WHMIS: What You Need to Know

A publication of the Office of Environmental Health and Safety, University of Toronto printed 1989, reprinted September 1992

TABLE OF CONTENTS
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. Introduction WHMIS Legislation and Exemptions Chemical Hazards Flammable substances Reactive Substances Health Effects of Toxic Substances Exposure Limits Protective Measures Hazard Symbols Labels Material Safety Data Sheet (MSDS) Glossary of Terms

INTRODUCTION
The Workplace Hazardous Materials Information System (WHMIS for short) is a comprehensive national system for safe management of hazardous chemicals which is legislated by both the federal and provincial jurisdictions. WHMIS is a tripartite effort of labour, industry, and government which took several years to develop; it is unique in that it represents a consensus of these three groups.

The WHMIS legislation provides that workers must be informed about the hazards in the workplace and receive appropriate training to enable them to work safely. To accomplish this, WHMIS requires all suppliers (manufacturers, importers, packagers and processors) to label and prepare Material Safety Data Sheets (MSDSs) for products they make, import, package, or process that meet the hazard criteria set out in the Controlled Product Regulations under the federal Hazardous Products Act.. The buyers of these controlled products must make sure that these products are correctly labelled and that MSDSs are available. Employers must set up worker education programs that instruct workers about the contents and significance of labels and MSDSs and how to work safely with hazardous materials.

In summary, WHMIS delivers the necessary information by means of:-

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cautionary labels on containers of controlled products the provision of an MSDS for each controlled product a worker education program

The ultimate goal is to create a safer workplace by providing workers with the knowledge and tools to enable them to work safely.

2. WHMIS Legislation and Exemptions

WHMIS extends through both Federal and Provincial legislative domains:-

1. 2.

Federal legislation - because it involves the sale and import of controlled products (hazardous materials), and Provincial legislation - once a controlled product enters a workplace, jurisdiction over the product shifts from federal to provincial governments (except for workplaces under federal jurisdiction, where the provisions of the amended Canada Labour Code apply).

Federal Legislation
The federal legislation was enacted through the passage of Bill C-70 on June 30, 1987. This Bill accomplishes the following:-

1.

It applies the labelling and other information requirements of WHMIS to suppliers of hazardous materials and establishes criteria for determining which substances are deemed hazardous.

For this purpose the Hazardous Products Act (HPA) [see below] was amended to apply the WHMIS labelling and MSDS provisions to materials which fall into one or more of the clases of hazardous materials listed in Schedule II of the Act. The materials included in these classes are known as "controlled products".

The Controlled Products Regulation (CPR) prescribes:

1. 2. 3.

the detailed scientific criteria for determining whether or not a product falls into one or more of the classes of controlled products, the information which must be disclosed on labels, and MSDSs, and the conditions under which certain controlled prodcuts are exempted from the requirements covering labels and MSDSs.

The Ingredients Disclosure List (IDL) was established, to be used by suppliers when preparing MSDSs; if a substance contains an ingredient appearing on this list in concentrations at or above the level shown for that ingredient, the ingredient must be named on the MSDS together with its percentage concentration in the substance.

2.

It allows manufacturers to protect legitimate confidential business information or "trade secrets", without compromising the information system. The Hazardous Material Information Review Act (HMIRA) is an entirely new law enacted to perform this function.

The regulations made under the HMIRA establish the criteria against which the validity of claims for trade secret protection will be decided.

3.

It applies WHMIS to employers and employees in workplaces under the federal labour jurisdiction by amending Part IV of the Canada Labour Code.

Provincial Legislation
The workplace falls under provincial jurisdiction and is governed by the Occupational Health and Safety Act.

This Act outlines the role of the employer, the supervisor and the employee in the workplace. It places duties on these groups to ensure that the worksite is made a safe and healthy place to work. The Act gives the worker the right to refuse unsafe work, the right to know about hazards on the job and the right to representation on a Joint Health and Safety Committee.

To implement WHMIS in Ontario, the legislature amended the Occupational Health adn Safety Act (OSHA) by means of Bill 79, passed on June 29, 1987.

A WHMIS regulation, Ontario Reg. 644/88 (Oct 31st, 1988), based on the tripartite model regulation, was adopted under the amended OHSA; this regulation sets out the employer duties under WHMIS. Bill 79 (see below) also amended the act to cover hazardous physical agents such as noise, vibration and radiation; so that the supplier and employer provide appropriate information respecting the device which emits hazardous physical agents.

An additional feature of the bill includes the requirement for workplace inventories; the employer is required to develop and maintain an inventory of hazardous materials and hazardous physical agents in the workplace.

Exemptions from WHMIS Legislation

The following products are exempt from the WHMIS legislation:-

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wood or wood products; tobacco or tobacco products; manufactured articles;

roducts being transported if handled in accordance with the requirements of the Transportation of Dangerous Goods Act (Ontario) or the

Transportation of Dangerous Goods Act (Ontario);

hazardous waste.

Exemptions from WHMIS Labelling and Material Safety Data Sheet Requirements
The requirements for Material Safety Data Sheets (see Section 11] and Supplier Labels, Laboratory Supply House Product Labels, and Laboratory Sample Labels (see Section 10) do not apply to the following:-

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explosives within the meaning of the Explosives Act(Canada); cosmetics, devices, drugs or food within the meaning of the Food and Drug Act (Canada); controlled products within the meaning of the Pest Control Products Act (Canada); prescribed substances within the meaning of the Atomic Energy Control Act (Canada); or products, materials or substances packaged as consumer products and in quantities normally used by the consuming public.

Note: Buyers/Users of these products must comply with all labelling requirements prescribed within the above acts and regulations. Employers are still required to educated employees regarding the hazards, safe handling, storage and disposal of such materials.

BILL C - 70
1.

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2.

Hazardous Products Act (HPA) Controlled Products Regulation (CPR) Ingredients Disclosure List (IDL)

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3.

