UCSF Chemical Hygiene Plan Updated January 21, 2016 1 Table of Contents Introduction………………………………………………………………………………….………………….4 Responsibilities………………………………………………………………………………………….……..4 Hazard Communication………………………………………………………………………………….…5 General Safety Requirements…………………………………………………………………….….…9 Safe Use and Storage of Chemicals………………………………………………………………….10 Flammable and Combustible Materials…………………………….……………………10 Corrosive Chemicals………………………………………………………………………………12 Oxidizers…………………………………………..……………………………………….………….13 Acutely Toxic Chemicals……………………………………..…………………………………15 Carcinogens……………………………………………………..……………………………………15 Pyrophorics……………………………………………………………………………………………17 Explosive Chemicals………………………………………………….…………..………………17 Peroxide Forming Chemicals……………………………………….…………………………19 Compressed Gases…………………………………………………………………………………19 Cryogens……………………………………………………………….………………………………20 Particularly Hazardous Chemicals (PHC’s)………………………………………………20 Purchasing and Maintaining Chemical Inventories…………………………….……………21 Control Measures to Reduce Exposures………………………………………………..…………22 Medical Consultation and Treatment………………………………………………..…………….24 Occupational Monitoring…………………………………………………………….………………….24 Emergency Procedures and Spill Clean-up…………………………………………….…………25 2 Disposal of Hazardous Chemicals……………………………………………………………….……26 Regulations………………………………………………………….…………………………………………28 3 Introduction UCSF is required by Title 8, Section 5191 of the California Code of Regulations to maintain a written Chemical Hygiene Plan with provisions capable of protecting employees from health hazards associated with hazardous chemicals in laboratories. All campus and medical center employees working in laboratories are required to follow the procedures and policies outlined in this plan. Responsibilities Chancellor The Chancellor is responsible for the establishment and implementation of environmental health and safety policies at all facilities under campus control. Appropriate vice chancellors, deans, chairs, laboratory directors, department managers, principal investigators, supervisors, and EH&S personnel are jointly and cooperatively responsible for the implementation, monitoring, and enforcement of these policies. Chemical and Environmental Safety Committee The Chemical and Environmental Safety Committee (CESC) consists of UCSF faculty and provides expert advice on Chemical Safety to the chancellor. The committee reviews technical, environmental and safety-related aspects of laboratory research and the use of hazardous and toxic substances, and recommends procedures and practices for the safe use of hazardous chemicals at UCSF. The committee also arbitrates campus disagreements regarding laboratory practices and has the authority to limit or revoke, as authorized by the chancellor an investigator’s authority to use hazardous or toxic materials at UCSF. Office of Environment Health and Safety The Office of Environmental Health and Safety (EH&S) is responsible for implementation and oversight of the Laboratory Safety Program. It provides technical guidance to personnel at all levels of responsibility on matters pertaining to laboratory use of hazardous chemicals and substances. Department Safety Advisors within EH&S are responsible for conducting quarterly inspections of laboratories to ensure safe practices. EH&S is also responsible in maintaining communications with regulatory agencies that includes preparation of reports, correspondence, maintaining records, and obtaining permits. The EH&S Executive Director acts for the Chancellor in this role. Chemical Hygiene Officer The Chemical Hygiene Officer within EH&S is responsible for maintaining the Chemical Hygiene Plan which must be updated at least annually. The chemical hygiene officer serves as an expert on chemical safety and in conjunction with the CESC recommends safe practices for the safe use of chemicals and creates and implements policies on hazardous chemical use at UCSF. 4 Deans and Department Chairpersons Deans and department chairpersons are responsible for ensuring Principal Investigators within their departments are providing a safe work place for their students and employees, and following UCSF policies as well as all local, state, and federal regulations relating to chemical safety. Principal Investigators and Laboratory Managers Principal investigators have a responsibility to provide a safe work place to all employees, students and visitors working in their laboratory. Principal Investigators must ensure all laboratory personnel receive adequate training, follow standard operating procedures for the safe use of hazardous chemicals in the laboratory including the proper use of personal protective equipment and the use of engineering controls where required. Principal investigators must take appropriate action to correct unsafe conditions and practices relating to the use of hazardous chemicals. Principal Investigators can delegate responsibilities to laboratory managers but are ultimately responsible for ensuring safe work practices are followed in their laboratories. Employees and Students All employees and students are required to follow standard operating procedures for the safe use of chemicals in the laboratory and are required to use adequate PPE when working with hazardous chemicals. Hazard Communication Definition of a Hazardous Chemical A hazardous chemical is any chemical which can cause a physical or a health hazard. The term "health hazard" includes chemicals which are carcinogens, toxic or highly toxic agents, reproductive toxins, irritants, corrosives, sensitizers, hepatotoxins, nephrotoxins, neurotoxins, agents which act on the hematopoietic systems, and agents which damage the lungs, skin, eyes, or mucous membranes. Training All UCSF employees and students are required to be trained before using hazardous chemicals in the laboratory. At UCSF training is provided through a combination of general online safety training provided by EH&S and lab specific training provided by the Principal Investigator or laboratory supervisor. To help ensure compliance with training requirements, PI’s are required to complete a Laboratory Safety Orientation Checklist for all new employees. 