R. Bohm P. McSwiggen R. Knurr W. Seyfried
Departmental Safety Training Records: - People who are up to date on safety training. - People who need to update their safety training. - People who need their basic safety training.
Forward
1. Introduction A. Purpose B. Scope and Application C. Coordination with Other University Standards D. Responsibilities 2. Standard Operating Procedures A. Use of Prudent Practices for Handling Hazardous Chemical in Laboratories B. Other References C. University Standards and Recommended Practices 3. Criteria for Implementation of Control Measures A. When to Use Fume Hoods B. When to Use Safety Shields or Other Containment Devices C. When to Use Personal Protective Equipment 4. Management of Fume Hoods and Other Protective Equipment A. Frequency and Type of Monitoring B. Acceptable Operating Range C. Responsibility for Monitoring D. Maintenance E. Training F. New Systems 5. Employee Information and Training. A. Information B. Training 6. Required Approvals 7. Medical Consultation and Examination. A. Criteria for Consultation or Examination B. Medical Service Provider C. Information for Examining Physician D. Report from Examining Physician 8. Personnel. A. Chemical Hygiene Officer B. College or Departmental Laboratory Safety Officer C. College or Departmental Safety Committee D. Department of Environmental Health and Safety E. Occupational Physician 9. Additional Employee Protection for Work with Particularly Hazardous Substances 10. Record keeping, Review and Update of Chemical Hygiene Plan. A . Record keeping B. Review and Update of Chemical Hygiene Plan
Appendix A - 29 CFR 1910.1450, Occupational Exposure to Hazardous Chemicals in Laboratories Appendix B - Limits of Exposure to Toxic and Hazardous Substances Appendix C - Other Standards and Guidelines Appendix D - Prudent Practices for Handling Hazardous Materials in Laboratories, pp. 21-29 and 154-212 Appendix E - University of Minnesota Specific Policies for Safe Practices in Laboratories Appendix F - Prudent Practices for Handling Hazardous Materials in Laboratories, pp. 30-153 Appendix G - Script, "Laboratory Chemicals and Your Health" Appendix H - Annotated Bibliography and Audio-Visual Materials References Appendix I - First Report of Injury Form Appendix J - Duties of a Departmental Laboratory Safety Officer Appendix K - Department of Environmental Health and Safety - Staff and Services Appendix L - Form BA 725 - MERTKA and Chemical Hygiene Plan Training Record Appendix M - Cardiovascular Division Laboratory Safety Information Sheet Appendix N - Laboratory Audit Checklist Supplemental Geology & Geophysics appendices Appendix O - Departmental SOPs (Standard Operating Procedures) Appendix P - Chemical inventories for each research group
The University of Minnesota has mandated that a Chemical Hygiene Plan (CHP) be developed for eachdepartment and ultimately for each working laboratory group within the University. This plan will be based on an appropriately modified version of the University of Minnesota's generic CHP. This plan must be on file in the home department and at the Department of Environmental Health and Safety (DEHS). The Geology and Geophysics Departmental Safety Committee is charged with the responsibility for implementing this program within the Department of Geology and Geophysics. The committee members, assigned by the Department Chair, were selected as those staff people who have high contacts with faculty and students and who control access to much of the laboratory activities conducted in the Department. Current members are: Calvin Alexander, Faculty Ron Bohm, Machine Shop Rick Knurr, Geochemistry Laboratory Peter McSwiggen (chair), Electron microprobe Laboratory Bill Seyfried, Dept. Chair Recognizing that each individual lab/PI does not need a complete CHP, we have written a general Departmental CHP. We have divided the Department into Research Groups along the lines of current research activities. Each group will be responsible for implementing within itself the mandated procedures presented below. The CHP will be made lab-specific for each research group by incorporating documents regarding specific lab procedures from that group. This document has two sections: (1) a draft of the respective responsibilities of departmental Principal Investigators (PIs) and of the Departmental Safety Committee and (2) the Departmental CHP plan. Both parts require annual revision. We will appreciate your input and comments. The current research groups in Geology and Geophysics are listed below. These are flexible and can be regrouped by bringing a verbal request to the committee. (The MN Geological Survey has a separate CHP)
I. Responsibilities of the Departmental Safety Committee 1. Annually update the Geology and Geophysics Departmental CHP. 2. Communicate the responsibilities of each PI to the departmental PIs and provide help and information if requested. 3. Provide department-wide training in a timely manner at periodic intervals. This training will cover the main features of the Departmental CHP, general lab safety procedures, and hazardous waste procedures. 4. Perform laboratory walk-throughs, as requested by the lab PIs, to assist Pis in identifying potential safety problems. 5. Keep an annually updated list of PIs, locations of the labs, and principle lab activities. 6. Work with the departmental PIs to develop a list of chemicals that require special approval before being used. Develop and implement procedures for approval of use of these chemicals that are on the pre-approval list and maintain a list of granted approvals. 7. Hold regular meetings (at least quarterly) to plan actions related to the above and to deal with safety issues as they arise.
II. Responsibilities of the Departmental researchers
Each PI (faculty, staff, post-doc) is responsible for the safe condition of the labs under his/her control and for meeting the basic requirements of the Departmental CHP. Departmental requirements listed below are based on the University of MN generic CHP and have legal mandates as well. 1. DEVELOP LAB SAFETY AND TRAINING LOG >> Establish and maintain a Lab Safety and Training Log. What to do: Purchase a notebook to be the Lab Safety and Training Log, keep it in an accessible location, and make brief entries with date, names of people involved, and a brief description of events. Record such things as the notes from an annual lab-specific safety meeting, training records, and any information/issues that come up. One notebook should be sufficient for several years. 2. REQUIRE INITIAL TRAINING >> Newly hired persons, including graduate students, must be trained in the safety issueslisted here before they begin lab activities on a regular basis. What to do: Start a training log for the new person. Document that they have either attended a session run by the Departmental Safety Committee or alternatively, have read Appendices C and G in the University's generic CHP or viewed the tape "Laboratory Safety and Your Health" at Walter Library. Enter the action in the Lab Safety and Training Log. Anyone who trains a new lab member is considered to be self-retraining. 3. MAINTAIN TRAINING AND SAFETY AWARENESS IN LAB >> Annually update: (1) general lab safety training of all people using the lab, including the PI, graduate students, undergraduate students and long-term guests, and (2) lab-specific training in special procedures. Keep a log of this training. **Everyone, including faculty, must have an updated Laboratory Saftety Standard (29 CFR 1910.1450) Training Record form on file within the department. What to do: (1) READ the Departmental CHP and briefly review the appendices derived from the University's generic CHP. This document can be accessed through the department's WEB page. Then sign a copy of the "Laboratory Safety Standard Training Record" and return it to the Department's Safety Committee. (2) Hold a lab-specific meeting to discuss and review your lab-specific procedures. Keep minute in the Lab Safety and Training Log. 4. DEVELOP REQUIRED WRITTEN PROCEDURES >> For Labs using hazardous chemicals: >Review the attached list of chemicals that require a written Standard Operating Procedure (SOP) and develop one for lab-specific use if any of these chemicals are in use in your lab. >Place a copy in a readily accessible place in the lab and with the Departmental Safety Committee for incorporation into the Departmental CHP. What to do: (1) Go through the list of chemicals in Appendix O. If you are using a chemical on the list, then a separate SOP is mandated for each one. Initially, inform the Committee that you are using a chemical requiring a SOP. Prepare the documents and file copies with the department immediately, if possible within a month. (2) If you are using a chemical that you feel needs special handling, and if it is not on the list, talk to a member of the Departmental Safety Committee. 5. DEVELOP OTHER WRITTEN PROCEDURES >> When a detailed process involves hazardous materials, a written procedures can be helpful part of a lab-specific CHP. Routine handling of such things as acids or gas cylinders is assumed to be covered in the basic training. However more involved processes sometimes require written procedures. These procedure should be included in the Lab's CHP and a copy given to the Departmental Safety Committee. 