Hazardous Materials Information Review Act (HMIRA) Regulation

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Part IV - Canada Labour Code Regulation

ONTARIO BILL 79
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Physical Hazards Regulation WHMIS Regulation Inventory Regulation

3. CHEMICAL HAZARDS
Chemical hazards may be described under three broad headings - flammability, reactivity and health.

Flammability
Flammable substances are those that readily catch fire and burn in air. A flammable liquid does not itself burn; it is the vapours from the liquid that burn. For a liquid, the flash point, auto-ignition temperature, explosive limits, vapour density and ability to accumulate an electrostatic charge are important factors in determining the degree of fire hazard.

Reactivity
Reactive chemical hazards invariably involve the release of energy (heat) in relatively high quantities or at a rapid rate. If the heat evolved in a reaction is not dissipated, the reaction rate can increase until an explosion results.

Some chemicals decompose rapidly when heated. Light or mechanical shock can also initiate explosive reactions. Some compounds are inherently unstable and can detonate under certain conditions of pressure and temperature, while others react violently with water or when exposed to air.

Health
Contact with many chemicals can result in adverse health effects. The nature and magnitude of toxic effects will depend on many factors including the nature of the substance, route of exposure, magnitude of the dose, duration of exposure, and individual susceptibility.

4. Flammable Substances
Flammable substances are those gases, liquids and solids that will ignite and continue to burn in air if exposed to a source of ignition.

Many flammable and combustible liquids and solids are volatile in nature; that is, they evaporate quickly and are continually giving off vapours. The rate of evaporation varies greatly from one liquid to another and increases with temperature. It is their vapours combined with air, not the liquid or solids themselves, that ignite and burn. In many instances, an increase in temperature creates a more hazardous condition because of the increase in the rate at which vapours are evolved.

Flash Point
This is the lowest temperature of the liquid at which it gives off enough vapour to form an ignitible mixture of vapour and air immediately above the liquid surface.

A liquid is classified as flammable or combustible depending on its flash point. A flammable liquid has a flash point below 37.8 C while a combustible liquid has a flash point greater than 37.8 C.

Example: Flash point of Acetone is - 17.8 C (*closed cup) and that of Aniline is 70.0 C (*closed cup).

The lower the flash point, the greater the potential fire hazard.

Flammable (Explosive) Range

This is the range between the lowest explosive limit (LEL) and the upper explosive limit (UEL).

The LEL is the lowest concentration of vapour in air which will burn or explode upon contact with a source of ignition. Below the LEL, the mixture is too lean (i.e. there is insufficient fuel).

The UEL is the highest concentration of vapour in air which will burn or explode upon contact with a source of ignition. Above the UEL, the mixture is too rich to burn (i.e. there is insufficient oxygen).

The LEL and UEL are usually indicated by the percentage by volume of vapour in air. Example - For diethyl ether, the LEL is 1.9% and the UEL is 36% by volume of air.

This range becomes wider with increasing temperature and in oxygen-rich atmospheres.

For most solvents the LEL lies in the range 1-5% in air and therefore good ventilation is essential in order to minimize the risk of forming a flammable or explosive atmosphere when such substances are used. However, it is significant that the LEL for most substances is considerably greater than the recommended hygiene standards for the concentration of vapour in the workroom air.

Auto-Ignition Temperature
The autoignition temperature of a substance is the minimum temperature required to initiate or cause self-sustained combustion, in the absence of a spark or flame.

Example:

1. 2.

A steam line or a glowing light bulb may ignite carbon disulphide (autoignition temperature is 100 C). Diethyl ether (autoignition temperature is 160 C) can be ignited by the surface of a hot plate.

Vapour Density
The vapour density is the ratio of the density of the gas or vapour to the density of air (vapour density of air = 1). Generally, vapours from flammable liquids are denser than air and thus tend to sink to ground level where they can spread over a large area.

Example:- Vapour density of ethyl alcohol is 1.59.

Sources of Ignition
A source of ignition represents a sufficiently high enough temperature to ignite a fuel. Common sources of ignition include:- open flames, hot surfaces, static electricity, smoking material, cutting and welding operations, radiant heat, frictional heat, electrical and mechanical (frictional) sparks, spontaneous combustion, and heat-producing chemical reactions.

Examples of generation of static electricity:-

1. 2. 3. 4.

A rapidly moving belt develops static electricity by coming in contact with the pulley and then moving away from it. Paper and cloth take on static charges when passing through machines. Paint spraying generates static. Static charges are produced by the flow of flammable liquids into or from tanks or other containers through pipes, hose, or even air, or by pouring from one container to another.

Static electricity accumulations sufficient to cause a spark can, however, be prevented by grounding, bonding, or humidification. The danger of fire and explosion presented by flammable liquids, generally, can be eliminated or minimized by strict observance of safe storing, dispensing, and handling procedures

5. Reactive Substances
Highly reactive chemicals can lead to reactions which involve the release of energy (heat) in relatively high quantities or at a rapid rate. Reaction rates almost always increase rapidly as the temperature increases. If the heat evolved in a reaction is not dissipated, the reaction rate can increase until an explosion results.

Examples of reactive hazards:-

1.

Some chemicals decompose when heated. The heat initiated decomposition of some substances, such as certain peroxides is almost instantaneous. Organic peroxides, are a special class of compounds that have unusual stability problems that make them among the most hazardous substances normally handled in laboratories.

2.

Some substances can detonate as a result of contamination. Mixtures of perchloric acid with a wide variety of materials, such as organic matter, can be highly unstable.

3.

Light and mechanical shock can also be initators of explosive reactions. Hydrogen and chlorine react explosively in the presence of light. Acetylides, ozides, organic nitrates and many peroxides are examples of shock-sensitive materials. Organic peroxides are a class of compounds even more shock sensitive than explosives such as TNT or picric acid.