5 Online Training Table 1 summarizes all online trainings required for the use of hazardous chemicals in laboratories. These trainings must be completed before employees begin work. Table 1: Required Online Training Training Required For Frequency Laboratory Safety for Researchers All Laboratory Workers before working in a laboratory and every 3 years Carcinogen Training All carcinogen users before authorized to use Formaldehyde Training All formaldehyde users before authorized to use Laboratory Specific Training Principal Investigators must ensure their employees receive training specific to the procedures and hazardous chemicals used in their laboratory. The training must address the hazards of the chemicals being used and precautionary measures that must be followed to safely use the chemicals. At minimum this training must include the following: 1. 2. 3. 4. 5. 6. Training on Standard Operating Procedures (SOP’s) for the use of hazardous chemicals. Where to find Safety Data Sheets for hazardous chemicals. Selection and Use of PPE that adequately protects against the hazards. Proper use of engineering controls such as fume hoods to control exposures. What to do in case of an emergency such as an exposure or chemical spill. Location and proper use of emergency equipment including deluge showers, emergency showers, and fire extinguishers. 7. How to report unsafe work conditions and get them fixed. Signs, Labels and Postings Hazard ID sign All main entrances to laboratories at UCSF must be posted with a Hazard Identification Sign that identifies the principal investigator of the laboratory and laboratory contacts. The sign identifies what types of hazardous materials are stored and used in the laboratory and describes what type of PPE is required for safely working in the laboratory. 6 Carcinogen Postings Designated areas where known or suspected carcinogens are used must be posted with an appropriate sign. Additional information about the proper signage is available on the Carcinogen Program webpage. Do Not Enter Postings Entry into some areas at UCSF is restricted to personnel trained for entry due to specific radiation, biological or chemical hazards. This communicates to custodians and facility management personnel not to enter the room before contacting the laboratory or EH&S. More information is available in the Custodial Staff Entering Restricted Areas Safety Update. Chemical Storage Area labeling Where flammable and corrosive chemicals are stored in cabinets or in refrigerators approved for their storage, the storage location must be labeled with the chemical hazard. Labeling of Chemical Containers Chemical containers from manufacturers are required to be labeled with pictograms, a signal word, hazard and precautionary statements, the product identifier, and supplier identification. A sample revised label, identifying the required label elements, is shown below: 7 The pictograms used on manufacturer’s labels and their meanings are shown below: At UCSF whenever a hazardous chemical is transferred to another container, the container must be labeled with the contents and hazards. See the Proper Labeling of Chemical Containers safety update for more information on labeling of chemical containers. 8 To assist with labeling of chemicals, a label template is available for download on the EHS website Safety Data Sheets Safety Data Sheets (formerly called Material Safety Data Sheets) are a detailed informational document prepared by the manufacturer of a hazardous chemical. They describe the physical and chemical properties include information on the hazards, engineering controls, personal protective equipment, storage and handling information, reactivity’s, and procedures for spills and first aid. Safety Data Sheets are available on the internet: https://ehs.ucop.edu/sds/#/ Other Sources for Chemical Safety: Cameo Chemicals is a database of hazardous chemicals which provides safety related information on thousands of chemicals, and contains a reactivity prediction tool which can be used to predict potential reactive hazards between chemicals. International Chemical Safety Card Database is a searchable database that contains safety related information for specific chemicals. General Safety Requirements Work Areas Working alone in a laboratory with hazardous chemicals is prohibited. Maintain a clear lab bench by returning containers and supplies to their storage location when not in use. Keep aisles spaces and corridors clear of clutter and obstructions. Maintain an 18 inch clearance under the fire sprinklers across the room. Never leave ongoing chemical reactions, exposed sharps, or energized electrical, mechanical, or heating equipment unattended. 9 Personal Hygiene Food and drink are prohibited in the laboratory. Never handle chemical containers or laboratory equipment without gloves. Never reuse disposable gloves. Wash your hands after removing your gloves and before leaving the laboratory. Keep loose hair tied back. Safe Use and Storage of Chemicals Chemicals must always be stored according to compatibility. A chemical storage segregation chart is available on the EH&S webpage to assist with this process. Incompatible chemicals must be stored in different locations or segregated from other chemicals using secondary containment. Flammable and Combustible Liquids Flammable solvents are defined as having a flash point of less than 100°F. Flashpoint is the minimum temperature at which a liquid forms a vapor above its surface in sufficient concentration that it can be ignited. Liquids with lower flashpoints ignite easier. Combustible liquids have a