Chemical Use, Storage, Spills and Waste Procedures

Transcription

1 TRENT UNIVERSITY Chemical Use, Storage, Spills and Waste Procedures A guide to some general principles and procedures for the use of chemicals in labs. TrentEmployee 4/2/2013 This is a guideline document which contains information on the safe use of chemicals, their safe storage, spill response procedures and instructions on chemical waste disposal.

2 Chemical Use, Storage and Waste Guide Table of Contents Preamble p. 2 Glossary p Introduction p Lab Rules and Recommended Procedures p Specific Chemical Hazards p Flammables p Oxidizers p Precautions to be Taken when using Oxidizers p Peroxygen Compounds p Use, Handling and Storage of Peroxygen Compounds p Testing for Peroxides p Corrosives p Precautions to be taken when using Corrosives p Other Reactive Materials p Water Reactive Chemicals p Pyrophoric Chemicals p Organic Peroxides p Explosives p Precautions to be taken when using Picric Acid p Cryogenic Materials p Designated Substances p Mercury p Isocyanates p Benzene p Asbestos p Nanomaterials p Other Toxic Materials p Compressed Gases p Chemical Storage p Chemical Storage Practices p Storage of Flammables and Combustibles p Storage Rooms for Flammable and Combustible Liquids p Approved Flammables Storage Cabinets p Chemical Segregation p Partial List of Incompatible Chemicals p Containment p Security p Chemical Spill Prevention and Preparedness p Training p Spill Kits p Spill Classifications p Spill Response p Complex Spill Response p Incidental Spill Response p Chemical Waste Procedures p Hazardous Waste Procedures DNA and LHS p Hazardous Waste Procedures ESB, SC and CSB p. 33 1

3 Preamble: This guide, Chemical Use, Storage, Spills and Waste, is to be used by those persons who use hazardous chemicals as part of their course of studies, research related activities or as part of their job. The rules, recommendations and guidelines stated in this guide are provided to assist the user in identifying, understanding and mitigating the risks associated with hazardous chemicals, their safe use, proper storage, dealing with spills and correct measures for disposal. Any deviations from the recommendations in this guide should always be towards a safer a protocol. This document forms an integral part of the Science Health and Safety Program as outlined in the Science Health and Safety Program Description. This document should be reviewed by all personnel who use hazardous chemicals and shall be reviewed by all personnel whose supervisor has indicated that they are required to have training in Chemical Use as part of their individual Health and Safety Training record. Supervisors shall determine what training is required by their personnel working in their labs in addition to any base training mandated by the University. This guide attempts to cover many of the common issues of chemical use, storage, spills and waste encountered, but by no means covers every issue. Where an issue is not covered here, the supervisor shall establish a procedure for the situation and communicate such to their personnel. Acknowledgements: This manual contains information obtained with permission from a variety of sources including University of Ottawa, University of Guelph, University of Western Ontario and University of Toronto. Glossary: Combustible liquid: means an liquid having a flash point at or above 37.8 o C and below 93.3 o C. Compressed gases: means any contained mixture or material with either an absolute pressure exceeding kpa at 21 o C or an absolute pressure exceeding 717 kpa at 54 o C or both, or any liquid having an absolute vapour pressure exceeding kpa at 37.8 o C. Corrosive liquid: means a liquid that, when contacting living tissue causes damage to the tissue, or when contacting organic matter and chemicals that react with the liquid, causes fire. Flammable liquid: means a liquid having a flash point below 37.8 o C and having a vapour pressure not more than kpa (absolute) at 37.8 o C. Flash point: means the minimum temperature at which a liquid within a container gives off vapour in sufficient concentration to form an ignitable mixture with air near the surface of the liquid. 2

4 Oxidizing material: means a material, other than ordinary atmospheres, that by itself is not necessarily combustible, but that may, generally by yielding oxygen, cause or contribute to the combustion of another material. PPE: means Personal Protective Equipment Pyrophoric chemicals: means those chemicals which ignite spontaneously upon contact with air. SOP: means Standard Operating Procedure which is a written procedure with step by step instructions (procedures) for working with a material or for a situation as defined by the SOP. Vapour pressure: means the pressure exerted by a liquid. 1.0 Introduction All chemicals used in the laboratories at Trent University should be used with the utmost caution according to good laboratory practices. There are certain chemicals or classes of chemicals, however that require specific handling precautions that are described briefly in the following sections. It is beyond the scope of this manual to address all the hazards and precautions of all of the chemicals that may be found in the University s laboratories as well as delve into the details of the hazards of the chemicals mentioned. For further information regarding the toxicity, safe handling and use of specific chemicals, the appropriate MSDS or references such as the following should be consulted: Prudent Practices in the Laboratory, Handling and Disposal of Chemicals, National Research Council National Academy Press. Laboratory Health and Safety Guidelines, 4 th edition. 2003, The Chemical Institute of Canada and L Ordre des Chemistes du Quebec. NIOSH Pocket Guide to Chemical Hazards, September 2007 Publication number ( 1.1 Basic Lab Rules: All labs which contain hazardous chemicals have some basic lab rules which shall be followed by all personnel working in that lab. 1. When working with hazardous material, the appropriate PPE shall be worn by the users and at a minimum include eye protection, gloves, lab wear as well as any other PPE recommended by the MSDS or the supervisor. It is important that the correct PPE be selected specifically for the Hazard identified to ensure that 3