4.

Other substances may form unstable substances during chemical operations or prolonged storage (eg. certain ethers, alcohols and aldehydes can form peroxides). For this reason bottles of materials prone to peroxidation should not be kept for prolonged periods once they have been opened.

5. 6.

Some chemicals are inherently unstable and can detonate under certain conditions of pressure and temperature (eg. acetylene). There are materials that are highly reactive when exposed to air (eg. finely divided metals:- calcium, metal hydrides:- potassium hydrides).

7.

Other compounds may react violently with water (eg. alkaline earth metals:- potassium, sodium). These compounds should therefore be handled under the surface of a hydrocarbon solvent such as mineral oil or toluene.

8.

Oxygen tanks -

Serious explosions have resulted from contact between oil and high-pressure oxygen. Oil should not be used on connections to an oxygen cylinder.

9.

Hazardous Polymerization:-

Polymerization is the process of forming a polymer by combining large numbers of chemical units or monomers into long chains ( e.g.polyethylene from ethylene or polystyrene from styrene). Uncontrolled polymerization can be extremely hazardous. Some polymerization processes can release considerable heat or can be explosive.

10.

Incompatible chemicals:-

When storing, using or disposing of chemicals, care must be exercised to minimize the consequences of accidental mixing of incompatibles by spillage or breakage. Such contact could result in a serious explosion or the formation of substances that are highly toxic or flammable or both.

Some incompatible groups include:-

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acids and bases flammables and toxics flammables and oxidizers oxidizers and reducers

6. Health Effects of Toxic Chemicals

There are many materials used in the workplace that can be hazardous. However, in order for them to affect your health, they must contact the body or be absorbed into the body. When assessing the potential health effects from working with a particular material it is necessary to understand difference between "toxicity" and "hazard".

1.

TOXICITY is the ability of a substance to produce an unwanted effect when the chemical has reached a sufficient concentration at a certain site in the body.

The more toxic a material is, the smaller the amount of it necessary to be absorbed before harmful effects are caused. The lower the toxicity, the greater the quantity of it necessary to be absorbed. The toxicity of a chemical is generally measured by experiments on animals (quite often rats). If it is measured in terms of the amounts of material necessary to cause death in 50% of the test animals. These values are called LD50 (lethal dose) or

LC50 (lethal concentration), and are usually given in weight of material per kg of body weight or airborne concentration of material per set time period respectively.

2.

HAZARD is the probability that this concentration in the body will occur.

Toxicity is an inherent property of the material. A material may be very toxic, but not hazardous, if it is handled properly and is not absorbed into the body. On the other hand, a material may have a very low toxicity, but be very hazardous.

Example:

1. 2.

An open container of an acid is much more hazardous than a closed container of the same material. Two liquids may possess the same degree of toxicity but present different degrees of hazard:-

One material may be non-irritating to the eyes and nose and odourless. The other may be irritating to the eyes or respiratory system and possess a pungent odour.

The latter material, because of its warning properties presents a lesser degree of hazard.

In order for toxicants to affect the human system either they must cause damage to external tissues, such as the skin or eyes, or they must be able to enter the body by some mechanism.

Routes of Entry
There are three primary routes of entry into the body: ingestion, skin or eye absorption, and inhalation.

Ingestion:- This means taking a material into the body by mouth (swallowing). Ingestion of toxic materials may occur as a result of eating in a contaminated work area.

Absorption- Substances that contact the eye and the skin may be either absorbed into the body or cause local effects. For the majority of organic compounds, the contribution from skin absorption to the total exposure should not be neglected.

Inhalation- This means taking a material into the body by breathing it in. In the lungs, very tiny blood vessels are in constant contact with the air we breath in. As a result, airborne contaminants can be easily absorbed through this tissue. In the occupational environment, this is generally the most important route of entry.

Health Effects - Chronic vs Acute

Once a toxic substance has contacted the body it may have either acute (immediate) or chronic (long term) effects.

Example: Spilling acid on your hand will cause immediate harm, i.e. a burn to the skin.

Exposure to asbestos or tobacco smoke may result in lung cancer after as much as twenty years (this is a long term effect).

Exposure - Chronic vs Acute

Exposure can be classified as chronic or acute. In chronic exposures, the dose is delivered at some frequency (daily or weekly usually) over a period of time. In acute exposures, the dose is delivered in a single event and absorption is rapid. Usually, a chronic exposure occurs at low concentration and acute exposure at high concentration.

Some materials may only cause harm if given acutely, not having any effect in the long term. Other materials may not exhibit an effect in the short term, but may cause problems after prolonged exposure.

Physiological Classification of Materials

This classification identifies toxic materials on the basis of biologic action.

Irritants - refers to some sort of aggravation of whatever tissue the material comes in contact with. e.g. ammonia, nitrogen dioxide.

Asphyxiants - exert their effects through a depletion of oxygen to the tissues e.g. - simple asphyxiants - carbon dioxide, nitrogen, methane, hydrogen chemical asphyxiants - carbon monoxide, hydrogen cyanide, hydrogen sulphide.

Narcotics or Anaesthetics - the main toxic action is the depressant effect upon the Central Nervous System. e.g. - many organics, chloroform, xylene.

Systemic Poisons - the main toxic action includes the production of internal damage e.g. Hepatotoxic agents - toxic effects produce liver damage. eg. carbon tetrachloride.

e.g. Nephrotoxic agents - toxic effects produce kidney damage eg. some halogenated hydrocarbons

Carcinogens - agents/compounds that will induce cancer in humans. e.g. benzene, arsenic, inorganic salts of chromium, nickel, beryllium.

Mutagens - agents that affect the cells of the exposed people in such a way that it may cause cancer in the exposed individiual or an undesirable mutation to occur in some later generation. e.g. radiation, variety of chemical agents that alter the genetic message.