6. BE AWARE OF ANY ESPECIALLY HAZARDOUS CHEMICALS AND PROCEDURES >> Review lists of governmentally-defined highly toxic materials. Review lab for any of these very dangerous materials. What to do: If any of these materials are used in your lab, then work with the Safety Committee to develop appropriate protocols and training. File the required documents requesting use permissions, protocols, and training 7. PROVIDE ACCESSIBLE INFORMATION ON CHEMICALS >> Copies of Material Safety Data Sheets (MSDS) for hazardous materials must be accessible in the lab. What to do: The committee suggests a folder/envelope mounted on the door of each room. Sheets are almost always supplied with orders or are available from the bound book of MSDSs located near Sharon's desk in the office (104 Pills). Copies of this MSDS book will also be available in the Reading Room (204 Pills), in the Geochemistry Lab (4 Pills), in LRC in 672 Civil Engineering, in the IRM in 290 Shepherd Labs, and in P168 in Kolthoff Hall. MSDS sheets are also available on the internet. Make certain that all people using the lab know where the lab-specific sheets are. 8. MAINTAIN SAFETY EQUIPMENT >> Keep appropriate types of safety equipment available in the lab and in good operating condition. Inspect on a regular basis. What to do: Go through your lab periodically. Check that aprons, goggles, gloves, coats, shields, safety switches, etc. are functional. Replace/repair broken items such as leaking gloves, cracked goggles, etc. Also, make sure you have the right safety equipment for the job. For example, HF should be handled with full face shields and long-sleeve plastic aprons (not just goggles and a lab coat); heavy liquids require special gloves. All hoods must have a "tell-tale" (small piece of yarn or tissue) taped to the opening, so that the presence of airflow is immediately detectable. Record your surveys in the Lab Safety and Training Log.
1. Introduction A. Purpose Guidance: Each PI must review the CHP and decide how to apply pertinent sections to the chemicals and procedures used in the laboratory. If changes, deletions and/or modifications are necessary, contact the departmental Laboratory Safety Officer to modify the text to address local hazards, policies and procedures. Geology and Geophysics modification: Within the Department of Geology and Geophysics, implementation of a Chemical Hygiene Plan (CHP) is ultimately the responsibility of each PI working with the Departmental Safety Committee. The respective responsibilities of the Departmental Safety Committee and each PI are defined in the attached front-material. On an annual basis, one member of the departmental safety committee will contact each PI to complete a safety review within that PI's laboratory. This Chemical Hygiene Plan describes policies, procedures, equipment, personal protective equipment and work practices that are capable of protecting employees from the health hazards presented by many hazardous chemicals used in laboratories. This Plan is intended to meet the requirements of the federal Occupational Safety and Health Administration (OSHA) standard, Occupational Exposure to Hazardous Chemicals in Laboratories, a copy of which is found in Appendix A. This Chemical Hygiene Plan is intended to safely limit laboratory workers' exposure to OSHA- regulated substances. Laboratory workers must not be exposed to substances in excess of the permissible exposure limits (PEL) specified in OSHA rule 29 CFR 1910, Subpart Z, Toxic and Hazardous Substances. PELs for regulated substances are provided in Appendix B. PELs refer to airborne concentrations of substances and are averaged over an eight-hour day. A few substances (listed under Individual Chemical Standard in the Federal column of Appendix C) also have "action levels". Action levels are air concentrations below the PEL which nevertheless require that certain actions such as medical surveillance and workplace monitoring take place. Guidance: Pay particular attention to the following paragraph. If you, as a PI or a Lab Safety Officer, suspect exposure concentrations exceed allowable levels, please contact the Department of Environmental Health and Safety for air monitoring assistance. Geology and Geophysics modification: The issue of monitoring regulated substances will be addressed in the annual review of safety in each laboratory. Changes that occur between reviews must be reported by the PI to the Safety Committee. An employee's workplace exposure to any regulated substance must be monitored if there is reason to believe that the exposure will exceed an action level or a PEL. If exposures to any regulated substance routinely exceed an action level or permissible exposure level there must also be employee medical exposure surveillance. B. Scope and Application Guidance: In this section, specify which researchers and laboratories in the department are covered by this standard. The text below provides guidance. Some departments have provided a list of PIs and locations, and a phrase describing of the type of research occurring in that area. Geology and Geophysics modification: The Safety Committee will generate and annually update a list of PI's and Laboratories including locations and research types. This list is attached at the end of the CHP and is hereby incorporated into the Departmental CHP. This standard applies where "laboratory use" of hazardous chemicals occurs. Laboratory use of hazardous chemicals means handling or use of such chemicals in which all of the following conditions are met: i) the handling or use of chemicals occurs on a "laboratory scale", that is, the work involves containers which can easily and safely be manipulated by one person, ii) multiple chemical procedures or chemical substances are used, and iii) protective laboratory practices and equipment are available and in common use to minimize the potential for employee exposures to hazardous chemicals. At a minimum, this definition covers employees (including student employees, technicians, supervisors, lead researchers and physicians) who use chemicals in teaching, research and clinical laboratories at the University of Minnesota. Certain non-traditional laboratory settings may be included under this standard at the option of individual departments within the University. Also, it is the policy of the University that laboratory students, while not legally covered under this standard, will be given training commensurate with the level of hazard associated with their laboratory work. Geology and Geophysics modification: Geology and Geophysics laboratories appear to meet the definition of "laboratory scale, so the above guidelines apply. These standards apply to all people working in the labs, including student employees, technicians, supervisors, lead researchers and physicians. Procedures for safe handing of chemicals must also be followed in field conditions. This standard does not apply to laboratories whose function is to produce commercial quantities of material. Also, where the use of hazardous chemicals provides no potential for employee exposure, such as in procedures using chemically impregnated test media and commercially prepared test kits, this standard will not apply. When laboratory work is limited to use of these commercially available kits, a Chemical Hygiene Plan is not required. C. Coordination With Other Standards and Guidelines Guidance: Several other University standards and state and federal rules pertain to activities carried out in research at the University. Each PI should check the regulations listed in Appendix C, and contact DEHS for more information on any standard that may apply to the laboratory operations. Although this standard deals only with use of hazardous chemicals, employees may also encounter potential physical, biological or radioactive hazards in the laboratory. Regulations and guidelines for these situations that are in effect at the University of Minnesota are listed in Appendix C. Geology and Geophysics modification: Geological research often involves use of heavy equipment, vehicles, power tools, and highly specialized or custom-made equipment. Radiation hazards are also a potential issue. The PI is responsible for checking the regulations listed in Appendix C. The Safety Committee will help establish the necessary contacts with DEHS. In the unlikely event that there is a conflict between provisions of various standards, the Department of Environmental Health and Safety should be contacted to assist in resolving the discrepancy. D. Responsibilities Guidance: Implementation of the Laboratory Safety Standard at the University is a shared responsibility. Employees, supervisors, Laboratory Safety Officers, department heads, deans, administrative staff, and DEHS staff all have roles to play. These roles are outlined generally below. The Laboratory Safety Officer should tailor these general descriptions to fit the reality of the distribution of responsibility within the department. i. Employer a. University-Wide The University of Minnesota, in conjunction with its colleges and departments, is responsible for developing and supporting a broad-based chemical hygiene program that will protect its laboratory employees from health effects associated with hazardous chemicals. Management is responsible for integrating safety into all of its activities, for promoting the same attitude among all levels of employment at the University, and for providing adequate time and recognition for employees who are given laboratory safety responsibilities. b. Colleges and Non-academic Departments Guidance: Insert the name of the