5 will protect against the hazard and that if necessary training for the use of the PPE is performed (eg., fit testing for respirators or the selection of the proper glove material for the chemical). 2. If PPE is recommended by the MSDS or the supervisor or by best practice than the PPE shall be provided by the supervisor to the lab worker. If the PPE is required by the supervisor then the lab personnel shall use the PPE. 3. The storage or consumption of food and drink in any area where hazardous chemicals are used or stored is prohibited. 4. Personnel working in areas where hazardous chemicals are stored or used shall be familiar with the proper care and use of the safety equipment located in that area (eyewash, deluge shower, fumehood, fire extinguisher etc ) 5. Smoking within all university buildings and facilities is prohibited. 6. Mouth pipetting of any nature is prohibited. 7. PPE shall not be worn outside of the lab in public areas or corridors to prevent contamination of those areas. 8. Safety interlocks or guards on laboratory equipment shall not be defeated in any way. 9. Where chemicals have been decanted from their original containers (either in their original concentration, in diluted form, or as a mixture/solution with other chemicals) the new containers shall be labelled with the name(s) of the chemical, the concentration and the appropriate hazard. 10. Working alone with hazardous material after hours is to be discouraged. If it must occur than workers are advised to inform their Supervisor and Campus Security of their location and the length of time they will be working. Working alone with some material (such as Fluoric acid) is prohibited. Supervisors shall determine when lab workers may work alone after hours. 11. Experiments should not be left unattended unless they have been designed to be safe to do so. 12. Unsafe conditions shall always be reported to the Supervisor as soon as possible. 13. Open toed footwear or high heeled shoes are prohibited from labs with hazardous material. 14. Working with chemicals which produce or may produce hazardous vapours, gases or fumes shall always be done in a fumehood. Work with perchloric acid shall always be done in the perchloric hood, Work with Fluoric acid shall follow the Fluoric Acid SOP. 15. Horseplay in labs is prohibited. Lab workers shall always maintain a professional level of deportment. 16. Lab personnel should always keep in mind that in the event of an emergency such as a fire alarm, or lock down, that any work going on at the time may be interrupted without warning. Personnel should always be prepared to secure hazardous material in a safe fashion until the emergency is over. 2.0 Specific Chemical Hazards 2.1 Flammables 4

6 Flammable materials present a serious hazard to laboratory personnel. Steps are to be taken to ensure appropriate use, handling and storage. Ensure containers are grounded and bonded appropriately when transferring liquid from one container to another. (If dispensing from large volume sources such as containers greater than 4 L made of metal). Ensure that potential ignition sources (in other words sources that could cause a spark) are identified and removed from the area surrounding the flammable material. Laboratories that store, use or handle flammable or combustible liquids are to conform to section 4.12 of the Ontario Fire Code. See section 2.2 for more information. Note that due to the highly flammable nature of diethyl ether, diethyl ether extractions are to be performed only in facilities with additional fire suppression systems and ventilation, as well as intrinsically safe wiring (i.e., spark proof receptacles and endcaps). The heating of flammable chemicals should never be done with an open flame, but with heating devices designed specifically for that purpose. 2.2 Oxidizers Oxidizers are capable of igniting flammable and combustible material even in oxygendeficient atmospheres as well as increasing the intensity of a fire by adding to the oxygen supply and causing ignition and rapid burning of normally non-flammable materials. Oxidizers can also: React with other chemicals, causing a release of toxic gases. Decompose and liberate toxic gases when heated. Burn or irritate skin, eyes, breathing passages and other tissues. Oxidizing Solids Solid oxidizing agents have the ability to form explosive mixtures with common materials such as sugar, charcoal, starch, sawdust and sulphuric acid. Examples of solid oxidizers include metallic: chlorates; perchlorates; (these are especially dangerous and their use should be avoided) nitrates; chromates; and permanganates. Oxidizing Liquids 5

7 Liquid oxidizers are often strong acids as well, making them powerful corrosives. Examples include: Perchloric acid: Use of perchloric acid should be avoided if possible. If its use is necessary, it must be done by personnel trained in specific handling procedures. Work involving heating of concentrated perchloric acid is to be performed in specialized, dedicated wash-down fume hoods (see Perchloric Acid Fumehood use section). Note that anhydrous perchloric acid and perchlorate crystals which may form around the cap of the container are shock-sensitive explosives. Other Strong Acids: Personal protective equipment when working with these compounds should include a face shield, goggles, synthetic rubber apron, lab coat and synthetic rubber gloves. HydroFluoric Acid: See Hydrofluoric Acid Use SOP Precautions to be taken when working with Oxidizers When using or storing oxidizers in the laboratory, the precautions to take include the following: 1. Keep away from flammable and combustible materials. 2. Keep containers tightly closed unless otherwise indicated by the supplier. 3. Store strong oxidizers in inert, unbreakable containers. The use of corks or rubber stoppers is not permitted. 4. Mix and dilute according to the supplier's instructions. 5. Dilute with water to reduce the reactivity of solutions. 6. The use of oxidizers should always be done in a fumehood. 7. Wear appropriate personal protective equipment. 8. Ensure that oxidizers are compatible with other oxidizers in the same storage area. 9. Reaction vessels containing oxidizers shall not be heated with oil baths Peroxygen Compounds These are chemically unstable compounds including peroxides, hydroperoxides, and peroxyesters that have a violently reactive oxygen. Some peroxygen compounds decompose slowly at room temperature, but rapidly at elevated temperatures. However, others decompose readily at room temperature and therefore must be refrigerated. 6