Teratogens - Agents or compounds that a pregnant woman takes into her body that generate defects in the fetus e.g. Thalidomide, possibly steroids

Sensitizers-Agents that may cause allergic or allergic-like responses to occur. After an initial exposure to a substance an individual may become sensitized to that substance. Subsequent exposures to the same substance, often at a much lower concentration than before, produce an allergic response. This response may be a skin rash (dermatitis) or an asthmatic-like attack, depending on the route of exposure. e.g. cutting oils, isocyanates in polyurethane foam operations and paint spraying operations, some laboratory solvents.

7. Exposure Limits
Exposure limits are established concentrations which, if not exceeded, will not generally cause adverse effects to the worker exposed. However, because of wide variation in individual susceptibility, a small percentage of workers may experience discomfort from some substances at concentrations at or below the established limit; a smaller percentage may be affected more seriously by aggravation of a pre-existing condition.

Exposure levels are intended for use as guidelines or recommendations in the control of potential health hazards and are not fine lines between safe and unsafe exposures, nor are they a relative index of toxicity.

The limits are based on industrial experience, and human and animal experimental evidence.

Exposure levels for many hazardous chemicals are included in the Regulation respecting the Control of Exposure to Biological or Chemical Agents - made under the Occupational Health & Safety Act of Ontario (O.Reg. 654/86). These are expressed as follows:-

TWAEV - Time-Weighted Average Exposure Value: The average airborne concentration of a biological or chemical agent to which a worker may be exposed in a work day or a work week.

STEV - Short Term Exposure Value: The maximum airborne concentration of a chemical or biological agent to which a worker may be exposed in any 15 minute period, provided the TWAEV is not exceeded.

CEV - Ceiling Exposure Value: The maximum airborne concentration of a biological or chemical agent to which a worker may be exposed at any time.

SKIN - This notation indicates that direct or airborne contact with the product may result in significant absorption of the product through the skin mucous membranes or eyes. Inclusion of this notation is intended to suggest that preventative action be taken against absorption of the agent through these routes of entry.

Except in certain circumstances these levels must be achieved without workers being required to wear and use personal protective equipment.

Note: The exposure limits listed on the MSDS may differ from the Ontario legal exposure limit.

Other notable occupational exposure limits that one may encounter on a Material Data Sheet (MSDS) are:-

1. 2.

Permissible Exposure Levels (PELs) of the USA Occupational Safety and Health Administration (OSHA). Threshold Limit Values (TLVs) of the American Conference of Governmental Industrial Hygienists (ACGIH).

See "Glossary of Terms" for definitions.

8. PROTECTIVE MEASURES
As previously indicated, exposure to toxic chemicals can seriously affect health. However, if appropriate precautions are taken, these chemicals can be handled safely. There are a variety of methods which provide protection from such exposures. The design of the workplace, the work practices and hygiene practices followed and the protective equipment worn, may all be essential in controlling exposure to toxic substances. The protective measures which must be considered, include:-

1. Elimination/Substitution
Ideally, the toxic substance used or generated should be eliminated. Since this is not always possible, substituting a less hazardous substance can often be effective in reducing work exposure to toxic substances.

eg. Is it necessary to use benzene for cleaning; usually, 1,1,1-trichloroethane will do the job just as well.

2. Engineering Controls
a. Isolation Hazardous processes or equipment can be segregated into separate rooms or areas or put in enclosures so as not to contaminate the whole workplace.

eg. Operator booths are common in crusher operations (extremely dusty environments), crane cabs in hazardous areas, etc.

b. Design or Change of Process Often simple considerations can significantly improve conditions.

eg. packaging of exact amounts of material to add to a process rather than pouring, pumping, scooping, etc. from a bulk supply

eg. grouping of hazardous operations for better control.

c. Local Suppression

Wetting or pelletizing of dusty materials or blanketing of toxic liquids.

eg. Use of damp mopping in contaminated, dusty areas

eg. Use of plastic balls or surface active agents in liquid tanks such as plating tanks.

d. Ventilation Ventilation is used to control airborne hazards in the form of dusts, fibres, mists, fumes, gases, and vapours. The two methods of applying ventilation to provide contaminant control are:- general dilution ventilation and local exhaust.

Dilution Ventilation - dilution of contaminated air with uncontaminated air in a general area, room, or building for the purpose of health hazard, nuisance control, and/or heating and cooling.

Local exhaust - involves the capture of pollutants at the source.

Air movement is achieved by either natural or mechanical methods such as fans, and the choice or type of ventilation depends on such factors as:

1. 2. 3. 4.

Toxicity or nuisance of the contaminant Method and rate of generation Physical state of the contaminant Relative costs of different types of ventilation.

3. Work Practices and Hygiene Practices

Work practices, procedures and hygiene practices supplement engineering controls. These practices represent on the job activities that reduce the potential for exposure to toxic substances and include:-

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Posting warning signs and labelling hazardous materials Preventive maintenance of equipment. Keeping records of employee exposure and making them available to employees Providing emergency facilities, such as eyewash fountains and deluge showers, where appropriate Prohibiting eating, drinking or smoking in areas where materials in use are toxic by ingestion or may be inhaled through smoking. Maintaining good housekeeping - good housekeeping provides for the removal of hazardous materials that might otherwise become airborne. In addition, a clean workplace tends to foster good work habits that probably reduce accumulations.

Maintaining personal Cleanliness - clean work clothes, regular showers and frequent washing will reduce skin contamination that may lead to skin absorption, dermatitis or ingestion. A further consideration for personel cleanliness is the possibility of an individual carrying toxic material home on work clothes or on the person and in turn placing the family at risk.

Training - Individuals should be well aware of the hazards of the materials being used and the precautions to be observed. An informed worker can make a rational decision to accept such work and to wisely use the equipment provided for his protection.

