture belongs to a well-defined, structurally related class of substances whose members are listed in a previous Report on Carcinogens as either known to be a human carcinogen or reasonably anticipated to be a human carcinogen, or there is convincing relevant information that the agent acts through mechanisms indicating it would likely cause cancer in humans. Conclusions regarding carcinogenicity in humans or experimental animals are based on scientific judgment, with consideration given to all relevant information. Relevant information includes, but is not limited to, dose response, route of exposure, chemical structure, metabolism, pharmacokinetics, sensitive sub-populations, genetic effects, or other data relating to mechanism of action or factors that may be unique to a given substance. For example, there may be substances for which there is evidence of carcinogenicity in laboratory animals, but there are compelling data indicating that the agent acts through mechanisms which do not operate in humans and would therefore not reasonably be anticipated to cause cancer in humans. The list of chemicals Known to be a Human Carcinogens and Reasonably Anticipated to be A Human Carcinogen as well as other information can be found at: (http://ntp.niehs.nih.gov/index.cfm?objectid=32BA9724F1F6-975E-7FCE50709CB4C932)
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APPENDIX G Laboratory Health and Safety Resources Regulatory and Standard Setting Agencies: Official Government Information: − Code of Federal Regulations http://www.access.gpo.gov/nara/cfr/cfr-table-search.html. available online via GPO Access Consumer Product Safety Commission; http://www.cpsc.gov/ Department of Agriculture; http://www.usda.gov/wps/portal/usdahome Department of Energy (DOE); http://www.energy.gov/ − DOE Environmental Safety and Health Home Page; http://www.hss.energy.gov/index.cfm Department of Transportation (DOT); http://www.dot.gov/ − DOT Office of Hazardous Materials Safety-Regulations, Clarifications and Exemptions: http://www.phmsa.dot.gov/ Environmental Protection Agency (EPA); http://www.epa.gov/ Food and Drug Administration (FDA); http://www.fda.gov/ National Institute for Occupational Safety and Health (NIOSH); http://www.cdc.gov/niosh/ New York State DEC; http://www.dec.ny.gov/ Occupational Safety and Health Administration (OSHA); http://www.osha.gov/ Other Chemical Hazard Information Sources: Agency for Toxic Chemical Substance & Disease Registry (ATSDR); http://www.atsdr.cdc.gov/ CCOHS: The MSDS-A Practical Guide to First Aid; http://www.ccohs.ca/products/publications/firstaid/ International Agency for Research on Cancer (IARC); (via Lyon, France) http://www.iarc.fr/ National Toxicology Program (NTP) Chemical Health and Safety Data; http://ntp.niehs.nih.gov/ntpweb/index.cfm?objectid=03610FD3-EEE1-D79C-9C441DA0299F41D0 National Toxicology Program (NTP) 10th Annual Report on Carcinogens; http://ntp.niehs.nih.gov/index.cfm?objectid=06F2561B-D0C1-8FDE-B673A8C0D27BFC83 NIOSH Information: − Chemical Occupational Safety and Health Database; http://www.cdc.gov/niosh/docs/81-123/ − NIOSH Analytical Methods; http://www.cdc.gov/niosh/docs/2003-154/ − NIOSH Pocket Guide to Chemical Hazards; http://www.cdc.gov/niosh/npg/ − Recommendations for Chemical Protective Clothing; http://www.cdc.gov/niosh/ncpc/ncpc1.html − 1988 OSHA PEL Project Documentation; http://www.cdc.gov/niosh/pel88/pelstart.html
OSHA's Chemical Sampling Information, including Occupational Exposure Limits; http://www.osha.gov/dts/chemicalsampling/toc/toc_chemsamp.html
Biosafety and Public Health Links: American Biological Safety Association; http://www.absa.org/ American Public Health Association (APHA); http://www.apha.org/ Centers for Disease Control (CDC); http://www.cdc.gov/ − CDC Office of Health and Safety Information System; http://www.cdc.gov/od/ohs/default.htm Page 87 of 99
−
CDC National Center for Environmental Health (NCEH); http://www.cdc.gov/nceh/default.htm
Health and Human Services; http://www.os.dhhs.gov/, and US Public Health Service; http://www.usphs.gov/ National Environmental Health Association (NEHA); http://www.neha.org/index.shtml World Health Organization (WHO); http://www.who.int/en/