8 Organic peroxides can violently explode when subjected to heat, friction, shock, spark, oxidizing and reducing agents or light. These compounds are very difficult to control in a fire due to their ability to generate their own oxygen upon combustion. Peroxygen compounds can seriously irritate the skin and eyes upon contact. Special consideration should be taken when using any compounds that have the capability of forming peroxides. The following are compound types that can be expected to form peroxides upon prolonged exposure to light or air: Ethers Aldehydes, ketones Compounds containing benzyllic, or allylic hydrogens Compounds with a vinyl or vinylidene group The following is a partial list of compounds that can form peroxides: Table 1 Partial List of Chemicals that May Form Peroxides Chemicals that form explosive levels of peroxides without concentration Isopropyl ether Butadiene Chlorobutadiene Potassium amide Potassium metal Sodium amide Tetrafluoroethylene Divinyl acetylene Vinylidene chloride Chemicals that are a peroxide hazard on concentration Acetal Cumene Cyclohexane Cyclooctene Cyclopentene Diacetylene Dicyclopentadiene Diethylene glycol dimethyl ether (Diglyme) Diethyl ether p-dioxane Ethylene glycol dimethyl ether Methyl acetylene Methyl cyclopentane Methyl i-butyl ketone Tetrahydrofuran (THF) Tetrahydronaphthalene (Tetralin) Vinyl ethers Use, Handling and Storage of Peroxygen Compounds Specific precautions to take when using, handling and storing peroxygen or peroxideforming compounds include the following: 1. Purchase and use only the minimum amount required. 2. Purchase with peroxide inhibitors whenever possible 3. Mark the receipt date on the container. 7

9 4. Mark the date the container was opened on the container. 5. Dilute solutions with inert solvents such as aliphatic hydrocarbons. Avoid the use of aromatic solvents, such as toluene, which can initiate the decomposition of some peroxides. 6. Avoid preparing peroxide solutions with volatile solvents as losses of solvent due to evaporation can cause unwanted concentration of peroxides. 7. Dispense quantities as required. Do not return unused materials to stock container. 8. Do not use metal spatulas. 9. Do not use glass containers with ground glass or metal lids. Use polyethylene containers with screw cap lids. 10. Store and use away from heat, ignition sources and light. 11. Store at the lowest temperature that is above the freezing point of the solution and that will not affect the solubility of solution. This will minimize the rate of decomposition of the peroxides. 12. Dispose after one month of the container being opened or if unopened, by the expiry date. 13. Treat any visible solids around the cap or in the container of peroxygen or peroxide-forming liquids with extreme caution as they could be explosive. Never open a container with visible crystals around the cap or on the outside of the container. Contact your supervisor immediately. 14. Ensure that solutions are free of peroxides before concentration using the tests described below. 15. If concentration is necessary, avoid evaporating to dryness. 16. Use a shield when evaporating or distilling any peroxide-forming compounds Testing for Peroxides Peroxide test strips can be purchased from laboratory supply companies. These allow a simple and quick qualitative determination of whether peroxides are present in a solution. Alternatively the following colourimetric test can be performed. (note: this test method should not be applied to solutions that may contain inorganic peroxides). 1. Prepare a 5 % (w/v) potassium iodide or sodium iodide aqueous solution. (5 g of KI or NaI per 100 ml of water). 2. Add a couple of drops of iodide solution prepared above to ~ 2 ml of glacial acetic acid. 3. Add ~ 2 ml of the solution in question to the ~ 2 ml of glacial acetic acid/iodide solution. 4. Yellow indicates a low concentration of peroxide (<0.01 %). Brown indicates a high/hazardous concentration of peroxide (> 0.01%). 8

10 2.3 Corrosives Corrosive chemicals are commonly found in laboratories as solids, liquids and gases. These materials have the ability to damage tissue at the point of contact. Soft tissues and mucous membranes (eyes, sinuses, lung tissue) are the most easily damaged. Corrosive Liquids Corrosive liquids can be particularly hazardous as they act rapidly upon contact. Examples of common corrosive liquids are: Strong acids (chromic acid, hydrochloric acid, nitric acid, hydrofluoric acid* etc. Strong bases (aqueous sodium hydroxide, potassium hydroxide, ammonia, etc.) Strong dehydrating agents (phosphorus pentoxide, calcium oxide, etc.) Strong oxidizing agents (peroxides, etc.) *Hydrofluoric acid may be fatal through inhalation, absorption or ingestion and causes extensive, deep and painful burns. Avoid use if possible, however if its use is unavoidable, personnel are to be specifically trained in its use and emergency response procedures. More information and use requirements are available in the Hydrofluoric Acid Use SOP. Corrosive Solids Inhalation of corrosive dusts presents a particular hazard as the point of contact and the tissue at risk, particularly the airways and lungs, is internal, creating an injury that may be difficult to treat and heal. Examples of corrosive solids are lithium oxide, sodium sulphide and phenol. Corrosive Gases Corrosive gases enter the body through inhalation as well as being readily absorbed through dissolution in skin and eye moisture. Typical examples are listed below: Ammonia Hydrogen chloride Hydrogen fluoride inhalation, absorption or ingestion may be fatal. Causes extensive, deep and painful burns. Avoid use if possible, however if its use is unavoidable, personnel are to be specifically trained in its use and emergency response procedures. Formaldehyde Bromine Chlorine Phosgene Sulphur Dioxide 9

