UCI Chemical Hygiene Plan CHEMICAL HYGIENE PLAN University of California, Irvine Medical Emergencies Important Telephone Numbers for UC Irvine Material Safety Data Sheets Glove Selection Tool Safety Training Registration Laboratory Safety Guidelines Fact Sheets for Hazardous Chemical Categories: General Labs Integrated Nanofab Research Facility (INRF) Standard Operating Procedures (SOP) Example Library CHP Table of Contents Appendices UCI Chemical Hygiene Plan FOREWORD All UCI laboratory personnel who work with laboratory chemicals must know and follow the standard operating procedures outlined in this plan. All laboratory operations involving particularly hazardous chemicals must be planned and executed in accordance with the standard operating procedures described in this plan. In addition, each laboratory worker is expected to practice safe personal chemical hygiene habits aimed at reducing exposures to potential hazards. This document was developed to comply with applicable federal and state requirements, and professional standards, including California Code of Regulations 8CCR§5191 "Occupational Exposure to Hazardous Chemicals in Laboratories". This Chemical Hygiene Plan (CHP) will be reviewed and evaluated for effectiveness at least annually and updated as necessary. It must be readily available to laboratory employees, their representatives and any regulatory agency inspector during normal working hours. Last Reviewed: June 2004 Chris Younghans-Haug, CIH, CSP, REHS David Melitz for School of Biological Sciences & School of Social Ecology Joe Rizkallah for School of Engineering Rama Singh for School of Physical Sciences John W. Chan, CIH NOTE: Contact your school’s EH&S Coordinator or Campus Chemical Hygiene Officer at (949) 824-6200 with any corrections or suggestions for change in this Chemical Hygiene Plan. Top of CHP Table of Contents Appendices UCI Chemical Hygiene Plan IMPORTANT PHONE NUMBERS FOR UC Irvine EMERGENCIES Fire ................................................................................................................... Dial 911 Medical Emergency ........................................................................................ Dial 911 Chemical Spills .................................................................... 824-6200, after hours 911 Radiation Incident ................................................................ 824-6200, after hours 911 Safety Incidents .................................................................... 824-6200, after hours 911 Student Health Services .................................................................................. 824-5301 Maintenance Emergency................................................................................. 824-5444 Poison Control ..................................................................................... 1-800-876-4766 UCI Emergency Information (Activated only during a disaster)..... 1-866-IRV-NEWS EH&S SERVICES EH&S Information General Safety Asbestos & Lead Information EH&S Coordinator Biological Sciences EH&S Coordinator College of Medicine EH&S Coordinator School of Engineering EH&S Coordinator Physical Sciences Biosafety Bloodborne Pathogens Chemical Hygiene Officer Ergonomics Emergency Management Information Environmental Protection Information Fire Safety Information & Assistance Food & Water Sanitation Hazardous Materials Spill Response Hazardous (Chemical & Radioactive) Waste Pick-up Industrial Hygiene Information Injury & Illness Prevention Program Laboratory Safety Information & Assistance Laser Safety Information & Assistance MSDS Information Occupational Health & Surveillance Personal Protection Equipment Radiation Safety Information & Assistance Radioactive Shipments Respiratory Protection Program Training Information & Assistance 824-6200 824-9940 824-8791 824-2221 824-4660 824-6579 824-2518 824-9888 824-9888 824-5730 824-2945 824-7147 824-4578 824-4077 824-4170 824-6200 824-4578 824-8342 824-9940 824-5730 824-6098 824-4817 824-8024 824-9940 824-6904 or 824-8772 824-7100 824-4817 824-6634 Anonymous Hazard Reporting: To anonymously report a hazard or health and safety concern, call 824-6200. If you are concerned about the caller ID system, consider using a pay phone. UCI Chemical Hygiene Plan TABLE OF CONTENTS FOREWORD IMPORTANT PHONE NUMBERS OBTAINING MEDICAL CARE TABLE OF CONTENTS LIST OF APPENDICES 1.0 Scope of Operations 1.1 Applicability 1.2 Exclusions 2.0 2.1 Chemical Hygiene Responsibilities Laboratory Supervisor 2.2 Environmental Health & Safety Coordinator 2.3 Group Chemical Coordinator 2.4 Laboratory Employees & Workers 2.5 Campus Chemical Hygiene Officer 2.6 UCI Facilities Manager 3.0 Identification and Classification of Hazardous Substances 3.1 Carcinogens 3.2 Reproductive Toxins 3.3 Toxic and Highly Toxic Agents 3.4 Hazardous Substances with Toxic Effects on Specific Organs 3.5 Sensitizers 3.6 Irritants 3.7 Corrosive Substances 3.8 Flammable and Potentially Explosive Substances 3.9 Select Agents (Toxins of Biological Origin) 4.0 Standard Operating Procedure for Working with Hazardous Substances 4.1 Chemical Procurement 4.2 Hazardous Chemical Storage 4.3 Handling Hazardous Chemicals 4.4 Handling Flammable and Potentially Explosive Substances 4.5 Segregation of Incompatible Substances 4.6 Handling Compressed Gases 4.7 Laboratory Use of Anesthetics UCI Chemical Hygiene Plan 4.8 Laboratory Equipment and Glassware 4.9 Personal Protective Equipment 4.10 Personal Work Practices 4.11 Container Labeling 4.12 Disposal 4.13 Inventory Maintenance 4.14 Source Reduction and Waste Minimization 5.1 Standard Operating Procedures for Working with Particularly Hazardous Substances Working with Select Carcinogens 5.2 Working with Embryotoxins (Special Precautions) 5.3 Working with Compounds with a High Degree of Acute Toxicity 5.4 Standard Operating Procedures for Work with Particularly Hazardous Substances 5.5 Working with Select Agents (Toxins of Biological Origin) 6.0 6.1 Standard Operating Procedures Applying to All Hazardous Chemical Work Industrial Hygiene Evaluation 6.2 Clean Areas 6.3 Housekeeping 6.4 Safety and Emergency Equipment 6.5 Unattended Operations 7.0 Standard Operating Procedures for Engineering Controls 7.1 Intent 7.2 Modification 7.3 Improper Function 7.4 Usage 8.0 Standard Operating Procedures for Laboratory Worker Information and Training 8.1 Hazard Information 8.2 Forms 8.3 Training 9.0 Standard Operating Procedures for Medical Consultations and Examinations 5.0 10.0 Standard Operating Procedures for Laboratory Activities Requiring Prior Approval UCI Chemical Hygiene Plan 10.1 Off-Hours Work 10.2 Working Alone 10.3 Hazardous Work 10.4 Restricted Chemicals Requiring Prior Approval 10.5 Laboratory/Equipment Relocation or Vacancy 11.0 Standard Operating Procedures for Record Keeping 12.0 Standard Operating Procedures for Fires, Chemical Spills, Releases and Accidents 12.1 Control of Fires 12.2 Personnel Exposures and Contamination 12.3 Contamination of Equipment/Facilities 12.4 Release to the Environment (Air, Water, Soil) 13.0 Standard Operating Procedures for Annual Chemical Hygiene Plan Audit 14.0 References and Recommended Reading Top of CHP Table of Contents Appendices UCI Chemical Hygiene Plan APPENDICES 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 34. What to do in case of a Medical Emergency flyer Laboratory Safety Guidelines Safety Representative (SR) Laboratory Hazard Assessment Work Unit Safety Training & Awareness Documentation form for Laboratories Voluntary Laboratory Inspection Form & Key Lists of Known & Suspected Carcinogens How to Access MSDS Information Standard Operating Procedures Guidelines & Template Procedures for Detecting and Removing Peroxide Contamination Table of Common Incompatible Substances Compressed Gas Safety Awareness Training & Supplemental Information Controlling Exposure to Waste Anesthetic Gases at UC Irvine Glove Selection Guidelines & Resources Hazardous Waste Management Information for UC Irvine UC Irvine Hazardous Waste Guidelines (8 ½ x 14 paper) Chemical Waste Pick Up Requests Special Handling Procedures for Some Particularly Hazardous Substances Cal/OSHA Reportable Hazardous Chemicals Supplemental Information Form for Chemical Requiring Cal/OSHA Registration Standard Operating Procedures (SOP) Library Designated Controlled Areas Select Toxins List Select Agent Program Emergency Notification Information sign for lab doors (for general Campus use) Emergency Notification Information sign for lab doors (for School of Physical Sciences use) Cal/OSHA Section 5191, Occupational Exposure to Hazardous Chemicals in Laboratories Cal/OSHA Section 5155, Airborne Contaminants (Permissible Exposure Limit Tables) Location of Required Safety Information sign Classes of Hazardous Chemicals—General Laboratories Classes of Hazardous Chemical—Integrated Nanofab Research Facility (INRF) Hazardous Materials Incidents UCI Emergency Procedures (Blue Flipchart) Circumstances Requiring Prior Approval Form Top of CHP Table of Contents Appendices UCI Chemical Hygiene Plan 1.0 Scope of Operations 1.1 Applicability This Chemical Hygiene Plan (CHP) applies to all personnel handling hazardous chemicals in research laboratories at UC Irvine. The CHP provides written safety procedures for conducting research laboratory chemical operations in a manner that protects people from harmful chemical exposures. 1.2 Exclusions The CHP does not cover work with radiation-producing devices, radioactive materials, biological agents, or the disposal of these wastes. Use of radioactive materials and biological agents must have prior approval of the UCI Radiation Safety Committee or Institutional Biosafety Committee. Permit forms and procedures can be obtained from EH&S at 824-6200. Please consult the UCI Radiation Safety Manual or UCI Biosafety Manual and related documents for additional information. Top of CHP Table of Contents Appendices UCI Chemical Hygiene Plan 2.0 Chemical Hygiene Responsibilities 2.1 2.2 Laboratory Supervisor The Supervisor's duties are the responsibility of the faculty member (Principal Investigator or Instructor) in charge of each laboratory. The Supervisor has direct responsibility for the health and safety of all personnel under his/her direction. The Supervisor's duties include the following: 1. Ensure that all laboratory workers under their control receive instructions and training to work safely with hazardous chemicals, respond appropriately when chemical accidents occur, and how to report injury and illnesses associated with occupational exposure to hazardous chemicals. 2. When injuries or illnesses occur at work, follow procedures outlined in the What to do in a Medical Emergency flyer. For non-emergencies, employee injuries and illnesses must still be reported: please visit the Worker’s Compensation website for details. The Supervisor should investigate all accidents and near-misses and take measures to help prevent reoccurrence, with consultation from the School's EH&S Coordinator when necessary. 3. Assist the school’s EH&S Coordinator with the execution of his/her duties whenever necessary. 4. Seek ways to improve chemical hygiene and laboratory safety. 5. Inform non-laboratory personnel (e.g., UCI Facilities Management and contract workers) of potential hazards when non-laboratory personnel are required to work in the laboratory environment. These laboratory hazards must be mitigated to provide a reasonably safe environment for repairs and renovations. 6. Identify hazardous conditions or operations, determine safe procedures and controls, and implement and enforce standard safety procedures. 7. Ensure that engineering controls (e.g., fume hoods, emergency showers and eyewashes) are operable and that personal protective equipment is available and used properly by laboratory staff working with hazardous chemicals. 8. Ensure delegated safety duties are completed on a timely basis. EH&S Coordinator UC Irvine EH&S Coordinator’s responsibility is to support the Laboratory Supervisor to implement the policies and procedures described in this CHP. These duties include the following: UCI Chemical Hygiene Plan 2.3 1. Review standard operating procedures for work involving hazardous substances upon request. 2. Conduct periodic laboratory safety surveys and safety survey follow-ups. 3. Assist Lab Supervisors and Laboratory Workers to implement EH&S policies and procedures. 4. Investigate accidents and provide written reports to EH&S Workers Compensation when appropriate. 5. Consult with the Laboratory Supervisor and the Campus Chemical Hygiene Officer (CHO) on hazard assessment and control in labs. 6. Consult with Facilities Management and contractors regarding potential lab hazards and provide information to minimize their risk of exposure to hazardous substances. Safety Representative A Safety Representative (SR) may be designated by the lab supervisor to be responsible for ensuring that hazardous chemicals are handled, stored, and disposed in accordance with this CHP. 1. Be designated by the Laboratory Supervisor. 2. Ensure completion of the Lab Hazard Assessment. 3. Develop standard operating procedures for avoiding lab hazards as needed. Assist with providing and documenting Work-Unit Specific Safety Awareness & Training beyond EH&S provided courses. 4. 2.4 5. Conduct laboratory safety self-assessments as needed. 6. Assist with maintaining the Chemical Inventory Database. 