flashpoint at or above 100°F. The National Fire Protection Association (NFPA) hazard classifications for flammable and combustible liquids are listed in Table 2: Table 2: Hazard classification for flammable liquids Class Flash point Boiling point I-A below 73°F (23°C) below 100°F (38°C) I-B below 73°F (23°C) at or above 100°F (38°C) I-C 73-100°F (24-38°C) ---- 10 Examples Acetaldehyde, Ethylamine, Chloroethane Ethyl Ether, Ethyl Mercaptan, Isopropylamine, 2-Methylbutane, Propylene Oxide, Tetramethylsilane Trichlorosilane Acetone, Acetyl Chloride, Acetonitrile Benzen, Cyclohexane, 1, 2- Dichloroethane, Diethylamine, Ethyl Acetate, >50% Ethyl Alcohol, Gasoline, Hexane, Isopropyl Alcohol, Methanol, Methyl Ethyl Ketone Petroleum Ether, Pyridine, Tetrahydrofuran Toluene, Vinyl Acetate, Triethylamine Amyl Acetate, Azidotrimethylsilane, 1Butanol, Chlorobenzene, Dicyclopentadiene, Ethylenediamine, Hydrazine, Methyl Isobutyl Ketone, Morpholine, Nitromethane, 2,4Pentanedione, 1-Pentanol, Propyl Alcohol Styrene, Trichloroethylene Hazard classification for combustible liquids II 101-140°F (39-60°C) ---- III-A 141-199°F (61-93°C) ---- III-B 200°F (93°C) or above ---- > 80% Acetic Acid, Acetic Anhydride, Boron Trifluoride, N,N-Dimethyl Formamide, Formaldehyde, Formic Acid, Kerosene 2Methoxyethanol, 3-Methyl-1-Butanol Propionic Acid, Thiophenol, WD-40® Lubricant Acetophenone, Aniline, Benzaldehyde Benzoyl Chloride, Benzyl Bromide, Benzylamine, Butyric Acid, DiethylPyrocarbonate, Dimethyl Sulfate, N,NDimethylacetamide, Dimethylsulfoxide, Ethanolamine, Hexyl Alcohol, 2-Mercaptoethanol, 1-Methyl-2pyrrolidinone, Nitrobenzene, 1-Octanol, Phenol p-Anisaldehyde, Benzyl Alcohol, 2Bromoethanol, Diethanolamine, Ethylene Glycol, Formamide, Glycerol, Hexadecane, Hydraulic Oil, Methyl Salicylate, Mineral Oil, Oxalyl Chloride, Polyethylene Glycol, Triethanolamine, Triton X®, Tween 20®, Hexanoic Acid General Storage and Handling Precautions Keep flammables away from all ignition sources including sparks, open flames, hot surfaces, and direct sunlight. Store flammables separate from other hazard classes, especially oxidizers and corrosives. Use secondary containment if incompatibles must be stored in the same location. Separate flammable gases from oxidizing gases with an approved non-combustible partition or by a distance of 20 feet. Store flammable liquids in approved safety containers or cabinets. In instances where static electricity may accumulate and ignite flammable vapors, ground and bond flammable liquid containers. Keep flammable liquids that require cold storage in laboratory safe and explosion proof refrigerators and freezers to avoid ignition of the materials by sparks or static electricity. Never store flammables in a refrigerator not designed and approved for flammable storage. 11 Container Size Limits: Individual glass containers of Class I-A liquids must not exceed 1 pint (500 mL) capacity. Individual glass containers Class 1-B liquids must not exceed 1 quart (1 liter) capacity. Exception: Class I-A and I-B liquids may be stored in factory-shipped glass containers up to 1-gallon or 4liter capacity if the required liquid purity would be affected by storage in metal containers or if the liquid would cause excessive corrosion of a metal container. Class I-A liquids can be stored in metal containers not larger than 1 gallon (4 liters) capacity, or U.L. listed safety cans not larger than 2 gallons (8 liters) capacity. A safety can is a listed container, having a spring-closing lid, spout cover and a flame arrester and so designed that it will safely relieve internal pressure when subjected to fire exposure. For liquids other than Class I-A liquids, the capacity of metal containers and safety cans must not exceed five gallons each. Flammable Storage Limits Outside of a Cabinet Laboratories are allowed to store no more than 10 gallons of flammable liquids outside of a flammable cabinet. Safety cans greater than 2 gallons in capacity must be stored in a flammable cabinet. Laboratories are allowed a maximum of 25 gallons of flammable liquids stored in safety cans outside of a flammable cabinet. Flammable Storage Limits Inside of a Cabinet The maximum quantity of Class 1A flammable liquids allowed to be stored in a flammable cabinet is 60 gallons. The maximum quantity allowed for all classes of flammable liquids is 120 gallons per cabinet. Corrosive Chemicals Corrosive chemicals include strong acids and bases which can destroy human tissue and corrode metals. Acids and bases are incompatible with one another and may react with many other hazard classes. Table 3 outlines the different types of corrosives. Table 3: Types of Corrosives Corrosive Inorganic Acids (non-oxidizing) Inorganic Acids (oxidizing) Organic Acids Bases Examples Hydrochloric Acid, Phosphoric Acid Nitric Acid, Perchloric Acid, Chromic Acid, Sulfuric Acid Acetic Acid, Formic Acid, Trichloroacetic Acid, Trifluoroacetic Acid Ammonium Hydroxide, Calcium Hydroxide, Potassium Hydroxide, Sodium Hydroxide 12 General Storage and Safety Precautions Segregate acids from bases. Segregate inorganic oxidizing acids (e.g., nitric acid) from organic acids (e.g., acetic acid), flammables, and combustibles. Segregate acids from chemicals that could generate toxic gases upon contact (e.g., sodium cyanide and iron sulfide). Segregate acids from water reactive metals such as sodium, potassium, and magnesium. Always handle concentrated corrosives in a fume hood with the sash properly aligned to provide splash protection. Store corrosives on lower shelves, at least below eye level and in compatible secondary containers. Concentrated solutions must always be handled in a fume hood. A laboratory coat, splash goggles, and chemically resistant gloves are required when handling corrosives. When diluting concentrated acids and bases, always add the concentrated solution to water slowly. All laboratories that use Hydrofluoric acid (HF) are required to have calcium gluconate on hand in case of an exposure. Users of HF must be trained on using the gluconate. Chemicals must always be stored according to compatibility. Incompatible chemicals must be stored in different locations or segregated from other chemicals using secondary containment. Additional Safety Information: Hydrofluoric Acid Safety Update Oxidizers An oxidizer is any material that readily yields oxygen or other oxidizing gas, or that readily reacts to promote or initiate combustion of combustible materials, and under some circumstances, can undergo a vigorous self-sustained decomposition due to contamination or heat exposure. The hazards associated with chemical oxidizers include the potential to: 1.) 