Chapter 45

CHEMICAL HYGIENE AND SAFETY PLAN

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45.10 Appendices

Appendix A. Regulations

Appendix B. Chemical Toxicology Overview

Appendix C. Carcinogens

Appendix D. Reproductive Toxins

Appendix E. Odor Threshold Table for Chemicals

Appendix A. Regulations

The purpose of LBNL’s Chemical Hygiene and Safety Plan is to establish procedures to protect employees from the hazards of the chemicals in their work area. This is also a legal requirement mandated by several Federal Occupational Safety and Health Administration standards, including The Hazard Communication Standard, The Exposure to Hazardous Materials in Laboratories Standard, and the OSHA PPE Standard. These are discussed in greater detail below.

Hazard Communication Standard (29 CFR 1910.1200)

The OSHA Hazard Communication Standard (HCS) is intended to reduce the incidence of chemically related occupational illnesses and injuries. The Standard establishes the minimum requirements that employers must adhere to for communicating hazards to workers. This standard is often referred to as the “worker right-to-know” standard.

The scope of the HCS applies more directly to shop, trade, and craft personnel (i.e., Facilities).

For a more in-depth explanation of the HCS in plain English, please click here.

Exposure to Hazardous Materials in Laboratories Standard (Lab Standard) (29 CFR 1910.1450)

Laboratory workers are protected by a related but different OSHA regulation, “Occupational Exposures to Hazardous Chemicals in Laboratories.”

The “Lab Standard” relies on the technical judgment of line management to inform all people who work in their laboratories of the steps to protect themselves from hazardous exposures to chemicals in the laboratory and what to do if an exposure should occur.

Employers must develop and implement a “Chemical Hygiene Plan.” This plan is a description of the facilities, rules, procedures and policies of the Laboratory that are directed at minimizing employee exposures to hazardous chemicals during normal operations and during unplanned events such as chemical spills. Additional information on chemical hygiene and prudent laboratory practices may be found in 29 CFR 1910.1450 Appendix A.

Material Safety Data Sheets (MSDSs)

Click here to go to the MSDSs

An MSDS is a technical bulletin detailing information about a hazardous chemical. Every chemical manufacturer or importer must develop or obtain an MSDS for each hazardous chemical it supplies (29 CFR 1910.1200(g)). Distributors also must provide MSDSs to other distributors and commercial purchasers of their hazardous chemicals. As an employer, LBNL must provide MSDSs for each hazardous chemical in the workplace. The OSHA Laboratory Standard (see section on Laboratories) incorporates the Hazard Communication Standard’s laboratory requirements regarding retention of labels and MSDSs. These provisions require that MSDSs for hazardous chemicals received with incoming shipments be maintained and made readily accessible to employees, and that labels not be removed or defaced unless immediately replaced with other appropriate ones. The Lab has developed an electronic MSDS database for employees to access.

The federal Standard is designed so that the MSDS is the most comprehensive source of written information for the employee. No standard format for the MSDS is specified but all required information must be included. The MSDS must be written in English and, at a minimum, must contain the following:

When an MSDS is prepared, the chemical has to be evaluated based on the mandatory hazards determination requirements. When uncertainty exists concerning a chemical’s hazards, the preparer should be conservative in the evaluation to ensure employee protection.

How to Read an MSDS

When reading an MSDS, please keep in mind that:

The purpose of the MSDS is to provide vital information on health and physical hazards. This part of the program will illustrate and describe each section of the MSDS to help you understand the data. You can use this information to plan training programs and to explain the MSDS to your employees. Some of the terms on the MSDS are quite technical; refer to the Glossary of Terms (Appendix 13) for help.

The MSDS must include, at a minimum, all eight of the described sections. The style and layout may vary. However, every section must be filled in, even if the item is not applicable (indicated by “N/A”). There should be no blank spaces. Note that some of the information, such as the chemical family, may be included but is not required. Remember that the information on the MSDS is prepared by the manufacturer of the product. Therefore, some data sheets contain excellent information, some are adequate, and others are poor. Other sources of data on toxic and health effects should be consulted for more complete information.

Product Identity

Identity: The name of the product as it appears on the label. A product may be a mixture of two or more chemicals.

Manufacturer’s name, address, and phone number: Self- explanatory. If the data comes from a source other than the manufacturer, the actual source must be indicated. The date of preparation or revision must be indicated.

Emergency telephone number(s):  24-hour number(s) that the manufacturer provides, so that emergency information can be obtained (e.g., medical emergencies).

Chemical family: The general class of compounds to which the hazardous substance or mixture belongs (e.g., ethers, acids, ketones, solvents). This term does not give you the exact content of the product.

Formula: The chemical formula may be given for single elements and compounds (e.g., sulfur dioxide (SO2), formaldehyde (HCHO)). This is not the formulation for mixtures.