7. Monitor the disposal of chemicals used in laboratory operations. Laboratory Employees & Workers All persons working with laboratory chemicals must know how to work safely with the chemicals they use and are responsible for following prudent chemical safety practices. If any person is unsure of a chemical hazard or safety procedure, he/she should consult with his/her supervisor. While the California Code of Regulations 8CCR§5191 "Occupational Exposure to Hazardous Chemicals in Laboratories" imposes standards on employers and employees, UC Irvine UCI Chemical Hygiene Plan attempts to have all persons working with hazardous chemicals in research laboratories implement the prudent practices described in this Chemical Hygiene Plan, including students and volunteers. 2.5 Campus Chemical Hygiene Officer (CHO) The Campus Chemical Hygiene Officer is responsible for the development, implementation, and periodic review of the Chemical Hygiene Plan to comply with state and federal standards concerning occupational exposure to hazardous chemicals in laboratories. 2.6 School Facilities Manager/Director The School Facilities Manager/Director is responsible for coordinating activities related to building repairs, maintenance, improvements, and laboratory moves and closures. The School Facilities Manager/Director will inform the EH&S Coordinator or EH&S of building repairs, maintenance, improvements, and laboratory moves and closures so that safety assessments can be performed. The Facilities Manager/Director has the responsibility for communicating to outside contractors and UC Irvine maintenance staff about potential hazards in the laboratories. Top of CHP Table of Contents Appendices UCI Chemical Hygiene Plan 3.0 Identification and Classification of Hazardous Substances Substances in the laboratory have properties that could cause harm to laboratory workers and others if handled improperly. Many lab chemicals are toxic or corrosive, or both. Compounds that are potentially explosive and/or highly flammable pose another significant hazard in laboratories. New and untested substances may be hazardous. The most important guideline for chemical safety is to treat all compounds as potentially harmful and minimize your chemical exposure. Before starting an experiment using hazardous chemicals, learn about its hazards and use this knowledge to plan the experiment. Hazards of two combined substances may be significantly greater than the hazards of either substance alone (e.g. toxic synergism). 3.1 Carcinogens Carcinogens are chemical or physical agents that cause cancer. Carcinogens are toxic substances causing damage to cells after repeated or chronic exposure. Their effects may only become evident after a long latency period and may cause no immediate harmful effects. Carcinogens are classified as “Particularly Hazardous Substances” and must be handled using the special precautions described in Section 5. Comprehensive lists of known & suspected carcinogens from peer-reviewed authoritative sources are available on the Internet. Many other compounds have limited evidence of carcinogenicity from animal studies. These compounds should be handled using the general procedures for work with hazardous substances outlined in Section 4. Lab workers should recognize that many chemicals in research laboratories have not been tested for carcinogenicity. Researchers should be familiar with the specific classes of compounds and functional group types that have been correlated to carcinogenic activity. The following section lists representative compounds in each class that are “reasonably anticipated to be carcinogens” based on animal tests. All new and untested compounds should be treated as hazardous substances and handled using to the procedures described in Section 4. UCI Chemical Hygiene Plan Classes of Carcinogenic Compounds Alkylating Agents Organohalogen compounds α-Halo ethers: *bis (chloromethyl) ether *methyl chloromethyl ether *1,2-dibromo-3-chloropropane *mustard gas (bis(2-chloroethyl)sulfide) *vinyl chloride carbon tetrachloride chloroform 3-chloro-2-methylpropene 1,2-dibromoethane 1,4-dichlorobenzene 1,2-dichloroethane 2,2-dichloroethane 1,3-dichloropropene hexachlorobenzene methyl iodide tetrachloroethylene trichloroethylene 2,4,6-trichlorophenol sulfonates: *1,4-butanediol dimethanesulfonate diethyl sulfate dimethyl sulfate ethyl methanesulfonate methyl methanesulfonate methyl triflouromethanesulfonate 1,3-propanesulfone epoxides: *ethylene oxide diepoxybutane epichlorohydrin propylene oxide styrene oxide aziridines: *ethylenimine 2-methylaziridine diazo, Azo, and Azoxy compounds: 4-dimethylaminoazobenzene electrophilic Alkenes and Alkynes: *acrylonitrile acrolein ethyl acrylate N-Nitroso Compounds *N-nitrosodimethylamine N-nitroso-n-alkylurea Aromatic amines: *4-aminobiphenyl *benzidine (p,p-diaminobiphenyl) *α-naphthylamine *β-naphthylamine aniline o-anisidine (2-methoxyaniline) 2,4-diaminotoluene o-toluidine Acylating agents Aromatic hydrocarbons β-Propiolactone β-Butyrolactone Dimethylcarbamoyl Chloride *benzene benz {a} anthracene benzo {a} pyrene UCI Chemical Hygiene Plan Natural Products (including anti-tumor drugs) Hydrazines Hydrazine (and hydrazine salts) 1,2-Diethylhydrazine 1,1-Dimethylhydrazine 1,2-dimethylhydrazine adriamycin cisplatin aflatoxins bleomycin safrole progesterone reserpine Miscellaneous Inorganic compounds: Miscellaneous organic compounds: *arsenic and certain arsenic compounds *chromium and certain chromium compounds chromium dioxide beryllium and certain beryllium compounds cadmium and certain cadmium compounds lead and certain lead compounds nickel and certain nickel compounds selenium sulfide *formaldehyde (gas) acetaldehyde 1,4-dioxane ethyl carbamate (urethane) hexamethylphosphoramide (HMPA) 2-nitropropane styrene thioacetamide *Cal/OSHA regulated (Section 5.5 applies) Exposure to certain combinations of compounds (not necessarily simultaneously) can cause cancer even at exposure levels where neither of the individual compounds would have been carcinogenic. 1,8,9- trihydroxyanthracene and certain phorbol esters are examples of “tumor promoters” that while not themselves carcinogenic can dramatically amplify the carcinogenicity of other compounds. 3.2 Reproductive Toxins Reproductive toxins include substances that cause chromosomal damage (mutations) and substances causing lethal or malformation effects on fetuses (teratogenesis). Many reproductive toxins cause damage after repeated low-level exposures. Effects only become evident after long latency periods. Information on reproductive toxicity of a specified chemical may be obtained from the Material Safety Data Sheets. See Section 14 for additional references and recommended reading. The following table lists materials present in some UC Irvine research labs that are suspected or known to be reproductive toxins: UCI Chemical Hygiene Plan Top of CHP Table of Contents Appendices Partial List of Reproductive Toxins Acrylic acid Aniline Benzene Cadmium Carbon Disulfide N,N-Dimethylacetamide Dimethylformamide (DMF) Dimethyl sulfoxide (DMSO) Diphenylamine Estradiol Formaldehyde Formamide Hexachlorobenzene Iodoacetic Acid Lead compounds Mercury Compounds Nitrobenzene Nitrous Oxide Phenol Polychlorinated biphenyls (PCBS) Polybrominated biphenyls (PBBS) Toluene Vinyl chloride Xylene The above list is not complete. The Laboratory Supervisor determines whether a chemical should be handled as a reproductive toxin. Laboratory workers should also consult with their personal physician regarding concerns about reproductive toxins. 3.3 Toxic and Highly Toxic Agents The California Code of Regulations 8CCR§5194 defines toxic and highly toxic agents as substances with median lethal dose (LD50) values in the following ranges: Route of Exposure Oral LD50 (albino rats) Skin Contact LD50 (albino rabbits) Inhalation LD50 (albino rats) 3.4 Toxic 50-500 mg/kg Highly Toxic <50 mg/kg 200-1000 mg/kg <200 mg/kg 200-2000 ppm/air <200 ppm/air Hazardous Substances with Toxic Effects on Specific Organs Substances included in this category are: 1. Hepatotoxins - substances that produce liver damage (e.g. nitrosamines, carbon tetrachloride). UCI Chemical Hygiene Plan 8. Nephrotoxins - agents causing damage to the kidneys (e.g. certain halogenated hydrocarbons). 9. Neurotoxins - substances that produce their primary toxic effects on the nervous system (e.g. mercury, acrylamide, carbon disulfide). 5. Agents that act on the hematopoietic system - substances that decrease hemoglobin function and deprive the body tissues of oxygen (e.g. carbon monoxide, cyanides). 6. Agents that damage lung tissue - (e.g. asbestos, silica). 3.5 Sensitizers A sensitizer (allergen) is a substance that causes exposed people to develop an allergic reaction in normal tissue after repeated exposure to the substance. Examples of sensitizers used in some UC Irvine labs include chromium, nickel, formaldehyde, isocyanates, arylhydrazines, diazomethane, benzylic and allylic halides and many phenol derivatives. 3.6 Irritants Irritants are defined as chemicals that cause reversible inflammatory effects on living tissue by chemical action at the site of contact. A wide variety of organic and inorganic compounds are irritants and consequently skin contact with all laboratory chemicals should always be avoided. 3.7 Corrosive Substances Corrosive substances cause visible irreversible destruction of, or visible alterations in living tissue by chemical action at the site of contact. Major classes of corrosive substances include strong acids (e.g., sulfuric, nitric, phosphoric, hydrochloric, and hydrofluoric acids), strong bases (sodium hydroxide, phosphoric potassium hydroxide, and ammonium hydroxide), and dehydrating agents (sulfuric acid, sodium hydroxide, phosphorus pentoxide, and calcium oxide).` 3.8 Flammables and Potentially Explosive Substances A number of highly flammable substances are in common use in UC Irvine laboratories. Potentially explosive substances are materials that decompose under conditions of mechanical shock, elevated temperature, or chemical action, with the release of large volumes of gases and heat. UCI Chemical Hygiene Plan 3.9 Select Agents (Toxins of Biological Origin) In recognition of the growing number of microbiological and biomedical laboratories working with toxins of biological origin, the following list of select agent toxins requires authorization from the campus Biosafety Officer (824-9888) prior to purchase or transfer of the material. Abrin Aflatoxins Botulinum Toxins Clostridium Perfringens Epsilon Toxin Conotoxins Diacetoxyscirpenol Ricin Saxotoxin Shigatoxin Staphylococcal Enterotoxins Tetrodotoxin T-2 toxin All users must obtain a Biological Use Authorization Number (BUA). The BUA is designed to track the acquisition and transfer of these specific agents and to establish a system of safeguards to be followed when specific agents are in use. Select Agents fall under the category of Particularly Hazardous Substances. Special handling procedures must be followed as listed under Section 5.0 and 5.5. Top of CHP Table of Contents Appendices UCI Chemical Hygiene Plan 4.0 Standard Operating Procedures for Working with Hazardous Chemicals in UCI Laboratories 4.1 Chemical Procurement To minimize the duplication of hazardous chemicals within research groups, use chemicals currently available in the group's inventory. Furthermore, use hazardous chemicals from other research groups when possible. Both procedures are cost-effective and will reduce the quantity of hazardous chemicals stored and help minimize hazardous waste. 1. The decision to buy a hazardous chemical must be a commitment to handle and use the chemical safely from receipt to disposal. 2. Prior to the purchase of a new hazardous chemical, check your lab's current inventory or, when reasonably feasible, in the inventories of other research groups. Everyone has an obligation to reduce workplace exposures and environmental releases of hazardous chemicals to the lowest achievable levels (See Section 4.14 for more information on source reduction and waste minimization). 3. Checking in hazardous chemical shipments must follow these procedures: a. Any package showing signs of leakage or breakage should not be accepted. If the damage to the package is minor or if the damage to the inside chemical container is uncertain, do not accept the package until it is opened in a fume hood by lab staff. If the delivery person insists on leaving the package, sign for the package but also record on the receipt that the package is damaged. b. Chemical containers must not be accepted without legible and intact labels. c. Staff working with the chemical must be familiar with the information on the Material Safety Data Sheet (MSDS). This information must be maintained for employees to access at all times when working with hazardous chemicals. See Accessing Material Safety Data Sheets. If you have problems with Internet access, contact MSDS Specialist at 824-6200. d. All peroxide-forming chemicals containers should be marked with the manufacturer’s expiration date. The researcher should write on the container the date when it is first opened. e. Chemicals that have limited shelf life should be labeled “Dispose after (date)” f. All containers of ether should be labeled “Use by (6 months from receipt) or Dispose.” UCI Chemical Hygiene Plan 4. 