11 2.3.1 Precautions to be taken when using Corrosives Specific precautions to take when using or handling corrosive materials include the following: 1. Ensure that acids are always added to water and not vice versa. 2. Be prepared for heat generation upon diluting or dissolving in water. 3. Ensure that all work is completed in a chemical fume hood with adequate ventilation (see Fumehood Training). 4. Personal protective equipment is to include: labcoat; goggles; appropriate gloves; and when working with volumes greater than 4 L, a synthetic rubber apron 2.4 Other Reactive Materials Water Reactive Chemicals The following situations may occur with water reactive chemicals upon contact with water: 1. Liberation of heat (causing potential ignition of the chemical itself or nearby flammable material); 2. Release of flammable, toxic, or oxidizing gas; 3. Release of metal oxide fumes (applicable to water reactive metals); 4. Formation of corrosive acids. Table 2. Water reactive Chemicals Examples of water reactive materials include: Alkali metals including lithium, sodium and potassium Silanes Aluminum chloride Phosphorus pentachloride Lithium aluminum hydride Ferrous sulphide Sodium borohydride Chlorosulphonic acid Silicon tetrachloride Sulphur chloride Thionyl chloride Alkylaluminums including triethylaluminum Magnesium Phosphorus Phosphorus pentasulphide Aluminum chloride Maleic anhydride Acetyl chloride Phosphoryl trichloride Stannic chloride Sulphuryl chloride Titanium tetrachloride. 10

12 Care must be taken to ensure that water reactive chemicals are handled and stored away from sinks, water baths or other sources of moisture Pyrophorics Pyrophoric chemicals are those which ignite spontaneously upon contact with air. Pyrophorics must be handled and stored in such a way as to prevent exposure to air, e.g. storage under an inert gas or under kerosene, use in glove boxes, etc. More information and use requirements are available in the Safe Use and Handling of Pyphorics SOP. Table 3. Pyphorics Examples of pyrophorics include: Grignard reagents Alkyllithium compounds including t- butyllithium Boron Finely divided metals including calcium, cobalt, cadmium, iron, manganese, chromium, lead, nickel, titanium Dichloroborane Diborane Diethylzinc 2-Furaldehyde Metal carbonyls e.g. lithium carbonyl, nickel carbonyl Metal hydrides, e.g. sodium hydride Non-metal hydrides e.g. diethyl arsine, diethyl phosphine Phosphine Phosphorus Organic Peroxides See section Explosives Explosives are regulated by the Canadian Explosives Act and corresponding regulations along with the Ontario Fire Code. Any work with explosive must be consistent with the following general requirements described below: 1. Working alone with explosive materials is prohibited 2. Storage locations for explosive materials are to be placarded in accordance with the Explosives Act. 3. Quantities of explosive materials are to be minimized with all additional material disposed of upon completion of the activity. 4. Written safety instructions and emergency procedures are to be prepared and must include at least the following information: 11

13 a. location of storage and use areas b. methods to control a fire emergency safely and efficiently c. contact information Precautions when using Picric Acid Picric acid (2,4,6-trinitrophenol) is a reagent found in departments across campus, being used in microscopy and as a component in some biological specimen preserving solutions. When dehydrated( in other words dry), picric acid can become a dangerous explosive. When in contact with metal, highly shock-sensitive picrate salts can be formed. The following guidelines are for the storage and handling of picric acid: 1. Picric acid must be stored in water. 2. Containers of picric acid are to be inspected at least every 6 months and distilled water added to the containers as necessary to ensure that the picric acid never dries out. 3. Containers and lids for storage of picric acid or solutions of picric acid are not to be of metal construction. 4. Metal spatulas are never to be used to remove material from its container. 5. Always wipe the neck of the bottle, and the cap with a wet cloth before returning to storage. If a container of dry picric acid is discovered, it is not to be touched and Security, the RMO and Science Facilities is to be contacted at ext.1333 immediately to arrange for safe disposal. 2.5 Cryogenic Materials Cryogenics are very low temperature materials such as dry ice (CO2(s)), liquefied air, nitrogen, helium, oxygen, argon and neon. The following hazards are associated with the use of cryogenics: 1. asphyxiation due to displacement of oxygen (for materials other than liquefied air and oxygen); 2. freezing and fracturing of materials from extreme cold; 3. frostbite; 4. explosion due to pressure build up; and 5. condensation of oxygen and fuel, such as hydrogen or hydrocarbons, resulting in explosive mixtures Precautions to be taken when using Cryogenic Materials The following are precautions for handling cryogenics: 1. Control ice build-up on containers. 12

14 2. Use only approved low-pressure containers equipped with pressure-relief devices. Lunch box Thermos-style bottles are not acceptable. 3. Protect skin and eyes from contact; wear eye protection and insulated gloves. 4. Wear safety goggles when breaking large pieces of dry ice or using mixtures of dry ice and solvent. 5. Wear a face shield when removing samples from storage dewars due to the possibility of rupture from pressure build-up. 6. Use and store in well-ventilated areas. Alarmed oxygen sensors are required in areas where the volume of gas could result in the displacement of oxygen to a level lower than what is tolerable by people, thereby causing an asphyxiation hazard. 7. Keep away from sparks or flames. 8. Use materials resistant to embrittlement. 9. Watches, rings, bracelets or other jewelry that could trap fluids against flesh should not be worn when handling cryogenic liquids. 10. To prevent thermal expansion of contents and rupture of the vessel, ensure containers are not filled to more than 80% of capacity. 11. Never store dry ice in a refrigerator/freezer (especially deep chest freezers). Dry ice will sublimate at -78 C and could asphyxiate the person opening the equipment. 2.6 Designated Substances There are eleven designated substances regulated under the Ontario Occupational Health and Safety Act due to their potential to cause serious health implications. Use of designated substances in research or teaching situations should be avoided. However because suitable substitution may not be possible, some of these substances may be found in university laboratories. Designated substances are listed below: 1. acrylonitrile; 2. arsenic; 3. asbestos; 4. benzene; 5. coke oven emissions; 6. ethylene oxide; 7. isocyanates; 8. lead; 9. mercury; 10. silica; and 11. vinyl chloride. 13