4. Personal Protective Devices

These include protective glasses and goggles, face shields, protective clothing (laboratory coats and gloves), skin creams, and respirators. It should be noted that respirators in particular, are not intended to be used as a primary means of control in lieu of other methods.

Two essential elements of protective equipment use are:-

1.

The choice of the proper type.

For example, when choosing respirators and hearing protectors, the factors to be considered include:-

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2.

type of hazard extent of exposure individual preference individual fit ease of supervision legislative requirements

The provision of an adequate maintenance program for the equipment.

A maintenance program for the equipment must be in the care of a qualified person and will include, at regular intervals:-

a) Inspection and Repair - All parts should be checked to be certain that materials have not deteriorated, valves are working, etc. As necessary, equipment must be replaced or repaired. With respirators, new filters or cartridges must be made available to workers at all times. With self contained breathing apparatus cylinders must recharged and all mechanisms checked.

b) Cleaning - Equipment must be cleaned, sterilized and dried after each use. While it is preferable for workers to have their own personal equipment, because of cost and other considerations, particularly with self-contained air supplied units sharing may be necessary. In such cases cleaning and sterilizing becomes very important.

c) Storage - Equipment should be stored in clean, dry locations protected against extremes of temperature, humidity and sunlight.

5. Other Safe Practices and Emergency Provisions

a) Leak and Chemical Spill Procedure

Prompt action is necessary to reduce and eliminate hazards created by a chemical spill.

1.

Wear proper personal protective equipment (e.g. gloves, respirators) as specified in the MSDS. 2. 3. 4. 5. 6. Absorb or neutralize liquids. Sweep solids into a container. Ventilate area to dispel vapours if required. Wash affected area with soap and water or detergent. All materials used in cleanup, including absorbed liquids are to be disposed as hazardous waste. Label waste appropriately.

If proper equipment is not available to safely contain and decontaminate a spill - evacuate the area and contact the appropriate personnel.

Section 4.3 of the University of Toronto Health and Safety Policy Manual details chemical spill procedures. Also, consult the pertinent MSDS.

b) Waste Disposal

The disposal of hazardous chemicals is regulated by Ontario environmental legislation. Generators of hazardous wastes are responsible for properly packaging and labelling such wastes.

Section 4.2 of the University of Toronto Health and Safety Policy Manual details chemical waste disposal procedures. Also, consult the pertinent MSDS.

c) Storage Requirements

The hazard potential presented by flammable, reactive and toxic substances can also be reduced by adherence to safe storage procedures.

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Quantities of these substances should be kept to a minimum. All containers must be labelled with the names of the contents and appropriate hazard warnings In laboratories or stockrooms, care should be taken to avoid exposure of chemicals to heat or direct sunlight. Always observe precautions regarding the proximity of incompatible substances (e.g. do not store alphabetically - store in compatible groups).

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Highly toxic chemicals should be stored in ventilated storage areas in unbreakable chemically resistant secondary containers. Properly labelled portable safety cans should be used for handling small quantities of flammable liquids. When not in use these portable cans should be kept in enclosed fire-resistant cabinets. Larger quantities of solvents should be stored in correctly designed ventilated stores.

Flammable liquids should not be stored in laboratory refridgerators unless the unit is an approved, explosion-proof, or laboratory-safe type.

9. Hazard Symbols
The WHMIS system groups hazardous materials into six classes or categories based on the type of hazard which they represent. These materials are also called controlled products. Each category has its own hazard symbol and it is important that the worker be able to recognize these.

A - COMPRESSED GAS

A compressed gas is a material which is a gas at normal room temperature (20 C) and pressure but is packaged as a pressured gas, dissolved gas or gas liquified by compression or refrigeration.

The hazard from these materials, aside from their chemical nature, arises from sudden loss of integrity of the container. A compressed gas cylinder is usually quite heavy and when ruptured can become a projectile with the potential to cause significant damage.

Acetylene and oxygen are examples of compressed gases.

B - FLAMMABLE AND COMBUSTIBLE MATERIAL

Flammable or combustible materials will ignite and continue to burn if exposed to a flame or source of ignition.

Materials are classified as a flammable gas, flammable aerosol, flammable liquid, combustible liquid, flammable solid, or reactive flammable material. Methane, acetone, aniline, and lithium hydride are examples of flammable materials.

C - OXIDIZING MATERIAL

An oxidizing material may or may not burn itself, but will release oxygen or another oxidizing substance, and thereby causes or contributes to the combustion of another material.

Ozone, chlorine, and nitrogen dioxide are oxidizing materials. These chemicals wil support a fire and are highly reactive.

D - POISONOUS AND INFECTIOUS MATERIAL

D1- Materials Causing Immediate and Serious Toxic Effects

These materials may be classified as toxic or very toxic based on information such as LD50 or LC50. Examples: Styrene, hydrogen cyanide are very toxic substances.

D2 - Materials Causing Other Toxic Effects

A pure substance or mixture that may be any one of the following: a carcinogen, teratogen, reproductive toxin, respiratory tract sensitizer, irritant or chronic toxic hazard. Examples: Asbestos causes cancer, ammonia is an irritant.

D3 - Biohazardous Infectious Material

This classification includes any organisms and the toxins produced by these organisms that have been shown to cause disease or are believed to cause disease in either humans or animals. For example, a blood sample containing the Hepatitis B virus is a biohazardous infectious material. It may cause hepatitis in persons exposed to it.

E - CORROSIVE MATERIAL

Corrosive materials can attack (corrode) metals or cause permanent damage to human tissues such as the skin and eyes on contact. Burning, scarring, and blindness may result from skin or eye contact.

Corrosive materials may also cause metal containers or structural materials to become weak and eventually to leak or collapse.

Ammonia, fluorine, and hydrochloric acid are examples of corrosive substances.

