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HAZARD COMMUNICATION STANDARD &Laboratory Standard HAZARDOUS CHEMICALS Hazardous Chemicals are used everyday at work and home. “Hazardous chemicals” are defined by the Occupational Safety and Health Administration (OSHA) as “any chemical which is a physical hazard or a health hazard” (29 CFR 1910.1200(c)) HAZARD COMMUNICATION STANDARD 29CFR1910.1200(A)(1) “The purpose of this section is to ensure that the hazards of all chemicals produced or imported are evaluated, and that information concerning their hazards is transmitted to employers and employees. This transmittal of information is to be accomplished by means of comprehensive hazard communication programs , which are to include container labeling and other forms of warning, material safety data sheets and employee training .” OSHA The Hazard Communication Standard (HCS) is based on a simple concept - that employees have both a need and a right to know the hazards and identities of the chemicals they are exposed to when working. They also need to know what protective measures are available to prevent adverse effects from occurring. HAZARD COMMUNICATION PROGRAM A written Hazard Communication Program (HCP) is required for all workplaces handling hazardous chemicals. An HCP is to ensure that: • Hazardous substances present in the work place are properly identified and labeled • Employees have access to information on the hazards of these substances. • Employees are provided with information on how to prevent injuries or illnesses due to exposure to these substances. • Identify hazards for routine and no routine assignments • Identify who has the responsibility for maintaining the program, the MSDS sheets, conduct training, etc. MAJOR ELEMENTS OF HCP Hazardous chemical inventory Labeling of chemical containers Availability of Material Safety Data Sheets (MSDS) Employee Training HAZARDOUS CHEMICAL INVENTORY A master list of hazardous chemicals used or produced in the facility is required. Used for emergency response purposes as well as to comply with various environmental, occupational, and fire code regulations. The inventory list will include the common identity or trade name of the product and the name and address of the manufacturer. LABELING OF CHEMICAL CONTAINERS Containers must be labeled at a minimum with: Name of the chemical Hazard warnings Name and address of its manufacturer impor ter If the hazardous chemicals are transferred into unmarked containers, these containers must be labeled with the required information, unless the container into which the chemical is transferred is intended for the immediate use of the employee who performed the transfer. STORAGE Flammable items 5gal size or larger must be stored in a flammable cabinet, although storage of all flammable containers is recommended where possible. Segregate incompatible materials such as acids and bases, not all containers alphabetically Air and Water reactive materials should be kept in air tight secondar y containers and discarded at regular inter vals af ter opening to prevent air from getting through the seal/septum. Follow Testing & Disposal frequencies for Peroxide forming Potentially Explosive Chemicals (PEC’s) Store only materials that are still useable (still (still good and you will use them later) Containers must be in good condition and contents and hazards legible. AVAILABILIT Y OF MATERIAL SAFET Y DATA SHEETS (MSDS) MSDS are required to maintain availability of MSDSs’ for all incoming hazardous chemicals to the facility. MSDS provides detailed information about a specific hazardous material and is intended to provide workers and emergency personnel with procedures for handling or working with that substance in a safe manner. Must be readily accessible to the employees during each work shift and in their work area(s) Should not have to go through supervisor for access This is seen as a potential barrier by OSHA! INFORMATION THAT AN MSDS MUST CONTAIN: 1. Chemical Identity: Name of the product. 2. Manufacturer’s Information: Name, address, phone number and emergency phone number of the manufacturer. 3. Hazardous Ingredients/Identity Information: List of hazardous chemicals. 