Part B
Part B
Part B
Safe work in a laboratory requires you to become aware of the properties and hazards of
chemicals and equipment. This part will help you identify chemical hazards and understand
Safety Data Sheets (SDS). SDS’s are prepared by the chemical manufacturer and are available
online or through request to the University of Wisconsin La Crosse (UWL) Environmental Health
and Safety Office. SDS’s aid in identifying hazards and providing guidance to protect user health
and safety. Later parts of this Guide describe the appropriate control measures to reduce the
hazards of laboratory chemicals.
This Part describes common hazards of chemicals and provides examples of some chemicals
that have the hazard characteristic being described. You should review each Safety Data
Sheet to determine the hazards associated with any chemical you use. The examples
included in this Part are not inclusive. Many chemicals present multiple physical and/or
.health hazards.
Check the flash point of each organic solvent you use. If the flash point of a solvent is
below room temperature, invisible vapor can form and be ignited by a spark, causing a fire
or explosion.
The flammable liquids of most concern in laboratories are those that have flash points below
room temperature or 77o F (25o C). The flash points for some common solvents include:
Xylene, which is often used as a less toxic and safer substitute for benzene, has a flash point of
29o C or 84o F, or just above room temperature. The vapors of flammable chemicals are invisible,
and a vapor trail to an ignition source away from the immediate area can result in a flashback.
Flammables are more hazardous at elevated temperatures due to more rapid vaporization.
REACTIVE CHEMICALS
Reactive chemicals have a propensity to undergo vigorous, sometimes spontaneous, reactions.
Under certain conditions, reactive chemicals may spontaneously generate large quantities of heat,
light, gases, or toxic chemicals. Reactive chemicals include explosives, acid sensitives, oxidizers,
reducers, water sensitives, and pyrophorics.
Oxidizers
Oxidizers are chemicals, which react with other substances and leave them electron deficient.
This reaction may result in fire or explosion. Oxidizers can supply oxygen to a fire. Two
examples are combustion in the presence of air (oxygen in air is an oxidizer) and nitrate salts
spilled on paper or wood.
Water-reactive Chemicals
Water-reactive chemicals react with water, water vapor or moist air to produce a flammable or
toxic gas, or other hazardous condition. A fire or explosion may result. Examples of water-
reactives include the alkali metals (such as lithium, sodium, and potassium), silicon tetrachloride,
acid anhydrides, and acid chlorides.
Pyrophoric Chemicals
Pyrophoric chemicals ignite on contact with air. The flame is sometimes invisible. Examples
of pyrophoric chemicals are boranes, triethylaluminum, alkyl lithiums and, white or yellow
phosphorus.
Peroxide-forming Chemicals
There are many compounds that have "peroxide" in their name. Some are hazardous and some
are relatively safe at ambient pressure and temperature. Some chemicals become peroxides when
exposed to air, when in storage, and during use. The commercially available reagent peroxides
are prepared and contained so that they can be used safely.
Most commercially available peroxide formers have a use before date. Once this date is
reached, the best option is to contact UWL Environmental Health and Safety to request
disposal. Additional inhibitor can be added to extend shelf life, but if doing so check
peroxide levels on a regularly scheduled basis.
The peroxides that form unintentionally are of great concern because of their unpredictability,
explosivity, and often-grave consequences. These occur mainly in liquids but can also form in
solids and even bottled gases.
Explosion Hazard. What all peroxides have in common is the oxygen-to-oxygen bond in
their molecular arrangement. Upon initiation, the molecule can rearrange its structure to bond
oxygen to other atoms (more stable bonds) or produce an oxygen molecule, thus reducing the
excess oxygen balance of the substance. A violent reaction can be initiated easily; mechanical
shock, excessive or rapid heating, or surface to surface friction, such as removing a cap or lid
from a bottle can initiate an explosion.
Peroxide Formation. When a substance takes on oxygen from the atmosphere, there are a
number of different courses that it could take. Many peroxide-formers will rearrange to non-
peroxide oxidized forms and cause no trouble beyond their eventual lack of usefulness.