F - DANGEROUSLY REACTIVE MATERIAL

Dangerously reactive materials may undergo vigorous polymerization, decomposition or condensation. They may react violently under conditions of shock or an increase in pressure or temperature. They may also react vigorously with water to release a toxic gas.

Ozone, hydrazine, and benzoyl peroxide are examples of dangerously reactive materials.

10. Labels
Labelling of controlled products is a basic requirement of the WHMIS system. Labelling requirements differ depending on whether the containers are supplier or workplace containers; whether the containers contain laboratory products, laboratory samples for analysis or non-laboratory products; and the size of the containers. The various labelling criteria are outlined below.

1. Supplier Labels
Suppliers must affix a label to containers of controlled products they supply. This label contains very detailed information on the product. Legislation requires that the labels on containers from suppliers holding 10 kg or more of a controlled product, or containing hazardous materials that do not fall into one of the categories on the following pages, display the following:

1. 2. 3.

Both official languages A distinctive WHMIS border Material identifier or product name - this is a designation or identification of a material, including any of the following: - the common name, chemical name, trade name, generic name, brand name, code name or code number.

4. 5. 6.

Supplier's name and address Reference to a material safety data sheet WHMIS hazard symbols and where the container holds 100 millilitres or more of a controlled product the label must also include:-

7. 8. 9.

Risk phrases - these must be appropriate to the class of material. Examples are given below. Precautionary measures - these are precautions to be taken when using or being exposed to the product. Examples are given below. First aid measure - these are statements that indicate the immediate first aid measures that can be taken by the victim or other persons. These statements relate only to acute hazards and not to chronic hazards.

2. Workplace Labels 2A Workplace Labels - General

These are required for chemicals used in the workplace (other than in the laboratory) that are not in their original supplier-labelled containers. This label does not need as much information as the supplier label. The following things are necessary:

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material identifier or product name reference to a material safety data sheet precautionary measures first aid measures

2B Workplace Decanted Products

Decanted products are materials that have been taken from one container and put in another container for short term use. This new container does not need a label if:

y y y y y

the container is portable and has been filled from a container to which a supplier or workplace label has been affixed; AND the material is under the control of and is used exclusively by the employee who filled the protable container; AND the container is used only during the shift in which the container was filled; AND the contents of the portable container are clearly identified; OR if all of the product is for immediate use.

e.g. workplace lables ae required on portable flammable storage cans whose contents will not be used up in a short time period.

3 Laboratory Labels 3A Laboratory Supply House Container

For products containers originating from a laboratory supply house, that are intended to be used solely in a laboratory and are of a capacity of less than 10 kg, the labels must include: -

y y y y y

product identifier reference to MSDS risk phrases precautionary measures first aid measures

3B Laboratory Container
Products intended solely for use, analysis, testing or evaluation in a laboratory that are in containers other than the ones received from the supplier. The products are not to be removed from the laboratory. The labels must include: -

product identifier

3C Samples for Analysis

i) Laboratory samples that are produced solely for evaluation, analysis, or testing within a laboratory and remain under the control of the researcher producing the chemical. The products are not removed from the laboratory. The labels must include: -

product identifier

(ii) Products that are supplied solely for analysis, testing or evaluation in a laboratory. The requirements apply to containers holding less than 10 kg. The lables must include:-

y y y y y

product identifier chemical or generic name of any hazardous ingredient supplier name supplier emergency telephone number the statement:" Hazardous Laboratory Sample. For hazard information or in an emergency, call [emergency telephone number]".

"Laboratory Sample" means a sample of a controlled product that is intended solely to be tested in a laboratory but does not included a controlled product that is to be used

y y

by the laboratory for testing other products, materials or substances, or for educational or demonstration pruposes.

Examples of Risk Phrases Flammable and Combustible Material

In use, may form explosive vapour-air mixture May form flammable dust-air mixture Contact with water liberates flammable gas Spontaneously flammable in air

Oxidizing Material
Risk of explosion by shock, friction, fire or other sources of ignition Contact with combustible material may cause fire Explosive when mixed with commbustible material

Poisonous and Infectious Material

Very Toxic Material Danger of very serious irreversible effects Rapidly absorbed through the skin May cause delayed lung injury May cause death

Toxic Material Eye irritant Lung irritant Skin irritant Danger of irreversible effects Lung sensitizer Skin sensitizer Danger of cumulative effects May cause cancer May cause heritable genetic damage May cause birth defects Danger of serious damage to health by prolonged exposure

Corrosive Material
Causes burn Liquid or vapour causes burns which may be delayed

Dangerously Reactive Material

Risk of explosion by shock, friction, fire or other sources of ignition Risk of explosion if heated under confinement

Special Risks
Explosive when dry Forms very sensitive explosive metallic compounds Heating may cause an explosion May cause fire Reacts violently with water Explosive with or without contact with air Explosive when mixed with oxidizing substances May form explosive peroxides Contact with acids liberates toxic gas Can become highly flammable in use Risk of serious damage to the eyes

Examples of Precautionary Statements

Keep in cool place Keep contents under... Keep container tightly closed Keep container dry Keep container in well-ventilated place Do no keep the container sealed Keep away from... Keep away from heat Keep away from sources of ignition - No smoking Handle and open container with care When using do not smoke Do not breathe dust Do not breathe gas/fume/vapour/spray Avoid contact with skin Avoid contact with eyes Do not empty into drains Never add water to this product

Take precautionary measures against static discharges Avoid shock and friction Wear suitable protective clothing Wear suitable gloves In case of insufficient ventilation, wear suitable respiratory protection Wear eye/face protection Avoid prolonged or repeated contact with the skin In case of fire use... If you feel ill, seek medical advice This gas deadens the sense of smell. Do not depend on odour to detect the presence of gas.

11. The Material Safety Data Sheets (MSDSs)

The material safety data sheet or "MSDS" is an important source of information for the worker at the worksite. It is one of the three basic elements of the WHMIS right-to-know-system.

