-------
Death or serious injury may be prevented by removing
the exposed person from the exposure area and by providing mouth-
to-mouth resuscitation. If there is an antidote for the chemical
exposure, it should be available if there has been adequate
preparation.
Once a person exposed to a toxic gas or vapor has been
removed from the exposure, it is safe to administer mouth-to-
mouth resuscitation. There will be very little gas or vapor in
the respiratory system of the exposed person and what there is
will be exhaled gradually (in dilute concentrations) only after
the rescuer has forced air into the victim and taken his mouth
away from the victim's mouth.
Inhalation of a few breaths of concentrated toxic gases
or vapors of some chemicals is likely to be followed by almost
instantaneous collapse and cessation of breathing (examples are
hydrogen sulfide and hydrogen cyanide). However, even if
breathing stops because of such an exposure, the heart will
usually continue beating for some time. Therefore, immediate
mouth-to-mouth resuscitation and emergency medical treatment are
very effective in preventing death.
If a person exposed to a toxic gas or vapor is not
breathing, give mouth-to-mouth resuscitation (or some other form
of artificial respiration) until normal breathing resumes or
until a resuscitator is available. (If a toxic liquid has been
splashed in the victim's face, wash it off quickly before you
begin mouth to-mouth resuscitation.)
Continuing emergency treatment of a person exposed to a
toxic gas or vapor should include treatment for shock and keeping
the exposed person as quiet as possible. Do not give the exposed
person any alcoholic beverage.
6. Emergency Treatment for Chemical Contact by Splashes
Chemicals in contact with the eyes and skin can cause
serious or life threatening emergencies that must be treated
quickly. One drop of corrosive chemical in an eye can cause
permanent blindness, and splashes of corrosive chemicals on the
skin can cause permanent tissue destruction. Some chemicals
splashed on a large portion of the body can cause death if they
are not washed off quickly.
Washing splashed chemicals from the eyes and body is
the most important emergency treatment. It takes precedence over
seeking medical assistance.
4 - 31
-------
If chemicals cone in contact with the eyes or body,
flush the chemicals off quickly and as thoroughly as possible.
Use copious amounts of potable water and wash for at least 15
minutes. Splashes of hot, concentrated or corrosive chemicals
will usually require washing for a longer period, up to several
hours. In case of chemical splashes in the eyes or on more than
a small area of the skin, emergency treatment by flushing with
water should always be followed by medical examination. Hake
sure that the medical facility knows as much as possible about
the chemicals splashed or contacted, particularly if the chemical
may have been absorbed so that further diagnosis and treatment
are needed. (There have been deaths as the result of material
absorbed from massive splashes with chromates and nitrates.)
a. Emergency Treatment For Chemical Splashes In The
Eyes
The most important emergency measure, if chemicals
are splashed in the eyes, is immediate washing of the eyes with
large quantities of potable water. To wash the eyes and exposed
surfaces effectively, hold the eyelids open and try to get the
injured person to roll his eyes while you are irrigating with
water. The eyes and the inside of the eyelids- should be washed
for at least 15 minutes before any effort is made to go to a
medical facility for follow-up treatment.
Immediate washing with water is essential, and
only a few seconds delay can result in some permanent damage.
Washing the eyes thoroughly is more important than reaching a
medical facility, and washing should not be delayed for any
reason. A victim should be transported for medical attention
only after a thorough washing.
Chemical burns to the eyes may be aggravated by
soft or extended wear contact lenses which can accumulate some
chemicals. Hard contact lenses may complicate effective
irrigation of the eyes, even though they may not aggravate a
chemical injury.
Eyes should not be irrigated with any neutralizing
agents as an emergency treatment. Any neutralizing solution is
less effective than plain water, because of the physiological
characteristics of the eye. Any acid in a neutralizing solution
will tend to react with the protein in the cornea to form an
insoluble barrier which will prevent washing out of any alkaline
solution trapped under the barrier. Medical tests have shown
that washing with potable water is the most effective emergency
treatment available in field situations.
4 - 32
-------
b. Emgrqpncv Treatment For Chemical Splashes On The
Skin
The most important emergency measure in case
chemicals are splashed on the skin is immediate washing with
large quantities of potable water. To keep chemicals splashed on
clothing from being washed through the cloth or onto the skin,
remove splashed clothing and wash the chemicals from skin with
large quantities of water. Speed and thorough washing are
important to reduce the extent of injury.
If the chemical has splashed on the victim*s face
or been inhaled, it will be important to see that there is an
open airway so the victim can breathe.
Remove all contaminated clothing and shoes, and
all clothing that may accumulate contaminated wash water. In
case of a splash on the body, it will usually be necessary to
remove all clothing.
Physical removal of splashed chemicals may be
speeded up by use of a wash cloth or by use of a detergent. In
no case, however, should any attempt be made to neutralize
splashed chemicals.
Since washing chemicals off of a person will
dilute and spread the chemicals, rescuers should recognize the
potential spread of contamination to themselves and the immediate
environment. If gloves and protective clothing are available
within a few seconds, so there is very little delay in emergency
washing, the rescuers may want to wear the protection to reduce
their contact with splashed chemicals. After the victim has been
washed, the rescuers will have to wash themselves to prevent any
injury from the chemical which has been washed off the victim.
The cold water from a hose or safety shower will
reduce chemical activity and burning during the initial 15 minute
flushing. For prolonged washing it will be desirable to find a
source of water in which the temperature can be adjusted to
prevent traumatic shock.
If the area of chemical contact is extensive or
the period of washing has to be prolonged, you will have to treat
the victim for shock. If the splashed person is conscious and
can swallow, give him plenty of non-alcoholic liquids to drink.
4-33
-------
UNIT 5
HEAT AND COLD STRESS
A. INTRODUCTION
Field crews often experience a variety of problems and
discomforts. By careful training and preparedness many of these
problems can be circumvented or prevented. In the case of
adverse weather conditions, personnel must rely on careful
preparation before going out in the field. Early recognition of
signs of weather related health problems and a well organized and
rehearsed emergency treatment program are needed.
B. HEAT STRESS
Warm blooded animals such as the human being maintain a very
precise body temperature. A slight deviation from the normal
98.6 internal temperature can dramatically alter the behavior of
the body and its functions. As external temperatures are
increased, heat due to metabolism increases internal temperature,
and the body responds by working to reduce the unwanted heat.
The result is increased heat rate, body temperature, respiration
and perspiration or heat stress. This additional burden on the
body functions can result in a variety of adverse health effects
ranging from cramps to collapse and even death.
1. Causes
Heat stress is caused by external heat sources such as
high ambient air temperature and direct sunlight, or internal
body heat build-up resulting from heavy work or prolonged use of
such protective gear as encapsulating suits.
a. External Heat Sources
Advanced planning and preparation will lessen the
chance of adverse health effects from high temperature. Work
which requires long hours in the sun should be scheduled if
possible in a time of the year when temperatures are moderate.
If the work must be done during the hot season, daily scheduling
should be arranged so that most of the strenuous work or work in
direct sunlight can be accomplished in the cooler morning or
evening hours.
If possible, investigate ambient air temperatures
before scheduling work. At some industrial sites, heat
generating processes may shut down during certain times of the
day.
5-1
-------
Other external factors such as high humidity and
altitudes nay increase the effects of heat on the body.
b. Internal Heat Sources
Many factors may affect the amount of heat
generated by the body. Human factors such as inadequate
acclimatization, fatigue, physical condition, the effects of
alcohol consumption, cardiac and respiratory conditions and some
medications all can cause increased body stress under high
temperatures. Before Agency personnel are assigned work
requiring exposure to some form of heat stress, a Preliminary
Medical Monitoring program should be conducted. Any indication
of systemic diseases or other physical problems should be
carefully considered before the employee is assigned to a team
working in high stress areas.
2. Preliminary Assessment
The following factors should be considered before
committing Agency personnel to an area of potential high heat
stress.
o Normal ambient air temperatures for the time
Agency personnel will be at the site
o Forecast winds and humidity
o Human factors such as medical problems,
accumulation and physical condition of the crew
o Exposure to direct sunlight
o Proximity of additional heat sources such as vats,
stacks, or pipes
o Required use of heat retaining equipment such as
encapsulating suits, respiratory gear, outer wear
such as rain gear or disposable suits
o Overall work load such as lifting and climbing
o Amount of prior acclimatization the crew members
have had
3. Emergency Information
Once a site has been scheduled, advance preparations
should be made in the event of an emergency problem. The
following steps should be taken.
5 - 2
-------
o Locate your exact position on a map, or in an
industrial site. Be sure you can give adequate
directions to ambulance or emergency crews.
o Determine the exact location of the nearest
emergency treatment center. In case an emergency
vehicle is not available, be sure you know how to
find the emergency center.
o Find the phone numbers of any emergency center,
emergency crew and ambulance.
o Locate a source of water for emergency cooling or
a room that is air conditioned.
o Make sure at least one member of the crew is well
versed in emergency first-aid for heat stress
victims.
4. On-Site Work Schedules
Plan to arrive early in the morning while it is
relatively cool. Lifting and hauling should be done immediately.
If work is to be done during the heat of the day in the
hottest months of the year, be sure to include time for adequate
rest periods. Rest gives the body an opportunity to rid itself
of accumulated heat, slows production of internal body heat, and
provides greater blood flow to the skin for cooling.
If respiratory equipment or encapsulating suits will be
worn without cooling vests when ambient temperatures are expected
to be over 90 degrees F, schedule work periods of only 15 to 20
minutes at a time. Factors such as the exact type of suit worn,
provision of cooling devices, amount of direct sun, and the
amount of physical activity involved will affect the maximum
working time at any ambient air temperature.
5. Equipment and Supplies
Careful planning in bringing the right equipment and
supplies can not only reduce workloads thus generation of
internal body heat, but can also protect against or prevent the
exposure that lends to heat stress.
The following equipment and supplies should be
considered when heat stress is a possibility:
o A reliable air thermometer for continuous
surveillance of ambient air temperatures
5-3
-------
o An oral fever thermometer for surveillance of
internal body heat
o Block and tackle for hoisting heavy equipment
o A large beach type umbrella or tarpaulin to
protect personnel from direct sunlight
o Protective heat shields, insulating or reflective
materials for intense heat areas
o Electric fans, blowers or other ventilating
equipment
o Large insulated containers of cool liquids both
for drinking and cooling
o Towels, blankets, sponges, and a plastic basin for
emergency cooling procedures
o First aid kit
o Emergency communication equipment for use between
ground crews and those at locations such as smoke
stacks or pits
o Body replacement fluids containing salts or other
electrolytes that are lost during perspiration, 2-
3 gallons per day per individual of a solution of
Gatorade, ERG, Squincher, or salt water made up of
1 teaspoon per 5 quarts of water are required
6. Clothing
In general, clothing should be selected to reduce heat
load. It also generally should be light in color and reflective.