4.2 Shipping of hazardous chemicals should only be performed by trained staff or under the direction of trained staff. See the Shipping Dangerous Goods webpage for details. Hazardous Chemical Storage 1. Chemicals received must be moved as soon as possible to the designated storage area. Glass containers larger than 1 liter (L) must be placed in carrying containers or kept in shipping containers during transportation. 2. The storage area must be well illuminated and have local exhaust ventilation, with all storage maintained below eye level. Bottles larger than 4 L must be stored on the lowest shelf of the storage area. All storage areas must have seismic safety restraints. 3. Chemicals must be segregated by hazard classification and compatibility in a well-identified area, as follows: a. Oxidizing acids, including mineral acids, must be separated from flammable and combustible materials. Acid-resistant trays must be placed under bottles of acids. b. Cyanides and sulfides must be separated from acids or protected from contact with acids. c. Oxidizers must be separated from flammables, organic materials and oxidizable inorganic substances. d. Acids and bases must be separated from each other. e. Chemicals that exhibit air and moisture sensitivity (e.g., organometallics, metal hydrides, etc) must be stored in a segregated area with provisions made to minimize the possibility of breakage, and other air or moisture contact. f. Carcinogens, suspected carcinogens, and other highly toxic materials must be stored in a secure area with restricted access. 6. Chemical storage areas must not be used as a preparation or repackaging area. 7. The storage area must be accessible during normal working hours. The storage area must be under the control of the Safety Representative (SR). 8. The amount of chemicals at the laboratory bench must be as small as possible. The container size must be selected to keep amounts of chemicals to the minimum needed to work efficiently. Exposure to sunlight or heat must be minimized. UCI Chemical Hygiene Plan 9. Stored chemicals must be checked by the SR for deterioration and container integrity, and by lab workers before each use. The inspection must also determine whether any corrosion, deterioration, or damage has occurred to the storage facility as a result of leaking chemicals. The SR must notify the Principal Investigator of any problems. 10. Inventories must be maintained in the laboratory and be updated at least annually. A copy of the inventory must be delivered to EH&S for the campus to keep permits current. If necessary, consult with the School EHS Coordinator for procedural updates for submitting chemical inventories. 11. The SR must conduct inspections of the laboratory for chemicals outside of the storage area. Chemicals not in current use must be returned to the storage area. 12. Substances that have been synthesized for the first time in the research laboratory must be stored in a manner consistent with their potential hazard as determined by analogy to known chemicals of similar composition. Top of CHP Table of Contents Appendices 4.3 Handling Hazardous Chemicals General precautions to be followed for the handling and use of all laboratory chemicals are: 1. Inhalation, ingestion, and skin contact with all chemicals must be avoided. 2. All laboratory workers must wash all areas of skin that may have been exposed to chemicals prior to leaving the laboratory. 3. Pipetting or siphoning by mouth is prohibited. 4. Eating, drinking, smoking, gum chewing, and application of cosmetics in areas where laboratory chemicals are present must be avoided. See Clean Area procedures. Hands must be washed thoroughly prior to performing these activities in clean areas or outside of the lab. 5. Refrigerators, glassware, containers, and utensils used for laboratory operations must never be used for the storage, handling, or consumption of food. Mark items “NOT FOR FOOD USE” or equivalent to prevent inadvertent use of laboratory items for food. 6. Substances of unknown hazards must be assumed to be hazardous, and any chemical mixture must be assumed to be as hazardous as its most hazardous component. UCI Chemical Hygiene Plan 4.4 7. Laboratory workers must be familiar with the chemical's hazard information from the container label, the Material Safety Data Sheet and other appropriate references. This familiarization must include symptoms of exposure and the precautions necessary to prevent exposure. 8. Specific precautions based on the hazardous characteristics of individual chemicals must be implemented as deemed necessary by Principal Investigator/Laboratory Supervisor. 9. If warranted, any lab specific practices can be documented in a written Standard Operating Procedure (SOP); complete sections 1-7 of the Standard Operating Procedure Template. Handling Flammable and Potentially Explosive Substances 1. Flammable Substances Flammable substances are among the most common of the hazardous materials found in UC Irvine laboratories. Flammable substances are materials that readily catch fire and burn in air. A flammable liquid itself does not burn; rather it is the vapors from the liquid that burn. The rate at which different liquids produce flammable vapors depends on their vapor pressure and increases with temperature. The degree of fire hazard also depends on the ability to form combustible or explosive mixtures with air, the ease of ignition of these mixtures, and the relative densities of the liquid with respect to water and of the gas with respect to air. To illustrate this point, an open beaker of diethyl ether set on the laboratory bench next to a Bunsen burner will ignite, whereas a similar beaker of diethyl phthalate will not. Ether has a much lower flash point. The flash point is the lowest temperature at which a liquid gives off vapor in sufficient concentration to form an ignitable mixture with air near the surface of the liquid. Many common laboratory solvents and chemicals have flash points that are lower than room temperature and have the potential to ignite and burn. Solvent Acetone Benzene Carbon disulfide Cyclohexane Diethyl ether Flash (°C) -17.8 -11.1 -30.0 Point Solvent Ethanol Hexane Methanol Flash Point (°C) 12.8 -21.7 11.1 -20.0 -45.0 Pentane Toluene -40. 0 4.4 These following basic precautions should be followed in handling flammable substances: UCI Chemical Hygiene Plan 2. a. Flammable substances should only be handled in areas that are free of ignition sources. Ignition sources include: open flames, electrical equipment (especially motors), static electricity, and hot surfaces. b. If you will be using a hot plate, stirring plate or heating mantle, do not proceed with your laboratory work until you know the autoignition temperatures of the chemicals likely to be released and can ensure that the temperatures of all exposed surfaces are less than those autoignition temperatures. Make certain that the temperature control device and the stirring/ventilating motor (if present) do not spark. c. Never heat a flammable substance with an open flame. d. When transferring flammable liquids to and from metal containers, use bonding and grounding wires to avoid static-generated sparks. e. Ventilation is one of the most effective ways to prevent the formation of flammable mixtures. A laboratory hood should be used whenever any more than a few milliliters (mL) of flammable substances are handled in any way that produces vapors. Potentially Explosive Substances Potentially explosive substances are materials that decompose under conditions of mechanical shock, elevated temperature, or chemical action, with the release of large volumes of gases and heat. Special precautions are required for the safe use of potentially explosive materials. Each researcher must evaluate the explosive hazards involved in his/her work and consult with the Laboratory Supervisor to develop adequate standard operating procedures. Work with potentially explosive materials will require the use of special protective apparel (face shields, goggles, gloves, laboratory coats) and protective devices such as explosion shields and barriers. Place the shields in suitable positions to protect yourself and others. Be sure that the shields are stabilized with weights or fasteners so that they cannot be knocked over. Organic peroxides are among the most hazardous substances handled in research laboratories. As a hazard class, they are low-power explosives, and hazardous because of their sensitivity to shock, sparks, and even friction (as little as a cap being twisted open). Many peroxides that are routinely handled in laboratories are far more sensitive to shock than most primary explosives such as trinitrotoluene (TNT). All organic peroxides are highly flammable, and most are sensitive to heat, friction, impact, light, as well as strong oxidizing and reducing agents. Organic peroxide procedures should be carried out only by knowledgeable laboratory workers.. Some peroxides in use at UC Irvine are commercial compounds such as m-chloroperoxybenzoic acid, benzoyl peroxide, hydrogen peroxide, and t- UCI Chemical Hygiene Plan butyl hydroperoxide. However, common solvents and reagents are known to form peroxides on exposure to air, and these chemicals often become contaminated with sufficient peroxides to pose a serious hazard. Classes of compounds that form peroxides by auto oxidation include: a. Ethers with primary and/or secondary alkyl groups, including acyclic and cyclic ethers, acetals, and ketals. Examples include diethyl ether, diisopropyl ether, dioxane, dimethyl ether, tetrahydrofuran, ethyl vinyl ether and alcohols protected as tetrahydropyran ethers. b. Hydrocarbons with allylic, benzylic, or propargylic hydrogens. Examples of this class of peroxide-formers include cyclohexene, cyclooctene, methyl acetylene, isopropylbenzene (cumene), and tetralin (tetrahydronaphthalene). c. Conjugated and unconjugated dienes and terpenes among which divinylacetylene is particularly hazardous. d. Saturated hydrocarbons with exposed tertiary hydrogens; common peroxide-formers include decalin (decahydronaphthalene) and 2,5dimethylhexane. e. Aldehydes including acetaldehyde and benzaldehyde Compounds belonging to the classes listed above cannot form peroxides without exposure to oxygen (or other oxidizers). After use and prior to storing these materials, flush the container with an inert gas such as nitrogen or argon before sealing. If the compound is not volatile, it may be advisable to degas the sample by vacuum or bubbling techniques. In some cases it may be appropriate to add an oxidation inhibitor, such as hydroquinone or BHT (2,6-di-t-butyl-4-methylphenol), to the sample. Containers should be tightly sealed and dated. Do not attempt to open bottles of liquid ethers (e.g. diisopropyl ether) containing crystallized material; contact EH&S for disposal. 3. Visual Identifiers Organic solvents in glass bottles provide the investigator with the ability to visually inspect the container and its contents. A flashlight can be used to either backlight or sidelight the bottle. Look for the following signs: a. Gross Contamination Hard crystal formation in the form of chips, ice-like structures, crystals, solid mass or cloudy media, are critical signs of gross organic peroxide contamination. Do not handle the container. Contact EH&S for proper disposal. b. Contamination UCI Chemical Hygiene Plan Clear liquid presenting wisp-like structures floating in suspension indicate early signs of peroxide contamination. Peroxide crystals may be found on the bottom of the container, side walls of the glass, threaded cap, and may also be found on the outside of the container. If an old container is found, every attempt should be made to inspect the container without picking up or moving the container. 4. Detection and Removal of Peroxides Refer to Procedures for Detecting and Removing Peroxide Contamination for specific procedures. Most labs will find it easier and more economical to use inventory management to prevent the problem of undesirable peroxide formation. 