The MSDS includes the following: relevant technical information on the substance; a list of its hazardous ingredients, (if it's a mixture); chemical hazard data, control measures such as proper engineering controls and personal protective equipment; instructions in accident prevention while using the substance, specific handling, storage and disposal procedures; and emergency procedures to follow in the event of an accident.

The information provided is expected to be comprehensive and must include what can reasonably be expected to be known about the material and the hazards it may present. MSDS's from different companies may not look the same but they should contain the same basic information.

The following pages include the various sections of a MSDS for acetone as well as explanantion of the corresponding relevant technical information. The order in which sections appear on a MSDS may vary from one supplier to another, but the content of each section is specified by the legislation.

Each section of a MSDS must be filled in, even if it only states: "not determined" or "not applicable".

y y y y y

Section 1 - Material Indentification Section 2 - Hazardous Ingredients Section 3 - Physical Data Section 4 - Fire and Explosion Data Section 5 - Reactivity Data

y y y y y y

Section 6 - Health Hazard Data Section 7 - First Aid Measures Section 8 - Preventative Measures Section 9 - Storage and Handling Section 10 - Spill Clean-up and Waste Disposal Preparation Date

GLOSSARY OF TERMS
Acute Exposure - a short-term exposure usually occurring at high concentration.

Acute Health Effect - an effect that develops either immediately or a short time after exposure.

Autoignition Temperature - the minimum temperature required to initiate or cause self-sustained combustion, in the absence of a spark or flame.

Biohazardous Infectious Material - a material that contains organisms and the toxins produced by these organisms that have been shown to cause disease or are believed to cause disease in either humans or animals.

Boiling Point - the temperature at which a liquid changes from a liquids to a gas, at normal atmospheric pressure.

Carcinogens - agents/compounds that may induce cancer in humans.

CAS Registry Number - a number assigned to a material by the Chemical Abstracts Service (CAS) to provide a single unique identifier.

Chemical Formula - sometimes called the molecular formula, indicates the elements that make up a chemical.

Chemical Name - a proper scientific name for the active ingredient of a product.

Chronic Exposure - a long-term exposure, usually occurring at low concentrations.

Chronic Health Effects - an effect that appears a long time after exposure.

Coefficient of Oil/Water Distribution - the ratio of the solubility of the chemical in an oil to its solubility in water.

Combustible Liquid - a liquid which has a flash point above 37.8 C.

Compressed Gas - a material which is a gas at normal room temperature (20 C) and pressure but is packaged as a pressurized gas, dissolved gas or gas liquified by compression or refrigeration.

Condensation - the process of reducing from one form to another denser form such as steam to water.

Controlled Products - Under the Controlled Products Regulation, a controlled product is defined as a material, product or substance which is imported or sold in Canada and meets the criteria for one or more of the following classes: -

y y y y y y

Class A - Compressed Gas Class B - Flammable and Combustible Material Class C - Oxidizing Material Class D - Poisonous and Infectious Material Class E - Corrosive Material Class F - Dangerously Reactive Material

Corrosive Material - a material that can attack (corrode) metals or cause permanent damage to human tissues such as skin and eyes on contact.

Cryogenics - materials which exist at extremely low temperatures, such as liquid nitrogen.

Dangerously Reactive Materials - materials that may undergo vigorous condensation, decomposition or polymerization. They may react violently under conditions of shock or increase in pressure or temperature. They may also react vigorously with water or water vapour to release a toxic gas.

Decomposition - the breakdown of a substance, often due to heat, decay or other effect, with the release of other compounds such as vapours or gases that may be flammable or toxic.

Density - the weight of a material in a given volume. It is usually given in grams per millilitre (g/ml).

Dilution Ventilation - dilution of contaminated air with uncontaminated air in a general area, room or building for the purposes of health hazard or nuisance control, and/or for heating and cooling.

Dose - amount of the agent that has entered the body through the various routes of entry.

Evaporation Rate - the rate at which a liquid changes to vapour at normal room temperature.

Explosive (Flammable) Limits - the lower explosive (flammable) limit (LEL) is the lowest concentration of vapour in air which will burn or explode upon contact with a source of ignition. The upper explosive (flammable) limit (UEL) is the highest concentration of vapour in air which will burn or explode upon contact with a source of ignition.

Explosive (Flammable) Range - the range between the lower explosive limit (LEL) and the upper explosive limit (UEL).

Exposure Limits- established concentrations which, if not exceeded, will not generally cause adverse effects to the worker exposed. Exposure limits differ in name and meaning depending on origin. For example:-

1.

The exposure levels for the hazardous chemicals that are included in the Regulation respecting the Control of Exposure to Biological or Chemical Agents - made under the Occupational Health and Safety Act of Ontario, are expressed as follow: -

TWAEV Time-Weighted Average Exposure Value: The average airborne concentration of a biological or chemical agent to which a worker may be exposed in a work day or a work week.

STEV Short Term Exposure Value: - The maximum airborne concentration of a chemical or biological agent to which a worker may be exposed in any 15 minute period, provided the TWAEV is not exceeded.

CEV Ceiling Exposure Value: The maximum airborne concentration of a biological or chemical agent to which a worker may be exposed at any time.

SKIN: This notation indicates that direct or airborne contact with the product may result in significant absorption of the product through the skin, mucous membranes or eyes. Inclusion of this notation is intended to suggest that preventative action be taken against absorption of the agent through these routes of entry.

2.

Threshold Limit Values (TLVs) are exposure guidelines developed by the American Conference of Governmental Industrial Hygienists (ACGIH). They have been adopted by several Canadian governments and others as their legal limits. They are expressed as follows:-

TLV-TWA Threshold Limit Value - Time-Weighted Average: The time-weighted average concentration for a normal 8 hour work day and a 40 hour work week, to which nearly all workers may be repeatedly exposed, day after day, without adverse effect.