2.) 3.) 4.) 5.) 6.) Increase the burning rate of flammable and combustible materials. Cause spontaneous ignition of flammable and combustible materials. Decompose rapidly. Evolve or emit hazardous gases. Undergo self-sustained decomposition, which can result in an explosion. React explosively if mixed with incompatible materials or if involved in a fire. 13 Identifying oxidizers by Chemical Name and Formula Oxidizers have excess oxygen and can sometimes be identified by prefixes and suffixes in the chemical name. Many oxidizers contain the prefix “per” and suffix “ate”. Table 4 lists some common oxidizer functional groups: Table 4: Common Oxidizing Groups Chemical Group Chemical Formula Peroxides O2-2 Nitrates NO3Nitrites NO2Perchlorates ClO4Chlorates ClO3Chlorites ClO2Hypochlorites ClODichromates Cr2O7-2 Permanganates MnO4Persulfates S2O8-2 Common Examples of Oxidizers Liquids Benzoyl Peroxide Bleach (sodium hypochlorite) Bromine Chromic Acid Nitric Acid Perchloric Acid Piranha Solution (sulfuric acid and hydrogen peroxide) Solids Ammonium Nitrate Potassium Nitrate Potassium Chlorate Sodium Nitrate Gases Chlorine Oxygen Nitric Oxide 14 Safe Handling and Storage of Oxidizers Segregate oxidizers from flammables and combustibles. Segregate oxidizers from reducing agents (zinc, alkaline metals, formic acid). Segregate organic oxidizers such as benzoyl peroxide from all other oxidizers. Special consideration must always be given when choosing containers for storage of oxidizers for both use and waste collection. A container formerly containing a combustible or flammable material should never be used to store an oxidizer and vice versa. Doing so may result in a delayed or spontaneous explosion . Special pressure vented caps are available from EH&S for containers that may evolve gas such as Piranha Solution. These caps can also be used for waste containers used to store other oxidizers and may help prevent an explosion due to accidental contamination of a waste container containing an oxidizer. Acutely Toxic Chemicals Overexposure to toxic chemicals can cause injury or death. LD50 is the most common way to express relative toxicity of a chemical. LD50 is the amount of a chemical that is sufficient to kill 50 percent of a population of test animals usually within a certain time. It is expressed in mg/kg, or milligrams of substance per kilogram of body weight. Generally, chemicals with an oral LD50 between 50-500 mg/kg are considered toxic, and chemicals with an LD50 of less than 50 mg/kg are considered highly toxic. General Safety Precautions for Toxics and Highly Toxics Toxic chemicals that produce fumes or dust should always be handled within a chemical fume hood. Maintain the lowest possible quantities of toxics in your laboratory. Keep containers tightly sealed to minimize exposure to personnel and contamination of other chemicals. Carcinogens A carcinogen (defined as “select carcinogen” by Cal/OSHA) is a substance or agent that meets one of the following criteria: 1. It is regulated by Cal/OSHA as a carcinogen. 2. It is listed under the category, “known to be carcinogens” in the Annual Report on Carcinogens published by the National Toxicology Program (NTP)(latest edition); or 3. It is listed under Group 1 (“carcinogenic to humans”) by the International Agency for Research on Cancer (IARC) 4. It is listed in either Group 2A or 2B by IARC or under the category, “reasonably anticipated to be carcinogens” by NTP, and causes statistically significant tumor incidence in experimental animals in accordance with any of the following criteria: 15 a. After inhalation exposure of 6-7 hours per day, 5 days per week, for a significant portion of a lifetime to dosages of less than 10 mg/m3. b. After repeated skin application of less than 300 mg/kg of body weight per week; or c. After oral dosages of less than 50 mg/kg of body weight per day. General Safety Guidelines Carcinogens are considered Particularly Hazardous Chemicals (PHC’s) at UCSF. Principal Investigators with carcinogens in their inventories are required to create laboratory specific SOP’s addressing the safe use of the carcinogen they are using. Although the specific SOPs will vary according to the material and procedures employed, the following guidelines are generally applicable for experiments involving carcinogens: Use the smallest amount of chemical that is consistent with the requirements of the work to be performed. Use containment devices such as laboratory fume hoods or glove boxes when volatilizing these substances, manipulating substances that may generate aerosols, and performing laboratory procedures that may result in uncontrolled release of the substance. Use high efficiency particulate air (HEPA) filters, carbon filters, or scrubber systems with containment devices to protect effluent and vacuum lines, pumps, and the environment whenever feasible. Use ventilated containment to weigh out solid chemicals. Alternatively, the tare method can be used to prevent inhalation of the chemical. While working in a laboratory hood, the chemical is added to a pre-weighed container. The container is then sealed and can be re-weighed outside