In direct sunlight special precautions should be taken to cover
the head and wear shatter proof sun glasses. When ambient
temperatures are below 100 degrees F, clothing should be loose-
fitting, porous and preferably made of cotton rather than
synthetics or wool. If ambient temperatures exceed 100 degrees
F, loose fitting clothing covering all exposed skin areas should
be worn.
7. Preparations for Emergency Treatment
The possible effects of heat stress should be taken as
seriously as any other life-threatening hazard. Field crews
should be trained to quickly recognize the symptoms and react
accordingly. Heat stress victims should be tended to as quickly
as possible. If help is more than 10 minutes away, crew members
should administer first aid.
5-4
-------
Vital information such as location and phone number of
emergency help, description on crew location and pertinent
medical information of crew members should be located in a
centrally kept place such as a crew vehicle.
Evacuation plans should be discussed with the entire
crew and, if possible, practiced before work begins. Stretchers,
harnesses, or block and tackle should not only be brought to the
site but made readily available to crews that might need them.
8. On-Going Evaluation
Ambient conditions are subject to change during a
working day. Conditions such as temperature, humidity and wind
should be recorded before work begins and throughout the day at
regular predetermined intervals. Two members should be assigned
this task with one acting as a back-up in case the first forgets
or is preoccupied. As monitored conditions change, increased^
vigilance for signs of heat stress will be necessary.
In situations where it is necessary to be on the site
for more than one day, a careful evaluation must be made of the
need for replenishment of supplies, and the potential need for
new equipment, caused by changing conditions, must be assessed.
Remember, what is the responsibility of everyone quickly becomes
the responsibility on noone. Assign the task of equipment and
supply evaluation to one responsible member of the crew.
If possible, two crew members should be given the
responsibility of visually monitoring crew members for signs of
heat stress. When one of the responsible members is in doubt,
consultation with the other observing member should be held.
Visual checks should be made and recorded at predetermined
intervals. Crews should be reminded of the necessity to replace
lost body fluids on a regular basis. It if recommended that
under heat stress, personnel should drink every 15 minutes to one
hour depending on the heat load. Under extreme heat conditions,
oral temperatures should be taken and recorded at breaks to
detect the onset of heat stress problems.
9. Recognizing The Symptoms Of Heat Stress
Heat stress manifests itself in four disorders. From
the most severe to the least severe, they are:
o Heat Stroke
o Heat Exhaustion
o Heat Cramps
o Sunburn
5-5
-------
a. Heat Stroke
Heat stroke (sometimes called sun stroke) is the
most serious of the heat stress disorders. In its most serious
form it is lethal. It results from excessively high body
temperature which in turn disturbs or interferes with the body's
own heat regulating system.
Normally, the body sweats, producing moisture for
evaporation from the skin. As most individuals know from
standing wet in a breeze, evaporation is an effective cooling
process. During heat stroke this perspiration evaporation
cooling process is interrupted, with a resultant quick rise in
internal body temperature.
Continuous exposure to high temperatures for as
little as three hours can produce heat stroke. RAPID COOLING IS
URGENT TO PREVENT DEATH.
(1) Symptoms Of Heat Stroke
Any or all of these symptoms may be present:
o Body temperature is extremely high,
often 106 degrees and above
o Skin is red, hot and dry; sweating is
absent
o Pulse is rapid and strong
o Possible convulsion or collapse
o Possible delerium, disorientation or
unconsciousness
If the person's body temperature is elevated
to 104 degrees F or above (orally), but sweating is occurring>
the person is probably in a stage just before heat stroke. The
person should be treated for heat stroke.
(2) Emergency Response To Heat Stroke
With the advent of heat stroke,, action must
be taken immediately if the life is to be saved.
o Call for emergency help.
o COOL THE PERSON RAPIDLY. Remove the
person from the heat stress area to an
air-conditioned room, vehicle, or at a
minimum, to a shaded area. Remove the
5-6
-------
person's clothing and begin to bathe the
body continuously with water, chilled if
possible. Fans or air currents such as
hand fanning will assist in the cooling
evaporation process. If possible,
submerse the body completely in chilled
water and massage continuously. Apply
cold packs if available.
In the event the victim is in a position such
as on a smoke stack where it is difficult to immerse him in
water, remove the victim's clothing and use a sponge and basin to
bathe the body until help arrives. Monitor the victim's body
temperature. When the back of the hand held against the victim's
cheek indicates normal skin temperature, or when the internal
body temperature reads 101 degrees F or below, discontinue the
cooling process. Wrap the person in a blanket to prevent shock.
If the person is conscious, let the person sip liquids. Do not
give alcoholic beverages or stimulants such as coffee or tea.
If the person's body temperature begin to
rise again, repeat the cooling process.
(3) Prevention Of Heat Stroke
The likelihood of heat stroke can be lessened
by protecting your body from radiant heat, breaking the work day
into short work rest periods, and drinking enough fluids to
replace those lost by sweating.
b. Heat Exhaustion
Heat exhaustion is also known as heat prostration
or heat collapse. Although heat exhaustion is considered less
severe then heat stroke, it is recognized that failure to quickly
treat heat exhaustion can lead to heat stroke.
Heat exhaustion is the result of cardiac
insufficiency stemming from failure of the circulatory system to
compensate for increased blood flow demands imposed by a need to
cool the body and from dehydration caused by profuse sweating.
If recognized and treated immediately, heat
exhaustion usually results in no permanent damage.
(1) Symptoms Of Heat Exhaustion
o Body temperature is normal or slightly
elevated or reduced
o Skin is clammy and pale, and there is
moist, profuse sweating
5-7
-------
o Pulse may be weak with low blood
pressure
o The person is tired and weak
o The person may complain of dizziness or
giddiness, and fainting is possible
o Possible muscle cramps
o Possible nausea or vomiting
o The mental state is generally rational
(2) Emergency Treatment Of Heat Exhaustion
Early recognition of heat exhaustion is
necessary if heat stroke is to be prevented.
o Move the victim into shade, or an air-
conditioned room or vehicle.
o Have the person lie down.
o Elevate the feet 8M-12.n
o Loosen tight fitting clothing.
o If the victim is conscious, have the
person sip a glass of electrolyte
replacement solution such as Gatorade,
ERG or Squicher. Repeat every 15
minutes for 1 hour. Stop fluids if
vomiting occurs.
If the symptoms persist or return, summon
medical help immediately.
(3) Prevention Of Heat Exhaustion
To prevent heat exhaustion, schedule frequent
rest periods. Replace lost body fluids by drinking electrolyte
liquids every 15 minutes to one hour.
c. Heat Cramps
Agency personnel working prolonged hours where
profuse sweating takes place may experience painful muscle pains
and spasms known as heat cramps. Although not life-threatening,
the resultant painful cramps may hinder work or cause a potential
hazardous situation such as when working at heights.
-------
Heat cramps are caused by the loss of salts
(electrolytes) due to sweating over a long period of tine.
Simple replacement of lost fluids with water without electrolyte
may be insufficient to prevent heat cramps.
(1) Symptoms Of Heat Cramps
o Painful muscle cramps and spasms
o Heavy sweating, vomiting, and or
convulsions
o Normal, or near normal, pulse and blood
pressure
o Rational behavior
(2) Emergency Treatment For Heat Cramps
o Quiet rest in a cool shaded area
o Gentle massage of affected area
o If the person is not vomiting, give
electrolyte fluids every 15 minutes for
an hour
(3) Medical Treatment Of Heat Cramps
If the heat cramps are not relieved by giving
fluids and the symptoms persist, the victim should be transported
to the nearest medical facility. Persistent symptoms may be
symptomatic of heat exhaustion or the beginning of heat stroke.
(4) Prevention Of Heat Cramps
o Salt food more heavily than normal.
o Drink electrolyte solutions.
o Eat salty food during heavy sweat
producing activities. (Salt tablets are
no longer recommended for general use.)
If you are on a low sodium diet or are taking
diuretics, consult your physician in advance of field activities
about replacement of salts. Be sure to explain any such problems
to your crew leader.
5-9
-------
d. Sunburn
Sunburn is the least serious of the four heat
disorders although by far the most common. It can result in
painful/ red/ swollen or blistered skin that may result in the
inability to continue work. Advanced cases may require medical
treatment and should be viewed as a precursor to more serious
heat disorders.
Sunburn is usually a first-degree burn of the
epidermis or first layer of skin. The affects of a sunburn may
not be noticed or felt for many hours after exposure.
(1) Symptoms Of Sunburn
o Skin redness
o Pain
o Swelling
o In severe cases, blisters, nausea,
vomiting, chills
(2) Emergency Treatment Of Sunburn
o Put cold water on the burned area as
quickly as possible.
o Severe burns should be submerged in cold
water or soaked with wet cloths.
o Elevate burned limbs.
o Do not break blister that would increase
the chance of infection.
(3) Medical Treatment Of Sunburn
o Seek medical help if pain, chills, and
vomiting persist.
(4) Prevention Of Sunburn
The first line of defense against sunburn is
to cover exposed parts such as the head, arms and legs. Those
individuals whose job requires a great deal of exposure to the
sun should take steps to gradually expose the skin to the sun for
20 minute intervals per day, extending the time as the skin
builds its own natural protection in the form of a tan. If this
is not possible or as a safe-guard for overexposure, sun lotions
and sun shields should be used.
5-10
-------
Lotion and ointments come in various degrees
of protection. Those Agency personnel with fair skin or being
exposed for the first time should use maximum protection. The
level of protection should be gradually reduced as the skin tans.
Heavy sweating can reduce the protection
levels of ointments and lotion in time. Personnel experience
heavy perspiration should reapply protection approximately every
hour.
It should be remembered that the rays of the
sun which cause ultraviolet can penetrate thin layers of cloud.
Sunburn protection should be worn on days that are lightly
overcast.