15 The designated substance regulations apply to employers and workers at workplaces where the substance is present and is likely to be inhaled, ingested or absorbed by the worker. The regulations require that the time weighted average exposure of the worker to the substance be less than limits prescribed in the regulations. Generally, the regulation contains three key components: 1. Assessment requires the Principle Investigator or supervisor to consider the level or likelihood of exposure of the worker to the substance. 2. Control program required if the assessment discloses that a worker is likely to be exposed to the substance. This documented program is to include engineering controls, hygiene practices, work practices and facilities to ensure that the worker exposure to the substance is controlled. 3. Monitoring requires air emissions monitoring and medical surveillance to determine actual exposure to the substance. It is the responsibility of the laboratory supervisor to ensure that the letter and intent of the regulations are met. See the Designated Substance SOP for more information. Below we discuss some Designated Substances commonly found in labs Mercury Elemental mercury, inorganic mercury salts and organic mercury compounds have the potential to cause serious acute or chronic toxic effects from the various routes of exposure. Containers are to be stored sealed with the cap/lid along with electrical tape, parafilm or an equivalent. All use and storage is to be in a well-ventilated area. Any skin or eye contact is to be rinsed with copious amounts of water and medical attention is to be sought immediately. See section 3 for spill clean-up procedure Isocyanates Various isocyanates have been determined to cause severe allergic reactions in certain individuals. Sensitization may also occur such that the allergic reaction becomes progressively worse with each exposure and occurs with exposures to very small amounts of the material. Reactions may include anaphylactic shock which can be fatal and hence requires immediate medical treatment. All laboratories, solutions or samples containing isocyanates should be clearly marked as containing such Benzene Benzene is a highly flammable, carcinogenic solvent that has severe effects on the blood and blood-forming organs. All use of benzene should be performed in a fume hood. If 14

16 practical, the use of benzene should be substituted with another appropriate solvent, such as toluene Asbestos Asbestos is a fibrous material commonly used in equipment and construction material due to its fire and heat resistant properties. Asbestos was attributed to a variety of respiratory health effects including cancer and whose use has since been abandoned in Canada. However, a significant amount of equipment and building materials manufactured before 1990 s contained asbestos including things like Transite materials (hard fibre board fire proof material), drywall, and heat resistant coatings and insulations. Older equipment may still contain asbestos linings or gaskets. Care should be taken when working on equipment suspected of containing asbestos (pre 1990). If in doubt contact the Risk Management Office prior to disturbing material. Where equipment or material containing Asbestos has been identified, it shall be labelled as such and entered into the university s asbestos inventory. These are just some examples of Designated Substances, for additional information please refer to the Occupational Health and Safety Act and its associated regulations and the Designated Substances SOP. 2.7 Nanomaterials Nanomaterials are defined as particles with at least one dimension that is less than 100 nm. Nanomaterials have been shown to have unique physical and chemical properties when compared to the corresponding micro- or macro-scale compounds. In addition there also appears to be different mechanisms of toxicity and therefore different and potentially more severe health effects although these differences are currently widely unknown. As such,use and handling of nanomaterials must be done with particular care and only after conducting a risk assessment to consider both the potential hazards and appropriate controls. Contact Science Facilities for assistance in conducting a risk and/or exposure assessment. Examples of controls include: 1. Identification of areas, equipment and containers that contain or are used with nanomaterials; 2. Embedding the nanomaterials in a solid matrix; 3. Working with the nanomaterials in solution within a chemical fume hood 4. Working with solid, dry, dispersible nanoparticles in a fully contained system or conducting the work within a biosafety cabinet (HEPA filtered) or fumehood. 5. Being diligent in housekeeping, wet wiping of potentially contaminated areas etc. 6. Wearing appropriate personal protective equipment (gloves, lab coat, eye protection, respiratory protection etc.) 15

17 Reference source: Greaves-Holmes, Wanda L Journal of Technology Studies, vol. 35, no. 1. pg Visit this web page to see the article. scholar.lib.vt.edu/ejournals/jots/v35/v35n1/pdf/holmes In addition, those looking to work with engineered nanomaterials should review the following document General Safe Practices for Working with Engineered Nanomaterials in Research Laboratories published by the Center for Disease Control and National Institute for Occupational Safety and Health (NIOSH). It can be found on here. 2.8 Other Toxic Materials Some other chemical materials warrant mentioning specifically because of their hazards and/or extensive usage. Their primary hazards are identified below: Ethidium bromide known mutagen. Chloroform relatively potent anaesthetic, suspected carcinogen. Cyanides/Nitriles acutely toxic. If use is unavoidable, personnel are to be specifically trained in its use and emergency response procedures. Contact Risk Management Office. Hydrogen sulphide acutely toxic. Attacks the respiratory system. Highly flammable. Formalin/Formaldehyde known carcinogen. 2.9 Compressed Gases and Gas Cylinders Compressed Gases are gases or (or sometimes liquids) stored under high pressure so that the gas can be used under higher than atmospheric pressure. They are often used with analytical equipment. The following precautions should be taken. 1. Cylinders of compressed gases must be properly secured (clamps, chains etc) in a upright fashion where the cylinder can t tip or fall over. 2. Cylinders must have the valve protection cap installed properly when moving the tank or when not in use. Cylinders must only be transported using the proper tank cart. 3. Use the correct regulator for the gas and cylinder in use. Never move a tank with the regulator attached. 4. Refer to the MSDS from the gas supplier for the type of gas you are using. 5. For additional information and precautions see: the Canadian Centre for Occupational Health and Safety (CCOHS) web site on handling Gas Cylinders. 16