of the hood. If chemical needs to be added or removed, this manipulation is carried out in the hood. In this manner, all open chemical handling is conducted in the laboratory hood. Use a properly functioning lab fume hood when handling carcinogens. If the process does not permit the handing of such materials in a fume hood, contact your DSA for reviewing the adequacy of ventilation measures. In addition to proper street clothing (long pants (or equivalent) that covers legs and ankles, and close-toed non-perforated shoes that completely cover the feet, wear a lab coat, appropriate eye protection and chemically resistant gloves. More Information about Carcinogen Use at UCSF: Quick Guide for Principal Investigators and Lab Supervisors Carcinogen Safety Program Formaldehyde Use Guidelines 16 Pyrophoric Materials Pyrophoric materials are chemicals that spontaneously ignite in the presence of air, some are reactive with water vapor, and most are reactive with oxygen. Because pyrophoric substances can spontaneously ignite on contact with air and/or water, they must be handled under an inert atmosphere and in such a way that rigorously excludes air and moisture. Some pyrophoric materials are also toxic and many are dissolved or immersed in a flammable solvent. Two common examples are organolithium reagents and white phosphorus. General Storage Requirements for Pyrophoric Materials Only minimal amounts of pyrophoric chemicals should be used in experiments or stored in the laboratory. These chemicals must be stored as recommended by the Manufacturer’s SDS. Suitable storage locations may include inert gas-filled desiccators or glove boxes; however, some pyrophoric materials must be stored in a flammable substance approved freezer. If pyrophoric or water reactive reagents are received in a specially designed shipping, storage or dispensing container (such as the Aldrich Sure/Seal packaging system), ensure that the integrity of that container is maintained. Ensure that sufficient protective solvent, oil, kerosene, or inert gas remains in the container while pyrophoric materials are stored. Additional Safety Resources: Safe Use of Pyrophoric Organolithium Reagents Explosive Chemicals Explosive chemicals can rapidly release tremendous amounts of destructive energy and cause death, serious injury, or severe property damage. Heat, shock, friction, or even static electricity can initiate explosions of these chemicals. Explosive chemicals include the following classes of chemicals: Nitrogen Oxides (e.g., Nitrates, Nitro) ethylidene dinitrate picric acid (dry) thallium aci-phenylnitromethanide trinitrotoluene (TNT) hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) 17 Oxides, Peroxides, and Related Chemicals benzoyl peroxide (97%) (dry) bis (1-chloroethylthallium chloride) oxide Nitrogen-Rich Chemicals (e.g., Azo-, Diazo, Triazo, Tetrazole) aluminum azide 5-aminotetrazole 1-bromoaziridine chromyl azide chloride diethyl diazomalonate hydrogen azide (>17%) lead azide mercury (I&II) azide molybdenum diazide tetrachloride sodium diazomethanide tetrazole 1,2,3-triazole Perchlorate Chemicals ammonium perchlorate ethyl perchlorate (the most explosive chemical known) hexyl perchlorate Acetylenic Chemicals n-chloro-3-aminopropyne propiolic acid 3-propynethiol 4-sodium hexakis(propynyl)ferrate Potentially Explosive Chemicals In addition to explosive chemicals, which constitute a known high hazard, there are chemicals that may become explosive, depending on how they are handled. This category is commonly referred to as potentially explosive chemicals and includes: Organic chemicals, such as ethers, that form peroxides through exposure to air or light Hydrated chemicals such as picric acid and 2,4-Dinitrophenlyhydrazine that can become shock sensitive when dry. Sodium amide that reacts with air or moisture. Certain alkyl nitrates (e.g., butyl nitrate or propyl nitrate) that become contaminated with nitrogen oxides. Certain normally stable perchlorates (e.g., pyridinium perchlorate or tetraethylammonium perchlorate) that becomes unstable at elevated temperatures. Precautions for Explosive and Potentially Explosive Chemicals Identify all explosive and potentially explosive chemicals in your inventory. 18 Always follow the safe storage guidelines outlined in the manufacturer’s SDS. For chemicals that may degrade to become potentially explosive, record the opening date and discard date directly onto the container. Keep explosive chemicals away from all ignition sources including open flames, hot surfaces, direct sunlight, and spark sources. Peroxide Forming Chemicals Overtime these chemicals can react with air to form peroxides that may explode with shock, heat, or friction. Some chemicals may also form peroxides when concentrated by evaporation or distillation. More information on the safe storage, handling and disposal of peroxide forming chemicals is available in the Managing Peroxide Forming Compounds Safety Update on the EH&S website. General Precautions for Peroxide Forming Chemicals Where possible always purchase peroxide formers with an inhibitor. All peroxide formers must be dated with date received and the date opened. Peroxide formers must be tested for peroxides periodically and before distillation to ensure dangerous peroxide formation has not occurred. Uninhibited peroxide formers such as Tetrahydrofuran should be stored under an inert gas to prevent peroxide formation. Compressed Gasses Gas cylinders containing compressed gases contain a lot of stored energy that can cause serious injury and property damage if the cylinder is damaged or knocked over. Additional hazards can arise from the toxicity, flammability, corrosively, or reactivity of the gas in the cylinder. Storage Precautions for Compressed Gases Segregate incompatible gases as you would other incompatible chemicals. Limit the quantity of compressed gas cylinders on site to what will be