Hazardous Chemicals

Chemicals pose health and safety hazards to personnel due to innate chemical, physical, and toxicological properties. Chemicals can be

grouped into several different hazard classes. The hazard class will determine how similar materials should be stored and handled and

what special equipment and procedures are needed to use them safely. Each chemical container, whether supplied by a vendor or

produced in the laboratory, must include labels that clearly identify the hazards associated with that chemical. More detailed hazard

information for specific chemicals can be found by referencing the SDS for that chemical.

There are numerous posting and labeling methodologies including the National Fire Prevention Association (NFPA) building and/or door

placarding that provides an overview of the key chemical hazards contained within that building or room. NFPA postings have the

familiar four color 1-4 number rating, which quickly supplies the hazard information broken down into four hazard classes, with 1

indicating a low level of hazard and 4 indicating a high hazard level. The four chemical hazard types correspond to the four color areas:

red indicates a flammability hazard, yellow indicates a reactive hazard, blue indicates a health hazard and the white area is reserved

for special hazards that are identified by hazard symbols or labels to indicate hazards such as radioactivity, biohazard, water reactive

chemicals, etc. Each of these hazards has a different set of safety precautions associated with them.

1. Flammability and Combustibility Hazards

A number of highly flammable substances are in frequent use in campus laboratories. Flammable

liquids include those chemicals that have a flashpoint of less than 100 degrees Fahrenheit (°F), and combustible liquids have a

flashpoint between 100-200 °F. These materials must be stored in flammable storage cabinets if aggregate quantities of 10

gallons/room or more are stored in the lab. Guidance on proper flammable liquid storage is provided in a FireNet from UC Davis Fire
Prevention. Flame-resistant laboratory coats must be worn when working with large volumes of flammable materials (>1L) and/or with

procedures where a significant fire

risk is present (e.g., when working with open flame, etc.). These materials pose a significant risk and should be treated with care, even

though use of these materials is fairly common in the laboratory setting. Particular attention should be given to preventing static

electricity and sparks when handling flammable liquids.

It is the vapors from flammable liquids that burn, rather than the liquids themselves. For a fire to occur, there must be: 1) vapor

concentration between the lower and upper flammability limits; 2) source of oxygen (often air); and 3) an ignition source. Careful

handling and use of chemical fume hoods are typically sufficient to prevent high vapor concentrations. Do not use open flames where

flammable vapors may be present. Ensure that containers are properly bonded and grounded before transferring flammable liquids

between metal containers or equipment.

2. Reactivity and Stability Hazards

Reactive and unstable substances are materials which may decompose, condense, vigorously

polymerize, or become self-reactive under conditions of shock, temperature, pressure, light, or contact with other materials, with the

release of large volumes of gas or heat. Examples of such chemicals include explosives, pyrophorics, peroxides, and water-reactive

chemicals. These substances pose an immediate hazard and procedures for their use and storage must be carefully reviewed and

followed. Such materials must also be stored in a manner to protect from light, heat, shock, friction, static discharge, contact with a

catalyst, or other conditions to which they are sensitive. Some materials, such as peroxide formers, may not be explosive, but may form

explosive substances over time.

Pyrophoric chemicals are a special classification of reactive materials that spontaneously ignite when in contact with air and require

laboratory-specific training. Flame-resistant (FR) laboratory coats must always be worn when working with pyrophoric chemicals.

Individuals working with pyrophoric materials must know the appropriate method(s) to quench the chemicals being used. Additional

information related to pyrophoric and water-reactive materials is provided in SafetyNet #135 – Procedures for Safe Use of

Pyrophoric/Water Reactive Reagents. Helpful safety videos on reactive and pyrophoric chemicals are available from the Dow Chemical

Company, and for organolithium chemicals from Yale University.

3. Oxidizers
 Oxidizers present a fire and explosion hazard when they come in contact with flammable or

combustible materials. They can: 1) speed the development of a fire and increase intensity, 2) cause substances which are normally

stable in air to rapidly burn, and 3) lead to spontaneous combustion of materials without an obvious ignition source. Oxidizers are

classified on a scale of 1-4 by the NFPA based on their potential to initiate spontaneous combustion. In addition to the flammability

hazards posed by oxidizers, they can also be corrosive or toxic.

4. Health Hazards

Cal/OSHA uses the following definition for health hazard in 8 CCR §5191:

“A chemical that is classified as posing one of the following hazardous effects: Acute toxicity (any

route of exposure); skin corrosion or irritation; serious eye damage or eye irritation; respiratory or skin sensitization; germ cell

mutagenicity; carcinogenicity; reproductive toxicity, specific target organ toxicity (single or repeated exposure); aspiration hazard.”