college/department/division in the title and first sentence, and identify the designated laboratory safety officer. Note whether the chemical hygiene plan pertains to the named division, department or entire college. Note that the plan has been modified to incorporate location-specific information. Geology and Geophysics modification: The members of the Geology and Geophysics Departmental Safety Committee are: Calvin Alexander, Faculty Ron Bohm, Shop and Building Manager Rick Knurr, Geochemical Laboratory Manager Peter McSwiggen, Electron Microprobe Laboratory Bill Seyfried, Departmental Chair This committee is selected to represent staff and facilities that are directly involved with much of the laboratory activity that goes on in the department. Each college and non-academic department that engages in the laboratory use of hazardous chemicals will identify at least one laboratory safety officer to serve as a focal point for laboratory health and safety activities within the unit and as liaison with the Department of Environmental Health and Safety. Colleges that are made up of a number of large laboratory-based departments are urged to assign laboratory safety officers within each department. (The laboratory safety officer is not to be confused with the Safety Coordinator system presently existing at the University. These are separate responsibilities, although they may be held by the same individual.) Each college and non-academic department will modify this generic Chemical Hygiene Plan to incorporate location-specific information and will submit a copy of the modified plan to the Chemical Hygiene Officer for approval. Each college and non-academic department will also identify the assigned laboratory safety officers within their units and will transmit that information to the Chemical Hygiene Officer. ii. Department of Environmental Health and Safety (DEHS) The Department of Environmental Health and Safety is responsible for preparing and updating the University's Chemical Hygiene Plan, for distributing it to departments who will implement the Plan, and for monitoring the progress of departments toward achieving compliance. Dawn Errede will serve as the Chemical Hygiene Officer for the University, and the entire DEHS staff will participate in providing resources for departments in the development of their individual health and safety programs. iii. Supervisor The immediate supervisor of a laboratory employee is responsible for scheduling time for the employee to attend designated training sessions and for assuring that potential hazards of specific projects have been identified and addressed before work is started. The supervisor is also responsible for enforcing safe work practices and for reporting hazardous conditions to the college or departmental laboratory safety officer. Geology and Geophysics modification: The supervisor is defined as the PI. Another person may be designated, but the primary responsibility for an individual lab resides with the PI. iv. Employee Each laboratory employee is responsible for attending safety training sessions, following safety guidelines applicable to the procedures being carried out, assuring that required safety precautions are in place before work is started, and reporting hazardous conditions as they are discovered. Employees who have significant responsibility for directing their own laboratory work are responsible for assuring that potential hazards of specific projects have been identified and addressed before work is started. Geology and Geophysics modification: An employee (for the purposes of needing safety training) is anyone working or supervising in a lab, including paid and non-paid students, professors, staff, post-docs and visitors using the lab. Appropriate training must be given to all. 2. Standard Operating Procedures Guidance: Subsections A, B, and C present the topics of the Standard Operating Procedures already included in Appendices D, E, and F. Each PI should review these subsections and appendices and adopt and train staff on all the SOPs which pertain to the chemicals and procedures used in the laboratory. Work with particularly hazardous or unique chemicals and/or procedures may not be covered by the SOPs listed below. In this case, the PI must write SOPs that describe the work to be conducted, and the safety measures to be taken by the employee. Procedures and written safety precautions included in laboratory notebooks may serve as laboratory-specifi SOPs. Keep these individual SOPs in the laboratory and train employees on their contents. Forward a list of these SOPs to the departmental Laboratory Safety Officer so they can be referenced in subsection D of the departmental CHP. Geology and Geophysics modification: Each PI should review Appendices D, E, and F and train staff on all the SOPs which pertain to the chemicals and procedures used in the laboratory. SOPs for non-standard procedures must be written up and given to the Safety Committee for incorporation into the departmental plan. Copies must also be available in the laboratories. The department will offer general training sessions twice a year on the most basic SOPs, such as for handling acids, bases, flamables, and compressed gas tanks. For required training outside these sessions, the Committee will provide information on written and visual training documents available at Walter Library. A. The laboratory operating procedures found in Prudent Practices in the Laboratory: Handling Hazardous Chemicals in Laboratories (National Research Council, 1995) are reproduced in Appendix D. Chapters 5 (Working with Chemicals) and 6 (Working with Laboratory Equipment) can be accessed by University of Minnesota personnel electronically from DEHS's web site (www.dehs.umn.edu). The following topics are covered in these sections of Prudent Practices: Working with Chemicals - Introduction - Prudent Planning - General Procedures for Working with Hazardous Chemicals - Working with Substances of High Toxicity - Working with Biohazardous and Radioactive Materials - Working with Flammable Chemicals -Working with Highly Reactive or Explosive Chemicals - Working with Compressed Gases Working with Laboratory Equipment - Introduction - Working with Water-Cooled Equipment - Working with Electrically Powered Laboratory Equipment - Working with Compressed Gases - Working with High/Low Pressures and Temperatures - Using Personal Protective, Safety, and Emergency Equipment - Emergency Procedures Geology and Geophysics modification: These practices described above are hereby incorporated into the departmental plan. B. A second useful manual is the American Chemical Society's Safety in Academic Chemistry Laboratories. This manual presents information similar to that found in Prudent Practices, but in a considerably condensed format. C. Certain standard operating procedures have been adopted by the University of Minnesota specifically forits own laboratories. Extensive and detailed policies regarding hazardous waste management are specified in the University's manual, "Hazardous Chemical Waste Management, 4th edition". Other more specific standard operating procedures are reproduced in Appendix E and are listed below. Geology and Geophysics modification: These practices are hereby incorporated into the departmental plan. PIs must be certain that training in hazardous waste is current for all people working in the labs. Specific University of Minnesota Policies for Safe Practices in Laboratories Corridors Disposal of Ethidium Bromide Extension Cords in University Buildings Eye Protection and Standard for Eye Protection General Purpose Fume Hoods and Additional Requirements for Radioisotopes and Perchloric Acid Hoods General Purpose Laboratory Hood Inspection Procedure Guidelines for Managing Peroxide-Forming Materials Quantity of Flammable and Combustible Liquids in University of Minnesota Laboratories Safe Practices During Servicing of Exhaust Systems in Research Facilities Termination of Laboratory Use of Hazardous Materials Use and Handling of Perchloric Acid Use and Storage of Compressed Gas Cylinders in University of Minnesota Buildings Use of Laboratory Glassware Subjected to Pressure or Vacuum D. Guidance: In this section, reference any laboratory-specific SOPs that the PIs in the department havedeveloped to cover chemicals and/or procedures not addressed in Subsections A, B, and C (above). Some departments include these SOPs in a separate appendix, and attach a Laboratory Safety Information Sheet to each protocol/procedure (Appendix F). In this section, simply note what specific SOPs have been developed and how employees can access them. The full text of SOPs developed by individual research groups is included in Appendix O, or can be obtained from the referenced PI, or from the Laboratory Safety Officer, for the Department of Geology and Geophysics. Safety information is included in each SOP, and may be highlighted in a Laboratory Safety Information Sheet, similar to the one included in Appendix F 3. Criteria for Implementation of Control Measures Guidance: This section does not require extensive tailoring. However, laboratory safety officers for some departments have provided descriptions and floor plans that identify the location of equipment such as fume hoods, biological safety cabinets, glove boxes, showers, eyewashes, fire extinguishers, etc. Geology and Geophysics modification: Chemical inventories will be done approximately annually. Floor plans should be prepared for