Examples of these are: benzaldehyde and other aldehydes, amines, mercaptans, sulfides, and
alkyl amides.
Other peroxide-formers will slowly polymerize and eventually become solid plastic.
Examples of these substances include styrene, vinyl acetate, and ethyl acrylate. Since these
chemicals may be packaged in air, peroxides can form even if the container has not been opened.
Most common in peroxide formation is that of soluble (they remain dissolved)
hydroperoxides and ketone peroxides from secondary alcohols, ethers, tertiary carbons (as in
decalin), and allylic and benzylic carbons (as in alkenes and alkyl benzenes). See Part D (Page
19) for a more extensive list of peroxide-forming chemicals and safe storage and use practices.
.
Oxygen-oxygen bonds are inherently unstable.
Heat and sunlight can accelerate the formation of peroxides.
Shock-Sensitive Explosives
Shock-sensitive explosives can spontaneously release large amounts of energy under normal
conditions, or when struck, vibrated, dropped, heated, or otherwise agitated. Some chemicals
become increasingly shock-sensitive with age. Of great concern in the laboratory is the
inadvertent formation of shock-sensitive explosives such as peroxides in solvents.
azides Acetylides
picrates Fulminates
oxalates (especially silver) Cyanates
carbides nitrides
• the following salts of organics and hydrazines, guanidines, etc.: nitrates, perchlorates and
chromates
• lead tetrachloride
• lead and silver chlorite
• mercury tartrate
This list is not inclusive. If you are in doubt as to the reactive or explosive potential of your
chemical procedures, consult an authoritative reference such as Bretherick's Handbook of
Reactive Chemical Hazards. Similar on-line resources are available. Suggested sources include,
but are not limited to the American Chemical Society, Chemical and Engineering News or
through a general web search for reactive chemicals.
Cryogenic Liquids
Cryogenic liquids are hazardous because of the physical and chemical characteristics of their
super-cooled state. Cryogenic liquids can cause fires (e.g., liquid oxygen) or explosions,
embrittlement of structural materials, asphyxiation, and tissue destruction.
You may have difficulty obtaining health hazard information on the chemicals you use. The
American Chemical Society's Chemical Abstracts service lists over ten million known chemicals.
The National Institute of Occupational Safety and Health's (NIOSH's) Registry of Toxic Effects
of Chemical Substances, which is a compendium of all toxicity tests, lists less than 200,000
chemicals. This leaves millions of chemicals that have not been tested for toxicity. Further, most
toxicity tests have been for acute toxicity. Most toxicity information is from animal studies, and
we have learned that species react differently and often unpredictably to various chemicals.
Some information is not directly applicable to humans. Therefore, we have much to learn about
the toxicity of chemicals.
Fortunately, Safety Data Sheets contain safety information for most commonly used
chemicals. Research laboratories, however, more frequently encounter the exotic, rare, and
newly synthesized chemicals for which toxicity data is sparse or non-existent. This emphasizes
the importance of handling all laboratory chemicals with the utmost care. Whenever you handle
laboratory chemicals, minimize your exposure by using fume hoods, personal protective
equipment (e.g., gloves), and applying safety procedures described in Part D of this Guide.
Primary Anesthetics
Primary anesthetics have a depressant effect upon the central nervous system, particularly the
brain. Examples include:
Simple Asphyxiants
Asphyxiants have the ability to deprive tissue of oxygen. Simple asphyxiants are inert gases
that displace oxygen. Examples include:
Chemical Asphyxiants
Chemical asphyxiants have as their specific toxic action the ability to render the body
incapable of utilizing an adequate oxygen supply. They are active at very low concentrations (a
few ppm in air). Examples include carbon monoxide, hydrogen sulfide and cyanides.
nitrites toluidine
benzene aniline
nitrobenzene
Carcinogens
A carcinogen commonly describes any substance that contains an agent that can initiate or
speed the development of malignant or potentially malignant neoplastic proliferations of cells.
Appendix D provides source lists for chemicals that are considered carcinogens.