18 3.0 Storage of Chemicals When not in use, Chemicals need to be stored in a safe and secure fashion. However, just locking them in cabinet may not be enough as incompatible chemicals stored together to lead to catastrophic outcomes (fires, explosions etc ) It is important that lab personnel understand how to safely store chemicals as well as use them. 3.1 General Storage Practices 1. Ensure that storage shelves are sturdy and secured to the wall or floor. 2. Ensure that material is kept back from the edges so that the material cannot easily fall off the shelf. 3. Store large and/or heavy containers on lower shelves. 4. Avoid storage of hazardous chemicals above eye level. 5. Window sills, heaters and ledges are not to be used as storage areas. 6. Avoid storage on the floor unless the chemical container is in its original shipping carton and packing or the container is an approved safety can. Containers stored on the floor can be easily knocked over spilling contents and are a tripping hazard. 7. Inspect chemicals in storage regularly to ensure that: a. There are no leaks. b. Caps and containers are in good condition. Look for signs of discolouration,cracks, bulging and pressure build up. c. Outside of containers are kept free of spills and stains. d. Containers are properly labelled. 3.2 Storage of Flammables and Combustibles Flammable liquid a liquid having a flash point below 37.8 C and having a vapour pressure not more than kpa (absolute) at 37.8 C as determined by ASTM D323, "Vapour Pressure Petroleum Products (Reid Method)". Combustible liquid any liquid having a flash point at or above 37.8 C and below 93.3 C Storage of flammable and combustible liquids in the laboratory is regulated by section four of the Ontario Fire Code. Maximum quantities listed below are for single labs (i.e. single fire compartments with a minimum fire resistance rating of one hour). Ensure that the flammable and combustible material in the open lab area is minimized and is for immediate use only (less than a total of 300 L of which no more than 50 L are flammable liquids, as per Ontario Fire Code) 17

19 Ensure that all additional flammable material (up to a total of 500 L of which not more than 235 L of flammable liquids) is stored in approved flammable storage cabinets. Ensure that flammable materials requiring storage conditions at refrigerated temperatures are stored in refrigerators/freezers designed and certified for this purpose. Household refrigerators are never to be used to store flammable liquids. Storage containers are to be less than 5 L unless they are safety containers conforming to ULC/ORD-C30 which must be less than 25 L Storage Rooms for Flammable and Combustible Liquids There are several designated flammable storage rooms at the University. Flammable storage rooms are to meet the following requirements: 1. not be located in the basement of a building; 2. separated from the remainder of the building with partitions having a minimum one-hour fire resistance rating and self-closing doors, hinged to swing outward; 3. have no openings communicating directly with the public portions of the building; 4. be equipped with a drain connected to a dry sump or holding tank; 5. have liquid-tight seals between interior walls and floor and a liquid tight ramped sill at any door which is not an exterior door; 6. have aisles of no less than 1 m; 7. have a suitable portable fire extinguisher; 8. have suitable spill clean-up materials; 9. have appropriate ventilation: 10. natural or continuous mechanical ventilation if no vapours can escape into the room; 11. continuous mechanical ventilation if flammable vapours may be released into the room (Refer to the Ontario Fire Code for specific requirements for mechanical ventilation). 12. The maximum quantity of flammable and combustible liquids permitted in flammable storage rooms is 1500 L Approved Flammable Storage Cabinets To be approved for storage of flammables, cabinets must conform to at least one of the following standards: Conform to ULC-C1275, Storage Cabinets for Flammable Liquid Containers ; Conform to ULI 1275, Flammable Liquid Storage Cabinets ; Be Factory Mutual Research Approved; or Be listed as meeting NFPA 30. Vents on flammable storage cabinets need to be capped with the plugs supplied with the cabinet itself. 18

20 3.2.3 Chemical Segregation It is critical that chemicals are stored according to a predetermined storage system to ensure that incompatible chemicals are not stored in close proximity to each other. Storage systems that account for necessary segregation are acceptable provided that they are clearly documented and understood by lab personnel. It is suggested that solvents/reagents etc. be labelled according to the storage system used to allow for continuous, easy and proper storage. A representative chemical segregation system that has been adopted by several other universities is described on the following pages. 19

21 Figure F Chemical segregation system CHEMICAL SEGREGATION AND STORAGE SYSTEM Water reactive/ Pyrophoric/ self-reactive Explosives Flammables (solids & liquids) Oxidizers (solids & liquids) Corrosive Acids (solids & liquids) Corrosive Bases (solids & liquids) Nonflammable solvents & regulated chemicals Ok No No No No No No No Explosives No Ok No No No No No No Low-hazard solids & liquids Water reactive/ Pyrophoric/ Selfreactive Flammables (solids & liquids) Oxidizers (solids & liquids) Corrosive Acids (solids & liquids) Corrosive Bases (solids & liquids) Nonflammable solvents & No No Ok No No Ok Ok No No No No Ok No No No Secondary containment required No No No No Ok No No < 2 M acidic solutions No No Ok No No Ok Secondary containment required No No Ok No No Secondary containment required Ok < 2 M caustic solutions Ok 20