Hazardous Materials / Hazardous Waste Management Links: DOT Office of Hazardous Materials Safety-Regulations, Clarifications and Exemptions; http://www.phmsa.dot.gov/ EPA's Emergency Management; http://www.epa.gov/emergencies/programs.htm EPA Office of Solid Waste and Emergency Response Brownfields Cleanup and Redevelopment; http://www.epa.gov/swerosps/bf/ Industrial Hygiene & Occupational Health Links: American Conference of Governmental Industrial Hygienists (ACGIH); http://www.acgih.org/home.htm American Industrial Hygiene Association (AIHA); http://www.aiha.org/Pages/default.aspx American Society of Heating, Refrigeration, and Air Conditioning Engineers (ASHRAE); http://www.ashrae.org/ *for a more detailed version of the list above, go to the University of Wisconsin website: http://www.uwm.edu/Dept/EHSRM/EHSLINKS/#REGULATORY_and_STANDARD%20SETTING%20A GENCIES
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APPENDIX H CFR 1910.1450 Occupational Exposures to Hazardous Chemicals in Laboratories, Final Rule January 31, 1990 The full text of this regulation can be found at http://www.osha.gov/pls/oshaweb/owadisp.show_document?p_table=standards&p_id=10106
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APPENDIX I Laboratory Specific Procedures (Laboratory workers should create their own procedures for processes and experiments in their lab and keep a binder of these procedures in the laboratory or with their copy of the Chemical Hygiene Plan). See Section 3.17 for information on how to write your own procedures.
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APPENDIX J Record of Laboratory Specific Training All researchers must complete laboratory safety orientation prior to commencement of work in a laboratory. The Orientation course is provided by the Environmental Health & Safety Manager, however it is not the only training that should be completed by the researcher. Faculty should ensure further training is completed in the laboratory on laboratory specific hazards and procedures. A record of those trainings should be noted below. Name of Person Trained
Name of Trainer
Date of Training
Training Topics
Add additional training logs to this appendix, as needed.
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Appendix K
Laboratory Safety Hazard Assessment Tool Phone: 315-268-6640 • Fax: 315-268-4437•Email:
[email protected] Website: http://www.clarkson.edu/dehs.html
This form must be completed by the PI, Lab Supervisor, or their designee to conduct a laboratory hazard assessment specific to activities in their laboratories. The laboratory hazard assessment identifies hazards to lab personnel and specifies personal protective equipment (PPE) to protect lab personnel during work activities. The person conducting the assessment must verify that it is complete and that training has been conducted. This assessment consists of four sections and serves as a step in satisfying PPE requirements. Section 1: Section 2: Section 3: Section 4:
Lab Information Laboratory Hazard Assessment Conduct PPE Training Verification of PPE Training
Environmental Health & Safety (EH&S) personnel are available to assist you with completing this form or with reviewing it after you have completed it. EH&S may also be consulted for specific questions such as chemical-resistant glove selection and limitations of various PPE by calling 315-2686640. Section 1: Lab Information Department Lab location(s) with building & room number(s) Principal Investigator & Lab Manager/Supervisor Activity Name & title of person conducting assessment Phone number Email address Date assessment completed
Section 2: Laboratory Hazard Assessment In this section, you will:
Conduct a hazard assessment of the laboratory to identify potentially hazardous job tasks performed in your area.
Conduct an assessment to determine if engineering, work practice and/or administrative controls can be used to control the hazards. If engineering, work practice and/or administrative controls cannot be used, identify the appropriate protective equipment that is needed to protect staff from exposure to hazards. Certify the hazard assessment for the laboratory by signing in Section 1.
The following checklists are an overview of common lab activities and associated potential hazards along with suggested engineering controls and applicable PPE. Check each box that describes activities performed by lab personnel.
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Are the following activities performed in the lab?