Corrosives
Corrosives are chemicals that can cause visible destruction of or irreversible alterations in living
tissue by chemical action at the site of contact. Corrosives also can react with metals causing
deterioration of the metal surface. Acids and bases are corrosives. Aqueous solutions of acids
with a pH less than 2, and bases with a pH greater than 12 are especially dangerous, and require
special precautions. Examples include:
Environmental Toxins
Some chemicals have been shown to be very toxic to wildlife, or can otherwise harm
ecosystems, but pose less of a risk to humans. Other factors that contribute to environmental
toxicity are persistency (resistance to degradation) and bioaccumulation as the chemical moves up
the food chain. With some known environmental toxins, the degree of human toxicity is uncertain
or controversial. DDT and polychlorinated biphenyls (PCBs) are examples of chemicals that have
been shown to cause reproductive failure in certain species, but appear to be less hazardous to
humans. Despite these species differences, careful use and disposal of environmental toxins is
warranted.
Hepatotoxic Agents
Hepatotoxic agents cause damage to the liver. Examples include carbon tetrachloride,
nitrosamines, and tetrachloroethylene.
Irritants
Irritants are materials that cause inflammation of mucous membranes. Inflammation of tissue
results from concentrations far below those needed to cause corrosion. Long term exposure to
irritants can result in increased mucous secretions and chronic bronchitis. Examples include:
ammonia hydrogen chloride
halogens (Fl2, Cl2 I2) phosgene
nitrogen dioxide arsenic trichloride
hydrogen fluoride ozone
diethyl/dimethyl sulfate phosphorus chlorides
alkaline dusts (hydroxides)
Irritants can also cause changes in the mechanics of respiration and lung function. Examples
include:
sulfur dioxide formaldehyde
sulfuric acid iodine
acetic acid formic acid
Acrolein
Nephrotoxic Agents
Nephrotoxic agents damage the kidneys. Examples include halogenated hydrocarbons and
uranium compounds.
Neurotoxic Agents
Neurotoxic agents damage the nervous system. The nervous system is especially sensitive to
organometallic compounds and certain sulfide compounds. Examples include:
Teratogens
Teratogenic chemicals (embryotoxic or fetotoxic agents) are those that cause fetal malformation
from maternal exposure during pregnancy. Teratogens are agents that interfere with normal
embryonic and fetal development without damage to the mother. These effects are not hereditary.
Embryotoxins are substances that act during pregnancy to cause adverse effects on the fetus.
These effects include embryolethality (death of the fertilized egg, the embryo, or the fetus) and
teratology (malformation, retarded growth, and postnatal functional deficits). Examples of
embryotoxins include organomercurials, lead compounds, and formamide.
Mutagens
A mutagen affects the genetic material of exposed cells. The effect is hereditary and becomes
part of the genetic pool passed on to future generations. Ethidium bromide is a mutagen
commonly found in biomedical research laboratories.
TOXICOLOGY OVERVIEW
The previous section described the various toxicological properties of chemicals. This section
explains routes of exposure, sites of action, and acute and chronic toxicity. These concepts are
important to understanding toxicity information on Safety Data Sheets (SDS’s) and for assessing
chemical exposure, which is discussed in the next section.
SKN: Applied to the skin, to test for irritation or for systemic toxicity through dermal
absorption.
In many cases, inhalation into the lung is the most critical route of exposure. This is because the
surface area for absorption of the inside lining of the lungs is as large as a football field; it
transfers chemicals directly into the bloodstream, and because of the large volumes of air that we
breathe.
Sites of Action
The effects of chemicals on the body are classified according to their sites of action. For a
chemical to express its intrinsic toxic characteristics, it must come in contact with a target organ.
If the effect is produced at the point of surface contact directly without first being absorbed into
the circulatory system, the lesions produced are considered local effects. Areas commonly
damaged by local effects include the eyes, skin, lung, and intestinal tract surfaces.
If the effects are produced in these tissues because of absorption and dissemination through
the circulatory system, or are produced in tissues or organs away from the site of original contact,
the lesions or effects are considered systemic effects. Chemicals can produce both of these types
of effects.