4. Depending on the state, the list may contain all chemicals even if they are not hazardous, or only those chemicals which have OSHA standards. 5. Since chemicals are often known by different names, all common (trade) names should be listed. 6. The OSHA Permissible Exposure Limit (PEL) for each hazardous ingredient must be listed. 7. Physical/Chemical Characteristics: Boiling point, vapor pressure and density, melting point, evaporation rate, etc. INFORMATION THAT AN MSDS MUST CONTAIN: 8. Fire and Explosion Hazard Data: Flash point, flammability limits, ways to extinguish, special firefighting procedures, unusual fire and explosion hazards. 9. Reactivity Data: How certain materials react with others when mixed or stored together. 10.Health Hazard Data: Health effects (acute= immediate; chronic= long-term), ways the hazard can enter the body (lungs, skin or mouth), symptoms of exposure, emergency and first aid procedures. 11.Precautions of Safe Handling and Use: What to do in case materials spill or leak, how to dispose of waste safely, how to handle and store materials in a safe manner. 12.Control Measures: Ventilation (local, general, etc.), type of respirator/filter to use, protective gloves, clothing and equipment, etc. MSDS AVAILABILIT Y Storage medium is flexible Paper copies, electronically stored, internet or other means that can provide a readable copy on site If stored electronically, employees must have access to computer Performance based standard MSDS MANAGEMENT (THE NEVER ENDING BATTLE) FORM of MSDSs: Paper copies-centralized/work locations Electronically scanned, stored Specialized software Manufacturer internet links POSTINGS AND NOTICES State/local “Right-to-Know” or OSHA Hazard Communication postings outlining employee rights must be posted. Hint-combine all relevant postings (e.g., emergency numbers, right-to-know postings, radiation notices) into one wall hanging. EMPLOYEE TRAINING The intent of training is to have information prior to occupancy exposure to chemicals to prevent the occurrence of adverse health ef fects. When Should Training Occur? At the time of an employee’s initial assignment Prior to assignments involving new exposure situations Refresher information and training “...shall be determined by the employer.” 29 CFR 1910.1450(f)(2) WHO SHOULD BE TRAINED? Any employee that is assigned to a work area where hazardous chemicals are present. 29 CFR 1910.1450(f)(2) This includes: Laboratory personnel Laboratory assistants Housekeeping staff Maintenance staff Student employees IDENTIFYING PERSONNEL FOR TRAINING Common exposure groups Job title classification Employee orientation Personnel records Routine inspections WHAT MUST BE INCLUDED? 29 CFR 1910.1450 OSHA Laboratory Standard Employees shall be informed of: The contents and appendices of 1910.1450 and made available to them The location, availability, and details of the written Chemical Hygiene Plan The PEL’s for OSHA regulated substances or OEL’s for other hazardous chemicals Signs and symptoms associated with exposure to the chemicals used in the laboratories WHAT MUST BE INCLUDED? Location and availability of reference material on the hazards, safe handling, storage, and disposal Material Safety Data Sheets (MSDS) availability and location Methods to detect presence or release of hazardous chemicals DO I HAVE TO TRAIN ON SPECIFIC CHEMICALS? Not always! “...Information and training may be designed to cover categories of hazards (e.g., flammability, carcinogenicity) or specific chemicals. Chemical specific information must always be available through labels and material safety data sheets.” 