Yes
No
Chemical Hazards Activity
Potential Hazard
Engineering Controls
Applicable PPE 2 - Safety glasses or goggles - Light chemical-resistant gloves - Lab coat
Working with small volumes (< 1 liters) of corrosive liquids.
- Eye or skin damage
Working with large volumes (> 1 liters) of corrosive liquids, small to large volumes of acutely toxic corrosives, or work which creates a splash hazard.
- Poisoning - Use a chemical fume hood or other engineering control - Increased potential for eye 1 whenever possible and skin damage
- Safety goggles - Heavy chemical-resistant gloves - Lab coat and chemical-resistant apron
Working with small volumes (< 1 liters) of organic solvents or flammable organic compounds.
- Skin or eye damage - Potential poisoning through skin contact
- Safety glasses or goggles - Light chemical-resistant gloves - Lab coat
Working with large volumes (> 1 liters) of organic solvents, small to large volumes of very dangerous solvents, or work which creates a splash hazard.
- Major skin or eye damage - Potential poisoning through skin contact - Fire
Working with toxic or hazardous chemicals (solid, liquid, or gas).
- Skin or eye damage - Potential poisoning through skin contact
Working with acutely toxic or hazardous chemicals (solid, liquid, or gas).
- Increased potential for eye - Use a chemical fume hood or or skin damage - Increased potential other engineering control 1 poisoning through skin whenever possible contact
- Safety goggles - Heavy chemical-resistant gloves - Lab coat
Working with an apparatus with contents under pressure or vacuum.
- Eye or skin damage
- Safety glasses or goggles, face shield for high risk activities - Chemical-resistant gloves - Lab coat, chemical-resistant apron for high risk activities
Working with air or water reactive chemicals.
- Severe skin and eye damage - Fire
- Safety glasses or goggles - Chemical-resistant gloves - Lab coat, flame resistant lab coat for high risk activities; chemical-resistant apron for high risk activities
Working with potentially explosive chemicals.
-
Splash Detonation Flying debris Skin and eye damage Fire
- Use a chemical fume hood or other engineering control 1 whenever possible
- Use a chemical fume hood or other engineering control 1 whenever possible
- Work in inert atmosphere, when possible
- Safety goggles - Heavy chemical-resistant gloves - Flame-resistant lab coat (e.g. Nomex) - Safety glasses (goggles for large quantities) - Light chemical-resistant gloves - Lab coat
- Safety glasses, face shield, and blast shield - Heavy gloves - Flame-resistant lab coat (e.g. Nomex)
Working with low and high temperatures. Are the following activities performed in the lab?
Yes
No
- Safety glasses - Lab coat - Thermal insulated gloves
- Burns - Splashes - Fire
Biological Hazards Activity Working with human blood, body fluids, tissues, or blood borne pathogens (BBP).
Potential Hazard - Exposure to infectious material
Working with preserved animal and/or human specimens.
- Exposure to infectious material or preservatives
Working with radioactive human blood, body fluids, or blood borne pathogens (BBP).
- Cell damage - Potential spread of radioactive contaminants - Potential BBP exposure
Engineering Controls - Use a Biosafety cabinet to minimize exposure3
Applicable PPE - Face shield, or facemask with goggles - Nitrile gloves - Lab coat or gown - Safety glasses or goggles - Protective gloves such as nitrile for unpreserved specimens (select protective glove for preserved specimens according to preservative used) - Lab coat or gown. - Safety glasses (goggles for splash hazard) - Nitrile gloves - Lab coat or gown - Safety glasses or goggles - Nitrile gloves for broken skin or skin rash - Lab coat or gown
Working with agents or recombinant DNA classified as Biosafety Level 1 (BSL-1).
- Eye or skin irritation
Manipulation of cell lines, viruses, bacteria, or other organisms classified as Biosafety Level 2 (BSL-2).
- Exposure to infectious material, particularly through broken skin or mucous membranes
Manipulation of infectious materials classified as Biosafety Level 2 facility with BSL-3 practices (BSL-2+).
- Exposure to infectious materials with high risk of exposure by contact or mucous membranes
-
Safety glasses or goggles Double nitrile gloves Lab coat or disposable gown Surgical mask
Manipulation of infectious materials classified as Biosafety Level 3 (BLS-3).