22 regulated chemicals Low-hazard solids & liquids No No No Secondary containment required Ok- ok to be stored together < 2 M acidic solutions no may not be stored together < 2 M caustic solutions Ok ok 21

23 3.2.4 Partial List of Incompatible Chemicals The following list is not complete and is intended for use as a guide only. Refer to the appropriate MSDS for incompatibilities of chemicals not found in the following table. Table 4 Partial List of Incompatible Chemicals Chemical Acetic acid Acetic anhydride Acetone Acetylene Alkali and alkaline metals e.g. sodium, potassium, lithium, magnesium, calcium, powdered aluminum Aluminum Alkyls Ammonia, anhydrous Ammonium nitrate Aniline Arsenic compounds Azides Bromine Calcium oxide Carbon, activated Carbon tetrachloride Chlorates Chlorine Chlorine dioxide Chromic acid Copper Is Incompatible with Chromic acid, nitric acid, alcohols, ethylene glycol, perchloric acid, peroxides, permanganates Hydroxyl-containing compounds e.g. ethylene glycol, perchloric acid Concentrated nitric and sulfuric acid mixtures, hydrogen peroxide Chlorine, bromine, fluorine, copper, silver, mercury Water, carbon tetrachloride and other halogenated alkanes, carbon dioxide, halogens Water Mercury, chlorine, calcium hypochlorite, iodine, bromine, hydrogen fluoride Acids, powered metals, flammable liquids, chlorates, nitrates, sulfur, fine-particulate organic or combustible materials. Nitric acid, hydrogen peroxide Reducing agents Acids Ammonia, acetylene, butadiene, butane, methane, propane, hydrogen, other petroleum gases, benzene, powered metals Water Calcium hypochlorite, oxidizing agents Alkali and alkaline metals e.g. sodium Ammonium salts, acids, powered metals, sulfur, fine-particulate organic or combustible substances Ammonia, acetylene, butadiene, butane, methane, propane, hydrogen, other petroleum gases, benzene, powered metals Ammonia, methane, phosphine, hydrogen sulphide Acetic acid, naphthalene, camphor, glycerol, turpentine, alcohols, flammable liquids Acetylene, hydrogen peroxide 22

24 Cumene Hydroperoxide Cyanides Flammable liquids Fluorine Hydrazine Hydrocarbons, flammable (butane, propane, benzene, etc.) Hydrocyanic acid Hydrogen fluoride Hydrogen peroxide Hydrogen sulfide Iodine Mercury Nitric Acid, Conc. Nitrites Nitroparaffins Oxalic Acid Perchloric acid Peroxides, organic Phosphorus (white) Phosphorus pentoxide Potassium Potassium chlorate Potassium perchlorate Potassium permanganate Selenides Silver and silver salts Sodium Sodium nitrate Sodium peroxide Organic and inorganic acids Acids Ammonium nitrate, chromic acid, hydrogen peroxide, nitric acid, sodium peroxide, halogens Store separately Hydrogen peroxide, nitric acid, oxidizing materials Fluorine, chlorine, bromine, chromic acid, peroxides Nitric acid, alkalis Ammonia, aqueous or anhydrous Copper, Chromium, iron, metals and metals salts, flammable liquids, aniline, nitromethane, combustibles (solid or liquid) Fuming nitric acid, oxidizing gases Acetylene, ammonia (anhydrous or aqueous) Acetylene, ammonia Acetic acid, acetone, aniline, chromic acid, prussic acid, hydrogen sulfide, flammable liquids and gases, nitratable substances e.g. copper, brass, heavy metals, organic products e.g. wood, paper Acids Inorganic bases, amines Silver, mercury and their salts Acetic anhydride, bismuth and its alloys, alcohols, paper, wood, oils Mineral or organic acids Sulfur, air, oxygen-containing compounds such as chlorates Alcohols, strong bases, water See alkali metals See chlorates See chlorates Glycerol, ethylene glycol, benzaldehyde, sulfuric acid Reducing agents Acetylene, oxalic acid, tartaric acid, ammonium compounds. See alkali metals Ammonium nitrate and other ammonium salts Methanol, ethanol, glacial acetic acid, anhydride, benzaldehyde, carbon disulfide, glycerol, ethylene glycol, ethyl acetate, methyl 23

25 Sulfides Sulfuric acid Tellurides acetate, furfurol Acids Lithium, sodium, potassium, chlorates, perchlorates, permanganates Reducing agents 3.3 Containment Care should be taken to ensure that chemicals/reagents/samples/solutions etc. are stored such that the risk of spills is minimized. Primary storage containers should be of a composition such that they are able to maintain their structural integrity, under normal storage and use, throughout the lifespan of the material they are holding. Purchase materials in safety-coated glass bottles if available. These are glass bottles that are covered in a thin plastic coating that is slip and impact resistant. These bottles are designed to contain liquid in the event that the glass is broken. Secondary containment should be used in all storage locations. This is containment in addition to the primary container to prevent release of material to the environment in the event that the primary container fails. Over-packs, spill trays etc. are examples of secondary containment. When transporting liquid chemicals in public areas such as corridors, always use safety bottle carriers that will act as secondary containment if a bottle is broken during transport. These carriers have a convenient handle and cap and make carrying 4 L glass bottles easier and safer. 3.4 Security All hazardous material should be stored in a secure fashion where only authorized personnel have access to the materials. In particular, chemicals classified as poisons should be in locked cupboards where only authorized personnel within a lab have access to the storage location. Supervisors are responsible for ensuring that only those personnel who they have authorized to use the material have access to these chemicals. Poisons include but are not limited to things like cyanides, arsenics and derivatives of these chemicals known to be poisonous. 24