29 CFR 1910.1200(h)(1) CHEMICAL CATEGORIES Irritants Corrosives Allergens Asphyxiants Carcinogens Reproductive and Developmental Toxins Neurotoxins Flammables Reactives Explosives IRRITANTS Irritants - noncorrosive chemicals that cause reversible inflammatory ef fects at site of contact Swelling and redness Contact should be avoided Example - ???? CORROSIVES Most common toxic chemicals found in labs Cause tissue destruction at contact site Solids, liquids, or gases May af fect eyes, skin, respiratory tract, GI tract Rapid ef fects! Examples of Corrosives: Corrosive liquids: bromine, sulfuric acid, aqueous sodium hydroxide, hydrogen peroxide Corrosive gases: chlorine, ammonia, nitrogen dioxide Corrosive solids: sodium hydroxide, phosphorus, phenol CLASSES OF CORROSIVES Strong acid Strong Strong oxide Strong acids: nitric, sulfuric, hydrofluoric, and hydrochloric bases: metal hydroxides, ammonia dehydrating agents : phosphorus pentoxide, calcium oxidizing agents: concentrated hydrogen peroxide ALLERGENS Cause adverse reactions by immune system due to previous sensitization Immediate or delayed Anaphylactic shock May cause allergic reactions in some people: diazomethane, dicyclohexylcarbodiimide, formaldehyde, various isocyanates, benzylic and allylic halides, certain phenol derivatives ASPHYXIANTS Interfere with the transportation of oxygen to vital organs Brain most easily af fected Simple asphyxiants displace oxygen from air: acetylene, carbon dioxide, argon, helium, ethane, nitrogen, methane Asphyxiants that bind to hemoglobin: carbon monoxide, hydrogen cyanide CARCINOGENS Can interact with DNA directly or indirectly Chronically toxic May have no apparent immediate ef fects Examples: ethylene oxide, tetrachloroethylene, hydrazine, benzene REPRODUCTIVE AND DEVELOPMENTAL TOXINS Adverse ef fects on fertility, gestation, lactation, general reproductive performance, lethality of fetus, retarded growth of fetus, postnatal functional deficiencies Female reproductive toxins: DES, thalidomide Male reproductive toxins: ethylene dibromide, dibromochloropropane NEUROTOXINS Adverse ef fects on CNS or PNS, permanent or reversible Many are chronically toxic Example: lead FLAMMABLES Readily catch fire and burn in air Most common fire hazard in lab For fire to occur, need three conditions: an oxidizing atmosphere: air, oxygen concentration within flammable limits ignition source Fire prevention: control vapors and ignition sources The MSDS will contain information for emergency responders. NATION FIRE PROTECTION ASSOCIATION (NFPA) LABELING SYSTEMS HAZARD COLOR Blue = Health hazard Red = Flammability White = Other hazards Scale: 0 (No known Hazard) to 4 (Extreme Hazard) HEALTH HAZARDS FLAMMABILITY REACTIVITY SPECIAL HAZARDS REACTIVES Water reactive Alkali metals (lithium, sodium, potassium) Organometallic compounds Hydrides Produce heat and flammable hydrogen gas which can ignite or combine with oxygen REACTIVES Pyrophoric Oxidation by oxygen or moisture in air occurs rapidly and ignition occurs Finely divided metals, metal hydrides, low -valent metal salts, and iron sulfides REACTIVES Incompatible chemicals Storage is important Concentrated oxidizing agents incompatible with concentrated reducing agents, etc. Volume is important EXPLOSIVES Explosive - a chemical compound or mechanical mixture that, when subjected to heat, impact, or other suitable initiation, undergoes a rapid chemical change which evolves large volumes of highly heated gases that exert pressure on the surrounding medium EXPLOSIVES Initiation by heat, light, mechanical shock and catalysts Some may be set of f by manipulation with a metal spatula Some are set of f by their own crystal formation EXPLOSIVES - PEROXIDES Organic peroxides are very hazardous and are sensitive to shock, sparks, etc.-more shock-sensitive than TNT Compounds that auto oxidize in air to form peroxides: aldehydes, ethers, etc. Very dangerous: ether bottles that have evaporated to dryness Best to store potential peroxide formers under and inert gas, like nitrogen, or use stabilizers or inhibitors EXPLOSIVES - DUSTS Usually suspensions of oxidizable particles Examples: flour, coal dust, magnesium powder, zinc dust, carbon powder, etc. Use with good ventilation, no ignition sources Spontaneously combustible some finely divided solids allowed to dry: zirconium titanium, Raney nickel, lead, etc. Dust Explosion Video: http://www.csb.gov/videoroom/detail.aspx?vid=61&F=0&CID=1&pg=1 &F_All=y HOW DOES EXPOSURE OCCUR? Routes of Exposure: Inhalation Contact with skin or eyes Ingestion Injection ROUTES OF EXPOSURE - INHALATION Form: Gases Vapors of volatile liquids Mists and sprays of both volatile and nonvolatile liquids