Hazardous Ingredients

If the product is a mixture, all hazardous ingredients must be listed. However, ingredients that are not hazardous, or make up less than 1% of the product (less than 0.1% for carcinogens), do not have to be reported.

Exposure standards, i.e., Threshold Limit Value (TLV) and Permissible Exposure Limit (PEL) are included in this section, or under Health Hazards. Note that the higher the number for a TLV or PEL, the less hazardous the substance. See the Glossary for definitions of TLV and PEL.

The % column is intended to show the approximate percentage by weight or volume of each hazardous ingredient compared to the total weight or volume of the product. Normally, percentages will be listed to the nearest 5%. When the substance constitutes less than 5% of the product, this is indicated.

CAS number: The Chemical Abstract Service registry number identifies specific chemicals only, not mixtures; it is optional.

Physical Data

This section contains very important data to help predict the behavior of the material in experimental situations. The information provided is for the material as a whole, rather than for each hazardous ingredient. Vapor pressure, vapor density, % volatiles, and evaporation rate all basically tell you the same thing: whether breathing the vapors will be a problem, thus indicating the need for proper ventilation.

Boiling point: The temperature at which a liquid changes to a vapor at a given pressure; usually in degrees Fahrenheit (oF) at the sea-level pressure of 760 millimeters of mercury (mm of Hg). For mixtures, the initial boiling point or the boiling range may be given. A low boiling point may be a special fire hazard.

Vapor pressure: Refers to the pressure exerted by a saturated vapor above its own liquid, usually stated in mm of Hg at 25oC (77oF). The lower the boiling point, the higher the vapor pressure. A high vapor pressure indicates easy evaporation.

Vapor density: Tells whether the material is heavier or lighter than air. This is useful information to indicate a confined-space hazard. If heavier than air, the material will concentrate in low places, such as floors, elevator shafts, sewers, or the bottom of tanks.

Percentage volatility by volume: How much of the material evaporates at room temperature. A substance that is 100% volatile will evaporate completely, leaving no residues.

Evaporation rate: The rate at which the material will evaporate when compared to the rate of evaporation of a known material, usually butyl acetate. If another material is used for comparison, it should be indicated. If the number is greater than 1, the product evaporates more easily than the comparison material.

Solubility in water: The percentage of a material (by weight) that will dissolve in distilled water, at room temperature.

Specific gravity: The ratio of the weight of a volume of material to the weight of an equal volume of water. For insoluble materials, a specific gravity of less than one means the material is lighter than water and will float. Greater than one means that it sinks in water.

Melting point: The temperature at which a solid becomes a liquid under normal room conditions.

Appearance and odor: A brief description of the material at normal room temperature and atmospheric conditions. Do not rely on odor to alert you to a dangerous exposure. Some substances can reach hazardous levels and have no noticeable odor.

Fire and Explosion Hazard Data

This section should clearly indicate whether the material is flammable. If it is flammable, make sure there are no ignition sources nearby and that you have the correct fire extinguisher on hand. If you work with solvents, peroxides, explosives, metal dusts, or other unstable substances, this section is very important.

Flash point: The lowest temperature at which the material gives off enough vapor to ignite; this will help determine storage and handling procedures. The method used to obtain this information should be stated (e.g., closed cup).

Flammable or explosive limits: The range over which a flammable vapor, when mixed with the proper proportions of air, will flash or explode if ignited. The range is designated by lower explosive limit (LEL) and upper explosive limit (UEL), and is expressed in percentage of volume of vapor in the air.

Extinguishing media: Indicates what type of fire extinguisher to use, such as water, fog, foam, alcohol foam, carbon dioxide, or dry chemical.

Special firefighting procedures:  Special handling procedures, personal protective equipment, and unsuitable firefighting substances should be listed. For example, water should not be used on fires involving reactive metals. General firefighting methods are not described.

Unusual fire and explosive hazards: Hazards that might occur as a result of overheating or burning of the material, including any chemical reactions or change in chemical form or composition.

Reactivity Data

This section indicates how unstable the substance is and lists conditions to avoid in order to prevent dangerous reactions. This information will help you handle and store the material properly.

Stability: The checked box will indicate whether the material is stable or unstable and under what conditions instability occurs.

Incompatibility: Lists materials and conditions to avoid. Such conditions may include extreme temperatures, jarring, or inappropriate storage. This is important to determining what other chemicals the material can be stored or used with.

Hazardous decomposition products:  A list of the hazardous materials that may be produced if the material is exposed to burning, oxidation, heating, or certain chemical reactions. The product shelf life should be included, when applicable.

Hazardous polymerization: Polymerization is a chemical reaction in which two or more molecules of a substance combine to form repeating structural units of the original molecule. A hazardous polymerization causes an uncontrolled release of energy (heat). If this reaction can occur, it must be indicated.