Acute Toxicity
All chemicals are toxic under some condition of exposure. Therefore, it is necessary to define
these conditions as well as the quantity involved in the exposure in order to compare the toxicity
characteristics of chemicals. Acute toxicity is defined as the toxic effects produced by a single or
multiple exposure to a substance by any route for a short period (e.g., less than one day). Acute
toxicity information is dominated by lethality data, levels of airborne exposure (LC50) or
ingestion dose (LD50) estimated to kill 50 percent of a specific population of animals under
controlled conditions and dose-response (mortality) relationships.
On SDS’s, the degree of acute toxicity is usually expressed by these acronyms for types of
toxicological studies:
LDLo: The lowest dose of a material introduced by any route, other than inhalation, over any
given period in one or more divided portions and reported to have caused death in humans or
animals.
LCLo: The lowest concentration of a material in air, which has been reported to cause death in
humans or animals.
LD50O: Lethal Dose to 50 percent of a population (of lab animals). Amount of dose, in mg/kg of
body weight, to kill one-half of the animals to which it is administered. Widely used as an index
of toxicity. The lower the LD, the more toxic the substance is.
LC50: Lethal Concentration to 50 percent of a population (of lab animals). Refers to an airborne
concentration of a contaminant that will kill one-half of the population of study organisms. Used
as an index of toxicity. The lower the LC50, the more toxic the substance is.
Toxicity Class Dose (amount of Probable Oral Lethal Dose Examples in Rat Oral
substance per kg (for a 70 kg Adult Human) Toxicity LD50 of
of body weight) Class Example
Practically >15 g/kg More than 1 quart Sucrose 29.7 g/kg
Non-toxic
Slightly 5-15 g/kg Between a pint and a quart Ethanol 14 g/kg
Toxic
Moderately 0.5-5 g/kg Between an ounce and a pint Sodium 3 g/kg
Toxic Chloride
Very 50-500 mg/kg Between a teaspoonful and an Caffeine 192 mg/kg
Toxic ounce
Extremely 5-50 mg/kg Between 7 drops and a teaspoon Sodium 6.4 mg/kg
Toxic Cyanide
Super toxic <5 mg/kg A taste (less than 7 drops) Strychnine 2.5 mg/kg
In addition to the above criteria, if any of these three criteria are satisfied for a particular
chemical, then it is considered extremely toxic:
1. A chemical that has a median lethal dose (LD50) of 50 mg or less per kilogram of body weight
when administered orally to rats.
2. A chemical that has a median lethal dose (LD50) of 200 mg or less per kilogram of body
weight when administered by continuous contact for 24 hours (or less if death occurs within 24
hours) with the bare skin of rabbits.
3. A chemical that has a median lethal concentration (LC50) in air of 200 ppm by volume or less
of gas or vapor, or 2 mg per liter or less of mist, fume, or dust, when administered by continuous
inhalation for one hour (or less if death occurs within one hour) to rats.
If any of these three criteria are satisfied for a particular chemical, then it is considered very
toxic:
1. A chemical that has a median lethal dose (LD50) of more than 50 mg per kilogram, but not
more than 500 mg per kilogram of body weight when administered orally to rats.
2. A chemical that has a median lethal dose (LD50) of more than 200 mg per kilogram but not
more than 1,000 mg per kilogram of body weight when administered by continuous contact for 24
hours (or less if death occurs within 24 hours) with the bare skin of rabbits.
3. A chemical that has a median lethal concentration (LC50) in air of more than 200 ppm but not
more than 2,000 ppm by volume or less of gas or vapor, or more than 2 mg per liter but not more
than 20 mg per liter of mist, fume, or dust, when administered by continuous inhalation for one
hour (or less if death occurs within one hour) to rats.
Chronic Toxicity
Latent effects, such as carcinogenicity or mutagenicity, are examples of long term or chronic
effects. The damage done from one large or multiple low-level exposures to a carcinogen are
often latent, that is, the cancer often does not show up until 10 to 20 years later. Likewise, the
effect of exposure to a mutagen will not manifest itself until the birth of offspring with
malformations resulting from the mutation.