5. Labeling of Peroxidizable Compounds Many compounds form explosive peroxides or can be explosively polymerized by the presence of peroxides. Commercially available samples of these compounds normally contain stabilizers or inhibitors to extend the shelf storage lifetime. Upon long term storage, the effect of the stabilizer becomes depleted. In addition, most distillation and purification steps normally separate stabilizers from the peroxidizable compound. Test samples of potential peroxide former before each use, especially if you intend to distill or concentrate a large volume (greater than one liter) of the solvent. Use the following lists as guidance for storage times. If a compound stored longer than the indicated periods is not disposed immediately, samples must be tested for peroxides before each use, especially if distillation is being planned. Ethers have limited shelf life and should be purchased in the smallest practical containers. Each container should have the manufacturer’s expiration date and date when first opened. For isopropyl and diethyl ethers, even unopened containers should be disposed prior to the manufacturer’s expiration date. Containers of isopropyl ether, divinyl acetylene, and vinylidene chloride should be tested for peroxide every 3 months after opening or should be discarded. If the peroxide concentration is within acceptable limits, the container can be closed and re-dated for the next scheduled test. Other peroxidizable compounds, such as ethyl ether, dioxane, tetrahydrofuran, etc. should be tested every 6 months after opening or discarded. If peroxide concentration is within acceptable limits, the container can be closed and re-dated for the next scheduled test. Contact EH&S for assistance in disposing of peroxides or other explosive materials. UCI Chemical Hygiene Plan For additional information about peroxides and peroxide forming chemicals, refer to NFPA 43B, “Code of Organic Peroxide Formulations”. The following recommendations for discard or testing timeframes were obtained from Prudent Practices for Disposal of Chemicals from Laboratories, Appendix I, National Academy Press, Washington D.C., 1983, pp.245-246. LIST A Severe peroxide hazard on storage with exposure to air. Discard within 3 months. Name CAS # Diisopropyl ether (isopropyl ether) 108-20-3 DivinylacetyleneA 821-08-9 Potassium metal 7440-09-7 Potassium amide 17242-52-3 Sodium amide (sodamide) 7782-92-5 A Vinylidene chloride (1,1-Dichloroethylene) 75-35-4 LIST B Peroxide hazard on concentration; do not distill or evaporate without first testing for the presence of peroxides. Discard or test for peroxides after 6 months after opening. Name CAS # Acetaldehyde diethyl acetal (acetal) 105-57-7 Cumene (isopropylbenzene) 98-82-3 Cyclohexene 110-83-8 Cyclooctene 931-88-4 Cyclopentene 142-29-0 Decalin (decahydronaphthalene) 91-17-8 Diacetylene (butadiene) 106-99-0 Dicyclopentadiene 77-73-6 Diethyl ether (ether or ethyl ether) 60-29-7 Diethylene glycol dimethyl ether (diglyme) 111-96-6 Dioxane (1, 4-dioxane) 123-91-1 Ethylene glycol dimethyl ether (glyme) 629-14-1 Ethylene glycol ether acetates Ethylene glycol monoethers (cellosolves) Furan 110-00-9 Methylacetylene 74-99-7 Methylcyclopentane 96-37-7 Methyl isobutyl ketone 108-10-1 Tetrahydrofuran 109-99-9 Tetralin (tetrahydronaphthalene) 119-64-2 A Vinyl ethers A Polymerizable monomers should be stored with a polymerization inhibitor which the monomer can be separated by distillation just before use. A Polymerizable monomers should be stored with a polymerization inhibitor which the monomer can be separated by distillation just before use. UCI Chemical Hygiene Plan Top of CHP Table of Contents Appendices LIST C Hazard of rapid polymerization initiated by internally formed peroxides. A Normal liquids; discard or test for peroxides after 6 months after opening.B Name Chloroprene (2-chloro-1,3-butadiene)C Styrene Vinyl acetate Vinylpyridine Normal gases; discard after 12 months.B Name ButadieneC TetrafluoroethyleneC VinylacetyleneC Vinyl chloride 6. CAS # 126-99-8 100-42-5 108-05-4 CAS # 106-99-0 116-14-3 689-97-4 75-01-4 Specific Hazards that May Lead to Fires or Explosions (See Section 12 for Control of Fires) The combination of certain compounds or classes of compounds can result in a violent chemical reaction leading to an explosion or fire. Other compounds pose explosion or fire hazards when exposed to heat, shock, or other conditions. Some of the specific compounds and combinations of compounds that may pose explosion or fire hazards and may be encountered in laboratories are listed below. This list is not complete. Researchers are expected to learn about the hazardous properties of chemicals involved in their research before using them. Use explosion shields to protect yourself and others. A Polymerizable monomers should be stored with a polymerization inhibitor which the monomer can be separated by distillation just before use. B Although air will not enter a gas cylinder in which gases are stored under pressure, these gases are sometimes transferred from the original cylinder to another in the laboratory, and it is difficult to be sure that there is no residual air in the receiving cylinder. An inhibitor should be put into any such secondary cylinder before one of these gases is transferred; the supplier can suggest inhibitors to be used. The hazard posed by these gases is much greater if there is a liquid phase in such a secondary container, and even inhibited gases that have been put into a secondary container under conditions that create a liquid phase should be discarded within 12 months C The hazard from peroxides in these compounds is substantially greater when they are stored in the liquid phase and, if so stored without inhibitors, they should be considered as in List A. UCI Chemical Hygiene Plan a. Acetylenic compounds are explosive in mixtures of 2.5%-80% with air. At pressures of 2 or more atmospheres, acetylene subjected to an electrical discharge or high temperature decomposes with explosive violence. Dry acetylides can detonate with the slightest shock. Many heavy metal acetylides are also shock sensitive explosives. b. Aluminum chloride should be considered a potentially dangerous material. If moisture is present, there may be sufficient decomposition (generating hydrochloric acid (HCl)) to build up considerable pressure. If a bottle is to be opened after long standing, it should be completely enclosed in a heavy towel. c. Ammonia reacts with iodine to give nitrogen triiodide, which is explosive, and with hypochlorites to give chlorine. Mixtures of ammonia and organic halides sometimes react violently when heated under pressure. d. Dry benzoyl peroxide is easily ignited and sensitive to shock and may decompose spontaneously at temperatures above 50 °C. It has reported to be desensitized by the addition of water to 20%. e. Carbon disulfide is both very toxic and very flammable; mixed with air, its vapors can be ignited by a steam bath or steam pipe, a hot plate, or a glowing light bulb. f. Chlorine may react violently with hydrogen or with hydrocarbons when exposed to sunlight. g. Diazomethane and related compounds should be treated with extreme caution. They are very toxic (potent carcinogens), and the pure gases and liquids explode readily. h. Dimethyl sulfoxide decomposes violently on contact with a wide variety of active halogen compounds. Explosions from contact with active metal hydrides have been reported. i. Diethyl, diisopropyl, and other ethers (particularly the branchedchain type) sometimes explode during heating or refluxing because of the presence of peroxides. Ferrous salts or sodium bisulfite can be used to decompose these peroxides, and passage over basic active alumina will remove most of the peroxidic material. In general, however, old samples of ethers should be disposed properly through EH&S. j. Ethylene oxide has been known to explode when heated in a closed vessel. Experiments using ethylene oxide under pressure should be carried out behind suitable barricades. UCI Chemical Hygiene Plan k. Halogenated compounds such as chloroform, carbon tetrachloride, and other halogenated solvents should not be dried with sodium, potassium, or other active metals. Violent explosions are usually the result of such attempts. l. Hydrogen peroxide in concentrations greater than 3% can be dangerous. Contact with the skin may cause severe burns. Thirty percent (30%) hydrogen peroxide may decompose violently if contaminated with iron, copper, chromium, or other metals or their salts. m. Liquid-nitrogen cooled traps that are open to the atmosphere rapidly condense liquid air. When the coolant is removed, an explosive pressure buildup occurs, usually with enough force to shatter glass equipment. Only sealed or evacuated equipment should be cooled. n. Lithium aluminum hydride should not be used to dry methyl ethers or tetrahydrofuran. Fires from this practice are very likely. The products of a LiAlH4 reaction with carbon dioxide have been reported to be explosive. Carbon dioxide or bicarbonate extinguishers should not be used on lithium aluminum hydride fires, which should be smothered with sand or some other inert substance. LiAlH4 reactions should be carried out in a fume hood, behind an explosion shield, and with proper safeguards to avoid exposure of the effluent hydrogen gas to spark or flame. Any stirring device must be spark-proof. o. Oxygen cylinders: Serious explosions have resulted from contact between oil and high-pressure oxygen. Oil should not be used on connections to any cylinder. p. Ozone is a highly reactive and toxic gas. Ozone is formed by the action of ultraviolet light on oxygen (air) and, therefore, certain ultraviolet sources may require venting to the exhaust hood. Liquid and solid ozone are explosive substances. q. Palladium on carbon, platinum on carbon, platinum oxide, Raney nickel, and other catalysts should be filtered from catalytic hydrogenation reaction mixtures carefully. The recovered catalyst is usually saturated with hydrogen and highly reactive and, thus, will inflame spontaneously on exposure to air. Particularly in large-scale reactions, the filter cake should not be allowed to become dry. The funnel containing the still-moist catalyst filter cake should be put into a water bath immediately after completion of the filtration. Another hazard in working with such catalysts is the danger of explosion if additional catalyst is added to a flask in which hydrogen is present. UCI Chemical Hygiene Plan r. Parr bombs used for hydrogenations have been known to explode. Parr bombs should be handled with care behind explosion shields, and the operator should wear goggles. s. Perchlorates: The use of perchlorates should be avoided whenever possible. Perchlorates should not be used as drying agents if there is a possibility of contact with organic compounds, or in proximity to a dehydrating acid strong enough to concentrate the perchloric acid to more than 70% strength (e.g., in a drying train that has a bubble counter containing sulfuric acid). Safer drying agents should be used. Seventy-percent perchloric acid can be boiled safely at approximately 200C, but contact of the boiling undiluted acid or the hot vapor with organic matter, or even easily oxidized inorganic matter (such as compounds of trivalent antimony), will lead to serious explosions. Perchlorate esters have the same shattering explosive effect as nitroglycerine. Oxidizable substances must never be allowed to contact perchloric acid. Beaker tongs, rather than rubber gloves, should be used when handling fuming perchloric acid. Perchloric acid evaporations should be carried out in a hood that has a good draft and a built-in water spray for the ductwork behind the baffle. After use, washing out the hood and ventilator ducts with water is necessary to avoid danger of spontaneous combustion. t. Permanganates are explosive when treated with sulfuric acid. When both compounds are used in an absorption train, an empty trap should be placed between them. u. Peroxides (inorganic): When mixed with combustible materials, barium, sodium, and potassium peroxides form explosives that ignite easily. v. Phosphorus (red and white) forms explosive mixtures with oxidizing agents. White phosphorus should be stored under water because it is spontaneously flammable in air. The reaction of phosphorus with aqueous hydroxides forms phosphine, which may ignite spontaneously in air or explode. w. Phosphorus trichloride reacts with water to form phosphorous acid, which decomposes on heating to form phosphine, which may ignite spontaneously or explode. Care should be taken in opening containers of phosphorous trichloride, and samples that have been exposed to moisture should not be heated without adequate explosion shielding to protect the operator. x. Potassium is in general more reactive than sodium. It ignites quickly upon exposure to humid air and, therefore, should be handled under the surface of a hydrocarbon solvent such as mineral oil or toluene. Oxidized coatings should be very carefully scraped UCI Chemical Hygiene Plan away before cutting the metal (explosions can otherwise occur). Potassium metal can form explosive peroxides. Metal that has formed a yellow oxide coating from exposure to air should not be cut with a knife, even when wet with a hydrocarbon, because an explosion can be promoted. y. Residues from vacuum distillations have been known to explode when the still was vented to the air before the residue was cool. Such explosions can be avoided by venting the still pot with nitrogen, by cooling it before venting, or by restoring the pressure slowly. z. Sodium should be stored in a closed container under kerosene, toluene, or mineral oil. Scraps of sodium or potassium should be destroyed by reaction with n-butyl alcohol. Contact with water should be avoided because sodium reacts violently with water to create explosions and fire. Reactions with sodium should be carried out in a fume hood, behind an explosion shield, and with proper safeguards to avoid exposing the effluent gas hydrogen to spark or flame. Any stirring device must be spark-proof. Carbon dioxide, bicarbonate, and carbon tetrachloride fire extinguishers should not be used on alkali metal fires. aa. m-chloroperbenzoic acid should only be stored in plastic containers. Researchers should take special care to do this after purifying commercial material to 99%. A sample of 99+% material stored in a glass sample bottle exploded in a laboratory in 1995 causing an injury to a researcher. 