Criteria by which a specific chemical is classified as a health hazard can be found in 8 CCR §5194, including the definition of a “simple

asphyxiant.” An overview of the major classes of “hazardous” and “particularly hazardous substances” and their related health and

safety risks are detailed below.

a. Corrosive Substances
 As a health hazard, corrosive substances cause destruction of, or alterations in, living tissue by

chemical action at the site of contact.

Major classes of corrosive substances include:

 Strong acids – e.g., sulfuric, nitric, hydrochloric and hydrofluoric acids;

 Strong bases – e.g., sodium hydroxide, potassium hydroxide and ammonium hydroxide;

 Dehydrating agents – e.g., sulfuric acid, sodium hydroxide, phosphorus pentoxide and calcium oxide; and

 Oxidizing agents – e.g., hydrogen peroxide, chlorine, bromine, perchloric acid, and nitric acid.

Symptoms of exposure for inhalation include a burning sensation, coughing, wheezing, laryngitis, shortness of breath, nausea, and

vomiting. For eyes, symptoms include pain, blood shot eyes, tearing, and blurring of vision. For skin, symptoms may include reddening,

pain, inflammation, bleeding, blistering and burns. As a physical hazard, corrosive substances may corrode materials they come in

contact with and may be highly reactive with other substances.

It is important to review information: 1). regarding the materials they may corrode, 2) their reactivity with other substances, and 3) on

health effects. In most cases, these materials should be segregated from other chemicals and require secondary containment during

storage.

b. Irritants

Irritants are non-corrosive chemicals that cause reversible inflammatory effects on living tissue by

chemical action at the site of contact. A wide variety of organic and inorganic compounds, including many chemicals that are in a

powder or crystalline form, are irritants. Consequently, eye and skin contact with all laboratory chemicals should always be avoided.

Smoke is a common example of an irritant which can irritate the nasal passages and respiratory system. Symptoms of exposure can

include reddening or discomfort of the skin and irritation to respiratory systems.

A sensitizer (allergen) is a substance that causes exposed people to develop an allergic reaction in

normal tissue after repeated exposure to the substance. Examples of sensitizers include diazomethane, chromium, nickel,

formaldehyde, isocyanates, arylhydrazines, benzylic and allylic halides, many phenol derivatives, and latex proteins. Sensitizer exposure

can lead to all of the symptoms associated with allergic reactions, or can exacerbate an individual’s existing allergies.

d. Hazardous Substances with Toxic Effects on Specific Organs

Substances included in this category include:

 Hepatotoxins –substances that produce liver damage, such as nitrosamines and carbon tetrachloride;

 Nephrotoxins –agents causing damage to the kidneys, such as certain halogenated hydrocarbons;

 Neurotoxins – substances which produce their primary toxic effects on the nervous system, such as mercury, acrylamide

and carbon disulfide;

 Agents which act on the hematopoietic system – e.g., carbon monoxide and cyanides which decrease hemoglobin

function and deprive the body tissues of oxygen; and

 Agents which damage lung tissue – e.g., asbestos and silica.

Personnel working with these materials should review the SDS for the specific chemical being used, and take special

note of the symptoms of exposure.

e. Particularly Hazardous Substances

others. To differentiate this risk characteristic, OSHA identifies two categories of hazardous chemicals:

1. Hazardous chemicals; and

2. Particularly hazardous substances.

Substances that pose such significant threats to human health are classified as "particularly hazardous substances". The Cal/OSHA

“Laboratory Standard” (8 CCR §5191) requires that special provisions be documented in laboratory SOPs to prevent the exposure of

laboratory personnel to PHSs, including:

1. Establishment of designated areas;

2. Use of containment devices (e.g., fume hoods, glove boxes);

3. Procedures for contaminated waste disposal; and

4. Decontamination procedures.

Particularly hazardous substances are divided into three primary types.

1. AcuteToxins

Substances that have a high degree of acute toxicity are interpreted by OSHA as being substances that "may be fatal or cause damage to

target organs as the result of a single exposure or exposures of short duration.” These chemicals, associated chemical waste, and

storage containers must be handled with care to prevent cross contamination of work areas and unexpected contact. These chemicals

must be labeled as “Toxic.” Empty containers of these substances must be packaged and disposed of as hazardous waste without rinsing

trace amounts into the sanitary sewer system. Many of these compounds can also be classified as corrosives, irritants, sensitizers, toxic

gases, Select Agent Toxins, or specific-organ toxins.