Chronic toxicity is the toxic effect resulting from repeated, low-level daily doses over a persons
or animals lifetime. These chronic effects can result from cumulative damage to tissues sustained
from each small dose, or they can result from accumulation of the toxic chemical in the body over
a long period of low-level exposure.
This assertion is the foundation of toxicology. It is very important to find out your degree of
exposure to a toxicant, not merely that a particular chemical is present in the laboratory.
On Safety Data Sheets, you will typically see these acronyms for standards and regulations
governing workplace chemical exposures:
IDLH: Immediately Dangerous to Life or Health: An atmosphere that poses an immediate threat
to life, would cause irreversible adverse health effects, or would impair an individual’s ability to
escape from a dangerous atmosphere.
SKIN: A notation on some of the TLV’s that indicates that the substance may be absorbed by the
skin, mucous membranes and eyes, either by air or direct contact, and that this additional
exposure must be considered part of the total exposure to avoid exceeding the TLV for that
substance.
TLV-STEL: Short-term Exposure Limit: a 15-minute time-weighted average that should not be
exceeded at any time during the workday, even if the 8-hour TWA is within the TLV-TWA.
Limits established to avoid: 1) irritation, 2) chronic or irreversible tissue damage, or 3) narcosis
of sufficient degree to increase the likelihood of accidental injury.
TLV-C: The Ceiling exposure limit; the concentration that should not be exceeded even
instantaneously.
PEL: Permissible Exposure Limit: Similar to a TLV, but established by OSHA as the legal limit
for employee exposure. Employers have the legal responsibility to ensure that their employee's
exposures do not exceed the PELs.
OSHA: Occupational Safety and Health Administration: Federal Government agency, part of the
Department of Labor, charged with ensuring the health and safety of private sector workplaces in
the United States establishes and enforces safety and health regulations.
NIOSH: National Institute for Occupational Safety and Health: Part of the Centers for Disease
Control of the Public Health Service of the U.S. Department of Health and Human Services. It
conducts research and development in Occupational Safety and Health and advises OSHA in
rulemaking and standard setting.
As noted above, the lung is usually the most critical route of entry. Exposures via other routes,
such as ingestion, and skin absorption, must also be taken into account to determine if an
excessive exposure is present.
In some cases, the Environmental Health and Safety (EHS) Office can measure your workplace
air concentrations of chemicals. Contact EHS if you are concerned about your exposure or would
like advice on controlling chemical exposure. Read the guidelines in Part D of this Guide on
controlling chemical hazards in the laboratory.
If you are concerned about effects to your health from exposure to a chemical, see a physician.
Students may receive medical care from the University Health Center. Call EHS for additional
guidance in seeking medical assistance for chemical exposures.
Information on the signs and symptoms of an overexposure can be obtained from a physician,
an SDS, and the American Association of Poison Control Centers (1-800-222-1222).
If you feel that you may have had a harmful exposure, see a physician immediately. For
emergency care, go to a hospital emergency room. If an exposure may be life threatening dial
911 for emergency transport. If the exposure is not life threatening, yet you desire to seek
medical care, contact University Police at 9-9999.
If you are concerned about effects to your health from exposure to a chemical, see a
physician.
REVIEW QUESTIONS
1. A certain chemical is known to cause cancer in humans. This chemical would be called:
a) a carcinogen.
b) toxic.
c) corrosive.
d) nephrotoxic.
e) a and b.
2. A flammable liquid will emit enough vapors to be ignited by a spark source at temperatures:
a) above absolute zero.
b) above its flash point.
c) above its ignition temperature.
d) above its freezing point.
3. What material will burst into flames upon contact with air?
a) explosives.
b) peroxide-former.
c) teratogenic.
d) pyrophoric.
6. A chemical is described as having a local effect. The damage to the body caused by it is:
a) widespread.
b) only where the chemical makes contact with the body.
c) inflicted upon everyone in the immediate vicinity of the chemical.
d) not inflicted on foreigners and tourists.
ANSWERS
1. e) a and b.
2. e) b and c.
3. d) pyrophoric.
4. e) Kidney.
5. b) A pregnant woman.
7. c) more toxic.
9. d) acute toxicity.