C. COLD STRESS
EPA personnel are often required to perform field work in
cold weather. Such conditions can lead to severe health problems
ranging from skin injury to loss of fingers and toes, from frost
bite and even death due to hypothermia. It is imperative for EPA
employees' health and safety that adequate planning and
preparation be undertaken prior to exposure to cold weather
conditions.
l. Causes Of Cold Stress
The human body functions normally within a very narrow
range of internal body temperatures. Although the body is
capable of compensating for loss of body heat for short period of
time, a drop of only 5 degrees of internal body temperature
usually results in disruption of normal activities. To prevent
this sudden loss of body heat, Agency personnel should recognize
the ways in which heat can be lost.
a. Radiation
Radiation is the loss of heat through the
radiation of heat from the body. Exposed skin areas because of
the heat can lose as much as 25% of the body's heat. Prevention
of this type of heat loss is primarily by insulation, in the form
of adequate clothing, such as hats, gloves, and thermal
underwear.
b. Conduction
Conduction is the loss of heat when it is
transferred to other objects: ladders, metal surfaces, wet
clothing, snow, ice, or water all resulting in the quick loss of
heat. Care should be taken to wear waterproof gloves and clothes
5-11
-------
when near wet surfaces. Gloves should always be left on during
contact with highly conductive materials. Clothes that are wet
should be dried or changed immediately.
c. Convection
The loss of heat due to the movement of air
currents is dramatic. Winds can result in body heat loss with
unbelievable speed. In many areas weather forecasts include the
estimated effect of winds on the body with what is called the
wind chill index. The wind chill index allows you to estimate
the equivalent temperature based on the thermometer reading and
the wind speed. By determining the wind chill, judgments can be
made about scheduling field activities and the amount and type of
clothes to be taken. To prevent loss of heat due to convection,
wind proof gear such as rubber, vinyl or poplin should be worn.
d. EYAPQIT^tion
Evaporation is a very effective natural cooling
process. Moisture for evaporation can come from external sources
such as rain or snow or internal sources such as perspiration.
External sources can be prevented by waterproof gear. The same
waterproof gear can also minimize heat loss due to evaporation of
sweat. Evaporation of sweat can also be reduced by wearing highly
absorbent clothing next to the skin.
2. Human Factors Contributing to Cold Stress
Before Agency personnel are assigned to field
activities with the possibility of cold stress, an analysis of
their general physical condition should be carried out to
ascertain the following factors that can contribute to cold
stress.
o Cardiac or respiratory conditions
o Fatigue or lack of acclimatization
o Inadequate sleep, food, or water
o Dehydration
3. Preliminary Assessment
Although little can be done about the weather, advance
planning and preparations can spell the difference between worker
hardships and reasonably comfortable working conditions.
5-12
-------
The crew chief is responsible for scheduling and should
assess weather conditions carefully during the period Agency
personnel will be at the site. The possibility of high winds,
low temperatures, snow, or rain must be carefully weighed before
a site is scheduled.
On-site conditions such as the openness of the work
area, availability of warm shelter, warm food and drinks and
drinking water must all be considered against predicted weather
conditions.
4. Availability Of Crew Members
If continuous Agency activity is required,
consideration should be given to assigning enough crew members to
allow alternate personnel to continue the activity while others
warm themselves.
Carbon monoxide poisoning and asphyxiation are always a danger
when vehicles or heaters are used. Care should be taken to
ensure adequate ventilation where these alternate heating sources
are used.
5. Preparation and Planning for Cold Weather Work
A great deal of unfavorable working conditions can be
avoided by careful and thoughtful planning. Check weather
conditions before scheduling outdoor work in highly exposed
areas. Plan to rotate crews regularly. Determine the
availability of shelter and food.
Prepare a checklist of required clothing, supplies, and
equipment needed for anticipated conditions. Arrange for
temporary shelter if none exists at the site. Arrange and
discuss emergency plans for treatment and evacuation if
necessary. Prepare for a change of scheduling if prevailing
weather conditions change during scheduled activities. Carry a
portable radio or monitoring equipment to keep informed of
predicted or changing weather conditions. Locate communications
equipment such as two way radios dr telephones. Schedule
activities to make maximum use of the warmer daylight hours,
including equipment retrevial and egress from the site. Make
allowances in scheduling for the extra time and added fatigue
heavy clothing adds. Assign two members of a team to monitor
weather on a regular basis and to evaluate the physical condition
of team members. Prepare supplies, equipment, clothing,
blankets, and food for the worst possible scenario of being
stranded at the site.
5-13
-------
6. Selection of Clothing for Cold Weather Work
The proper selection of clothing is the best possible
defense against cold stress. Clothing should be selected keeping
three factors in mind:
o Insulation Value
o Absorption ability
o Wind resistance
Studies have shown that multiple layers of clothing
have more insulating volume than single thick layers of equal
thickness. Each layer traps air between it and the next layer to
provide an effective insulation layer. Multiple layers also have
the advantage of being removable one at a time as weather
conditions or work may load dictate. Inner layers should be
porous as in insulating underwear. Outer layers would be non-
porous, wind and water proof. Intermediate layers should be of
good insulating properties such as found in wool.
In determining protective clothing, be sure to give
special consideration to the head, hands, and feet, the three
areas of the body most commonly injured by cold.
Heat loss from the head is much greater than the ratio
of surface area exposed to the rest of the body. As much as 25%
of the entire body heat loss may come from the head alone. Head
covering should be well lined and loose fitting with a means of
protecting the ears. Since EPA personnel often are in areas
exposed to high winds, some means of securing the protection to
the head should be considered. Hard hats are often inadequate
for heat loss protection. Insulating head protection should be
selected to accommodate hard hats if required.
Protection for hands and feet should be selected with
the same properties in mind as head protection. Well insulated
but loosely fitting materials should be selected. Fur lined
mittens with water resistant covering are the best, although
gloves may be required for dexterity. Fur lined or insulated
boots in a size larger than normally warn during warmer weather
will allow for air space insulation and multiple layers of socks.
Boots should be of water proof material such as rubber or
leather, treated with water proofing. In some instances steel
toed boots will be required. Soles should be designed for sure
footing on slippery surfaces or in snow. Always carry extra
pairs of socks and gloves. Wet gloves or socks quickly lose
their insulation value and can materially add to body heat loss.
Wet socks or gloves should be changed immediately.
5 - 14
-------
7. Symptoms of Cold Stress Disorders
a. Hypothermia
Hypothermia is the progressive lowering of body
temperatures with accompanying rapid and progressive mental and
physical collapse. Hypothermia is the most serious of the cold
stress disorders and is responsible for the largest percentage of
cold stress fatalities.
A number of factors can induce or speed up the
onset of hypothermia. Extended exposure to cold with aggravating
circumstances such as moisture, winds, fatigue, hunger, and
inadequate clothing or shelter, and heavy perspiration wich rapid
cooling all play a role in hypothermia.
Hypothermia usually occurs between the
temperatures of 30 - 50 degrees F, temperatures that most people,
believe are not dangerous. Crew members should be alert for
symptoms of hypothermia, especially when temperatures are
dropping rapidly or when they are exposed to rain, snow, or ice.
Hypothermia is extremely rapid when the body is
submerged in cold water. Even moderately cold water at 65
degrees F and below quickly robs the body of vital heat.
Unconsciousness and death may occur as rapidly as thirty minutes
after submersion in water temperatures of 32 degrees F. Crew
members that have been totally submerged in cold water should be
treated as extreme emergency cases.
In the early stages of hypothermia the body begins
to lose heat faster than it can produce it, and it makes efforts
to stay warm by shivering. When the body can no longer generate
heat fast enough to overcome heat loss and when energy reserves
are exhausted, a second stage begins. The body temperature
begins to drop. This affects the ability of the brain to make
rational judgements and may result in loss of muscular control or
consciousness, as Table 5-1 shows.
5-15
-------
TABLE 5-1
EFFECTS OF LOSS OF BODY TEMPERATURE
Internal Body Temperature
95 Degrees F and above
90 to 95 Degrees F
86 to 90 Degrees F
80 to 86 Degrees F
80 Degrees F and Below
Symptoms
Person is conscious and alert,
but may have shivering that
becomes uncontrollable as
temperature nears 95 degrees
F. Respiration increases at
first.
Person is conscious but
disoriented and apathetic.
Shivering is present, but
diminishes as temperature
drops. Below 93 degrees F,
respiratory rate gradually
diminishes and pupils begin to
dilate.
Person is semi-conscious.
Shivering is replaced by
muscular rigidity. Pupils are
Cully dilated at 86 degrees F.
The person is unconscious and
respiration is diminished.
Respiration is barely
detectable or non-detectable.
Death usually follows.
5-16
-------
(1) Emergency Treatment of Hypothermia
Hypothermia should be considered a major
medical emergency. All but the very mild cases should be treated
by qualified medical personnel at a medical facility. The
following on-site treatment is for very mild cases or when
waiting for medical help to arrive.
(A) Mild Cases
Move victim to shelter and warmth as
soon as possible. Wet clothing should be removed; it drains body
heat. Replace with warm dry clothing. Provide beverages.
(B) Severe Cases
While waiting for medical treatment
remember that in more severe cases of hypothermia the body has
lost a great deal of internal body heat. Heavy clothes or
blankets are only of value in keeping heat in. In the case of
hypothermia it is necessary to get external heat to the body.
Clothing only prevents this external heat from reaching the body.
Therefore strip the victim of his clothes. If possible submerge
the victim*s body in a bath of 105 to 110 degrees F water.
Remain with the victim if there is loss of mental or physical
ability or if the victim is unconscious. If a bath is not
possible, warm towels should be wrapped around the body,
particularly around the head, neck, sides, and groin. Keep the
towels warm. Do not use hot water. If available, use electric
blankets, hot water bottles or heating pads.
Once the victim has been warmed, wrap in
blankets or sleeping bags with an external source of heat if
possible. Although sleeping bags or blankets provide no heat
themselves, they do prevent any further heat loss.
In remote locations with no other heat
source available, lives have been saved by body to body contact
with the victim being sandwiched between two others.
Victims of hypothermia should be checked
for signs of frostbite.
b. Frostbite
Frostbite is the second most severe manifestation
of cold stress. Frostbite is the freezing of some part of the
body as a result of exposure to very low temperatures. Frostbite
most likely will affect hands, feet, ears, and exposed parts of
the face. As long as circulation remains good, frostbite will
not occur. The chances of frostbite occurring increase in strong
wind conditions.
5-17
-------
There are three stages of frostbite, classified
according to the amount of skin damage. Severity can range from
frostnip/ which only damages the surface skin, to superficial
frostbite, which involves the skin and the tissues immediately
beneath it, to deep frostbite, a much more serious injury with
damage that may effect deeper tissue and even bone, often
requiring amputation.
(1) Symptoms Of Frostbite
Skin first turns ' red and later becomes pale
or waxy white. There may be tingling, stinging, or coldness
followed by numbness; or the frostbite may be unnoticed by the
person.