each laboratory showing chh(IZE="+1" FACE="Times"> A. When to Use Fume Hoods Geology and Geophysics modification: PI's are responsible on a case-by-case basis for determining which procedures must be done in a fume hood. The laboratory fume hood is the major protective device available to laboratory workers. It is designed to capture chemicals that escape from their containers or apparatus and to remove them from the laboratory environment before they can be inhaled. Characteristics to be considered in requiring fume hood use are physical state, volatility, toxicity, flammability, eye and skin irritation, odor, and the potential for producing aerosols. A fume hood should be used if a proposed chemical procedure exhibits any one of these characteristics to a degree that (1) airborne concentrations might approach the action level (or permissible exposure limit), (2) flammable vapors might approach one tenth of the lower explosion limit, (3) materials of unknown toxicity are used or generated, or (4) the odor produced is annoying to laboratory occupants or adjacent units. Procedures that can generally be carried out safely outside the fume hood include those involving (1) water-based solutions of salts, dilute acids, bases, or other reagents, (2) very low volatility liquids or solids, (3) closed systems that do not allow significant escape to the laboratory environment, and (4) extremely small quantities of otherwise problematic chemicals. The procedure itself must be evaluated for its potential to increase volatility or produce aerosols. In specialized cases, fume hoods will contain exhaust treatment devices, such as water wash-down for perchloric acid use, or charcoal or HEPA filters for removal of particularly toxic or radioactive materials. B. When to Use Safety Shields or Other Containment Devices Geology and Geophysics modification: PI's are responsible on a case-by-case basis for determining which procedures must be done using safety shields or other containment devices. Safety shields, such as the sliding sash of a fume hood, are appropriate when working with highly concentrated acids, bases, oxidizers or reducing agents, all of which have the potential for causing sudden spattering or even explosive release of material. Reactions carried out at non-ambient pressures (vacuum or high pressure) also require safety shields, as do reactions that are carried out for the first time or are significantly scaled up from normal operating conditions. Other containment devices, such as glove boxes or vented gas cabinets, may be required when it is necessary to provide an inert atmosphere for the chemical procedure taking place, when capture of any chemical emission is desirable, or when the standard laboratory fume hood does not provide adequate assurance that overexposure to a hazardous chemical will not occur. The presence of biological or radioactive materials may also mandate certain special containment devices. High strength barriers coupled with remote handling devices may be necessary for safe use of extremely shock sensitive or reactive chemicals. Highly localized exhaust ventilation, such as is usually installed over atomic absorption units, may be required for instrumentation that exhausts toxic or irritating materials to the laboratory environment. Ventilated chemical storage cabinets or rooms should be used when the chemicals in storage may generate toxic, flammable or irritating levels of airborne contamination. C. When to Use Personal Protective Equipment Geology and Geophysics modification: PI's are responsible on a case-by-case basis for determining which procedures must be done using personal protective equipment. Eye protection is required for all personnel and any visitors whose eyes may be exposed to chemical or physical hazards. Side shields on safety spectacles provide some protection against splashed chemicals or flying particles, but goggles or face shields are necessary when there is a greater than average danger of eye contact. A higher than average risk exists when working with highly reactive chemicals, concentrated corrosives, or with vacuum or pressurized glassware systems. Contact lenses should not be worn in the laboratory. Chemicals can be concentrated under contact lenses and contact lenses will interfere with eye flushing in case of emergency. Lab coats or other similar clothing protectors are strongly encouraged for all laboratory personnel. Lab coats are required when working with select carcinogens, reproductive toxins, high degree of acute toxicity, strong acids and bases, and any substance on the OSHA PEL list carrying a "skin" notation. See Appendix B for chemical listings. Gloves made of appropriate material are required to protect the hands and arms from thermal burns, cuts, or chemical exposure that may result in absorption through the skin or reaction on the surface of the skin. Gloves are also required when working with particularly hazardous substances where possible transfer from hand to mouth must be avoided. Thus gloves are required for work involving pure or concentrated solutions of select carcinogens, reproductive toxins, substances which have a high degree of acute toxicity, strong acids and bases, and any substance on the OSHA PEL list carrying a "skin" notation. Gloves should be carefully selected using guides from the manufacturers. General selection guides are available (see Prudent Practices, p. 159); however, glove-resistance to various chemicals materials will vary with the manufacturer, model and thickness. Therefore, review a glove-resistance chart from the manufacturer you intend to buy from before purchasing gloves. Bare feet are not permitted in any laboratory. Sandals and open-toed shoes are strongly discouraged in all laboratories and are not permitted in any situation where lab coats and gloves are required. Respiratory protection is generally not necessary in the laboratory setting and must not be used as a substitute for adequate engineering controls. Availability of respiratory protection for emergency situations may be required when working with chemicals that are highly toxic and highly volatile or gaseous. If an experimental protocol requires exposure above the action level (or PEL) that cannot be reduced, respiratory protection will be required. Rarely, an experimental situation may potentially involve IDLH (immediately dangerous to life or health) concentrations of chemicals, which will require use of respiratory protection. All use of respiratory protective equipment is covered under the University of Minnesota Respiratory Protection Program. Supervisors shall designate areas, activities, and tasks which require specific types of personal protective equipment as described above. 4. Management of Fume Hoods and Other Protective Equipment Guidance: Each PI should identify the safety equipment to be used in the laboratory, and ensure that all employees are properly trained in its use. Since no two fume hoods operate exactly alike, be sure you and your staff understand the operating principals and use safe operating procedures. Please call Environmental Health and Safety for assistance. The Laboratory Safety Officer should insert the name and phone number of the Facilities Management Zone or Hospital Engineers which serves the laboratories in the department [in the underlined section]. Geology and Geophysics modification: Mechanical problems in Pillsbury Hall should initially be brought to the attention of the Building and Shop representative on the Departmental Committee (currently Ron Bohm and other shop staff: 624-4069). If help is not available, call the CLA Zone office at 626-8119. For labs in other buildings, the PI should contact the main office for that building and post the information. A. Monitoring Safety Equipment Fume hoods must be monitored daily by the user to ensure that air is moving into the hood. Any malfunctions must be reported immediately to the appropriate Facilities Managment Zone Office. The hood should have a continuous reading device, such as a pressure gauge, to indicate that air is moving correctly. Users of older hoods without continuous reading devices should attach a strip of tissue or yarn taped to the bottom of the vertical sliding sash. The user must check to ensure the hood and baffles are not blocked by equipment and bottles, as air velocity through the face may be decreased. DEHS staff will measure the average face velocity of each fume hoods annually with a velometer or a thermoanemometer. A record of monitoring results will be made. Geology and Geophysics modification: PI's are responsible on a case-by-case basis for determining that hood mechanisms are functioning in labs under his/her jurisdiction. This includes placing a tell-tale (tissue or yarn strip) in each hood. Eye washes must be flushed weekly by the user. This will ensure that the eye wash is working, and that the water is clean, should emergency use become necessary. The user should coordinate with the Pillsbury Hall shop (4-4069) or the CLA Zone (6-8119) to ensure that emergency showers and eye washes are checked annually. Fire extinguishers will be checked annually by Environmental Health and Safety. The user is responsible for checking regularly to ensure that other protective equipment is functioning properly. Environmental Health and Safety staff can assist with these evaluations, should assistance be necessary. General laboratory conditions must be monitored periodically by the users. A generic