used within a reasonable period of time. Store cylinders upright. Two chains or straps must be used to secure cylinders - one across the lower third and one across the upper third of the cylinder. Keep cylinders away from heat and open flames. Leave the valve protection cap on the cylinder unless it is in use. More requirements and guidelines for the safe use of gas cylinders is available in the Compressed Gas Cylinder and Cryogenic Liquid Safety Update 19 Cryogens These materials are extremely cold (-100°C to -270°C). Upon contact with cryogenic materials, living tissue can freeze and become brittle enough to shatter. Additional hazards include rapid pressure buildup, oxygen enrichment, and asphyxiation. Rapid pressure buildup could lead to an explosion if a cryogen is improperly contained. Cryogenic liquids and gases have many properties and hazardous characteristics in common with compressed gases. General Precautions for Using Cryogens Store and handle in a well-ventilated area. When liquid cryogens are converted to the gaseous phase, they may create an oxygen deficiency. Do not use cryogens in small enclosed areas. Use only approved storage vessels (i.e., thermos-like evacuated, double-walled containers) with pressure relief mechanisms. Non-approved vessels may explode. Secure containers so they will not tip over or obstruct an aisle, hallway, or corridor during an earthquake. Liquid nitrogen and liquid helium are capable of liquefying oxygen from air. This form of oxygen enrichment can become a strong fire or explosion hazard. Use appropriate protective equipment for handling cryogens: insulated holders for carrying vessels; eye protection, goggles, or face shields, and cryogenic gloves. More requirements and guidelines for the safe use of cryogens available on the Compressed Gas Cylinder and Cryogenic Liquid Safety Update Particularly Hazardous Chemicals (PHC) Particularly hazardous chemicals are chemicals for which additional precautions are required. Particularly hazardous chemicals include select carcinogens, reproductive toxins, and substances with a high degree of acute toxicity. At UCSF, PHC’s include hazardous chemicals listed in: Case No.: BA392069 PROSECUTION ENFORCEMENT AGREEMENT ADMINISTRATIVE ENFORCEMENT TERMS AND CONDITIONS PENAL CODE SECTION 1385 APPENDIX A California Code of Regulations, Title 22 Section 66261.126 Appendix X (extremely hazardous waste) 40 CFR Protection of Environment Part 355 Appendix A (extremely hazardous substances) California Code of Regulations, Title 8 Article 110 Regulated Carcinogens National Toxicology Program 12th Report (known to be human carcinogens) World Health Organization - International Agency for Research on Cancer (Agents Classified as Group 1, 2A & 2B) Proposition 65 Reproductive and Developmental Toxins 20 A complete list of UCSF's PHC's is available on the EH&S website. Requirements for Using PHC’s Prior to using PHC’s, PI’s must develop, review and approve a standard operating procedures specific to the procedures performed in their laboratory. The SOP must include safety precautions necessary for safely using the chemical including conditions to avoid, special requirements for safe use and storage, appropriate PPE and engineering controls, and procedures for first aid and spills. Chemical Use Authorizations Whenever a particularly hazardous chemical is added to a Principal Investigator’s inventory, a Chemical Use Authorization is automatically generated in RIO. CUA’s must include: A list of personnel authorized to use the chemical. An SOP that addresses all safety concerns for use of the chemical in the laboratory. A training verification demonstrating that all personnel have read and have been trained in the SOP. Approval by the Principal Investigator. SOP’s Use the UCSF SOP Template to create lab specific SOP’s for PHC’s in your laboratory. Chemical Specific SOP’s can be download from UCSF's PHC list on the EH&S website. Principal investigators are required to enter laboratory specific information. SOPs must be reviewed and signed by the PI and uploaded into the corresponding Chemical Use Authorization (CUA) in Research Information Online (RIO) . Laboratories who do have PHC’s that do not have a completed CUA are not allowed to use the chemical and must label the chemical with a do not use label from EH&S. Purchasing Chemicals and Maintaining Chemical Inventories The decision to procure a specific quantity of a specific chemical is a commitment to handle it responsibly from receipt to disposal. Laboratories should make a conscious effort to only order the quantity needed for their laboratory procedures which can be safely stored in their laboratory. Whenever there is a significant change in chemical amounts, chemical functionality, the introduction of new equipment, new chemicals, a new procedure, or a new work space, PI approval must be given prior to ordering the chemical to ensure that conditions exist to protect the worker. Purchasing Restrictions 21 Ordering regulated carcinogens listed under Title 8 of CCR, §5209. Carcinogens requires prior approval from EH&S. Whenever these chemicals are ordered, the order is flagged and sent to the Chemical Hygiene Officer (CHO) for approval prior to the order being completed. The carcinogens listed under this regulation have additional requirements that the CHO must verify are in place prior to authorizing a lab to use one of these chemicals. Maintaining a Chemical Inventory Principal Investigators are responsible for maintaining an accurate chemical inventory of their laboratory. At UCSF inventories must be updated annually through RIO. More information about how to submit a chemical inventory for your laboratory can be found in the Online Chemical Inventory FAQ. Control Measures to Reduce Exposures Limiting exposure to chemicals can be achieved through administrative controls, engineering controls and personal protective