(A) Superficial Frostbite
The skin in affected areas turns white
or gray-white with a waxy appearance. The skin is firm to the
touch moving easily across the softer tissue beneath. There is
usually little or no feeling in the area.
(B) Deep Frostbite
Tissue is pale, cold and solid to the
touch. All sensation is lost. Blisters and swelling follow
thawing of parts.
(2) Emergency Treatment
(A) Frostnip
Frostnip is easily reversed in the field
by the application of body heat. Placing the hands under the
armpits or in other warm parts of the body will reverse frostnip.
The heat of respiration can also help the hands. Do not rub or
massage affected areas; apply heat.
(B) Superficial Frostbite
Superficial frostbite can be reversed by
application of body heat or external heat.
(C) Deep Frostbite
The most effective method of minimizing
damage due to severe frostbite is by immediate application of
external heat. Remove the victim to warm shelter. Remove
gloves boots, socks, and other clothing that will prevent heat
from reaching the affected area. Warm extremities in a carefully
controlled bath of warm water between 104 and 107 degrees F until
color and feeling return to the area. If warm water is not
5-18
-------
available, warn packs or towels between 100 and 112 degrees F, or
heating pads will suffice. Radiant heat such as that from a
stove, fireplace or heater should be used with great caution, as
burns may result before feeling is restored. Never use snow to
thaw frostbite. Never rub or massage frozen or damaged areas, as
this increases the likelihood of tissue damage.
Keep frostbitten areas elevated. Do not
allow victims to walk on frostbitten feet. Have the victim move
or exercise toes or fingers as soon as possible.
(3) Prevention of Frostbite
Treatment of frostbite is a painful
experience that may result in amputation of the affected part.
If is far easier to take the necessary steps to prevent
frostbite. Insist that crews prepare adequately for frostbite
with warm clothing, shelter, and team surveillance.
5-19
-------
UNIT 6
PREPARATION FOR FIELD ACTIVITIES
A. INTRODUCTION
Operating on a regular basis in a known environment, such as
an office or factory, quickly familiarizes the individual with
the hazards that can be expected. Field activities, on the other
hand, present a wide variety of unknowns that must, be anticipated
and prepared for. EPA field crews can go a long way in
preventing accidents and hazards by training themselves to devote
pre-activity time to careful and thorough investigation of the
upcoming activity. It is no product of luck that careful
planning and reduced accidents go hand-in-hand. While the
material in this unit is oriented toward team inspection
activities, the principals are applicable to single-person
inspections as well.
B. PLANNING FOR FIELD ACTIVITIES
Planning for field activities should be done as a team
effort. By drawing on the experience and training of the team
members, a more comprehensive plan can be drawn up than can be
done by a single individual.
1. Team Member Selection
Selecting the proper team members is an important first
step. The first criterion for selection should be that members
have visited the site or similar sites before. Experienced
individuals will be able to provide a wealth of valuable
information rather than the guesswork that would guide a team
that lacks actual experience.
The second criterion for selection is physical
conditioning. Inquire whether potential team members have had
experience in the expected site conditions in the past and if
they have been recently acclimated to the expected work load or
anticipated adverse weather conditions. Be wary of selecting
someone who would "just like to get out of the office for
awhile," if they are going to face heavy workloads or severe
temperature extremes. Make sure that all team members are
physically fit and in compliance with applicable health and
safety certification and medical monitoring requirements.
Interview them to discuss any limitations they may have. In many
cases the fear of heights, or the fear of small, tight places or
protective equipment may not show up on physical exams, but it
6-1
-------
could severely limit the effectiveness of crews during regular
work routines as well as emergencies. Such conditions may also
increase the likelihood of accidents.
Select an appropriate number of team members to
accomplish the job safely. During heavy workloads or extreme
weather conditions, anticipate that work will take longer and
crew members will have to be relieved on a regular basis for rest
and recuperation. When hazards are anticipated, never assign a
crew member to work alone, even for a short period of time unless
the worker has been provided with two-way communication.
2. Team Assessment of Potential Hazards
All discussion of up and coming activities should be
done with all team members present. Arrange for an open forum
type of discussion. Avoid telling crew members what they must
do. The collective contributions of a carefully selected team
are better than those of the most experienced individual.
Appoint one member to be responsible for summarizing in
writing the suggestions of crew members. The saying "What is the
responsibility of all, is the responsibility of nonen provides
little consolation to crew members who need something that has
been forgotten.
Organize the discussion along a prearranged format.
This helps eliminate forgetting a crucial subject.
If information is needed that cannot be provided by the
crew members during the discussion, assign a member to get that
information and relay it to the member responsible for writing
the summary.
3. Discussion Format - Past Experience
Ask crew members to discuss their past experiences at
the site or similar sites. If no selected crew irsmbers has had
similar past experiences, ask other Agency personnel to sit in
briefly to discuss their experiences. By setting the stage, crew
members can make intelligent suggestions based on known facts.
Ask each crew member to briefly outline the field
experiences they have had, as well as the training they have
received. Such a discussion builds confidence in team members,
reveals weaknesses in past experience and training, and points
out inexperienced crew members who may need special assistance or
training.
6-2
-------
4. Site Evaluation
Secure a map, or photographs, of the site to be
visited. Each member should become thoroughly familiar with the
site, its relative location in regard to roads, shelters and
emergency help centers such as treatment centers and hospitals.
Crew members should not only know how to reach and leave the
site, but also how to communicate that information to emergency
squads.
Evaluation of existing or potential two-way
communication is essential. In most cases, site communication
is by telephone. Find exactly where the telephone is located at
the site and verify it is working. Secure the telephone numbers
of emergency help in the area. Assign a crew member to call and
verify the accuracy of the numbers. On sites where extreme
hazards are anticipated, calls should be made to the local
emergency centers, informing them of the exact time and date the...
crews will be operating at the site. This is particularly crucial
at rural sites or at sites near small towns where volunteers
operate the emergency equipment. Never assume a town has
emergency equipment available. over 50% of the towns in this
country have no immediate emergency help available; call and
verify.
On sites where telephone communication is not
available, anticipate the use of two-way radios. Determine if
there is a possibility that there may be interference with two-
way signals from sources of interference such as transmission
lines, hills or tall structures. When arriving on site, a check
should be made with emergency help. If the radios depend on
batteries, extra sets of fresh batteries should be brought.
Examine the site for natural physical hazards such as
deep ponds, streams, marshes, cliffs, lack of ingress and egress,
high winds, poor visibility, tidal changes, high seas or rough
water, wave action, poor footing, prevailing winds and abrupt
wind direction changes, abrupt changes in weather patterns, heavy
snows, flash flooding, avalanches, mud slides, and ice storms.
Where adverse weather conditions are a possibility, it
may be necessary to carry out some preliminary investigations
about past conditions at the anticipated time Agency personnel
will be working at the site. Local residents, radio stations,
and newspapers can often provide the needed information. If the
site is to be visited within three days to a week, a long range
weather forecast can be gotten from the local TV, radio station,
Coast Guard or the National Weather Bureau. Assign a crew member
to complete this task and report this information to the team
members.
-------
Careful assimilation of both a physical and mental
picture of the site is invaluable in proper preparation. Only by
knowing all the facts can a comprehensive plan be put together
with a minimum of omissions.
5. Assessing the Hazards
Once a crew is familiar with the physical layout of the
site, a unit-by-unit assessment of the potential hazards should
be undertaken. Hazards can be categorized into the following
units:
o
Transportation
o
Atmospheric
o
Chemical
o
Fire and Explosion
o
Physical and Mechanical
o
Radiation
o
Biological
o
Weather Related
o
Drowning
Each of these units is covered in detail in a separate
section of this manual. Careful analysis of these sections will
provide the team with information needed for the planning
necessary to meet the hazards associated with each site. Figure
6-1 is an example of the information that should be compiled and
recorded during the planning period. A copy of this summary
along with pertinent medical records or information should be
kept in a file and taken along for reference in the event of an
emergency where the information might be needed. A second copy
should be filed with a supervisor before leaving for the site.
Such information is particulary important for visits to sites
where crews may be stranded or lost.
-------
FIGURE 6-1
SAMPLE PLANNING GUIDELINE FOR FIELD ACTIVITIES
Project Title:
Location s . ¦
EPA files exist and have been reviewed? Yes No
Names and Telephone Numbers for Contacting You:
Names Position Tel. Number
Crew Members:
Med. Training Recieved Medical or
Name Mont. Field Respiratory Phy. Restrictions
Length of Proposed Activity:
Crew Lodging Arrangments: Motel/Hotel
Location: Telephone #
6-5
-------
Anticipated Hazards:
Driving distance Hauling test equipment
Hauling chemicals Hauling supplies
Noise . Thermal hazards
Flammable Hazards Moving hazards
Weather: heat cold wind rain thunderstorms
Toxic Substances (List)
Heights: ;
Vechicle(s) and Equipment
Motor vechicles: sedan van pickup
Mobile laboratory Other (list)
Vehicle safety check made: yes no
Vehicle appears okay or needs (list)
Watercraft
Boat will be used yes no
Boat safety check made yes. no
Site access:
Identification
Permits^
Visitors Agreement
Special problems
6
- 6
-------
Type of Communication needed
Emergency and Rescue
Is first aid available in the area? Yes No
Location Telephone #
Is ambulance available? on site on call Tel.#
Nearest hospital with emergengy services. Location
Type ; -
Heavy and special rescue services available yes no.
What
Emergency Signals and Communication
Fire Signal is ;
Evacuation signal is
Severe weather signal is
Toxic release signal is
'Personal Protective Equipment/Clothing (Check if needed)
1. Eves and Head
Safety glasses Type
Face shield Goggles
Hard Hat. Type
Hearing protection . Type
Other
2. Body. Hands. Feet
Coveralls Type
Foul weather gear
Fully encapsulating gear
6-7
-------
Safety footwear Type
Boot/shoe covers
Gloves Type
Other special equipment/clothing
3. Respiratory Protection
Air-Purifying Respirator Type
SCBA . Type
Emergency Escape Mask Type
4. Special Health and Safety Equipment
Life belt
Safety line
Other (list)
5. Miscellaneous
Extra clothing
Socks Shoes Boots
Coveralls Outer clothing
Undergarments Other (list)
Water
Drinking
Flushing
Other (list)
6-8
-------
fl^A-Haneous Rope_ String
Matches Food—
Other
-------
C. ON-SITE EVALUATION
No matter how thorough and complete the pre-site briefing
is, there will always be hazards not anticipated or covered.