7. If warranted, any lab specific practices can be documented in a written Standard Operating Procedure (SOP); complete sections 1-7 of the Standard Operating Procedure Template. Also, examples of SOPs for many hazardous chemicals are located in the SOP Library . Top of CHP Table of Contents Appendices 4.5 Segregation of Incompatible Substances When transporting, storing, using, or disposing of any chemical, ensure that the substance cannot accidentally come in contact with an incompatible material. Such contact could result in a serious explosion, the formation of substances that are highly toxic or flammable or both. See Table of Common Incompatibilities for more examples. 4.6 Handling Compressed Gases Because of their high pressure, cylinders of compressed gases present physical hazards. Guidelines for handling compressed gas cylinders follow: UCI Chemical Hygiene Plan 1. Except during transportation (see Section 4.6.4 below), compressed gas cylinders of all sizes must be restrained at all times by straps, chains, or a suitable stand to prevent the cylinder from falling. 2. When a cylinder is empty, mark it "EMPTY" or "MT" or use the tag system supplied by the vendor. Close the valve and replace the valve protection cap. Cylinders should not block egress from the laboratory. 3. During transportation of cylinders, the protective caps must be securely in place. For cylinders over 2 feet, an appropriate cart must be used. 4. Compressed gas cylinders must not be exposed to temperatures higher than 50°C (122°F). 5. Lecture bottles of reagent gases must be used according to the following guidelines: 6. a. Whenever possible, lecture bottles must be purchased from a supplier that allows the return of partially filled or empty cylinders. b. Compatible regulators must always be used, taking into account any properties of the gas. c. At least once a year, the SR must inspect the stored lecture bottles for signs of leakage and/or corrosion. The SR must determine which lecture bottles will not be used during the next 12 months and return these to a supplier for proper reuse or disposal. Leaking cylinders of flammable, oxidizing, corrosive or toxic gases represent a serious hazard, and must be handled according to the following procedures: a. DO NOT transport leaking cylinders of toxic gases in elevators or hallways. Leave the area and call EH&S for assistance. b. If a minor leak is suspected, a flammable gas leak detector or a soapy solution (Snoop) must be used; under no circumstances must a flame be used for leak detection. c. Shut off the main cylinder valve upon confirmation of a minor leak, the cylinder must be immediately transported to a fume hood or gas cabinet. EH&S must then be notified of the leak. d. If a major leak of a hazardous gas develops, all personnel must be evacuated from the area (see Section 12 for further details). e. Compressed gas cylinders that are leaking inside gas cabinets must be left in place and reported to the EH&S Emergency Response Team by dialing 824-6200 during normal working hours (M-F, 8AM-5PM) or 911 after hours. UCI Chemical Hygiene Plan 7. Flashback or flame arresters are recommended when working with highly flammable fuel gases such as acetylene and hydrogen gas. 8. Ensure equipment is grounded when working around flammable gases. A comprehensive Compressed Gas Safety Awareness Training Supplement is provided in the Appendices. 4.7 4.8 Laboratory Use of Anesthetics Anesthesia commonly used in some research laboratories include: nitrous oxide, halothane, enflurane, methoxyflurane, trichloroethylene, and urethane. Exposure to waste anesthetic gases and vapors during surgical procedures is harmful to researchers. Open bench surgeries involving gaseous anesthetics should employ waste gas scavenging systems that are connected to non-recirculating exhaust systems. 1. Refer to the Controlling Waste Anesthetic Gases for procedures to minimize exposure to waste anesthetic gases. 2. Exhaust systems must be used in conjunction with scavenger systems. Contact EH&S prior to installation of scavenger systems to existing building ventilation. Laboratory Equipment and Glassware Each laboratory worker must keep the work area clean and uncluttered. All chemicals and equipment must be properly labeled in accordance with Section 4.11. The work area must be regularly cleaned and all equipment properly cleaned and stored. The following procedures must apply to the use of laboratory equipment and glassware: 1. Laboratory equipment must be used only for its intended purpose. 2. All glassware will be handled and stored with care to minimize breakage; glassware must be disposed of in the following ways: a. All broken glassware, Pasteur pipettes, slides, cover slips and other glassware which could puncture that are not contaminated with infectious material, radioactive material, or hazardous material must be placed in the assigned broken glass container in each laboratory. This container must be labeled both in English and Spanish with the words "BROKEN GLASS/VIDRIO ROTO”. b. Pasteur Pipettes, slides and cover slips that are contaminated with infectious material must be disposed of in one of the following ways: UCI Chemical Hygiene Plan 4.9 i. Sterilized in an autoclave permitted by Orange County Health Agency and EH&S and then disposed of in the broken glass container. ii. Decontaminated with bleach or other appropriate decontaminant and then disposed of in the broken glass container. iii. Transferred to a medical waste disposal site in a sharps disposal container. 3. All needles, scalpels, and blades must be disposed of in a sharps disposal container. Full sharp containers are brought to medical waste disposal sites for pickup and destruction off-campus. 4. All glass apparatus must be carefully inspected for cracks and other flaws before evacuation. Whenever feasible, evacuated or pressurized glassware must be taped or a shield placed between the glassware and the operator to contain glass fragments and chemicals in the event of implosion. 5. All laboratory equipment must be inspected on a regular basis by the laboratory workers, and replaced or repaired as necessary. 6. Frozen ground glass joints should be taken to the Glass Shop in Rowland Hall for “unsticking”. Cooling the glassware is sometimes effective. Serious cuts have occurred from researchers trying to do this themselves. 7. Use proper traps (filters or adsorbants) to protect house vacuum lines. Personal Protective Equipment 1. Safety glasses meeting ANSI Z87.1 are required for laboratory workers and visitors to the laboratory as procedures dictate and will be worn at all times when in the laboratory. 2. Chemical goggles and/or a full-face shield must be worn during chemical transfer and handling operations as procedures dictate. 3. Laboratory coats are provided and must be worn at all times in the laboratory. Laboratory coats must be removed immediately upon discovery of significant contamination. 4. Appropriate chemical-resistant gloves must be worn at all times when skin contact with chemicals may occur. Wear two layers of gloves when added protection is needed. Reusable gloves must be inspected and washed prior to re-use. Replace damaged or deteriorated gloves immediately. Gloves must be washed prior to removal from the hands. UCI Chemical Hygiene Plan Remove gloves immediately after working with toxic solvents that are readily absorbed through skin, such as phenol or carbon disulfide. Many researchers use latex gloves for work with hazardous chemicals due to the wide availability of this type of glove. About 10% of the population will exhibit an allergic sensitivity to latex products. Generally, nitrile gloves are preferable over latex and vinyl for most hazardous chemical work, but it is important to consult the Glove Selection Guidelines and Resources document, chemical vendor, or EH&S when selecting the proper glove for hazardous chemical work. 5. Thermal-resistant gloves must be worn for operations involving the handling of heated materials and exothermic reaction vessels. Thermalresistant gloves must be asbestos free and should be replaced when damaged or deteriorated. 6. All personnel using respirators must obtain prior approval from EH&S and participate in the UC Irvine Respiratory Protection Program. 7. Remove all contaminated personal protective equipment before leaving the laboratory. 8. Refer to Personal Protective Equipment in the Laboratory Safety Guidelines for more information. Consult with your School EH&S Coordinator for assistance. Top of CHP Table of Contents Appendices 4.10 Personal Work Practices 1. The Laboratory Supervisor must ensure that each laboratory worker knows and follows the rules and procedures established in this plan. The Work-Unit Specific Awareness and Training template is used to design a consistent and lab-specific laboratory worker training, in support of communicating the rules and procedures established in this plan. 2. All laboratory workers must remain vigilant to unsafe practices and conditions in the laboratory and must immediately report such practices and/or conditions to the Laboratory Supervisor. The Laboratory Supervisor must correct unsafe practices and/or conditions promptly. Recurring hazardous situations and unsafe practices should be incorporated into the Work-Unit Specific Awareness and Training to increase laboratory workers understanding in the problematic areas. UCI Chemical Hygiene Plan 4.11 3. Long hair and loose-fitting clothing must be confined close to the body or tied back to avoid being caught in moving machine/equipment parts and contaminated. 4. Do not wear high-heeled shoes, open-toed shoes, sandals, or shoes made of woven material. 5. Never perform unauthorized experiments. 6. Do not work alone in the laboratory without authorization. 6. Shorts, cutoffs, and miniskirts unnecessarily expose your skin to potential corrosives and are not safe. 7. Jewelry including rings, bracelets, and wristwatches in the laboratory can become contaminated and damaged by chemicals increasing chances of chemical exposure. Also, wearing jewelry increases probability of accidental contact with electrical sources or catch-points on equipment causing accidents. 8. Use volatiles inside the chemical fume hood. 9. Exposure to any laboratory chemical by any route--dermal, inhalation, ingestion, injection--must be avoided. 10. Chemicals must never be deliberately tasted or smelled. 11. Loose fitting, insulated gloves must be worn when handling cryogenics. Where splashing could occur during transfer of cryogenics, safety goggles and face shields should be worn. Boiling and splashing always occur when charging a warm container or when inserting warm objects into the liquid. 12. Never wear or bring lab aprons or lab coats or jackets into areas where food is consumed. 13. Do not prepare or store (even temporarily) food or beverages in the same area as hazardous chemicals. Never consume any food or beverage when you are in a chemical area. Do not chew gum or tobacco, and do not smoke or apply cosmetics in the laboratory. 14. Wash hands thoroughly after working with hazardous chemicals and before leaving the lab. Container Labeling 1. All chemical containers in the laboratory must be labeled including waste containers. The label must be informative and durable, and at a minimum, will identify contents and hazards. UCI Chemical Hygiene Plan 4.12 2. When hazardous chemicals are transferred out of the original container, a completed Hazardous Materials label must be affixed to the unlabeled container. View an example of a blank EH&S Hazardous Materials label at the EHS Website. EH&S recommends using the preprinted labels available in various electronic file formats from the Hazardous Waste Management website. Be careful to use the label designed for materials, not waste. 3. All waste container labels must include the words “Hazardous Waste,” the chemical name(s) of all constituents and the weight percentage, the Principal Investigator's name, department location (building name, room number and telephone number), and the date waste was first generated. View an example of a blank EH&S Hazardous Material Waste label at the EHS website. The EH&S preprinted waste labels—various electronic file formats available from the Hazardous Waste Management website-provide space for all required information. See Hazardous Waste Guidelines for an example of waste labeling (printable on 8 ½” X 14” legal size paper). 4. Exceptions for labeling requirements can be made for the following: a. Chemical transfers from a labeled container into a container that is intended only for the immediate use of the laboratory worker who performed the transfer. Such chemicals must be used up before container is left unattended. b. Synthetic intermediates prepared in the laboratory by the researcher must be labeled with either the chemical structure or a number that serves to uniquely identify the substance. Any known or suspected hazards must also be indicated on the label. 5. Portable containers must be labeled by the individual using it. 6. All chemical containers must be periodically inspected by the SR to ensure that labels have not been defaced or removed. Disposal Disposal of all hazardous materials and wastes must be arranged through EH&S. Utilize the on-line chemical waste pick-up request service. Intentional environmental discharges of hazardous materials and wastes to land, air, or water are prohibited. No hazardous chemicals and wastes may be disposed in trashcans, drains or by evaporation. 