- Exposure to infectious materials with high risk of exposure, particularly through the inhalation route
-
Safety glasses or goggles Double nitrile gloves Full disposable gown or Tyvek suite Respirator Shoe covers or dedicated shoes
Working with live animals (Animal Biosafety Level 1).
- Animal bites - Allergies
- Use a Biosafety cabinet to minimize exposure3
- Use in BL 3 Laboratory Only
- Safety glasses or goggles - Nitrile gloves - Lab coat or gown
- Safety glasses or goggles - Nitrile or vinyl gloves for broken skin or skin rash - Lab coat or gown - Consider need for wire mesh glove
Working with live animals (Animal Biosafety Level 2).
- Animal bites - Exposure to infectious material - Allergies
Are the following activities performed in the lab?
Yes
Safety glasses or goggles Nitrile or vinyl gloves Lab gown Hair cover Shoe covers Surgical mask Consider need for wire mesh glove
Radiological Hazards
No
Activity
Potential Hazard
Engineering Controls - Use in Chemical Fume Hood if dispersible or volatile
Applicable PPE - Safety glasses - Impermeable gloves - Lab coat
Working with radioactive materials.
- Potential spread of radioactive materials
Working with radioactive materials in hazardous chemicals (corrosives, flammables, liquids, powders, etc.).
- Spread of contamination - Hazards for the specific chemical
- Safety glasses (or goggles for splash hazard) - Light chemical-resistant gloves (applicable to the chemical hazard) - Lab coat
Working with ultraviolet radiation.
- Conjunctivitis - Corneal damage - Skin redness
- UV face shield and goggles - Lab coat
Working with infrared emitting equipment (e.g. glass blowing).
- Cataracts - Burns to cornea
- Appropriate shaded goggles - Lab coat
Are the following activities performed in the lab?
Yes
- Use a Biosafety cabinet to minimize exposure3
-
Laser Hazards
No
Activity
Potential Hazard
Engineering Controls
Applicable PPE
Open Beam Performing alignment, troubleshooting or maintenance that requires working with an open - Eye damage beam and/or defeating the interlock(s) on any Class 3 or Class 4 laser system.
- Appropriately shaded goggles/glasses with optical density based on individual beam parameters
Viewing a Class 3R laser beam with magnifying optics (including eyeglasses).
- Eye damage
- Appropriately shaded goggles/glasses with optical density based on individual beam parameters
Working with a Class 3B laser open beam system with the potential for - Eye damage producing direct or specular - Skin damage reflections.
- Appropriately shaded goggles/glasses with optical density based on individual beam parameters - Appropriate skin protection
- Eye damage - Skin damage
- Appropriately shaded goggles/glasses with optical density based on individual beam parameters - Appropriate skin protection
Non-Beam Handling dye laser materials, such as powdered dyes, chemicals, and solvents.
- Cancer - Explosion - Fire
- Gloves - Safety glasses - Flame-resistant lab coat or coveralls
Maintaining and repairing power sources for large Class 3B and Class 4 laser systems.
- Electrocution - Explosion - Fire
- Electrical isolation mat - Flame-resistant lab coat or coveralls
Working with a Class 4 laser open beam system with the potential for producing direct, specular, or diffuse reflections.
Are the following activities performed in the lab?
Yes
No
Physical Hazards Activity
Potential Hazard
Engineering Controls
Applicable PPE - Safety glasses or goggles for large volumes - Impermeable insulated gloves - Lab coat
Working with cryogenic liquids.
- Major skin, tissue, or eye damage
Removing freezer vials from liquid nitrogen
- Vials may explode upon rapid warming - Cuts to face/neck and frostbite to hands
- Face shield - Impermeable insulated gloves - Lab coat
Working with very cold equipment or dry ice.
- Frostbite - Hypothermia
- Safety glasses - Insulated gloves (possibly warm clothing) - Lab coat
Working with hot liquids, equipment, open flames (autoclave, Bunsen burner, water bath, oil bath).