laboratory audit form is included in Appendix G, and may be tailroed for use by individual laboratories. The departmental Laboratory Safety Officer or the University's Chemical Hydiene officer may also use this form for spot-checks of the laboratories. Geology and Geophysics modification: The Geology Laboratory Audit form (specific to the department) is hereby added to Appendix G. B. Acceptable Operating Range The acceptable operating range for fume hoods is 80 to 150 linear feet per minute, at the designated sash opening (usually 18 inches). If, during the annual check, a hood is operating outside of this range, DEHS staff may request that you check to ensure the baffles are adjusted properly, and that the exhaust slots are not blocked by bottles and equipment. If these adjustments do not help, DEHS staff will report the deficiency to the appropriate Facilities Management Zone for servicing. C. Maintenance During maintenance of fume hoods, laboratories must clean out and if necessary, decontaminate the fume hood and restrict use of chemicals to ensure the safety of maintenance personnel. See "Safe Practices During Servicing of Exhaust Systems in Research Facilities" in Appendix E. D. Training Training in the appropriate use and care of fume hood systems, showers, eyewashes and other safety equipment will be included in the initial and update training described in Section 5. E. New Systemsx When new ventilation systems, such as variable air volume exhaust, are installed in University facilities, specific policies for their use will be developed by the Department of Environmental Health and Safety and employees will be promptly trained on use of the new equipment. 5. Employee Information and Training Guidance: All employees including PIs must be trained on the topics listed in subsections A and B. Training must occur at initial hire, and at annual refresher intervals. The Chemical Hygiene Plan itself, when tailored, should serve as the training manual. Reading and/or oral presentation of the contents of the CHP manual may be supplemented by video and slide presentations (listed in Appendix H). Make sure staff are trained on the details of all applicable general and laboratory-specific Standard Operating Procedures and document the training on University form BA 725A. A. Information It is essential that laboratory employees have access to information on the hazards of chemicals and procedures for working safely. Supervisors must ensure that laboratory employees are informed about and have access to the following information sources: Geology and Geophysics modification: The departmental CHP and the appendices will be kept in the library and in the departmental offices. Each lab group should have at least one copy available. Copies of the appendices can be requested from DEHS if a copy is needed in an individual lab. See form in Departmental CHP. i. The contents of the OSHA standard, Occupational Exposure to Hazardous Chemicals in Laboratories, and its appendices (29 CFR 1910.1450), a copy of which is found in Appendix A of this Chemical Hygiene Plan. ii. The University of Minnesota Chemical Hygiene Plan, which is available to all employees and can be found in the Learning Resource Centers of the various campus libraries and in the Department of Environmental Health and Safety. Individual department Chemical Hygiene Plans are available within those departments. iii. The Permissible Exposure Limits (PEL) for OSHA regulated substances, which can be found in Appendix B. Also included in Appendix B is the ACGIH Threshold Limit Value (TLV) list. A list of OSHA health hazard definitions, and lists of "select carcinogens", reproductive toxins, and chemicals having a high degree of acute toxicity, are included in Appendix B. iv. Signs and symptoms associated with exposures to hazardous chemicals. Laboratory Chemical Safety Summaries (LCSSs) for 88 commonly-encountered laboratory chemicals are included on pages 235-413 of the 1995 edition of Prudent Practices. LCSSs are similar to Material Safety Data Sheets (MSDS), but are tailored to the hazards of the laboratory using those chemicals. The LCSSs include toxicity information, and signs and symptoms of exposure to the chemicals. v. Material safety data sheets (MSDS) for laboratory chemicals are available from the Department of Environmental Health and Safety and are also located in department offices and in many individual laboratories. Departments that receive MSDS directly with chemical shipments will make such information available to the employees using the chemicals, and will also send a copy of the MSDS to the Department of Environmental Health and Safety. Geology and Geophysics modification: PI's are responsible on for saving and filing in an accessible location all MSDS sheets applicable to the individual lab. There are 3 sources of MSDS sheets. 1. They are shipped with chemicals when ordered. 2. The department also has several copies of a book with MSDSs for the 500 most commonly used chemicals. This book is in the office, Room 104 Pillsbury. Copies of this MSDS book will also be available in the Reading Room (204 Pills), in the Geochemistry Lab (4 Pills), in LRC in 672 Civil Engineering, in each of the three lab groups in Shepard Labs and in the two lab groups in Kolthoff Hall. 3. They are available electronically (Directions transcribed directly from Terri Bonfiglio, DEHS Newsletter, Winter 1995). Material Safety Data Sheets (MSDS), and Registry of Toxic Effects of Chemical Substances (RTECS), are now available on CD from the Department of Environmental Health and Safety (DEHS) and can be accessed with any IBM/compatible or Macintosh microcomputer connected to the campus-wide network. Here's how: MACS Login to the DEHS Mac Server (in the Apple Talk Zone 'DEHS') as a guest. Select CD Access from the list of Appleshare resources. Drag the Optinet and CCINFO folders to your hard disk. Read the Readme 1st document for installation and access instructions. IBM/COMPATIBLES Login to the DEHS_INFO Novell server as a guest. Navigate to the OPTINET subdirectory. Copy the files from the OPTINET subdirectory on the server to a subdirectory called OPTINET on the root level of your hard disk. For the installation and access instructions, read the readme.doc. DEHS has a 10-concurrent user license for University students, staff, and faculty. If the CDs are busy when you try to connect, try again in about an hour. If problems persist, call Terri Bonfiglio at 626-2103 or Marty Davis at 624-0681. vi. Information on chemical waste disposal and spill response is found in the University of Minnesota guidebook, Hazardous Chemical Waste Management, 4th edition. B. Training Each laboratory supervisor is responsible for ensuring that laboratory employees are provided with training about the hazards of chemicals present in their laboratory work area and methods to control exposure to such chemicals. Such training must provided at the time of an employee's initial assignment to a work area where hazardous chemicals are present and prior to assignments involving new potential exposure situations. Refresher training must be provided annually. Colleges and non-academic departments that engage in the laboratory use of hazardous chemicals are responsible for identifying employees who require training and for developing and delivering training programs for such employees. DEHS offers training on the third Thursday of each month that covers general laboratory safety issues, hazardous waste management, and biohazardous material handling. Departments are welcome to send employees to this "base" training at no charge. However, laboratory supervisors must provice additional training on laboratory-specific hazards to ensure all the OSHA-required training topics havebeen adequately addressed. Call DEHS at 626-6002 to register trainees. Geology and Geophysics modification: The department will offer two general training sessions a year (beginning of fall and spring quarters), incorporating the guidelines given below. For new hires starting at the time of the training sessions, this session will meet the requirement. For other times, library material is available. The trainee must (1) do the work before starting work in the lab and (2) give the original of Form BA 725A (signed by self and supervisor) to the Chair of the Departmental Safety Committee. This work will take 1-2 hours. PI's are responsible for filing a statement with the department that they have read and understand the departmental modification of the UMN CHP. Training logs must be kept for general and laboratory-specific SOPs. Employee training programs will include, at a minimum, the following subjects: i. Methods of detecting the presence of hazardous chemicals (observation, odor, real-time monitoring, air sampling, etc.) ii. Basic toxicological principles, including toxicity, hazard, exposure, routes of entry, acute and chronic effects, dose-response relationship, LD50, threshold limit values and permissible exposure limits, exposure time, and health hazards related to classes of chemicals; iii. Good laboratory practice, including general techniques designed to reduce personal exposure and to control physical hazards, as well as specific protective mechanisms and warning systems used in individual laboratories. Appropriate use of fume hoods is to be specifically addressed; iv. Description of information available, including Material Safety Data Sheets; v. Emergency response actions appropriate