Before launching in to a work routine take time to acquaint the
entire crew with the on-site hazards.
First tour the site. Look for hidden hazards such as broken
railings or ladders, dangerous or unprotected machinery, low or
heated pipes, discharges or outlets carrying dangerous materials,
new construction, open trenches or unsafe scaffolding, or any
other hazards not discussed at the briefing.
Second, if there is a safety department or knowledgeable
company employee, ask for a briefing of any known hazards that
exist at the site. Request information as to evacuation routes
and warning signals, medical staffing or other on-site emergency
help, and the location and type of protective gear that is at the
disposal of Agency personnel. Take a few moments to walk the
crew through the emergency evacuation route. Physically locate
and acquaint crew members with the on-site, available safety
gear. Remember, no matter how much experience your crew members
have had, they cannot possibly know and prepare for the on-site
hazards as well as the people who work at the site everyday.
Ask the company employee to alert the safety department,
medical or emergency staff, and all those in the vicinity of
where Agency personnel will be working of the exact time and
location of EPA personnel. This is particulary important in
confined space entry. Find out if company rules require special
safety gear such as steel-toed shoes or respirators. Do not
ignore company safety policy. It was undoubtedly imposed for
good reason.
Assign a crew member to keep a log of any unexpected hazards
encountered during the work at the site and how these hazards
were handled. Such records will go a long way in helping the
next crew prepare for similar hazards and emergencies. List any
extra gear that is recommended to take along that was not taken
on this site visit.
When contemplating entry into a confined space or
atmosphere, such as a manhole, in addition to crew monitoring,
request information from company employees as to past hazards or
events such as production discharges that might quickly and
significantly change the degree of hazards associated with the
confined space. Agency employees may not have enough time for
evacuation if a toxic discharge catches them unaware in a
confined area.
6-10
-------
Whenever possible, always send Agency personnel in pairs.
The "buddy system" has repeatedly been shown to save lives. When
entering into a suspected hazardous environment, one team member
should always remain behind with constant visual or voice
communication with the second. Buddy teams must be taught to
recognize danger and respond to it effectively using methods of
rescue that have been taught rather than headlong rush into
hazardous areas to save a fallen team member.
Where only one Agency person has been assigned to a site,
have that employee request to be accompanied by an on-site
company employee knowledgeable with the area to be inspected or
sampled.
Remember, the buddy system is a safety precaution only. It
is not a protective procedure. Never enter highly hazardous
areas without thorough monitoring and protective gear. At its
best, the buddy system speeds up rescue. At its worst, it
prevents the loss or injury of one instead of two people.
Neither is acceptable if the accident could have been prevented
at the start.
It is estimated that fire and rescue teams prepare and train
for emergencies 40 hours for every hour they actually are
involved in an emergency. There is no substitute for effective
preplanning. Never go out on even a small detailed activity
without devoting a block of time anticipating and planning for
hazards and emergencies. The National Safety Council reports
that most accidents occur around the home or within three miles
of the home, a time when few people anticipate an accident and
fewer prepare for it.
6-11
-------
UNIT 7
TOXICOLOGY
A. INTRODUCTION
Toxicology is the science of poisons. If is the study of
how chemical and physical agents interact with biologic systems
to produce some negative response in affected organisms.
Responses are measured and evaluated according to the amount of
substance administered (DOSE) and the route of exposure.
Essentially all substances are poisons. The difference
between a substance being toxic, non-toxic, or beneficial is
determined by the dose. Toxicity is a measure of a substance's
capacity to produce injury in living organisms.
It is important that response personnel become aware of
toxicological data and how they are obtained. Route of entry and
target organs of chemicals in the body determine how personnel
should be protected in addition to maximum exposure limits. By
knowing and understanding the fundamentals of toxicology,
employees will be better able to determine the hazards they are
faced with at the work site. Employees should ask themselves the
following questions prior to entering any work site:
o What toxic agents are present?
o How will they enter the body?
o How will they affect the body?
o How toxic are they?
B. TOXICITY TESTS
In order to gain information on the human toxicity of
substances, controlled laboratory tests are run on animal species
which, hopefully, can be correlated to human responses. The
design of toxicity tests involves selection of :
o A test organism (which can range from cellular material
to higher order plants and animals)
o A biological endpoint (observable or measurable
response) which can range form subtle physiological or
behavioral changes to death
o A test period (exposure time) - A dose or series of
doses
7-1
-------
1. Test Organisms
Test organisms obviously vary significantly in
physiology from humans. The proper selection of test animals
requires a knowledge of which species most closely resembles
humans with respect to the chemical of interest. The goal of
animal toxicity tests is to predict chemical effects on humans.
Thus, the fate of a chemical in humans, as well as its fate in
various animal species, must be known in order to choose the best
suited test species for a particular chemical.
In addition, the endpoint of choice plays a role in
determining test species. If, for instance, the carcinogenicity
of a chemical is being tested, the test organism of choice will
be one with a short life span. It would be impossible
economically to study carcinogenic effects in an organism whose
life span is twenty years. Valuable research time would be lost,
essentially wasting 20 years worth of human lives waiting for
results from as single study. Han can't afford to wait this long
to determine if chemicals he is being exposed to are carcinogenic
or not. Expenses would be prohibitive also.
Mutagenic effects can also be measured and extrapolated
into possible carcinogenic effects. In this case species with
extremely short life spans can be used to measure genetic
effects.
Once a test species has been chosen, individual
organisms are used which show as little variation among
themselves as possible. Organisms are chosen of equal age, sex,
and strain.
They must be healthy prior to testing so that harmful
responses can be judged objectively. Controls are always used in
toxicity tests. These organisms are treated exactly like test
organisms with the exception that the dose administered does not
contain the chemical being tested. At the end of the testing
period, controls and test organisms are compared to see if
controls remained healthy throughout the testing. If so, all
detrimental effects observed in the test animals are attributed
to the chemical tested. There will be variation in response
among tested organisms. Given identical doses, the majority of
organisms will have a particular response, but a few will have
little or no reaction and a few will have an extreme reaction.
Another consideration when choosing a test organism is
population size. It is imperative that a large population size
be used for toxicity tests in order to ensure statistically sound
data. Financially, this limits the species of choice (rabbits
chosen over dogs, for example) to smaller, easy to care for ones.
7-2
-------
2. Biological Endpoint
The most common endpoint of choice in toxicity testing
is death. One reason for this choice is its objectiveness. Many
other endpoints, such as dermatitis or liver damage, leave room
for judgement error. In addition, the chosen endpoint must be a
reproducible response. That isf in test after test, the same
endpoint should be obtainable in response to the same dose(s).
Test data are plotted on a dose response curve, if is
from this curve that the dose (generally measured in milligrams
(mg) of test substance per kilogram (Kg) of body weight of the
test organism) which killed a certain percentage of test
organisms is calculated. This calculated amount is called the
lethal dose. The majority of toxicity tests (sometimes called
bioassays) are designed to calculate the exact dose which kills
50% of the test organisms. This called the median lethal dose,
or LD50 and is a relative measure is of toxicity. For example,
if substance B has an LD50»1000 mg/Kg, and substance A has an
LD50s500 mg/Kg, given equal doses, substance A is more toxic than
substance B (Figure 1). Other lethal doses (LD20 and LD80, for
example) sometimes used in addition to the LD50 to judge the
toxicity of chemicals at different doses. As seen in Figure 2,
some chemicals (D) are very toxic at low doses and then, as the
dose increases, toxicity inceases only slowly. The opposite can
also occur, where a chemical has a low toxicity at low doses, but
as the dose increases slightly, toxicity increases greatly (C).
When chemicals are dosed into the organism's
environment rather than into the organism itself - as with
airborne contaminants (for inhalation testing), or aquatic
toxicity testing (where the test chemical is dosed into the water
column), measurement of relative toxicity is based on median
lethal concentration, or LC50.
7-3
-------
t/1
l/l
Ul <9
f
100
2 50
FIGURE 1
I
TOO
tooo
00SC (mg/kg)
This Illustration Indicates that compound A is more to* 1c
than I- that Is, A gives the saac response (SOX deaths)
as 8 at a Tower dose.
FXCORE 2
100
S
•8
W M
5 5
ft 3
U 4
i
20 . .
OOSC (mg/ig)
From this Illustration, compound C could be assumed to be
more toxic than compound 0, based on L0so. This could
be Misleading because at lower doses thi situation Is
reversed: at LOg), 0 Is aore toxic than C.
7-4
-------
3. Terns
Terms often encountered when evaluating toxicity data
include:
a. Median Lethal DosefLpSp):
A calculated dose of a chemical which is expected
to kill 50% of an entire defined experimental population.
b. Median Lethal Concentration (LC50): ____
A calculated concentration of a substance in air,
water, or feed, exposure to which, for a specified period of
time, is expected to kill 50% of an entire defined experimental.
c. Lethal Dose Low fLDlOl;
The lowest dose, other than LD50, of a substance
introduced by any route which has been reported to cause death in.
the species of interest.
d. TQXto Pose frovf (TPIQ);
The lowest dose of substance introduced by any
route over a given period of time which is reported to produce
any toxic effect in humans or carcinogenic, neoplastigenic, or
teratogenic effects in animals or humans.
e. Toxic Concentration Low fTClOl:
The lowest concentration of a substance in air,
water, or feed to which humans or animals have been exposed for a
given time period which produced any toxic effect in humans or
carcinogenic, neoplastigenic, or teratogenic effects in animals
or humans.
C. EXPOSURE TIME
Toxic effects are produced by acute or chronic exposure to
chemicals:
o Acute exposure - a single exposure or multiple exposure
occurring within a short time (24 hours or less).
Usually it is a large single dose.
o Chronic exposure - several small doses over a longer
period of time (usually months to years).
-------
Exposures may also be of an intermediate length, termed
subacute, subchronic, or short term exposure:
o Subacute exposure - exposure usually lasts 3 to 5 days.
o Short term exposure - exposure(s) usually lasts one to
two weeks.
o Subchronic exposure - exposure(s) generally lasts three
months.
0. DOSE - DOSES
The frequency administration of a chemical also adds to
characterization of its exposure. Generally speaking,
fractionating the dose reduces the effect. Where a single large
dose of a substance produces a given severe effect, halving the
dose and administering it in two equal, separate doses may
produce less than half of the original effect. In addition,
dividing the original dose into ten doses may cause no ill
effects at all. This decrease in additive effects occurs when
metabolism or excretion takes place between successive doses of
the toxic agent, or when the injury produced is partially or
fully reversed between administrations of the agent.