- Burns resulting in skin or eye damage
- Safety glasses or goggles for large volumes - Insulated gloves (impermeable insulated gloves for liquids, steam) - Lab coat
Glassware washing.
- Lacerations
- Heavy rubber gloves - Lab coat
Working with loud equipment, noises, sounds, alarms, etc.
- Potential ear damage and hearing loss
- Earplugs or ear muffs as necessary.
Working with a centrifuge.
- Imbalanced rotor can lead to broken vials, cuts, exposure.
- Safety glasses or goggles - Lab coat - Vinyl or nitrile gloves
- Ear damage
-
Working with a sonicator.
Safety glasses or goggles Lab coat Vinyl or nitrile gloves Ear plugs
Working with sharps.
Is the following activity performed in the lab?
Yes
No
- Safety glasses or goggles - Lab coat - Vinyl or nitrile gloves
- Cuts
Nanomaterial Hazard Activity Working with engineered nanomaterials.
Potential Hazard
No
Applicable PPE - Goggles - Gloves - Lab coat
- Inhalation exposure - Dermal exposure
Is the following activity performed in the lab?
Yes
Engineering Controls
Other Hazards Activity
Potential Hazard
Engineering Controls
-
−
-
-
-
-
-
-
Applicable PPE -
Standard Lab Safety Attire Reminders
Footwear: must completely cover the feet - no sandals or flip-flops. Clothing: must completely cover the legs - no shorts or short skirts. Jewelry, especially rings and watches, should not be worn when working with chemicals. Long hair or loose items should be tied back or removed.
Please note that you may be asked to leave the lab if you do not come prepared to work safely in the lab with proper lab attire. 1
Activities not conducted inside a chemical fume hood or with other engineering controls (such as a local exhaust at the workbench) should be evaluated by the EH&S Department to determine if the activity presents a respiratory hazard. 2 Chemical-resistant gloves are to be selected based on the specific chemical(s) used. Contact the EH&S Department for assistance if needed. 3 Activities that cannot be conducted inside a biosafety cabinet should be evaluated by the CHB Biosafety Officer.
Section 3: Conduct PPE Training PPE training consists of two parts: Part 1 is a general presentation provided at New Employee Lab Safety training and Part 2 is site specific training conducted by the lab supervisor. Verification is required to document that training has been conducted (see the following page). Step 1 The PI or lab supervisor assures that the employees attend the New Employee Lab Safety Training held by the Environmental Health & Safety Department Office upon hire. Step 2 1. The PI, lab manager, or their designee reviews the completed Hazard Assessment Tool (this document) with the employee. It describes the tasks in the lab when employees need PPE to protect themselves from exposure to hazards. In this step, the hazard assessment is used as a training tool. 2. While discussing lab activities and the associated hazards with lab staff, the supervisor will address how their lab obtains PPE, what types of PPE are used in the lab and for which tasks, where and how the PPE is stored and maintained, how to properly use the PPE, and discuss any limitations of the PPE. The supervisor should also discuss general PPE safety practices, including not wearing PPE outside of lab hazard areas (e.g. hallways and eating areas). Step 3 When the supervisor believes the employee has demonstrated understanding, the employee(s) and the supervisor then sign the following Verification of PPE Training form (next page) to document that PPE training has been conducted. A copy of this signed form is to be maintained in each employee’s file as well as sent to the Environmental Health & Safety Department Office (Box 5542;
[email protected]). Step 4 Repeat or conduct refresher training with all staff on an annual basis or whenever the hazard assessment is updated.
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Section 4: Verification of PPE Training The following employees of (laboratory) have attended the New Employee Lab Safety Training and have received the following training: 1. 2. 3. 4. 5.
When PPE is necessary What PPE is required How to properly don, doff, adjust, and wear PPE The limitations of PPE The proper care, maintenance, useful life, and disposal of PPE EMPLOYEE NAME
EMPLOYEE SIGNATURE
As a part of this training, employees were informed of the personal protective equipment selected by this facility for their use. By my signature and those of the employees listed above, we certify that each employee has demonstrated his/her understanding of this training. (Signature of Trainer)
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