1. Certain hazardous wastes are either too reactive or too toxic for disposal with the solvent waste. These wastes must be properly segregated and transferred to EH&S. Chemical treatment of reactive (and some toxic) hazardous waste may render it non-reactive (or non-toxic), and suitable for disposal. Prudent Practices for Handling Chemicals in Laboratories contains detailed instructions for the destruction and subsequent disposal of many hazardous wastes. However, California regulations prohibit the UCI Chemical Hygiene Plan treatment of hazardous waste without specific approval by a regulatory agency. Therefore, chemical treatment should not be performed without prior consultation with the EH&S. Examples of hazardous wastes that must be segregated from other incompatible waste include: a. Acids of pH 2 or less (Do not mix different acids); b. Acid chlorides, acid anhydrides, and related compounds; c. Alkaline basic solutions of pH 12.5 or greater (Do not mix different bases); d. Alkali metals and other water reactive chemicals; e. Heavy metal solutions and salts; f. Halogenated organics; segregate non-flammable from flammable; g. Non-halogenated flammable; h. Peroxide-forming chemicals; i. Strong oxidizers; j. Chemical carcinogens (See Section 5); k. Cyanides and sulfide containing solutions; and l. Other toxic materials. organics: segregate non-flammable from REFERENCE: “Hazardous Waste Guidelines” flyer 2. 4.13 Empty containers can be reused as waste containers or disposed as regular trash, providing they have not contained Particularly Hazardous Substances (PHS). Empty is defined as drip free in the case of liquids, and reasonably scraped clean in the case of solids. EH&S will accept empty containers, especially those having plastic Safe-Cote® feature, for redistribution to others as waste containers. Contact EH&S to arrange empty container disposal or for disposal of containers previously holding extremely hazardous materials. Inventory Maintenance Each research group must maintain an inventory of chemicals. This inventory will be kept in a web-based computer database available from EH&S. The inventory listing includes the full name of each chemical, its physical state (at room temperature), the quantity on hand, the container size and container type, and the storage location (by room number). Labs may have additional procedures for chemical inventory maintenance; consult with the Lab Supervisor for labspecific procedures. UCI Chemical Hygiene Plan 4.14 Source Reduction and Waste Minimization Laboratory workers are obligated to use the smallest amounts of hazardous materials (called source reduction) and to generate the least amount of hazardous wastes (called waste minimization) as is practical. This includes: an obligation to review experimental protocols to evaluate the potential for substitution of non-hazardous or less hazardous reagents or analytical techniques; using "micro scale" procedures; and using materials that can be easily neutralized and detoxified. Current information on these subjects can be obtained from EH&S. Top of CHP Table of Contents Appendices UCI Chemical Hygiene Plan 5.0 Standard Operating Procedures for Working with Particularly Hazardous Substances The chemicals, concentrations, and forms commonly used in laboratories are classified as hazardous substances, and the general operating procedures for working with these chemicals are detailed in Section 4. However, some substances pose a significantly higher threat to human health because of their toxicology, concentration, and form. These high hazard materials are classified as "Particularly Hazardous Substances" (PHSs). There are four categories of Particularly Hazardous Substances: select carcinogens, reproductive toxins (embryotoxins), compounds with a high degree of acute toxicity, and “select agents” (toxins that are biological in origin). General procedures for working with particularly hazardous substances are presented in detail in Section 5.4 and 5.5. Special Handling Procedures for Certain PHS is provided in the Appendices. 5.1 Working with Carcinogens Comprehensive lists of known & suspected carcinogens from peer-reviewed authoritative sources are available on the Internet. The following is a partial list of carcinogens found in laboratories at UC Irvine. This list is not complete. Each laboratory worker (in consultation with the laboratory supervisor) must evaluate each chemical involved in their work. Container labels and MSDSs communicate whether a chemical is carcinogenic. Acrylonitrile Dimethylcarbamoyl Methylene Chloride Benzene Cadmium Chloride Cadmium Compounds Chemotherapeutic Agents Chloromethyl Ether 1,2-Dibromoethane Diaminobenzidine Dimethyl Sulfate N-ethyl-N-nitrosourea Epichlorohydrin Ethyleneimine α-Naphthylamine β-Naphthylamine Propylene Oxide Silica, (crystalline) Ethylene Oxide Formaldehyde N-Methyl-N-Nitrosourea Styrene Oxide Vinyl Bromide Vinyl Chloride NOTE: Some carcinogens must be reported to Cal/OSHA. Please see Cal/OSHA Reportable Hazardous Chemicals to determine if the Supplemental Information Form for Chemical Requiring Cal/OSHA Registration must be completed. Contact EH&S at 824-6200 for assistance. Carcinogens must be handled in accordance with the procedures described in Section 5.4 . UCI Chemical Hygiene Plan 5.2 Working with Reproductive Toxins Below is a partial list of reproductive toxins uses in some UC Irvine research laboratories: Acrylic Acid Aniline Benzene Carbon disulfide Cadmium N,N-Dimethylacetamide Dimethylformamide Dimethyl Sulfoxide Formaldehyde Formamide Glycol Ethers (EGME, EGEE, and their acetates) Hexachlorobenzene Iodoacetic Acid Lead Compounds Mercury Compounds Nitrobenzene Nitrous Oxide Phenol Toluene Vinyl Chloride Xylene The above list is not complete. Each laboratory worker (in consultation with the laboratory supervisor) must evaluate each chemical involved in his/her work. Container labels and MSDSs communicate whether a chemical is carcinogenic. 1. Reproductive toxins will only be handled in fume hoods that have passed the EH&S performance test within the last 12 month and utilizing appropriate protective equipment (to prevent skin contact) prescribed by the supervisor. Contact EH&S Fume Hood Testing at 824-6200 if fume hood performance cannot be verified. 2. Reproductive toxins will be stored in adequately ventilated areas with the primary container placed inside an unbreakable sealed outer container. 3. The Laboratory Supervisor must be notified of spills and other exposure incidents. A brief written description of the incident should be shared with lab staff. These compounds must be handled in accordance with the procedures described in Section 5.4 . 5.3 Working with Compounds with a High Degree of Acute Toxicity Below is a partial list of compounds with a high degree of acute toxicity used in some UC Irvine research laboratories. Acrolein Acrylic Acid Acrylonitrile Allyl Alcohol Allylamine Bromine Chlorine 1,2-Dibromoethane Dimethyl Sulfate Ethylene Oxide Hydrazine Hydrogen Cyanide Hydrogen Fluoride Hydrogen Sulfide Nickel Carbonyl Nitrogen Dioxide Osmium Tetroxide Ozone Phosgene Sodium Azide Cyanide Salts UCI Chemical Hygiene Plan Diazomethane Diborane Methyl Fluorosulfonate Methyl Iodide Arsine The above list is not complete. Each laboratory worker (in consultation with the laboratory supervisor) must evaluate each chemical involved in his/her work. Container labels and MSDSs communicate whether a chemical is carcinogenic. These compounds must be handled in accordance with the procedures described in Section 5.4. 5.4 Work with Particularly Hazardous Substances (Written Standard Operating Procedures—SOPs) In addition to the general procedures for working with hazardous substances described in Section 4, researchers should read and understand the SOP written by the Laboratory Supervisor or SR to protect workers. If a material is being used for the first time, the Laboratory Supervisor/Principal Investigator or SR should coordinate with the user to write the SOP. EH&S maintains an SOP Library on its website which can be tailored to meet the specifics of the laboratory. In writing the SOP, the following procedures must be incorporated when working with any Particularly Hazardous Substance (PHS) in a form or concentration that poses an extreme health concern. Use the SOP Guidelines & Template as a resource. Please complete all ten (10) sections of the SOP template. 1. Information Before beginning a laboratory operation involving a PHS, each researcher must consult the manufacturer’s Materials Safety Data Sheet (MSDS) and other appropriate literature (see Section 14 and Appendix J) for information about the properties of the substances. 2. Designated (Controlled) Work Areas Special work areas should be designated for work with select PHSs, embryotoxins, and compounds with high acute toxicity. The rooms, including storage areas for the PHSs, should have restricted access. Signs indicating "Authorized Personnel Only" should be posted at entrances to these work areas, and if necessary, the areas should be locked. Only personnel with special instruction on the hazards and safe handling of PHSs should be permitted access to the areas. Designated areas must be maintained at an air pressure less than that of surrounding areas. 3. Engineered System Protection All work involving PHSs should be done in fume hoods, glove boxes or similar devices to reduce the risks of laboratory worker exposure. 4. Handling of Contaminated Waste Whenever possible PHSs should be detoxified by some procedure that can be reasonably expected to convert essentially all of the toxic substances to UCI Chemical Hygiene Plan nontoxic substances (for a discussion, see Prudent Practices for Handling Chemicals in Laboratories). As hazardous waste treatment is prohibited without specific approval by a California regulatory agency, lab workers must consult with EH&S prior to employing any waste treatment method. If detoxification is not feasible, waste solvents and wastewater contaminated with PHSs must be collected for disposal by EH&S in closed, impervious containers. Transfers to waste containers must be performed in the same hood in which the experiment was performed to ensure that laboratory workers are not exposed to the material. These containers must be properly labeled (as described in Section 4.11.3), waste containing appreciable amounts of carcinogens must carry the warning: CANCER AGENT. 5.5 5. Personal Hygiene Laboratory workers using PHSs must take extra precautions in maintaining good personal hygiene. Dispose gloves and wash hands before leaving the restricted area. No food, beverage or tobacco products will be permitted in the restricted areas. 6. Protection of Vacuum Systems To protect vacuum lines and pumps, use the proper traps or filters. These include High Efficiency Particulate Air (HEPA) filters or high efficiency scrubber. 7. Protective Apparel Lab coats, gloves and other appropriate protective apparel should be used at all times when working with PHSs to prevent skin contact. 8. Preparation for Accidents Laboratory workers must take precautions to minimize the potential for accidents or spills involving PHSs. Containers of such substances should be stored in pans or trays made of polyethylene or other unbreakable material. During an experiment involving the use of PHSs, the working surface of the hood should be covered with a removable liner of adsorbent plastic-backed paper. Work with PHSs should be done with the smallest amounts possible. Purchases of the chemicals should be restricted to minimal amounts necessary to prevent uninterrupted work. 9. Prior Approval For substances listed in Cal/OSHA Article 110, prior approval is required from the Laboratory Supervisor. See Appendix C for a list of these chemicals and the registration form. Working with Select Agents (Toxins of Biological Origin) UCI Chemical Hygiene Plan 1. All researchers working with Select Agent Toxins (see Select Agent List) must register with EH&S before any agent can be ordered. Follow procedures in the Select Agent Program. Contact the Biosafety Officer at 824-6200 for assistance. 