to individual laboratories; vi. Applicable details of the departmental Chemical Hygiene Plan, including general and laboratory- specific Standard Operating Procedures; vii. An introduction to the Hazardous Chemical Waste Management guidebook. The script for the training program, Laboratory Chemicals and Your Health, is included in Appendix G as an example of information meeting the requirements of items i-iii above. Laboratory Chemicals and Your Health is available in either slide-tape or video format. A list of audio-visual material available from the Department of Environmental Health and Safety, the University Library System, and other resources is included in Appendix H. 6. Required Approvals Guidance: This section requires action. As stated in Section A, the PIs in the department must consider the toxicity of the chemicals used, the hazards of each procedure, and the knowledge and experience of the laboratory workers, and decide which will require approval prior to use. Each PI should forward a list of the selected SOPs to the departmental Laboratory Safety Officer for reference in this section of the CHP. If none of the SOPs require prior approval, the PI should note this fact and forward a brief explanation to the LSO. The LSO should then change the underlined portion of Subsection A to read Geology and Geophysics modification: The list of chemicals/SOPs requiring pre-approval in the Department of Geology and Geophysics are provided below/in Appendix Q" If the department does not use PIH gases, this paragraph may be deleted. Subsection B also requires action. The LSO must work with the PIs to develop a prior approval procedure. This procedure should be described in Subsection B, and substituted for the underlined wording. A. Laboratory employees are required to obtain special approval for use of certain hazardous chemicals. Each department will develop a list of chemicals requiring pre-approval, based upon the chemical, physical and toxicological characteristics of the material, as well as quantity, concentration, and potential for exposure during actual use. At a minimum, use of concentrated chemicals bearing the description Poison Inhalation Hazard - Gases, Category I (Department of Transportation designation) will require approval prior to use. PIH chemicals are highly toxic gases at ambient temperature and pressure. They are listed on page 4 of Appendix B. Geology and Geophysics modification: The Departmental Safety Committee will work with the PIs to develop a list of chemicals that require pre-approval. An initial suggested list is given at the end of the plan and before the appendicies. B. Each department will develop a procedure for obtaining special approval. Approval will depend upon the actual procedure to be carried out, the availability of adequate laboratory facilities, and the capabilities of the persons proposing to perform the work. A written record of approvals will be kept within the department. Geology and Geophysics modification: The Departmental Safety Committee will develop a procedure for approval of use of chemicals that are on the pre-approval list and maintain a list of granted approvals. Approval will depend upon the actual procedure to be carried out, the availability of adequate laboratory facilities, and the capabilities of the persons proposing to perform the work. 7. Medical Consultation and Examination Guidance: This section requires minimal tailoring. PIs must be aware of when an employee is entitled to receive medical attention, and must ensure employees are also aware of the process that will be followed. Geology and Geophysics modification: The department will be certain that all employees who work with hazardous chemicals will have an opportunity to receive medical attention, including any follow-up examinations which the examining physician determines to be necessary. Records will be kept as prescribed below. A. All employees who work with hazardous chemicals will have an opportunity to receive medical attention, including any follow-up examinations which the examining physician determines to be necessary, under the following circumstances: i. Whenever an employee develops signs or symptoms associated with a hazardous chemical to which the employee may have been exposed in the laboratory, the employee will be provided an opportunity to receive an appropriate medical examination. ii. Where exposure monitoring reveals an exposure level routinely above the action level (or in the absence of an action level, the PEL) for an OSHA regulated substance for which there are exposure monitoring and medical surveillance requirements, medical surveillance will be established for the affected employee as prescribed by the particular standard. iii. Whenever an event takes place in the work area such as a spill, leak, explosion or other occurrence resulting in the likelihood of a hazardous exposure, the affected employee will be provided an opportunity for a medical consultation. Such consultation will be for the purpose of determining the need for a medical examination. The Chemical Hygiene Officer will be contacted whenever the need for medical consultation or examination occurs, or when there is uncertainty as to whether any of the above criteria have been met. B. All medical examinations and consultations will be performed by or under the direct supervision of a licensed physician and will be provided without cost to the employee, without loss of pay and at a reasonable time and place. The University of Minnesota's Occupational Medicine Program is located in Boynton Health Service. If off-hours medical attention is required, the employee should be taken to the University Hospitals Emergency Room. A University of Minnesota First Report of Injury form (see Appendix I) should be filled out for any incident resulting in a medical consultation or medical examination. In the event of a life-threatening illness or injury, dial 911 and request an ambulance. C. The University of Minnesota will provide the examining physician with the following information: i. The identity of the hazardous chemical(s) to which the employee may have been exposed; ii. A description of the conditions under which the exposure occurred including quantitative exposure data, if available; and iii. A description of the signs and symptoms of exposure that the employee is experiencing, if any. The above information will be collected and transmitted by the employee's supervisor or department and will be submitted to the Department of Environmental Health and Safety as well as to the examining physician. D. The examining physician will provide to the Department of Environmental Health and Safety a written report including the following: i. Any recommendation for further medical follow-up; ii. The results of the medical examination and any associated tests; iii. Any medical condition which may be revealed in the course of the examination which may place the employee at increased risk as a result of exposure to a hazardous chemical found in the workplace; and iv. A statement that the employee has been informed by the physician of the results of the consultation or medical examination and any medical condition that may require further examination or treatment. The written opinion will not reveal specific findings of diagnoses unrelated to occupational exposure. The Department of Environmental Health and Safety will notify the employee's department of the results of the medical consultation or examination. 8. Personnel Guidance: Compliance with the Laboratory Safety Standard is a shared responsibility. In Subsection B, note whether the CHP covers an entire college, a department or a specific laboratory only. Provide the name of the Laboratory Safety Officer, and describe the LSO's assigned responsibilities. As noted in Subsection B, Appendix J includes typical responsibilities of a departmental LSO. Some of these responsibilities may be delegated to safety committee members (if a safety committee exists), or additional duties may be added at the discretion of the department. In Subsection C, note whether or not a safety committee has been formed, and if so, what its responsibilities are. The following individuals and groups have responsibilities for implementation of various aspects of the University of Minnesota's Chemical Hygiene Plan. A. Chemical Hygiene Officer The University of Minnesota's Chemical Hygiene Officer is Dawn C. Errede, Department of Environmental Health and Safety. Ms. Errede is a Certified Industrial Hygienist (CIH) and chemical hygiene specialist with an M.S. in Environmental Health. Address: W-140 Boynton Health Service. Phone: 612-626-2330. B. College or Departmental Laboratory Safety Officer Geology and Geophysics modification: The responsible officers for the Department of Geology and Geophysics are the members of the Safety Committee as listed above. The committee chair has the lead responsibility, but the structure of the committee is designed to cover a wide range of laboratory activities and all members and the PI's are responsible for describing and observing safe practices. For 1996-1997, the committee is: Calvin Alexander, Faculty Ron Bohm, Shop and Building Manager Rick Knurr, Geochemical Laboratory Manager Peter McSwiggen, Electron Microprobe manager Bill Seyfried, Departmental Chair This committee is selected to represent staff and facilities that are directly involved with
much of the laboratory activity that goes on in the department.