When chronic effects occur, it is a sign that the agent
accumulates in the body (absorption exceeds metabolism and
excretion) or that effects caused by the agent are irreversible.
Accumulation can also be a result of the frequency of dosing-
there many not be time enough for recovery between doses.
E. DOSE-RESPONSE RELATIONSHIP
The most fundamental concept in toxicology is the dose-,
response relationship. This relationship is based on
assumptions:
o The effect (response) is a result of the known toxicant
administered.
o The response is, indeed, related to the dose through
this reasoning:
o The response is a function of the concentration of
toxicant at a specific site,
o the concentration of toxicant at this specific
site is a function of the dose administered, and
o therefore, response and dose are causally related.
7-6
-------
It is this correlation between the degree of a chosen
response of the test organism's biologic system and the amount of
toxic substance delivered that forms the basic dose-response
relationship. When plotted graphically, this relationship forms
the classic sigmoid curve time and time again (as Figures l and
2) which is indicative of toxicity test results.
As stated previously, the median lethal dose (LD50) is the
most frequently used endpoint in toxicity testing. This relative
toxicity is measured for virtually every new chemical which is
manufactured. Mice or rats are the most frequently used test
animals for such testing.
The concept of LD50,s is not without its shortcomings. The
great majority of LD50 data are calculated based on acute
bioassays. Chronic toxicity cannot be extrapolated from these
data because nothing is known with regard to distribution,
bioaccumulation, metabolism, or excretion of the chemical in the^
body. For example, polychlorinated biphenyls (PCBs) were found
to be relatively non-toxic in acute toxicity tests, but time has
proved PCBs to be highly toxic after chronic exposure. This lack
of chronic toxicity testing has taken it toll on human health in
the past.
Another shortcoming of LD50 data is that there is often
little information to go on for choosing a test species that
mimics human exposure. Each chemical affects the body
differently and thus it is difficult to pick a species which is
affected similarly and with the same sensitivity as humans. For
example, nearly all chemicals known to be carcinogenic in man are
also carcinogenic in animals. One exception, however, is
arsenic, which, although a human carcinogen, is not carcinogenic
to animal species. In addition, as seen if Figure 2, the LD*° is
a single dat point and does not indicate the exact shape of the
dose-response curve. The interval between a non-toxic dose and a
lethal dose is not defined without further testing. It would be
easy to get the wrong impression about the toxicity of a chemical
from such data.
F. RELATIVE INDEX OF TOXICITY
When trying to interpret animal toxicity data as they apply
to humans, it is necessary to use a conversion factor. To do
this, LDSO's (mg/kg) from animal studies are multiplied 70 kg
(the average weight of man) to give a rough estimate of human
toxicity. This conversion is used assuming that humans have
sensitivity to that of the test species to the chemical tested.
-------
All toxicity test data (i.e., LD50) yield information
pertaining to the relative toxicity of tested substances. Some
chemicals are capable of producing death in microgram quantities
while others are essentially harmless in gram quantities.
Toxicologists often classify chemicals based on computed L050's.
Categorizing chemical toxicities makes it clearer when the
toxicologist answers the question, "How toxic is this chemical?"
An example of such a classification scheme is given in Table 7-1.
TABLE 7-1
TOXICITY RATING CHART
Probable Oral Lethal Dose for Humans
Toxicity Bating or Class Dose
For Average Adult
1. Practically nontoxic
2. Slighty toxic
3. Moderately toxic
4. Very toxic
>15 g/kg More than 1 quart
5-15 g/kg Between pint & quart
0.5-5 g/kg Betwe&i ounce & pint
50-500 mg/kg Between teaspoonful
6 ounce
5-50 mg/kg Between 7 drops
ft teaspoonful
<5 mg/kg a taste (less than
7 drops)
5. Bctremely toxic
6. Supertoxic
Source t Toxicology: The Basic Science of Poisons, p. 12
second ed., Osull, Klaassen & Antiur («5.), 1980.
7-8
-------
The LD50 of various chemicals can vary widely depending on
their relative toxicities, as seen in Table 7-2.
TABLE 7-2
Approximate Acute LD50 of a selected variety of chemical
agents (for test animals).
Agent
TSJOr-
mg/kg
Toxicity Class*
ethyl alcohol
sodium choloride
ferrous sulfate
morphine sulfate
phenobarbitol sodium
DDT
Picrotoxin
Strychnine sulfate
nicotine
D-tubocurarin
Hmicholiniun-3
Tetrodotoxin
Oioxin (TCSO)
Botalinus toxin
10,000
4,000
1,500
900
150
100
5
2
1
0.5
0.2
0.10
0.001
O.00001
Slightly toxic
Slightly toxic
Moderately toxic
Moderately toxic
Moderately toxic
Very toxic
Extremely toxic
Extremely toxic
Extremely toxic
Extremely toxic
Supertoxic
Supertaxie
Supertoxic
Supertoxic
* There has been no conversion here from animal data to potential human
toxicity. This column is used here to illustrate how toxicity classes
(Tab.le ) are related to actual u£0 data for various chemicals.
Source: Toxicology: The Basic Science of Poisons, second
ed, Doull, Klaassen t Amdur (eds.), 1980.
7
9
-------
G. FACTORS INFLUENCING TOXICITY
Many factors affect the dose-response relationship and
should be considered not only when designing toxicity test but
also when interpreting toxicity data in specific situations.
Some of these factors attribute to differences in the absorption,
distribution, metabolism.-or excretion of toxic substances. These
factors can be divided into the following categories:
o factors related to the toxic substance
o factors related to exposure
o factors inherent to the person exposed
o environmental factors related to the exposed person
H. FACTORS RELATED TO THE TOXIC SUBSTANCE
o chemical composition - impurities which alter the
toxicity of a substance; chemical stability: pH;
selection of binding group for the test chemical
o physical characteristics - particle size; method of
formulation (alters the chemical nature of the compound
or affects its); volatility; and solubility
o stability and storage of the substance - egradion
products can be more or less toxic than the original
substance
o solubility in body fluids - the more soluble, the more
readily absorbed and distributed to target organs
o carrier - the substance used as a medium in which to
deliver the toxicant
o intentional and non-intentional additives - such as
colorings, preservatives, stabilizers, emulsifiers, and
surfactants
I. FACTORS RELATED TO EXPOSURE
o dose
o concentration
o volume (large volumes needed for low toxicity
chemicals)
o route - gastrointestinal tract, inhalation, skin/eye
contact, ingestion
7-10
-------
o rate - even if a single dose (if, for example,
administered by IV), the difference in delivery of a
few seconds versus a minute can produce huge
differences in the concentrations of toxicant in nearby
organs
o site of delivery - the distribution and metabolism of
toxicants is affected depending upon the administration
site
o duration and frequency of exposure
o administration time - season and time of day affect the
subject's susceptibility
J. FACTORS INHERENT TO THE PERSON
o Sex - Many substances have unequal toxicity to males
and females. The larger percentage of fat on females
allows them to store (and accumulate) more fat-soluble
substances. Differences in sex hormones also affect
the toxicity of various substances. Susceptibilities
of males and females is also different to teratogens as
well as some carcinogens.
o Age - Infants, children, adults and older people all
have differences in their circulatory systems,
musculature, metabolism and excretory systems. These
differences contribute to differences in distribution
and toxicity of substances. For instance, newborns are
less susceptible to central nervous system (CNS)
stimulants than adults, but more susceptible to
suppressants.
o Weight - Body weight of individuals can affect
toxicity of substances due to differences in fat
content, blood volume and body size. In addition, when
comparing test species, those whose body weights are
smaller tend to have a disproportionate decrease
compared to larger organisms. Some suggest that body
surface area should be used to compare toxicities among
species in order to alleviate this discrepancy.
o Nutrition - Diet can change factors in body
composition, physiological and biochemical functioning
and nutritional status of persons. If liver damage has
occurred due to toxic effects of some chemical, then
high protein and carbohydrate diets are used clinically
to treat these patients. Vitamin deficiency also
affects toxicities.
7-11
-------
o Emotional Status - Crowded living conditions cause an
increase in the toxicity of CNS stimulants. Emotional
stability can influence the toxicity of many toxicants.
o Genetics - The presence or absence of different enzymes
in the individuals can changes the toxic effects of
chemicals. For example, individuals lacking the enzyme
G6Pd tend to suffer damage to their red blood cells
when given aspirin or some antibiotics.
o Disease - Diseased animals tend to be more susceptible,
to toxic substances, than healthy ones. It is
difficult to take toxicity data calculated fo-r healthy
animals and interpret it for weakened or diseased
animals. Smokers are also more susceptible to many
toxicants than are non-smokers.
o Immunological status - Differences in the immune
systems of individuals can affect the toxicity of
certain chemicals. Underactive as well as overactive
immune systems can alter susceptibilities to toxic or
relatively non-toxic substances in the body.
K. ENVIRONMENTAL FACTORS RELATED TO EXPOSED PERSONS
o Physical factors - Temperature, barometric pressure,
and radiation are among the major factors influencing
toxicity of various substances. The majority of body
processes are temperature dependent and thus either an
increase or a decrease in body temperature or
environmental temperature can affect toxicities. It
has also been shown that altitude (pressure) affects
the toxicity of some substances, such as digitalis and
ethanol. It is probably the changes in oxygen tension
that causes these changes. The effects of ionizing
radiation, UV radiation and visible light need to be
studied further. Exposures can alter distribution,
metabolism and excretion of some chemicals through
effects on enzyme systems and blood-tissue barriers.
o Social factors - Crowding, handling of test animals,
and cage conditions all influence toxicity of chemicals
to test species.
o Presence of other chemicals - The effects of a single
chemical can be altered significantly by the addition
of one or more other chemicals. The outcome of this
chemical interaction between substances is defined
according to resulting effects:
7-12
-------
Additive - The effect of 2 chemicals is the sum of
the toxicity of each individually such as with 2
organophosphate pesticides. (Ex. 2+3M5).
Synergistic - The effect of 2 chemicals is much
greater than the sum of each alone such as with
carbon tetrachloride and ethanol. (Ex. 2+2"6).
Potentiation - The effect of 2 chemicals, one of
which is non-toxic alone, is much more toxic than
the effect of the toxic chemical alone, as with
isopropanol (not hepatotoxic) and carbon
tetrachloride (a hepatotoxin) (Ex. 0+4-6). Thus
the isopropanol increases the toxicity of carbon
tetrachloride.