26 4.0 Chemical Spill Prevention, Preparedness and Clean up Prevention of chemical spills is the most important aspect of a chemical spill response program. However laboratory personnel should be aware of spill clean-up procedures and be prepared to respond should a spill occur. 4.1 Training It is the responsibility of the laboratory supervisor to ensure that lab personnel are trained in appropriate chemical spill response specific to the chemicals contained within their laboratory. Training should be documented. Lab personnel are responsible for ensuring that they are aware of the spill clean-up procedures for any chemical(s) prior to their using said chemical(s). 4.2 Spill Kits Each laboratory using hazardous chemical materials shall have easy access to a chemical spill kit that is prominently located, readily visible and identifiable. A spill kit may be shared between laboratories provided that all personnel are aware of its location and it is easily accessible at all times. Exact contents of a spill kit should be based on the hazardous properties of the materials present. Table 5 lists the recommended minimal requirements for spill kits. Table 5 Minimum Requirements for Chemical Spill Kits Item Universal Chemical Absorbent Pads and/or Universal Chemical Absorbent Powder (silica free) Plastic Scoop Large Polyethylene Bags Gloves Characteristics and/or Recommended Quality High absorption capacity Chemically inert Good for all chemicals o Acids, including hydrofluoric acid o Bases o Flammable liquids o Formaldehyde o Organic peroxides Polypropylene Strong composition Leak proof To be used as pail liners Nitrile/Silver shield combination preferred At least 2 pairs 25

27 Chemical Goggles 20 L Plastic Pail with Lid Plastic Dust Pan and Broom Splash resistant At least 2 pairs Labelled as SPILL KIT To contain spill equipment When emptied to be used as disposal container for contaminated absorbents Leak proof Polypropylene bristles Other items you may want to add to your chemical spill kit, depending on the hazards present in the lab are: disposable Tyvek suits; synthetic rubber aprons; duct tape; ph paper; hazardous waste tags; and specific neutralization mixtures. When using acid or base neutralization mixtures, one should be prepared for heat generation and sputtering of the liquid. Table 6 lists examples of specific neutralization mixtures. Table 6 Examples of Neutralization Mixtures Available for Spill Response Neutralizer Type Acid Neutralizers Caustic Neutralizers Examples Sodium bicarbonate Neutrasorb (colour change once neutralized) Spill-X-A Calcium carbonate (for hydrofluoric acid spills) Citric acid powder Neutracit-2 (colour change once 26

28 neutralized) Spill-X-C Solvent Neutralizers (reduce vapours and increase flashpoint) Activated charcoal Solusorb Spill-X-S Spilfyter vapour suppressor kit If mercury or mercury compounds are present in the laboratory (including mercury in thermometers), the lab supervisor must ensure a mercury spill kit is available. Table 7 lists the recommended contents for a mercury spill kit. Table 7 Mercury Spill Kit Contents Item Sulphur powder or commercially available mercury amalgamation powder Mercury vapour suppression spray Mercury decontamination liquid, wipes or sponges Aspirator Disposal container with lid Mercury indicator powder (optional) Characteristics and/or Recommended Quality Effectively amalgamates mercury and suppresses vapours Prevents further mercury vaporization For surface decontamination Could be a Pasteur pipette and bulb Preferably plastic Indicates presence of mercury Good for suspected contamination issues and for use after clean-up It is recommended that an inventory list be included on/in spill kits to allow for easy inspection. Inspections should be performed regularly and documented, e.g. on an inspection tag. Inspections should include verifying contents and ensuring that supplies are unexpired and in good condition. Science Facilities maintains chemical spill containment and clean up supplies in Science Complex rm. 132, DNA Loading Dock A and LHS Loading Dock D. These are additional 27

29 resources which can be used to supplement the in-lab spill kits, but are not a replacement. Mercury spill supplies and are also available at these locations. 4.3 Spill Classification Complex spills Complex spills are those which involve chemicals or quantities of materials in excess of those outlined in Table 8, and require further assistance for clean-up. Table 8 Guidelines for the Classification of a Complex Spill Material Air and water reactive materials Flammable liquids Combustible liquids Non-flammable organic liquids Concentrated acids Concentrated bases and alkalis Mercury Oxidizers Highly toxic, highly malodorous materials (e.g. phenol, mercaptoethanol, hydrofluoric acid) Low hazard material Compressed gas leaks Radioactive materials Quantity Any quantity Greater than 4 L Greater than 4 L Greater than 4 L Liquids greater than 1 L Solids greater than 1 kg Liquids greater than 1 L Solids greater than 1 kg Greater than 30 ml Liquids greater than 1 L Solids greater than 500 g Liquids greater than 1 ml Solids greater than 50 g At the discretion of laboratory personnel If the leak cannot be stopped by closing the valve on the gas cylinder. See Radiation Safety Program for proper procedures for radioactive spill response. The above table provides guidelines for quantities only. Other considerations for classifying a spill as complex include whether or not respiratory protection is required and whether any personal injuries have been sustained. Laboratory personnel should never attempt to clean-up a spill if they have not been trained in the proper chemical spill response or are unsure of the proper procedures. All Complex spills are to be reported to Security, RMO and Science Facilities by calling Campus Security ext Incidental Spills These are minor spills not meeting the requirements of a complex spill that can be responded to by trained laboratory personnel. 4.4 Spill Response 28