C. College or Departmental Safety Committee The designation of a safety committee to assist the safety officer in his/her required duties
is strongly encouraged.
D. Department of Environmental Health and Safety The Department of Environmental Health and Safety offers assistance in a wide range of
health and safety issues. A departmental organizational chart, list of services offered, and staff phone numbers are included in Appendix K. Address: W-140 Boynton. Phone: 612-626-6002.
E. Occupational Physician The University of Minnesota's Boynton Health Service provides occupational medicine
services. The phone number for the Occupational Medicine program, which covers Research Animal Resources, respiratory protection, and pesticide exposures only, is 612-625-4906. Non hospital employee chemical exposures should go through Boynton's urgent care.
9. Additional Employee Protection for Work with Particularly Hazardous Substances Guidance: Like Section 6, this Section also requires action. Again, the PIs in the
department must consider the toxicity of the chemicals used and the hazards of each procedure, and decide whether the procedure requires the use of additional protective measures. The additional protective measures should be incorporated in the Standard Operating Procedure. Each PI should forward a list of these SOPs to the departmental Laboratory Safety Officer for reference in this section of the CHP. If none of the SOPs require additional protective measures, the PI should note this fact and forward a brief explanation to the LSO. EHS staff are available to help PIs evaluate the need for additional protective measures.
Geology and Geophysics modification: Laboratory research groups will evaluate their
chemical use and protocols to make certain that especially hazardous materials are properly managed.
Additional employee protection will be considered for work with particularly hazardous
substances. These include select carcinogens, reproductive toxins and substances which have a high degree of acute toxicity (see Appendix B). Pp. 90-93 fo the 1995 edition of Prudent Practices provide detailed recommendations for work with particularly hazardous substances. These pages may be accessed from DEHS's web site at www.dehs.umn.edu. Also DEHS has hard copies of the entire 1995 edition available for departmental Laboratory Safety Officiers. Laboratory supervisors and principal investigators are responsible for assuring that laboratory procedures involving particularly hazardous chemicals have been evaluated for the level of employee protection required. Specific consideration will be given to the need for inclusion of the following provisions:
A. Planning; B. Establishment of a designated area; C. Access control D. Special precautions such as: ¥ use of containment devices such as fume hoods or glove boxes ¥ use of personal protective equipment ¥ isolation of contaminated equipment; ¥ practicing good laboratory hygiene; and ¥ prudent transportation of very toxic chemicals. E. Planning for accidents and spills; F. Special storage and waste disposal practices. 10. Record keeping, Review and Update of Chemical Hygiene Plan Guidance: This section requires little tailoring. Please identify individuals, the
department, or college as appropriate in the underlined portions of this section.
Geology and Geophysics modification: Records must be kept by (1) each lab group in
the Safety and Training Log, and (2) by the department as represented by the Safety Committee.
A. Record keeping i. Exposure evaluation Any records of exposure evaluation carried out by individual departments
(including continuous monitoring systems) will be kept within the department and also sent to the Department of Environmental Health and Safety. Results of exposure evaluations carried out by DEHS will be kept by DEHS and sent to the affected department. Raw data will be kept for one year and summary data for the term of employment plus 30 years.
ii. Medical consultation and examination Results of medical consultations and examinations will be kept by the Boynton
Health Service for a length of time specified by the appropriate medical records standard. This time will be at least the term of employment plus 30 years as required by OSHA.
iii. Training Individual employee training should be recorded on form BA 725 (see
Appendix L) and should be kept in the individual's department or college for five years. These forms may be audited by the University Audit Department.
iv. Fume hood monitoring Data on annual fume hood monitoring will be kept in the Department of
Environmental Health and Safety. Fume hood monitoring data are considered maintenance records and as such the raw data will be kept for one year and summary data for 5 years.
B. Review and Update of Chemical Hygiene Plan On an annual basis, this Chemical Hygiene Plan will be reviewed and evaluated for
effectiveness by the Department of Environmental Health and Safety and updated as necessary. Any changes in the Chemical Hygiene Plan will be transmitted to college and departmental laboratory safety officers, who are responsible for carrying out a similar review and modification of their plans, and submitting a revised copy to the Chemical Hygiene Officer.
Provisional list of chemicals requiring special regulation
Guidance: Departments may choose to add other chemicals to the above list: for example,
sulfur- containing compounds such as mercaptans can cause significant odor problems when used in the laboratory. Pre-approval of the conditions under which they can be used may prevent odor complaints.
Note: Tables 1-5 list governmentally regulated chemicals; Table 6
lists departmentally regulated chemicals
Table 1 Poisonous Gases
The gases on this list are either on the Department of Transportation's Category 1 list, or the
Linde Specialty Gases company's Group 6 - Very Poisonous list. These chemicals are highly toxic gases at ambient temperature and pressure. They have an extremely high potential for causing significant harm if not adequately controlled.