Antagonism * The effect of 2 chemicals which
interfere with each other so that the toxicity of
the 2 is less than additive effects of both (Ex.
2+2«3). This relationship forms the basis for
antidotes. There are 4 types of antagonists:
1. Functional: Two chemicals are
counterbalanced by having the opposite effect
on the same physiological function [Example:
Blood pressure is unaltered by dosing with
both a barbiturate (decreases pressure) and
norepinephrine (increases pressure).]
2. Chemical: The reaction between two chemicals
produces a less toxic product: [Example:
dimercaprol chelates metals such as arsenic,
lead and mercury, decreasing their toxicity.]
3. Dispositional: Absorption, metabolism,
distribution or excretion is altered so that
less reaches the target organ as a result of
the addition of another substance. [Example:
The absorption of a substance is decreased by
a dose of ipecac.]
4. Receptor site competition - when two
chemicals bind to the same receptor site:
That is, the less toxic chemical blocks
binding of the more toxic chemical thereby
reducing the overall toxicity. [Example:
Atropine is given to treat organophosphate
pesticide poisoning.]
7-13
-------
L. ACUTE AND CHRONIC EXPOSURES
At a facility site, workers may be subjected to both acute
and chronic exposures of toxicants.
In general, acute exposures to chemicals in air are more
typical in transportation accidents, fires, or releases at
chemical manufacturing or storage facilities. Acute exposures
occur when workers must be close to the substances in order to
control the release (patching a tank car, off loading a corrosive
material, etc.) or contain and treat the spilled material. Once
the immediate problems have been alleviated, exposures tend to
become more chronic as cleanup progresses.
Chronic exposures usually are likely to be associated with
long-term remedial operations. Contaminated soil and debris from
emergency operations may be involved, soil and ground water may
be polluted, or containment systems may hold diluted chemicals.
At abandoned waste sites, however, personnel engaged in sampling
or handling containers, bulking compatible liquids, etc. face an
increased risk of acute exposures from splashes, mists, gases, or
particulates.
The effects of acute or chronic exposure to toxicants can be
manifested in many ways. There are local effects, systemic
effects, acute effects (noticed right away) chronic effects and
effects which do not show up until a generation or more later.
We will look now at effects other than local and systemic.
M. CARCINOGENIC EFFECTS
Agents that cause cancer in organisms are carcinogens. It
is the exposed organism that develops cancer although, generally
speaking, most cancers do not develop until 20 to 30 years after
exposure to the harmful agents. There are two types of
carcinogenic mechanisms:
1. Genotoxic
These are carcinogens that interact with DNA-altering
genes. There are three types:
o Direct or primary carcinogens: chemicals that act
without any bioactivation, for example, bis-
(chloromethyl) - ether, ethylene dibromide, and
dimethyl sulfate.
o Procarcinogens: chemicals that require
biotransformation to activate them to a carcinogen
- for example, vinyl chloride and 2-naphthylamine.
7-14
-------
o Inorgarnic carcinogen: leads to altered genetic
expression by selective alteration in fidelity of
DNA replication (chromium, nickel, arsenic).
2. Epigenetic
These are carcinogens that do not interact directly
with genetic material. Several types are possible:
o Co-carcinogen: increases the overall response to
a carcinogen when they are administered together-
for example, sulfur dioxide, ethanol, and
catechol.
o Promoter: increases response of a carcinogen when
applied after the carcinogen, but will not induce
cancer by itself - for example, phenol and
saccharin.
o Solid state: works by unknown mechanism, but
physical form vital to effect (asbestos and metal
foils).
o Hormone: usually is not genotoxic, but alters
endocrine balance; often acts as promoter (DES and
estrogens).
o Immunosuppressor: mainly stimulates virally
induced, transplanted, or metastatic neoplasms by
weakening the host's immune system
[antilymphocytic serum, used in organ
transplants).
Some carcinogens may have a "safe" threshold level
below which no cancer develops, while other carcinogens may have
a "zero" threshold - that is, cancer could result from one
molecule and one exposure. For example, some genotoxic
carcinogens induce cancer after a single exposure, act in a
cumulative manner, or act with other genotoxic carcinogens to
affect the same organs. on the other hand, some epigenetic
carcinogens only induce cancer under high concentrations and long
exposure times.
Human lifestyle is the most common cause of cancer, as
seen in Table 7-3.
7-15
-------
TABLE 7—3
OUEES CT BCMW GUOSS
CauM « of Total Deaths Due to Cancer
Occupational 1 to 51
Leukemia, lyrrphotm, etc. 10 to 151
Lifestyle 72%
lbbaoco-related 231
Tobacco S alcohol 51
Olet —
Nitrite, mycotoxins, etc. St
Iatrogenic (caused by doctor) it
High fat 44%
Of all cancers, only lung cancer has significantly
increased over the years.
Deaths due to cancer in the U.S. rank second only to
heart disease, the leading killer (see Table 7-4).
TABLE 7—4
ONCER CEKEB RASE
Cancer ranks second to heart disease as a cause of death in
the U.S.t
Cause of Death Oeath Fate/100,000* I of Total Deaths
All causes
866
100.0%
Heart disease
433
50.01
Cancer
184
21.21
Cerebrovascular
77
8.9%
Accidents
48
5.5%
Pneumonia
20
2.3%
Cirrhosis
14
1.6%
All Others
90
10.5%
*1979 Unadjusted rates iron The Nbrld Almanac and Book of Facts, 1982
7 - 16
-------
There are many industrial chemicals that facility site
workers can come into contact vith which induce cancer. A few of
these include halogenated hydrocarbons, and polynuclear aromatic
amines. Such chemicals as benzene, benzyl chloride,
benzo(a)pyrene, nitrosamines and acrylonitrile are included.
Facility site workers must be careful to protect themselves from
exposure to all substances, as many new carcinogens are detected
each year by researchers. Regulatory agencies, such as OSHA
(Occupational Safety and Health Administration) use this
scientific evidence to place standards and exposure limits on
known and suspected carcinogens [see Table 7-5).
TABLE 7-5
Category
CXAS5ZFXCATIGN OF SOBSTRNCES AOCDTODG 10 WUKhU)
GSA Kt£ FOR 0UC310GENS*
Scientific Evidence Model Standard Exposure Limit
I.
Confirmed
carcinogen
Carcinogenic In
hurans, In 2
mamnalian species
or in repeated tests
in the sane species
Emergency
tenporary
standard;
permanent
standard in 6
months
Lowest feasible
level, or banned
if suitable sub-
stitute is
available
II. Suspect Evidence from only one
carcinogen animal species or if
evidence is inconclu-
sive
III. Insufficient evidence
to classify it in a
higher category
IV. SUbstanees that could
fall Into the 3 higher
categories, but not
found In U.S. work-
places
Permanent stand-
ard
Low enough to
prevent acute or
chronic toxic
effects
Do standard, but
would be listed as
needing more data
Mb standard, listed
to alert to potential
danget
* From Identification, Classification, and Regulation of Occupational
Carcinogens. OSHA Proposed Rule, 42FR54148* Oct. 4, 1977.
7-17
-------
N. TERATOGENIC EFFECTS
Teratology is the study of congenital malformations.
Teratogenic effects are manifested in the offspring of parents,
resulting from direct exposure of the embryo or fetus to the
toxic agent itself. Examples of known teratogens include
diethylstilbestrol (DES) and thalidomide. Congenital
malformations can be caused by:
o heredity
o maternal diseases (German measles, other viruses)
and maternal malnutrition
o physical injury
o radiation
o drug and chemical exposures
Host structural abnormalities take place during the
embryonic period (5-7 weeks), when many women are unaware of
their pregnancy.
Physiologic and minor defects occur during the fetal period
(8-36 weeks).
It is necessary to evaluate chemical exposure during each
day of pregnancy, as, with thalidomide, birth defects in rats
occurred only when the drug was administered during the twelfth
day of gestation. Animal studies have implicated many chemicals
as being teratogenic. These include aspirin, caffeine, quinine,
thiadiazole, boric acid, DMSO, chloroform, carbon tetrachloride,
benzene, xylene, cyclohexanone, propylene glycol, acetamides,
formamides and sulfanamides. Of these chemicals, fewer have been
shown to be human teratogens including:
o
aspirin
o
alcohol
o
anesthetic gases
o
organic mercury compounds
o
PCB's
o
ionizing radiation
7-18
-------
o German measles
o thalidomide
o dioxin
Any female field activity personnel who may even suspect
that they are pregnant should consider reassignment throughout
the gestation period.
O. MUTAGENIC EFFECTS
Mutagens are agents which cause a change in genetic material
(DNA) of parental egg or sperm cells. The parent is not
affected, but the offspring suffer the harmful effects.
Agents known to be human mutagens include:
o ethylene oxide (a hospital sterilant)
o ethyleneimine (an alkylating agent)
o ionizing radiation
o hydrogen peroxide
o benzene
o hydrazine (used in rocket fuel)
The concern over DNA damage caused by mutagenic agents goes
beyond harm to the gene pool. It is possible and there is much
evidence suggesting that cell mytations may also cause
carcinogenic or teratogenic effects. It appears that
carcinogenicity, mutagenicity and teratogenicity may be
interrelated due to scientific evidence linking DNA as a target
for carcinogens.
o Many carcinogens are also mutagens.
o Inhibitors and inducers of carcinogenesis affect
mutagenic activity.
o Chemicals often are tested for mutagenic and
carcinogenic activity in the same cell systems.
o Defects in DNA repair predispose to cancer development.
o Several inheritable or chromosomal abnormalities
predispose to cancer development.
7-19
-------
Initiated dormant tumor cells persist, which is
consistent with a change in DNA.
Cancer is inheritable at the cellular level and,
therefore, may result from an alteration of DNA.
Most, if not all, cancers display chromosome
abnormalities.
7-20
-------
STUDENT EXOOSES
I. Rate the following chemicals from least toxic to most toxic
based on their LD50S for oral dosage to rats (in mg/kg) i
Benzene ¦ 3800
Calcium chloride - 1000
Caffeine - 192
1,2-dichloreethane - 680
Nicotine - S3
Sodium chloride - 3900
ZI. Construct a dose-response relationship (graphically) for a
conpound with the following lethal concentrations!
W10 » 200 mg/kg (caused death in 51 of the animals)
U>2(t * 600 mg/kg
IDS0 ¦ 1000 mg/kg
U)g0 ¦ 1400 mg/kg
III. From the LDcQa given in Exercise X, give the Toxicity
Rating or Class that each chemical fits into through use of Table
1. taneirber that 1 kg ¦ 1000 g.