Health Hazard Data

This section lists routes of entry (inhalation, skin absorption, ingestion), and gives signs and symptoms of overexposure, such as skin rash, tremors or dizziness. Short-term (acute) and long-term (chronic) health hazards, such as the ability to cause cancer (carcinogenicity), birth defects (teratogenicity), or “target organ” damage, should be listed. Some products cause both types of effects. Unfortunately, this important section often lacks adequate information, especially on the health effects of long-term exposure.

Instructions for first aid and emergency procedures for victims of acute inhalation, ingestion, or skin or eye contact must be included. Medical conditions that can be aggravated by exposure must also be detailed.

Information on exposure standards, such as TLV, PEL, or STEL, and toxicity data (indicated by an LD50 number), may be included here. Toxicity data is only an estimate of the degree of toxicity, based on experiments with test animals.

Precautions for Handling

This information will help you prepare for emergencies by having the proper materials and equipment on hand. This section lists methods, special equipment, and precautions necessary to control and clean up spills, leaks, and other releases. For example, if respirators are required to clean up a spill, that fact should be shown.

Acceptable waste-disposal methods, as well as prohibited methods, are described. The user will also be alerted to any potential environmental danger to the general population, crops, water supplies, etc.

Instructions for safe handling and storage, such as the warning not to store acids and bases together, may be given. Any additional special precautions not addressed elsewhere in the MSDS should also be listed here. These may include instructions for storage life or transportation, such as special packaging or temperature control.

Control Measures

This section is essential for protecting employees from overexposure. It lists personal protective equipment, such as proper gloves, safety glasses, or respirators, ventilation necessary to work safely with the material, and work/ hygienic practices. Types and descriptions of necessary equipment should be specified (e.g., organic vapor cartridge, neoprene gloves). If the material has a low TLV, indicating a dangerous health hazard, local ventilation is recommended, not general or dilution ventilation. Remember, engineering controls, such as the right kind of ventilation, are always preferable to relying on respirators.

Manufacturers may withhold certain information (such as specific chemical identities and/or amounts of its components) as proprietary on a Material Safety Data Sheet if the information is considered a trade secret. The Chemical Hygiene Officer has a legal right to obtain this information from the manufacturer to evaluate the potential health risk if potential overexposure or adverse health effects are suspected.

Appendix B. Chemical Toxicology Overview

Definitions

Toxicology is the study of the nature and action of poisons.

Toxicity is the ability of a chemical substance or compound to produce injury once it reaches a susceptible site in, or on, the body.

A material’s hazard potential is the probability that injury will occur after consideration of the conditions under which the substance is used.

Dose-Response Relationships

The potential toxicity (harmful action) inherent in a substance is exhibited only when that substance comes in contact with a living biological system. The potential toxic effect increases as the exposure increases. All chemicals will exhibit a toxic effect given a large enough dose. The toxic potency of a chemical is thus ultimately defined by the dose (the amount) of the chemical that will produce a specific response in a specific biological system.

Routes of Entry into the Body

There are four main routes by which hazardous chemicals enter the body:

Most exposure standards, such as the Threshold Limit Values (TLVs) and Permissible Exposure Limits (PELs), are based on the inhalation route of exposure. These limits are normally expressed in terms of either parts per million (ppm) or milligrams per cubic meter (mg/m3) concentration in air. If a significant route of exposure for a substance is through skin contact, the MSDS, PEL and/or TLV will have a “skin” notation. Examples of substances where skin-absorption may be a significant factor include: pesticides, carbon disulfide, carbon tetrachloride, dioxane, methanol, acetonitrile, mercury, thallium compounds, xylene, and hydrogen cyanide.

Types of Effects

Examples: carbon monoxide or cyanide poisoning.

Examples: strong acids or alkalis.

Examples: arsenic affects the blood, nervous system, liver, kidneys and skin; benzene affects bone marrow.

 Example: heavy metals.

Example:  exposure to alcohol and chlorinated solvents; or smoking and asbestos.

Other Factors Affecting Toxicity

Physical Classifications

A gas is a substance that is in the gaseous state at room temperature and pressure.

A vapor is the gaseous phase of a material that is ordinarily a solid or a liquid at room temperature and pressure.

When considering the toxicity of gases and vapors, the solubility of the substance is a key factor. Highly soluble materials, like ammonia, irritate the upper respiratory tract. On the other hand, relatively insoluble materials, like nitrogen dioxide, penetrate deep into the lung. Fat-soluble materials, like pesticides, tend to be retained longer in the body and have a cumulative effect.

An aerosol is composed of solid or liquid particles of microscopic size dispersed in a gaseous medium.