2. Special Practices Standard practices listed under Biosafety Level 2 and Biosafety Level 3 (for reference see Biosafety in Microbiological and Biomedical Laboratories, USDHHS, CDC/NIH, 4th Edition, pages 20 and 27) (www.cdc.gov/od/ohs/biosfty/bmbl4/b4ai.htm) should be reviewed and incorporated as appropriate into protocols for work with toxins. a. Training specific to the toxin is required and must be documented for all laboratory workers. b. Approved users must maintain an inventory control. c. Toxins must be stored in locked storage rooms, cabinets or freezers. d. Access to areas containing toxins should be restricted to those whose work assignments require access. e. Preparation of primary containers of toxin stock solutions and manipulations of primary containers of dry forms of toxins should be conducted in a chemical fume hood, glove box, or a biological safety cabinet. f. Users should verify that hood or biological safety cabinet is working properly before initiating work. g. All work should be done within the effective zone of the hood or biological safety cabinet. The effective zone is 6 or more inches into the hood or cabinet. h. When toxins are in use, the room should be posted to indicate “Toxins In Use – Authorized Personnel Only”. i. All high risks operations should be conducted with two knowledgeable individuals present. Each must be familiar with the procedures, maintain visual contact with the other and be ready to assist in the event of an accident. j. The interior of the hood, glove box, or cabinet should be decontaminated periodically, for example, at the end of a series of related experiments. Until decontaminated, the hood, box, or UCI Chemical Hygiene Plan cabinet should be posted to indicate that toxins are in use, and access to the equipment and apparatus must be restricted to necessary, authorized personnel. Top of CHP Table of Contents Appendices k. Lab coats and eye protection should be worn when working in an open front containment system. l. When handling dry forms of toxins that can easily become electrostatically charged: i. Do not wear latex gloves that help to generate static electricity. ii. Use a glove bag within a hood or biosafety cabinet, glove box, or class III biosafety cabinet. m. When handling toxins that are also irritants, necrotizing to skin, or extremely toxic from dermal exposure, select gloves that are known to be impervious to the toxin. n. Consider both toxin and diluents when selecting gloves. o. Protect vacuum lines with HEPA filters to prevent entry of toxins into the lines. p. Sink drains should be protected by HEPA filters when water aspirators are used. UCI Chemical Hygiene Plan 6.0 Standard Operating Procedures Applying to All Hazardous Chemical Work 6.1 6.2 Chemical Exposure Evaluation 1. Chemical exposure evaluations will be conducted by EH&S personnel as necessary. 2. Air sampling will be conducted if there is reason to believe that exposure levels for regulated substances may exceed the action level, or in the absence of an action level, the Cal/OSHA Permissible Exposure Level (PEL). Cal/OSHA has established action levels for a few chemicals. Some examples are in Cal/OSHA Reportable Chemicals. 3. Results of air sampling studies performed in the laboratory will be maintained by EH&S. 4. When laboratory personnel have identified a potential for chemical exposure, EH&S may be requested to conduct an industrial hygiene evaluation of the workplace. Clean Areas Eating, drinking, smoking, gum chewing, and application of cosmetics must occur in designated Clean Areas. See Clean Area procedures. Hands must be washed thoroughly prior to performing these activities in clean areas or outside of the lab. 6.3 Housekeeping 1. Each laboratory worker is responsible for the cleanliness of his or her workspace, and is jointly responsible for common areas of the laboratory. The Supervisor/Principal Investigator must insist lab areas are kept neat and orderly. 2. The following standard operating procedures apply to the housekeeping standards of the laboratory: a. All apparatus must be thoroughly cleaned and returned to storage after use. b. All aisles, exits, fire-extinguishing equipment, eyewashes, showers, electrical disconnects and other emergency equipment must remain unobstructed. c. All chemical wastes will be disposed in accordance with Section 4.12. UCI Chemical Hygiene Plan 6.4 Safety and Emergency Equipment 1. Telephone numbers of emergency personnel, supervisors and other contacts should be posted near phones and kept updated. 2. The Emergency Notification Information (ENI) placard on the lab door should be updated by lab staff as needed to maintain accuracy. New placards are available from the School EH&S Coordinator, by calling 8246200, or downloading them from Internet: use the one for the General Campus or for School of Physical Sciences. 3. All laboratory personnel will be trained in the proper use of fire extinguishers when hired and receive refresher training as needed. Prior to the procurement of new classes of hazardous chemicals, the laboratory workers must verify that existing extinguishers and other emergency equipment are appropriate for such chemicals. 4. All laboratory workers who might be exposed to chemical splashes must be instructed in the location and proper usage of emergency showers and eyewashes. a. Facilities Management (FM) in accordance with ANSI Z358.1 and manufacturer’s specifications must perform inspections of emergency showers and eyewashes and maintain inspection records. b. Equipment is tagged with the most recent inspection dates. c. Location signs for safety and emergency equipment must be posted. d. A minimum space of thirty inches (30) must be maintained clear of any obstructions in front of emergency equipment. 6.5 Unattended Operations When laboratory operations are left unattended (continuous operations, overnight reactions, etc.), the following standard operating procedures will be employed: 1. The laboratory worker and the Principal Investigator/Laboratory Supervisor will review work procedures to ensure the safe completion of the operation. 2. Provisions must be made for interruption of utility service during the unattended operation (loss of water pressure, electricity, etc.). 3. Automatic temperature shut-off controls should be employed where run-away temperatures would lead to fire, explosion, or generation of toxic gases. Top of CHP Table of Contents Appendices UCI Chemical Hygiene Plan 7.0 Standard Operating Procedures for Engineering Controls 7.1 Intent The engineering controls installed in the laboratory are intended to minimize laboratory worker exposure to chemical and physical hazards in the workplace. These controls must be maintained in proper working order for this goal to be met. 7.2 Modification Engineering controls must not be modified unless testing by EH&S indicates that worker protection will continue to be adequate. 7.3 Improper Function Improperly functioning engineering controls must be reported immediately to the Supervisor/Principal Investigator immediately and the Facilities Management. The system must be taken out of service until repairs have been completed and adequate performance re-verified by EH&S. 7.4 Usage All laboratory workers must follow proper work practices when using the engineering controls. 1. 2. Local Exhaust Ventilation The following procedures must apply to the use of local exhaust ventilation: a. Openings of local exhaust vents must be placed as close as possible to sources of the air contaminant. b. When the vents are in the open position, the exhaust fans must be kept on. c. After the completion of work, the fan must be left on for an additional amount of time sufficient to clear residual contaminants from the ductwork. d. Periodic inspections of the ventilation system will be conducted by EH&S. A record of each inspection must be maintained by EH&S, and the last test date posted on the system. Laboratory Hoods The laboratory fume hoods must be utilized for chemical procedures that could release hazardous chemical vapors or dust. Fume hoods must be left on at all times (except for maintenance). The following work practices must apply to the use of fume hoods: UCI Chemical Hygiene Plan 3. a. Adequate fume hood ventilation performance must be confirmed prior to opening chemical containers inside the hood. An inward flow of air can be confirmed by holding a piece of tissue paper at the face of the hood and observing the movement of the paper. b. The sash of the hood must be closed when is not in use for safety reasons as well as energy conservation. At all other times, the sash height must be maintained as low as possible, never above the position marked by EH&S on the fume hood itself. c. Storage of chemicals and equipment inside the hood must be kept to a minimum to maintain optimal fume hood performance. d. Interference with the inward flow of air into the hood must be minimized. e. Each fume hood will be tested annually. The fume hood must provide an average open face velocity of 100 linear feet per minute (lfpm) with a minimum of 80 lfpm at any point. A record of each inspection must be maintained by the EH&S office, and the last inspection date posted on the hood. g. Evaporation in the hood must not be used for the disposal of volatile chemicals. h. Report fume hood performance problems to EH&S at 824-6200. Cold Rooms In the event of an electrical failure in a cold room, the following provisions will be followed: The emergency personnel listed on the "In Case of Emergency Contact" sheet must be immediately notified and be asked to report any hazards associated with the loss of electricity and warming of the cold room. Appropriate measures must be undertaken to restore power. Dry ice must not be used inside cold rooms. This practice could result in the displacement of oxygen and cause asphyxiation. 4. Hazardous Materials Storage Cabinets When approved storage cabinets are used, the following prudent safety practices must be followed: a. Only compatible materials must be stored inside the cabinet. UCI Chemical Hygiene Plan Top of CHP Table of Contents Appendices b. Chemicals of similar vapor density must be stored together when using mechanical ventilation (e.g., heavier than air vapors are vented through the bottom vent and lighter than air vapors through the top vent). c. Paper or cardboard must not be stored inside cabinets with chemicals. d. Storage cabinets must not be overloaded. Doors must be able to close, and double stacking of hazardous chemicals prohibited. UCI Chemical Hygiene Plan 8.0 Standard Operating Procedures for Laboratory Worker Information and Training 8.1 8.2 Hazard Information 8.1.1 “Occupational Exposure to Hazardous Chemicals in Laboratories”, California Code of Regulations Title 8, Section 5191. Visit this web page to access the Cal/OSHA regulation relating to protecting employees from occupational exposure to hazardous chemicals. 8.1.2 The location of the UC Irvine Chemical Hygiene Plan as well as other required safety information is provided on the Location of Required Safety Information flyer. The Chemical Hygiene Plan provides written safety procedures for protecting employees from occupational exposure to hazardous chemicals. 8.1.3 “Permissible Exposure Limits (PEL) for Chemical Contaminants”, California Code of Regulations, Title 8, Section 5155. Visit this web page for regulatory exposure limits for many airborne contaminants; the actual values are in Table AC-1, under the “View Graphic” links. Please contact EH&S for exposure limits where there is no applicable Cal/OSHA regulation. 8.1.4 Staff response to chemical spills is described in Section 12.2 of the Chemical Hygiene Plan as well as in Hazardous Materials Incidents within the UC Irvine Emergency Procedures. 8.1.5 Reference Materials on the hazards, signs & symptoms of exposure, safe handling, storage & disposal of hazardous chemicals: Material Safety Data Sheets Classes of Hazardous Chemicals o General Laboratories o Integrated Nanofab Research Facility (INRF) Standard Operating Procedures (SOP) Library Campus EH&S website Chemical Safety, National Institute of Occupational Safety and Health Training Each laboratory worker must receive training at the time of initial assignment to the laboratory, and prior to assignments involving new classes of chemicals, Particularly Hazardous Substances, and hazardous operations. Training must include: UCI Chemical Hygiene Plan Methods and observations that may be used to detect the presence or release of a hazardous chemical; The physical and health hazards of chemicals in the work area; The measures workers can take to protect themselves from these hazards, including specific procedures the employer has implemented to protect workers such as appropriate work practices, emergency procedures, and personal protective equipment to be used. 1. Lab workers must take Laboratory Safety & Chemical Hygiene Plan Workshop for Laboratory and Research Personnel from campus EH&S. This course covers applicable details of the written UC Irvine Chemical Hygiene Plan. New employees are required to attend the next training session presented after the date of their initial hire. 2. There may be other required EH&S provided safety trainings for work involving other categories of hazardous materials; for example, radioactive materials and blood borne pathogens. See also the Basic Research Requirements matrix. 3. The Principal Investigator, Laboratory Supervisor, Safety Representative (SR) will apprise all laboratory workers of jobspecific hazardous chemicals and operations used in the PI’s laboratory. The Laboratory Awareness & Training Record template is designed to help provide consistent and lab-specific laboratory worker training. Top of CHP Table of Contents Appendices UCI Chemical Hygiene Plan 9.0 Standard Operating Procedures for Medical Consultations and Examinations Medical consultation or examination is provided: 1. When a laboratory employees develops signs or symptoms associated with a hazardous chemical to which the employee may have been exposed in the laboratory. 2. Where employee exposure monitoring reveals an exposure level above the action level for a Cal/OSHA regulated substance for which there are exposure monitoring and medical surveillance requirements. (Also, medical surveillance will be established as prescribed by the particular Cal/OSHA standard.) 3. When an event takes place in the laboratory such as a spill, leak, explosion or other occurrence resulting in a hazardous exposure to the laboratory employee. Medical consultations and examinations will be provided under the direct supervision of a licensed physician. Contact the Campus Occupational Health Nurse at 824-6200. Top of CHP Table of Contents Appendices UCI Chemical Hygiene Plan 10.0 Laboratory Activities Requiring Prior Approval Prior approval must be obtained from the Principal Investigator/Laboratory Supervisor for laboratory activities that present specific, foreseeable hazards to the laboratory workers. These activities include off-hours work, working alone, hazardous operations, and unattended operations. 