TLV-STEL Threshold Limit Value - Short Term Exposure Limit: a 15 minute time-weighted average exposure which should not be exceeded at any time during a work day even if the 8 hr TWA is within the TLV. Exposures at the STEL should not be repeated more than 4 times a day and there should be at least 60 minutes between successive exposures at the STEL.

TLV-C Threshold Limit Value - Ceiling: the concentration that should not be exceeded during any part of the working exposure.

Other exposure limits include the Permissible Exposure Limits (PEL) which are legal exposure limits in the United States.

Flammable Limits - "See Explosive Limits".

Flammable Substance - one that will readily catch fire and continue to burn in air if exposed to a source of ignition.

1. 2. 3.

Flammable Aerosol- a material that is packaged in an aerosol container which can release a flammable material. Flammable Gas- a gas which can readily catch fire and continue to burn. Flammable Liquid - a material that gives off a vapour which can readily catch fire and continue to burn. A flammable liquid has a flashpoint below 37.8 C.

4.

Flammable Solid- a material which can readily catch fire and continue to burn vigorously and persistently. This may occur from friction, absorbing moisture, from spontaneous chemical change, or by retaining heat from manufacturing or processing.

5.

Reactive Flammable Material- a material which is a dangerous fire risk because it can react readily with air or water.

Flashback - this occurs when a trail of flammable material is ignited by a distant source of ignition. The flame then travels back along the trail of gas, vapour or aerosol to its source.

Flashpoint - the lowest temperature of a liquid at which it gives off enough vapour to form an ignitable mixture of vapour and air immediately above the liquid surface.

Freezing Point - the temperature at which a liquid becomes a solid, at normal atmospheric pressure.

Hazard- the potential for harmful effects.

Hazardous Combustion Products - chemicals which may be formed when a material burns. These chemicals may be flammable, toxic or have other hazards.

Hazardous Decomposition Products - formed when a material decomposes (breaks down) because it is unstable, or reacts with materials such as water or oxygen in air.

Hazardous Ingredient - Under the Hazardous Products Act, a chemical must be listed in the Hazardous Ingredients section of a MSDS if:-

y y y y

it meets the criteria for a controlled product; it is on the Ingredient Disclosure List; there is no toxicological information available; or the supplier has reason to believe it might be hazardous.

Hazardous Polymerization - Polymerization is a process of forming a polymer by combining large numbers of chemical units or monomers into long chains (polyethylene from ethylene or polystyrene from styrene). Uncontrolled polymerization can be extremely hazardous. Some polymerization processes can release considerable heat or can be explosive.

Ingestion - means taking a material into the body by mouth (swallowing).

Inhalation - means taking a material into the body by breathing it in.

Irritant - some sort of aggravation of whatever tissue the material comes in contact with.

LC50 - the concentration of a material in air which causes death in 50% of a group of test animals. The material is inhaled over a set period of time, usually 4 hrs. LC stands for lethal concentration.

LD50 - the weight of material which causes the death in 50% of a group of test animals. It is usually expressed in weight of material per weight of test animal. LD stands for lethal dose.

LEL (Lower Explosive Limit) - See "Explosive Limits".

Local Exhaust Ventilation - involves the capture of pollutants at the source.

Material Causing Immediate and Serious Toxic Effects - classified under "Poisonous and Infectious Material" as toxic or very toxic based on information such as the LD50 or LC50.

Material Causing Other Toxic Effects - classified under "Poisonous and Infectious Material" as a material causing toxic effects such as skin or respiratory sensitization, carcinogenicity, mutagenicity, etc.

Melting Point - the temperature at which a solid material becomes a liquid.

Mutagen - an agent that affects the genes or cells of the exposed people in such a way that it may cause cancer in the exposed individual or an undesirable mutation to occur in some later generation.

NA Number - See "UN number".

Odour Threshold - the airborne concentration, usually in part per million, at which an odour becomes noticeable.

Oxidizing Material - gives up oxygen easily or can readily oxidize other materials.

Permissible Exposure Limits (PEL) - legal limits in the U.S.A. set by the Occupational Safety and Health Administration (OSHA).

pH - a measure of the acidity or basicity (alkalinity) of a material when dissolved in water.

Polymer - a natural or man-made material formed by combining units, called monomers, into long chains.

Polymerization - a process of forming a polymer by combining large numbers of chemical units or monomers into long chains.

Parts Per Million (ppm) - represents the concentration of gases or vapour in air. For example, 1 ppm of a gas means that 1 unit of the gas is present for every 1 million units of air.

Sensitization - the development, over time, of an allergic reaction to a chemical.

Solubility - the ability of a material to dissolve in water or another liquid.

Solvent - a material which is capable of dissolving another chemical.

Specific Gravity - the density of a liquid compared to the density of an equal amount of water.

Stability - the ability of a material to remain unchanged in the presence of heat, moisture or air.

Teratogen - agents or compounds that a pregnant woman takes into her body that generate defects in the fetus.

TLV - See "exposure Limits".

Toxicity - ability of a substance to cause harmful effects.

Trade Name - the name under which a product is commercially known.

TWA - See "Exposure Limits".

UEL (Upper Explosive Limits) - See "Explosive Limits".

UN Number - a four digit number assigned to a potentially hazardous material or class of materials. UN (United Nations) numbers are internationally recognized and are used by fire fighter and other emergency response personnel for identification of materials during transportation emergencies. NA (North American) numbers are assigned by Transport Canada and the US Department of Transport to materials they consider hazardous and to which a UN number has not been assigned.

Vapour - a gaseous form of a material which is normally solid or liquid at room temperature and pressure.

Vapour Density - the density of a vapour compared to the density of an equal amount of air.

Vapour Pressure - the pressure of a vapour in equilibrium with its liquid or solid form.

Ventilation - the movement of air.

Volatility - the ability of a material to evaporate.