2. ReproductiveToxins

Reproductive toxins include any chemical that may affect the reproductive capabilities, including chromosomal damage (mutations),

effects on fetuses (teratogenesis), and adverse effects on sexual function and fertility. Reproductive toxins can affect the reproductive

health of both men and women if proper procedures and controls are not used. For women, exposure to reproductive toxins during

pregnancy can cause adverse effects on the fetus; these effects include embryo lethality (death of the fertilized egg, embryo or fetus),

malformations (teratogenic effects), and postnatal functional defects. For men, exposure can lead to sterility.
Examples of embryo toxins include thalidomide and certain antibiotics such as tetracycline. Women of childbearing potential should

note that embryo toxins have the greatest impact during the first trimester of pregnancy. Because a woman often does not know that

she is pregnant during this period of high susceptibility, special caution is advised when working with all chemicals, especially those

rapidly absorbed through the skin (e.g., formamide). Pregnant women and women intending to become pregnant should consult with

their laboratory supervisor, personal physician, and EH&S before working with substances that are suspected to be reproductive

toxins. SafetyNet #108 – Pregnancy and Reproductive Hazards in the Workplace: Chemical and Radiological Hazards provides additional

information on this subject.

3. Carcinogens

Carcinogens are chemical or physical agents capable of causing cancer or tumor damage after repeated or long-duration exposure, and

their effects may only become evident after a long latency period. Chronic toxins are particularly insidious because they may have no

immediately apparent harmful effects.

Comprehensive UC Davis requirements related to carcinogens is provided in the UC Davis Chemical Carcinogens Manual. Please consult

this manual for detailed information. SafetyNet #139 – Guidelines for Handling Formaldehyde and SafetyNet #140 - Guidelines for

Handling Dichloromethane (Methylene Chloride) provide information specific to formaldehyde and dichloromethane respectively.

Contact EH&S for additional information on carcinogens and campus requirements.

f. Nanomaterials

The increasing use of nanomaterials in research laboratories warrants consideration of the hazards they may pose. As is the case with

many new technologies, the health effects of nanomaterials have not been thoroughly investigated. Consequently, the uncertainty

surrounding the toxicity of nanomaterials merits a cautious approach when working with them.

Nanomaterials include any materials or-9particles that have an external dimension in the nanoscale (~1 – 100 nanometers, 10 meter).

Nanomaterials occur naturally in the environment, are products of incomplete combustion, and are produced via chemical synthesis.

Synthesized nanomaterials are referred to as Engineered Nanomaterials (ENMs). Materials whose properties do not differ significantly

between their nanoscale and larger forms are generally excluded from ENMs. Some examples of ENMs include fullerenes (carbon buckey-

balls), carbon nanotubes, carbon nanofibers, quantum dots, and metal oxide nanoparticles.

Nanomaterials can be categorized by the risk of potential exposure they pose to personnel based on the physical state of the materials

and the conditions in which they are used. In general, the risk of exposure is lowest when nanomaterials are bound in a solid matrix with

little potential to create airborne dust or when in a non-volatile liquid suspension. The risk of exposure increases when nanomaterials

are used as fine powders or are suspended in volatile solvents or gases. The parent compound of the nanomaterial should also be taken

into consideration when evaluating the potential hazards associated with exposure (e.g., a highly toxic compound such as cadmium

should be anticipated to be at least as toxic and possibly more toxic when used as a nanomaterial). Laboratory personnel using or

preparing nanomaterials must utilize a combination of engineering controls, SOPs, and personal protective equipment to minimize

potential exposure to their self and others.

The UC Davis Chemical and Laboratory Safety Committee has adopted the detailed guidance related to nanomaterials from the

California Nanosafety Consortium of Higher Education’s “Nanotoolkit: Working Safely with Engineered Nanomaterials in Academic
Research Settings” and the National Institute of Occupational Safety & Health’s (NIOSH) “Safe Practices for Working with Engineered

Nanomaterials in Research Laboratories”. A useful video on nanoparticle safety is available from the Dow Chemical Company. Given the

uncertainty of the health and environmental hazards posed by nanomaterials, SOPs are required for the preparation, use, storage, and

disposal of nanomaterials. All nanomaterials, including solutions containing nanomaterials, are to be disposed as hazardous

waste. SafetyNet #132 - Nanotechnology: Guideliness for Safe Research Practices has been prepared to provide additional guidance on

these materials. Contact [email protected] for additional information if needed.

g. Compressed Gases & Cryogenic Liquids

Compressed gases and cryogenic liquids present pressure and asphyxiation hazards in the workplace. Both compressed gases and

cryogenic liquids may also present additional health hazard and/or flammability concerns. Given these hazards, special handling and

storage requirements must be followed to mitigate the associated risks. More detailed information on compressed gases can be found

in SafetyNet #60 - Compressed Gas Safety, while additional information on cryogenic liquids is contained in SafetyNet #58 - Safety

Precautions for Cryogenic Liquids.