Solid chemicals: particles, fibers, dusts ROUTES OF EXPOSURE - INHALATION Particle size influences deposition location in respiratory tract >5 microns - nose 1-5 microns in trachea and small airways <1 micron deposited in lungs location of deposition af fects local toxicity and absorption ROUTES OF EXPOSURE - INHALATION Water-soluble particles will dissolve within minutes to days Fat-soluble particles will clear rapidly into the blood Those that are neither will be retained in lungs for a long time: metal oxides, asbestos, silica. ROUTES OF EXPOSURE - INHALATION Main factor af fecting airborne chemical concentrations: vapor pressure Vapor pressure - tendency of molecules to escape from liquid or solid phase into gaseous phase The higher the vapor pressure, the greater the possible chemical concentration. ROUTES OF EXPOSURE - INGESTION GI tract: mouth, esophagus, stomach, small and large intestines 5 m long, SA = 200 m 2 Local and systemic toxicity Absorption occurs along entire tract and depends on many factors Absorption increases with SA , permeability, residence time, fat-solubility ROUTES OF EXPOSURE – SKIN CONTACT Direct injury/local toxic ef fects Skin irritation Allergic skin reactions Burns Systemic toxicity entry via hair follicles, sebaceous glands, sweat glands, and cuts or abrasions of outer skin layer ROUTES OF EXPOSURE – SKIN CONTACT Absorption depends on chemical concentration, reactivity, solubility, condition of skin, part of body exposed, duration of exposure Thin skin more vulnerable DMSO increases penetration of chemicals through skin ROUTES OF EXPOSURE - INJECTION Mechanical injury with glass or metal objects, syringes Intravenous route EXPOSURE LIMITS Exposure Limits: Permissible Exposure Limits (PEL) Concentrations expressed in parts per million (ppm) or milligrams or cubic meter Threshold limit value (TLV) TLV-Time Weighted Average (TLV-TWA) TLV-Short-Term Exposure Limit (TLV-STEL) TLV-Ceiling Limit (TLV-C) Typically, the lower the exposure limit, the more harmful the material is to your health. Take more precautions with it (limit quantity and don PPE) to protect yourself and others. OSHA LABORATORY STANDARD 29 CFR 1910.1450 Performance standard Development and implementation of Chemical Hygiene Plan Primary emphasis on administrative controls to protect workers Readily accessible CHEMICAL HYGIENE PLAN Plan should include: Responsibilities Standard Operating Procedures Plans for Controlling Chemical Exposures Engineering Controls Medical Consultation and Review Chemical Hygiene Officer Special Provisions for Hazardous Chemical Use CONTROL OF CHEMICAL HAZARDS Engineering Design specifications Isolation Ventilation Administrative Scheduling Location Substitution CONTROL OF CHEMICAL HAZARDS Employers must provide you with: Personal Protective Equipment (PPE). Respirators Chemical barriers Gloves, lab-coats, boots Lanyards (Fall Protection) Noise attenuation Ear plugs, ear muf fs Safety glasses Hard hat RESPONDING TO ACCIDENTS AND EMERGENCIES 24/7 Hotline number/paging system very helpful Personnel should know the notification and evacuation procedures for your institution Know the location of safety showers, eyewash stations, and fire extinguishers Drills for safety personnel and employees EMERGENCY CLEAN UP Spill Containment Supplies Spill control pillows Inert absorbents such as vermiculite, clay Neutralizing agents for acid and alkali spills Scoops, brooms, pails, bags, dust pans Appropriate PPE, warning signs, etc. Central storage location(s) Re-supply responsibility PREVENTION IS BETTER THAN CURE! Before undertaking any chemical related activity, become familiar with the hazards of the chemicals involved. Be sure you know and be sure you follow the safety precautions that protect you and others from those hazards. Become familiar with the hazards of the apparatus and operations involved Should know the notification and evacuation procedures for the facility/ institution Know the location of safety showers, eyewash stations, and fire extinguishers Participate in drills for safety personnel and employees Know the location of Spill Containment Supplies and PPE Remember to replenish used supplies!