The toxic potential of an aerosol is only partially described by its airborne concentration. For a proper assessment of the toxic hazard, the size of the aerosol’s particles must be determined. A particle's size will determine whether a particle is deposited within the respiratory system and the location of deposition. Particles above 10 micrometers tend to be deposited in the nose and other areas of the upper respiratory tract. Below 10 micrometers, particles enter and are deposited in the lung. Very small particles (<0.2 micrometers) are generally not deposited but exhaled.

Physiological Classifications of Chemicals 

Chemicals and hazardous materials can be classified according to the effect they have on individuals.

Irritants

Irritants are materials that cause inflammation of mucous membranes with which they come in contact. Inflammation of tissue results from exposure to concentrations far below those needed to cause corrosion. 

Examples include:

Irritants can also cause changes in the mechanics of respiration and lung function.

Examples include:

Long-term exposure to irritants can result in increased mucous secretions and chronic bronchitis.

A primary irritant exerts no systemic toxic action, either because the products formed on the tissue of the respiratory tract are nontoxic or because the irritant action is far in excess of any systemic toxic action.

Example: hydrogen chloride.

A secondary irritant’s effect on mucous membranes is overshadowed by a systemic effect resulting from absorption.

Examples include:

Simple Asphyxiants

Simple asphyxiants are gases that displace oxygen.

Examples include:

Chemical Asphyxiants

Chemical asphyxiants reduce the body’s ability to absorb, transport, or utilize inhaled oxygen. They are often active at very low concentrations (a few ppm).

Examples include:

·         Carbon monoxide

·         Cyanides

·         Hydrogen sulfide

Primary Anesthetics 

Primary anesthetics have a depressant effect upon the central nervous system, particularly the brain.

Examples include:

Hepatotoxic Agents

Hepatotoxic agents cause damage to the liver.

Examples include:

Nephrotoxic Agents

Nephrotoxic agents damage the kidneys.

Examples include:

Neurotoxic Agents

Neurotoxic agents damage the nervous system. 

The nervous system is especially sensitive to organometallic compounds and certain sulfide compounds.

Examples include:

Hematopoietic System Toxins

Some toxic agents act on the blood or hematopoietic system. The blood cells can be affected directly or the bone marrow (which produces the blood cells) can be damaged.

Examples include:

Pulmonary Toxins

There are toxic agents that produce damage of the pulmonary tissue (lungs) but not by immediate irritant action. Fibrotic changes can be caused by free silica and asbestos. Other dusts can cause a restrictive disease called pneumoconiosis.

Examples include:

Carcinogens

A carcinogen is an agent that can initiate or increase the proliferation of malignant neoplastic cells or the development of malignant or potentially malignant tumors. 

Known human carcinogens include:

Reproductive Toxins (Mutagens and Teratogens)

A mutagen interferes with the proper replication of genetic material (chromosome strands) in exposed cells. If germ cells are involved, the effect may be inherited and become part of the genetic pool passed onto succeeding generations.

A teratogen (embryotoxic or fetotoxic agent) is an agent that interferes with normal embryonic development without causing a lethal effect to the fetus or damage to the mother. Effects are not inherited.

Examples include:

Sensitizers

A sensitizer is a chemical that can cause an allergic reaction in normal tissue after repeated exposure to the chemical. The reaction may be as mild as a rash (allergic dermatitis) or as serious as anaphylactic shock.

Examples include:

Appendix C. Carcinogens

Carcinogens

Carcinogens are agents that cause neoplasms (tumors) in humans and/or animals. Below are links to the OSHA Carcinogen Web Site and several lists of carcinogens from various sources. These include lists from the National Toxicology Program (NTP) and the International Agency for Research on Cancer (IARC):

Links

 

Appendix D. Reproductive Toxins

Reproductive toxins are chemicals that can damage the reproductive systems of both men and women. Exposure to these agents before conception can produce a wide range of adverse effects including reduced fertility, unsuccessful, an abnormal fetus, reduced libido, or menstrual dysfunction. Maternal exposure after conception may cause perinatal death, low birth weight, birth defects, developmental and/or behavioral disabilities, and cancer.

The following table is a list of reproductive toxins. It is not an exhaustive list, so other sources of information such as MSDSs should be consulted. This list was derived from the State of California Safe Drinking Water and Toxic Enforcement Act(Proposition 65) list of chemicals known to the state to cause reproductive toxicity and from a list of reproductive toxins developed by Brookhaven National Laboratory

Appendix E. Odor Threshold Table for Chemicals

This is a respiratory protection guide from 3M Corporation that contains a table of odor thresholds. These start on page 15 of the enclosed PDF document. An odor threshold is the lowest airborne concentration that can be detected by a population of individuals. While odor thresholds can serve as useful warning properties, they must be used cautiously because olfactory perception varies among individuals. Moreover, as the table indicates, some odor threshold concentrations are above their respective Occupational Exposure Limits. For assistance in interpreting these data, contact your Division's Industrial Hygiene representative.

 

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