equipment. Administrative Controls Administrative controls are changes in work practices to reduce the duration, frequency and severity of exposure. Examples of administrative controls include Substituting a less hazardous chemical for a more hazardous one. Modifying a procedure to make it less hazardous Develop and follow standard operating procedures that are designed to reduce the chances of exposure. Engineering controls All laboratories at UCSF are designed to have a minimum of 6 air changes per hour. This airflow reduces employee exposure to airborne contaminants and removes excess heat. Because airflow is greater in laboratory areas compared to non-laboratory areas, airflow is negative with respect to the hallway, keeping odors and hazardous gases, dusts, and vapors out of the hallway and other public areas. Fume Hoods Fume hoods are ventilated enclosures designed to trap airborne contaminants and chemical vapors and exhaust them outside the building away from the user and the laboratory environment. At UCSF, EH&S tests and certifies all fume hoods annually. When used properly they can be an effective tool to protect laboratory workers from chemical hazards. When using a fume hood always follow these safe practices: Ensure the fume hood has been certified within the last year by checking the calibration sticker on the front of the hood. 22 Close the sash to the 18 inch mark indicated on the front of the hood to ensure adequate face velocity and to protect against splashes, fire, and explosions. Always work as far back as possible within the hood or at least 6 inches from the face of the hood. Do not use the hood for storage of chemicals. Cap all containers when not in use. Avoid storing bulky items or equipment in the hood when possible as this can restrict airflow in the hood. When equipment is required to be placed in a hood, it should be elevated at least 2-3 inches by placing securely on blocks to assist with airflow. Always verify proper function of the hood before use by checking the fume hood monitor or alarm before beginning work. If you notice a fume hood is not functioning properly stop using the hood, close all the containers, close the sash, post a do not use sign on the fume hood, and submit a work order to Facilities Management for repair. Personal Protective Equipment (PPE) All campus research laboratories are required to complete the Laboratory Hazard Assessment Tool (LHAT) and update it at least annually. LHAT facilitates identification of hazards and identifies the Personal Protective Equipment (PPE) to be used during the specified work activities. All laboratory personnel are required to wear PPE when working with chemicals. At a minimum this includes pants and closed toe shoes, chemically resistant gloves, a laboratory coat, and eye protection. Glove Selection When working with hazardous chemicals, select gloves that provide adequate protection to the chemical hazards. Disposable nitrile gloves provide short term protection against a broad range of chemicals but do not protect against all chemicals. Glove manufacturer’s websites can be consulted to determine the best glove for protecting against a chemical. Glove selection resources are available on the UCSF webpage here: http://www.ehs.ucsf.edu/glove-selection-guide Respiratory Protection Administrative and Engineering Controls should always be used first to help ensure exposures to dust and fumes are below the Permissible Exposure Limits (PEL’s). If this is not feasible, a respirator is required. Use of a respirator has several requirements which may include the following: Annual medical evaluations and fit testing. Education and training on the proper use, storage and cleaning procedures for respirators. Training on how to adjust equipment and ensure proper fit to maximize protection from dusts and fumes. If you think your laboratory procedures require the use of a respirator contact your Department Safety Advisor for assistance. 23 Medical Consultation and Treatment Medical Consultation: For situations, which require immediate medical attention, always proceed to the nearest emergency room or call 9-911. Employees who work with hazardous chemicals have an opportunity to receive medical attention under the following circumstances: When an employee develops signs or symptoms that may be related to the use of hazardous chemicals Where exposure monitoring reveals exposures above an action level or permissible exposure limit for an OSHA regulated substance for which exposure monitoring and medical surveillance is required Whenever an event takes place in the work area resulting in the likelihood of hazardous exposure, a consultation determines the need for a medical exam How to get a medical consultation For immediate consultation for a suspected exposure contact the Poison Control Hotline at 1-800-2221222. Follow incident reporting instructions on the Occupational Health Services website to obtain medical consultation or evaluation. All medical exams and consultations must be performed under the direct supervision of a licensed physician and provided at no cost to the employee, without loss of pay, and at a reasonable time and place. Occupational Monitoring Cal/OSHA Laboratory Standards require employers to monitor hazardous material levels in the work area if there is concern that the exposure levels may exceed permissible exposure levels. Evidence that may suggest overexposure includes symptoms of overexposure such as dizziness or headache, a hazardous materials accident, or monitoring that reveals routine levels exceeding permissible exposure levels. If such monitoring indicates that possible overexposure occurred, the employer must reduce those levels. The employer must re-monitor the hazardous levels after implementation of corrective action to make sure the problem has been abated. Occupational Exposure may include radiation, chemicals, biological, or be physical in nature. These include noise, chemical vapor, ergonomics, indoor air quality, electrical safety, radioactive waste, and others. EH&S can monitor for most air contaminants. Upon request, can provide air monitoring for labs using formaldehyde or other chemicals, and nonroutine air monitoring. 