Arsine Boron trichloride Chlorine pentafluoride Chlorine trifluoride Cyanogen Cyanogen chloride Diborane Dinitrogen tetroxide Fluorine Germane Hydrogen selenide Nitric oxide Nitrogen dioxide Nitrogen trioxide Nitrosyl chloride Oxygen difluoride Phosgene Phosphine Phosphorus pentafluoride Selenium hexafluoride Stibine Sulfur tetrafluoride Tellurium Hexafluoride Tetraethyldithiopyrophosphate Tetraethylpyrophosphate
Table 2: Shock Sensitive Chemicals
The classes of chemicals listed below may explode when subjected to shock or friction. Therefore users must have appropriate laboratory equipment, information, knowledge and training to use these compounds safely. * Acetylenic compounds, especially polyacetylenes, haloacetylenes, and heavy metal salts of
acetylenes (copper, silver, and mercury salts are particularly sensitive)
* Acyl nitrates * Alkyl nitrates, particularly polyol nitrates such as nitrocellulose and nitroglycerine * Alkyl and acyl nitrites * Alkyl perchlorates * Amminemetal oxosalts: metal compounds with coordinated ammonia, hydrazine, or similar
nitrogenous donors and ionic perchlorate, nitrate, permanganate, or other oxidizing group
* Azides, including metal, nonmetal, and organic azides * Chlorite salts of metals, such as AgClO2 and Hg(ClO2)2* Diazo compounds such as CH2N2 * Diazonium salts, when dry * Fulminates such as mercury fulminate (Hg(CNO)2) * Hydrogen peroxide (which becomes increasingly treacherous as the concentration rises above
30%, forming explosive mixtures with organic materials and decomposing violently in the presence of traces of transition metals
* N-Halogen compounds such as difluoroamino compounds and halogen azides * N-Nitro compounds such as N-nitromethylamine, nitrourea, nitroguanidine, and nitric amide * Oxo salts of nitrogenous bases: perchlorates, dichromates, nitrates, iodates, chlorites,
chlorates, and permanganates of ammonia, amines, hydroxylamine, guanidine, etc.
* Perchlorate salts (which can form when perchloric acid mists dry in fume hoods or associated
duct work. Most metal, nonmetal, and amine perchlorates can be detonated and may undergo violent reaction in contact with combustible materials)
* Peroxides and hydroperoxides, organic * Peroxides (solid) that crystallize from or are left from evaporation of peroxidizable solvents (see the following Section 3) * Peroxides, transition-metal salts * Picrates, especially salts of transition and heavy metals, such as Ni, Pb, Hg, Cu, and Zn * Polynitroalkyl compounds such as tetranitromethane and dinitroacetonitrile * Polynitroaromatic compounds especially polynitrohydrocarbons, phenols, and amines (e.g., dinitrotoluene, trinitrotoluene, and picric acid) Note: Perchloric acid must be used only in specially- designed perchloric acid fume hoods that have built-in wash down systems to remove shock-sensitive deposits. Before purchasing this acid, laboratory supervisors must arrange for use of an approved perchloric acid hood.
Table 3. Pyrophoric Chemicals
The classes of chemicals listed below will readily oxidize and ignite spontaneously in air. Therefore, users must demonstrate to the department that they have the appropriate laboratory equipment, information, knowledge and training to use these compounds safely. Grignard reagents, RMgX Metal alkyls and aryls, such as RLi, RNa, R3Al, R2Zn Metal carbonyls such as Ni(CO)4, Fe(CO)5, Co2(CO)8 Alkali metals such as Na, K Metal powders, such as Al, Co, Fe, Mg, Mn, Pd, Pt, Ti, Sn, Zn, Zr Metal hydrides such as NaH, LiAlH4 Nonmetal hydrides, such as B2H6 and other boranes, PH3, AsH3 Nonmetal alkyls, such as R3B, R3P, R3As Phosphorus (white)
Table 4. Peroxide-Forming Chemicals
The chemicals listed below can form explosive peroxide crystals on exposure to air, and therefore require special handling procedures after the container is opened. Some of the chemicals form peroxides that are violently explosive in concentrated solution or as solids, and therefore should never be evaporated to dryness. Others are polymerizable unsaturated compounds and can initiate a runaway, explosive polymerization reaction. All peroxidizable compounds should be stored away from heat and light. They should be protected from physical damage and ignition sources. A warning label should be affixed to all peroxidizable materials to indicate the date of receipt and the date the container was first opened. Due to these special handling requirements, users must have the appropriate laboratory equipment, information, knowledge and training to use these compounds safely. A. Severe Peroxide Hazard with Exposure to Air (discard within 3 months from opening) diisopropyl ether (isopropyl ether)vinylidene chloride (1,1-dichloroethylene) sodium amide (sodamide) divinylacetylene (DVA) potassium metal potassium amide B. Peroxide Hazard on Concentration. Do not distill or evaporate without first testing for the presence of peroxide. (discard or test for peroxides after 6 months) acetaldehyde diethyl acetal (acetal) cumene (isopropylbenzene) cyclohexene cyclopentene decalin (decahydronaphthalene) diacetylene (butadiene) dicyclopentadiene diethyl ether (ether) diethylene glycol dimethyl ether (diglyme) dioxane ethylene glycol dimethyl ether (glyme) ethylene glycol ether acetates ethylene glycol monoethers (cellosolves) furan methylacetylene methylcyclopentane methyl isobutyl ketone tetrahydrofuran (THF) tetralin (tetrahydronaphthalene) vinyl ether C. Hazard of Rapid Polymerization Initiated by Internally-Formed Peroxides i. Liquids (discard or test for peroxides after 6 months) chloroprene (2-chloro-1,3-butadiene) styrene vinyl acetate vinylpyridin ii. Gases (discard after 12 months) butadiene tetrafluoroethylene (TFE) vinylacetylene (MVA) vinyl chlorid
Table 5. Carcinogens, Reproductive Toxins or Highly Toxic Chemicals
The chemicals listed below are extremely hazardous. Workers must have knowledge of the dangers of these chemicals prior to use, and documentation of training in safe working procedures. * Biologically active compounds ¥ protease inhibitors (e.g. PMSF, Aprotin, Pepstatin A. Leopeptin); ¥ protein synthesis inhibitors (e.g.cycloheximide, Puromycin); ¥ transcriptional inhibitors (e.g. a-amanitan and actinomycin D); ¥ DNA synthesis inhibitors (e.g. hydroxyurea, nucleotide analogs (i.e.dideoxy nucleotides), actomycin D, acidicolin); ¥ phophatase inhibitors (e.g.okadaic acid); ¥ respiratory chain inhibitors (e.g.sodium azide); ¥ Kinase inhibitors (e.g. colcemid); and ¥ mitogenic compounds (e.g. concanavalinA). * Castor bean (Ricinus communis) lectin: Ricin A, Ricin B, RCA toxins, Cycloheximide: Highly toxic * Diisopropyl fluorophosphate: highly toxic cholinesterase inhibitor; the antidote, atropine sulfate and 2-PAM (2- pyridinealdoxime methiodide) must be readily available * Jaquirity bean lectin (Abrus precatorius) * N-methyl-N'-nitro-N-nitrosoguanidine: carcinogen (this chemical forms explosive compounds upon degradation) * Phalloidin from Amanita Phalloides: used for staining actin filaments * Retinoids: potential human teratogens * Streptozotocin: potential human carcinogen * Urethane (ethyl carbamate): an anestheic agent, potent carcinogen and strong teratogen, volitile at room temperature
Table 6. Additional chemicals requiring Geology and Geophysics Departmental approval of handling methods. Consult Safety Committee to obtain approval.
hydrofluoric acids heavy liquids for particle separation ether phenols