10.1 Off-Hours Work Laboratory personnel are not permitted work after hours in the laboratory, except when prior approval from the Principal Investigator/Laboratory Supervisor has been obtained. After hours are defined as 8PM - 7AM Monday through Friday and from 8PM Friday to 7AM Monday. 10.2 Working Alone When laboratory personnel will be working alone, the PI/Laboratory Supervisor must evaluate the condition or activity to determine if the situation may pose a risk or serious hazard to workers or property. Each situation must be evaluated on a case-by-case basis to determine if working alone will be permitted. Important considerations are: 1. Tasks and hazards involved in the work; 2. Consequences resulting from a worst-case failure; 3. The possibility of an accident or incident that would prevent an worker from calling for help; 4. The worker’s training and experience; 5. Physical condition or handicaps. Laboratory workers should confirm that another worker is present on the same floor of the building before undertaking any laboratory operation. 10.3 Hazardous Work All hazardous operations must be performed during a time when at least two personnel are present in the laboratory. For undergraduate workers, this applies to all laboratory operations. The Principal Investigator and/or the EH&S Coordinator must make the determination of hazardous operations. UCI Chemical Hygiene Plan 10.4 Restricted Chemicals Requiring Prior Approval All laboratory workers must obtain prior approval, using the Circumstances Requiring Prior Approval form before using any Cal/OSHA Reportable Chemicals or any of the following hazardous chemicals: Diazomethane Hydrogen Cyanide Hydrogen Fluoride (anhydrous) Fluorine Carbon Monoxide Nickel Carbonyl Ozone Perchloric Acid Chlorine Phosphine The Laboratory Supervisor/Principal Investigator may designate additional hazardous chemicals that require their prior approval before use. 10.5 Laboratory/Equipment Relocation or Vacancy The PI and/or the Facilities Manager must notify the EH&S Coordinator of the potential departure or relocation at least one month prior to move so that the PI receives the Laboratory Relocations Guide to help prepare the lab for closure. Generally, a PI vacating a laboratory must prepare the lab by properly transferring or disposing all hazardous materials and wastes, and decontaminating all work surfaces and storage units. EH&S must inspect the area and equipment and perform surface wipes and lab tests when necessary. All laboratory space must pass an EH&S clearance prior to the vacancy. Equipment being transferred to a different UCI Campus location must be prepared to prevent harm to movers, and to preclude spills and leakage of hazardous materials. Each lab move-out is unique and early consulting with the EH&S Coordinator is advised to make this process go smoothly. All salvageable equipment going to UCI Surplus must be free of hazardous materials and thoroughly decontaminated. Unsalvageable electronic equipment, refrigerators, and freezers are disposed through EH&S after decontamination. The clearance consists of verifying proper labeling and packaging of hazardous materials, which include dry and liquid chemicals, radioactive, biohazard and/or other hazardous waste materials. The clearance may include EH&S performing surface wipe tests for radiation contamination, corrosives, and organic peroxides. EH&S posts clearance signs on rooms and laboratory equipment. Top of CHP Table of Contents Appendices UCI Chemical Hygiene Plan 11.0 Standard Operating Procedures for Record Keeping 1. Accident reports will be retained by the Worker’s Compensation at Human Resources. 2. Exposure records for hazardous chemicals and harmful physical agents will be maintained by EH&S for at least 30 years. 3. Medical records for laboratory employees exposed to hazardous chemicals and harmful physical agents will be maintained by the University’s medical provider for the duration of employment plus 30 years. 4. Training and inspection records are maintained for 5 years. 5. Employees may request copies of their exposure records by contacting EH&S at 824-6200. Employees may request access to their medical records by contacting the University medical provider. Top of CHP Table of Contents Appendices UCI Chemical Hygiene Plan 12.0 Standard Operating Procedures for Fires, Chemical Spills, Releases and Accidents 12.1 Control of Fires UCI Policy states that personnel are not required to fight fires. The following guidelines should be followed to prevent and minimize injury and damage from fires. 1. Be prepared! Know where all of the fire extinguishers are located in your laboratory, what types of fires they can be used for, and how to correctly operate them. Know where the nearest fire alarm is located. Know the location of safety showers and fire blankets. 2. Fires in small vessels can usually be suffocated by loosely covering the vessel. Never pick up a flask or container of burning material. 3. A small fire that has just started can sometimes be extinguished with a laboratory fire extinguisher. Remember R.A.C.E. Rescue--First, help clear people from the lab. Announce--Call 911 and activate the fire alarm. Contain the fire by closing doors to the fire room. Extinguish—only after calling 911 and activating the alarm, and only if confident that it can be done successfully and quickly. Always be between the fire and an exit from the laboratory. Do not underestimate fires, and remember that toxic gases and smoke may present additional hazards. To extinguish a small fire remember P.A.S.S. Pull safety pin from handle. Aim nozzle at base of fire. Squeeze the trigger handle. Sweep from side to side (watch for reflash). 4. Small fires involving reactive metals and organometallic compounds (such as magnesium, sodium, potassium, metal hydrides, etc.) should be extinguished with a Class D (Met-L-Kyl fire extinguisher or equivalent) or by covering with dry sand. 5. In the event of a more serious fire, evacuate the laboratory, close the door on the fire room, activate the nearest alarm, and call 911. Help direct floor occupants to the building's assembly area. Be prepared to meet and advise the Fire Department and EH&S Emergency Response Team with information of hazardous substances present in the laboratory. UCI Chemical Hygiene Plan 6. 12.2 Personal injuries can result from fires. If a person’s clothing catches fire, they should “stop, drop, and roll” or be doused with water from the safety shower. Immediately dropping to the floor and rolling can sometimes extinguish minor clothing fires. Fire blankets should only be used as a last-resort measure to extinguish fires since they tend to hold in heat and to increase the severity of burns. Quickly remove contaminated clothing, douse the person with water, and place clean, wet, cold cloth on burned areas. Wrap the injured person in a blanket to avoid shock and get medical attention promptly. Control of Chemical Exposure and Spills You might become aware of a chemical accident because of visual appearances or odors, including liquid puddles, broken containers on the floor with nearby liquids or solids, strong petroleum or acrid odors. All incidents involving hazardous materials spills must be reported immediately to the PI/Laboratory Supervisor. The following are standard operating procedures for controlling chemical exposure during chemical spills, releases and accidents: 12.21 Personnel Exposures/Contamination 1. Remove exposed/contaminated individual(s) from area, unless it is unsafe to do so because of (1) medical condition of victim(s), or (2) potential hazard to rescuer(s). 2. IN ALL INSTANCES, IMMEDIATELY notify UCI Police Emergency 9-1-1 if immediate medical attention is required. If using a cell phone, call 949-824-5223. If working at the Orange Campus, call 714-456-6123 for medical response. 3. Notify EH&S to report the exposure. If incident occurs during normal working hours, notify EH&S at 949-824-6200. If after hours, notify UCI Police Emergency 9-1-1 who will then contact EH&S. If using a cell phone, call 949-824-5223. 4. Administer First Aid as appropriate. 5. Flush contamination from eyes/skin using the nearest emergency eyewash/shower for a minimum of 15 minutes. 6. Remove any contaminated clothing. 7. Stand by to provide information or assistance (including MSDS) to emergency response personnel (in cases where they are dispatched). 12.22 Contamination of Equipment/Facilities UCI Chemical Hygiene Plan 12.3 1. Do not attempt any clean up or decontamination procedures alone and without wearing proper protective equipment, including appropriate respiratory protection where airborne hazards may exist. (Personnel must be trained and certified before using respiratory protection). Unless the incident is a small spill of relatively innocuous material, DO NOT ATTEMPT SPILL CLEAN UP WITHOUT EH&S ASSISTANCE. 2. Avoid spreading contamination by restricting access to the equipment/area only to individuals who are properly protected and trained to deal with the type of hazard which exists (e.g., radioactive, corrosive, flammable, biological). 3. Report details and/or request assistance from EH&S (824-6200) if the incident occurs during normal working hours. If the incident occurs after hours, contact UCI Police Emergency 9-1-1. 4. If a liquid spill, attempt to contain it by using appropriate absorbent material. 5. Attempt to decontaminate the equipment/area using appropriate methods under EH&S direction. If material is radioactive, assess radiation levels with appropriate monitoring devices before and after decontamination. 6. Stand by to provide information/assistance to emergency response personnel (in cases where they are dispatched). Release to the Environment (Air, Water, Soil) 1. Stop the release, if safe to do so. Report release to UCIPD who will notify EH&S. 2. Follow standard operating procedures described above (Section 12.2) for chemical exposures or contamination of equipment/facility. REFERENCE: Flipchart. Top of CHP Table of Contents Appendices Hazardous Materials Incidents, Blue UCI Emergency Procedures UCI Chemical Hygiene Plan 13.0 Standard Operating Procedures for Annual Chemical Hygiene Plan Audit EH&S will review and evaluate the effectiveness of the Chemical Hygiene Plan at least annually. Based on this review, necessary updates will be made to the written Chemical Hygiene Plan. Top of CHP Table of Contents Appendices UCI Chemical Hygiene Plan 14.0 References and Recommended Reading (Available for loan from EH&S) American Chemical Society. Edition). 2003. Safety in Academic Chemistry Laboratories, (Seventh American Chemical Society. The Waste Management Manual for Laboratory Personnel. 1990. Beyler, R.E. and V.K. Meyers. “What Every Chemist Should Know About Teratogens”. J. Chem. Ed. 1982, 59, 759-763. Biosafety in Microbiological and Biomedical Laboratories, 4th Edition. US Department of Health and Human Services, Center for Disease Control and Prevention and National Institute of Health. 1999. Freeman, N.T. Introduction to Safety in the Chemical Laboratory. Academy Press, 1982. Furr, A.K., Ed. Handbook of Laboratory Safety (Third Edition). 1989. A 704 page reference on all aspects of lab safety. Green, Michael E. Safety In Working With Chemicals. MacMillan Publishing Co., Inc. 1978. Lenga, R.E., Ed. The Sigma-Aldrich Library of Chemical Safety Data (Second Edition), 2 volumes, 1988. This 4,098 page work provides information on the properties of over 14,000 compounds. Toxicity data, health hazards, and suggested methods of first aid, handling, storage, and waste disposal are also included). Lewis, R.J., Ed. Rapid Guide to Hazardous Chemicals in the Workplace (Second Edition). 1990. (Concise compilation of properties and safety data (PELs, TLVs, etc.) for 800 substances). Lunn, G.B. and E.B. Sansone. Destruction of Hazardous Chemicals in the Laboratory. 1990. (Detailed procedures for destruction of hazardous substances via chemical reactions). Manufacturing Chemists' Association, Inc. Guide For Safety In The Chemical Laboratory. D. Van Nostrand Company, Inc. 1954. Pipitone, David A., Safe Storage of Laboratory Chemicals. Wiley & Sons, Inc. 1984. UCI Chemical Hygiene Plan Proctor, N.H., J.P. Hughes, and M. L. Fischman. Chemical Hazards of the Workplace (Second Edition). 1988. (573 pages; includes fairly detailed discussions of the toxicology of 438 hazardous substances). Prudent Practices for Handling Hazardous Chemicals in Laboratories, National Academy Press, Washington, D.C., 1995. Shepard, T.H. Catalog of Teratogenic Agents, Sixth Edition. Johns Hopkins University Press, Baltimore, 1989. (Definitive work on teratogens). Steere, N.V. and M.M. Renfrew, Eds. Safety in the Chemical Laboratory. 4 volumes, 1967-1981 (collection of articles from “Safety in the Chemical Laboratory” feature of the Journal of Chemical Education). Toxic and Hazardous Industrial Chemicals Safety Manual, prepared by the Japanese International Technical Information Institute, 1988. (700 pages; safety data on 702 compounds). Top of CHP Table of Contents Appendices