24 Emergency and Spill Cleanup Procedures Chemical Spills Whether a chemical spill can be safely cleaned up by laboratory staff depends on multiple factors including the hazards of the chemicals spilled, the size of the spill, the presence of incompatible materials, and whether you have adequate training and supplies to safely clean up the spill. Small chemical spills ( < 1 Liter) of low toxicity which do not present a significant inhalation hazard by being volatile or a dust are generally safe to clean up by laboratory personnel. To clean up a small spill: 1. Donn appropriate PPE including a laboratory coat, splash goggles, and appropriate chemically resistant gloves. 2. Contain the spill to prevent it from spreading by using a berm or absorbent material from a spill kit. 3. Use absorbent to absorb the spill. 4. Clean the area with a soap and water. 5. Dispose of the spilled material as hazardous waste. For large spills or spills that present a significant health hazard that are not safe to clean up call the UC Police Department at one of the following numbers: From a campus Campus Phone: 9-911 SFGH, China Basin, or a cell phone: (415) 476-1414 If the spill presents a situation that is immediately dangerous to life or health (IDLH) or presents a significant fire risk, notify everyone in the laboratory and evacuate the laboratory. Emergency showers and eyewashes Before beginning work in the laboratory all employees must be familiar with the location of emergency showers and eyewashes and how to use them. The pathways to and around emergency equipment must be kept clear at all times to allow for unobstructed access. Emergency Eyewashes Immediately flush eyes for at least 15 minutes. Any delays can result in serious damage. Ask someone in the laboratory to assist you. Use your hands to open your eyelids while rotating the eyeballs in all directions to remove contamination from around the eyes. Seek medical attention after washing the affected area for 15 minutes by calling 9-911 or proceeding to the nearest emergency care facility. 25 Emergency Showers Remove contaminated clothing, shoes, jewelry and your laboratory coat. Ask someone in the laboratory to assist you. Immediately flush the area with copious amounts of water for at least 15 minutes. If your eyes do not require flushing attempt to protect the eyes from cross contamination. Seek medical attention after washing the affected area for 15 minutes by calling 9-911 or proceeding to the nearest emergency care facility. Disposal of Hazardous Chemicals Waste Determination A chemical waste is considered a hazardous waste if it is listed as a hazardous waste by state and federal regulations or exhibits certain characteristics of ignitability, corrosiveness, reactivity, and toxicity. Hazardous waste has important labeling, storage, and disposal requirements which must always be followed. EH&S lists chemicals which are Non-Hazardous Chemical Waste on the EH&S webpage. These chemicals are approved to be disposed down the drain. All other chemicals must be managed as a hazardous waste at UCSF. Chemicals which are Considered Hazardous by Exhibiting a Characteristic Ignitable: Ignitable wastes can create fires under certain conditions, undergo spontaneous combustion, or have a flash point less than 60°C (140°F). Primary alcohols in concentrations of 24% or less by volume are not considered ignitable. Corrosive: Aqueous wastes with a pH less than or equal to 2.0 or greater than or equal to 12.5 are corrosive. A liquid waste may also be corrosive if it is able to corrode metal containers, such as storage tanks, drums, and barrels. Reactive: Reactive wastes are unstable under normal conditions. They can cause explosions or release toxic fumes, gases, or vapors when heated, compressed, or mixed with water. Examples include lithiumsulfur batteries and unused explosives. Toxic: A waste is considered toxic if it has an Oral LD50 less than 2,500mg/kg, Dermal LD50 less than 4,300 mg/kg, 96 hour Aquatic Bioassay less than 500 mg/kg, or contains 0.001% by weight of 16 different carcinogens. 26 Labeling of Waste All hazardous waste containers must be labeled with a hazardous waste tag using WASTe as soon as the first drop of waste is added to the container. Proper Storage Hazardous waste should be stored in a designated location according to compatibility and storage recommendation for the chemical hazard. Incompatible waste should be stored in separate locations or segregated with secondary containment. Flammable waste should be stored in an approved flammable cabinet and corrosive waste should be stored in an approved corrosive cabinet. Arranging for Disposal WASTe automatically notifies EH&S to pick up waste containers once they reach the maximum accumulation time of 180 days storage in the laboratory. Arranging for disposal prior to 180 days can be done through WASTe Questions about Hazardous Waste and Using WASTe Most questions about using WASTe are addressed in the online FAQ and Tutorials. For additional questions about managing hazardous waste or to set up a WASTe account for your laboratory email: [email protected] 27 Regulations §5191. Occupational Exposure to Hazardous Chemicals in Laboratories. §5194. Hazard Communication §3203. Injury and Illness Prevention Program. §3380. Personal Protective Devices. Article 110. Regulated Carcinogens §5209. Carcinogens. §5533. Design, Construction, and Capacity of Storage Cabinets. §5532. Design, Construction, and Capacity of Containers. §5538. Office, Educational and Institutional Occupancies. 28
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