Benzene -
Calcium chloride -
Caffeine -
1,2-dicfiloroethane -
Nicotine -
Sodiun chlorite -
7-21
-------
UNIT 8
CHEMICAL HAZARD RECOGNITION
A. DEFINITIONS
Many very important regulations have been passed in recent
years, regarding hazardous materials and hazardous wastes. In
response to these regulations, a great many informational
resources have been developed to assist those affected by the
regulations. These resources can be very helpful to those who
are involved in protecting the health are safety of all those
coming in contact with these hazardous substances if time and
effort are spent collecting and learning to use these diverse and
sometimes very comprehensive aids. In order to use informational
resources to recognize chemical hazards, it is necessary to
understand terms (or "jargon").
B. DEPARTMENT OF TRANSPORTATION
One of the earliest efforts to organize the handling of
hazardous materials was instituted by the Department of
Transportation (DOT) in the 49 CFR 172.102 Hazardous Material
Tables. This comprehensive guide is still one of the most
frequently used sources of information pertaining to hazardous
materials available. Many other guides such as the Emergency
Response Guide (ERG), the Coast Guard's Chemical Hazard Response
Information System (CHRIS), and the National Fire Prevention
Association's Fire Protection Guide on Hazardous Materials
utilize definitions formulated by DOT. The following are the
most important definitions:
o Explosive A — Materials that have a mass explosion
hazard such as TNT.
o Explosive B ~ Materials that have a fire hazard such
as solid rocket fuels.
o Explosive C — Materials that have only a relatively
small hazard as compared to explosives A and B.
Examples are common fireworks.
o Poison A — Poisonous gases or liquids that are
extremely dangerous even in very small amounts, such as
hydrogen cyanide.
8-1
-------
o Flammable Gas — A compressed gas is considered
flammable when either a mixture of 13% or less (by
volume) with air forms a flammable mixture or the flam-
mable range with air is wider than 12% regardless of
the lower limit. Methane Propane and Acetylene are
examples.
o Nonflammable Gas — Those gases that will not burn in
any concentration of air or oxygen. A number of these
gases, however, will support combustion. Examples are
anhydrous ammonia and oxygen.
o Flammable Liquid -- Any liquid with a flash point below
100 degrees C. Examples are benzene, toluene, xylene,
acrylonitrile.
o Combustible Licruid — Any liquid that has a flash point
above 100 degrees C and below 200 degrees C. Examples
are fuel oil, and creosote.
o Flammable Solid — Any solid material that is prone to
cause fires through friction or contact with water, or
spontaneous combustion and when, ignited, burn
vigorously. Examples are calcium carbide, magnesium
metal, potassium metal, sodium metal.
o Oxidizers A substance such as chlorate,
permanganate, inorganic peroxide, or a nitrate that
yields oxygen readily to stimulate the combustion of
organic material. Examples are calcium hypochlorite
(HTH), hydrogen peroxide, and ammonium nitrate.
o Organic Peroxides — An organic compound which contains
the bivalent -0-0- structure and which may be
considered a derivative of hydrogen peroxide where one
or more of the hydrogen atoms have been replaced by an
organic radical.
o Poison B — Those substances, liquid or solid, other
than Class A poisons or irritating substances, that
have been considered toxic to humans or are presumed to
be toxic to because they fall into any one of the
following categories when tested on laboratory animals:
(1) oral toxicity, (2) inhalation toxicity, (3) skin
absorption toxicity. Examples are tetraethyl lead, and
potassium cyanide.
o Irritant Materials — A liquid or solid substance which
upon contact with fire or when exposed to air gives off
dangerous or intensely irritating fumes. Examples are
brombenzyl cyanide, Chloracetophenone, and tear gas.
8-2
-------
o Infectious Substance/Etioloaic Agent — Viable
microorganisms or their toxins, which cause or may
cause human disease ("etiologic agents'*), are those
agents listed in 49 CFR 72.3 (c). Examples are Polio
virus, enterotoxin, or csorvnebacterium diphtheriae
bacteria. Such agents may be found in body parts,
excreta, sewage, diagnostic specimens, or biological
products.
o Radioactive Substances — Those products which emit
various types of radiation that consists of particles
or photons of energy, such as neutrons, gamma rays, or
x-rays. Examples are cesium, barium, and uranium.
o corrosive Liquids — A liquid that causes visible
destruction or irreversible alterations in human skin
or tissue at the site of contact or in the case of leak
age from its container, a liquid that has a severe
corrosion rate on steel. Examples are hydrochloric
acid, sulfuric acid, and hydrofluoric acid.
o Corrosive Solid — A solid that causes visible
destruction or irreversible alternations in human skin
tissue at the site of contact. Examples are potassium
hydroxide, soda lime, and sodium hydroxide.
o ORM-A — Items that are anesthetic, irritant, or
noxious. Examples are carbon tetrachloride,
chloroform, 1,1,1 trichlorethylene, and
trichlorethylene.
o ORM-B — Items which can damage vehicles through
aluminum corrosion. Examples are metallic-mercury, and
calcium oxide.
o ORM-C — Catch-all category. An example is asbestos.
o ORM-E ~ Hazardous waste category. Usually a mixture
of substances that demonstrate one or more of the
characteristics of ignitability, reactivity,
corrosivity, EP toxicity. The container or shipping
name usually contains the abbreviation NOS (not
otherwise specified.)
The recognition of hazardous materials, wastes, or
substances can be further aided by the use of lists
formulated by specific acts, regulations or agencies.
8-3
-------
C. THE RESOURCE CONSERVATION AND RECOVERY ACT (RCRA)
1. Hazardous Haste Defined
Under RCRA a waste is defined as hazardous if it
basically meets any of the following criteria:
a. If it exhibits ignitability, corrosivity,
reactivity, and or extraction procedure toxicity.
b. If it is waste from a nonspecific source, or
discarded commercial products, off-specification products,
container residues, or spill residues.
c. If it is a mixture of solid waste and a hazardous
waste, and exhibits one of more of the following: ignitability,
corrosivity, reactivity, or extraction procedure toxicity.
Since there are further criteria for classifying wastes
as hazardous, students should refer to 40 CFR Part 261, subpart A
for further details.
2. EPA Hazardous Characteristics Definitions
a. Ignitability (I) - A solid waste is considered
ignitable if a representative sample of the waste has any of the
following properties:
(1) It is a liquid other than an aqueous solution
containing less than 24% alcohol by volume and has a flashpoint
less than 60 degrees C.
(2) It is not a liquid and is capable under
standard temperature and pressure, of causing fire through
friction, absorption of moisture or spontaneous chemical changes
and, when ignited, burns so vigorously and persistently that it
creates a hazard.
(3) It is an ignitable compressed gas.
(4) It is an oxidizer.
b. Corrosivity (CI - A solid waste is considered
corrosive if a representative sample of the waste has either of
the following properties:
(1) It is aqueous and has a pH less than or equal
to 2 or greater than or equal to 12.5 as determined by a pH meter
or other EPA approved method.
8-4
-------
(2) It is a liquid and corrodes steel without
agitation at a rate of 6.35 mm per year at a test temperature of
130 degrees F.
c. Reactivity fR) - A solid waste is considered
reactive if a representative sample of the waste has any of the
following properties:
(1) It is normally unstable and readily undergoes
violent change without detonating.
(2) It reacts violently with water.
(3) It forms potentially explosive mixtures with
water.
(4) It generates toxic gases, vapors, or fumes
when mixed with water in sufficient quantity to be dangerous to
human or environmental health.
(5) It is a cyanide or sulfide bearing waste
which, when exposed to pH conditions between 2.5 and 12.5 can
generate gases, vapors, or fumes which present a danger to public
or environmental health.
(6) It is capable of detonation or explosive
reaction if it is subjected to a strong initiating source or if
heated under confinement.
(7) It is readily capable of detonation or
explosive decomposition or reaction at standard temperature and
pressure (STP).
d. EP Toxicity (E\ - A solid waste is considered EP
toxic if using the test methods set forth in Appendix II of Part
261, the extract from a representative sample of the waste
contains any of the contaminants listed in Table 8-1 at a
concentration equal to or greater than the value given in the
table.
-------
TABLE 8—1
Maximum concentration of contaminants
far characteristic of EP Ttodcity
EPA
Maximum
hazardous
Contaminant
concentration
waste number
(milligrams per
liter)
0004
Arsenic
5.0
0005
Barium
100.0
0006
Cadmium
1.0
0007
Chromium
S.O
0008
Lead
5.0
0009
Mercury
0.2
0010 Selenium 1.0
0011 Silver 5.0
0012 Ehdrin U,2,3,4,10-10-hexa- 0.02
chloro-1,7-epoocy -4,4a,5,6,7,8,8a-octahydro-
l,4-end^5,6-dij»th-ano-naphthalene.
0013 Lindane (1,2,3,4,5,6-hexa-chlor- 0.4
ocyclohexane, gaums isomer.
0014 Methaxychlor (1,1,1-Trichloro-
2,2-tois (p-iwethoxyphenyl ethane).
0015 Texaphene (C10K10C12 Technical 0.S
chlorinated caiqphene 67-69%
chlorine).
0016 2r4D* (2,4-Dichlorophenoocyaceticacid).lO.O
0017 2,4,5-TP, Sllvex (2,4,5-Trichlo- 1.0
rophenoocypropionic acid).
8-6
-------
e. Acute Hazardous Waste (H) - A hazardous waste is
considered acute if it (l) exhibits characteristics
(ignitability, corrosivity, reactivity, EP toxicity), (2) has
been found to be fatal to humans in low doses. If human data are
unavailable the following animal toxicity will be considered an
oral LD50 (rat) of less than 50 mg/kg, an inhalation LC50
(rabbit) of less than 200 mg/kg. It is also considered acutely
hazardous if it is otherwise capable of causing or significantly
contributing to an increase in serious irreversible or
incapacitating reversible illness, or (3) it contains any of the
toxic constituents listed in Appendix A, Figure 5.
f. Toxic Waste m - a waste is considered toxic if
it contains any constituent listed in Appendix A, Figure 4, using
the test methods listed in 40 CFR or meets the criteria which
classify it as capable of posing a substantial present or
potential hazard to human or environmental health when improperly
treated, stored, transported, disposed of, or otherwise managed.
3. Hazardous Waste List
For a specific hazardous wastes list, see Appendix A,
Figure l at the end of this manual.
D. CERCLA (SUPERFUND)
CERCLA, enacted December 11, 1980, established broad federal
authority to deal with releases or threats of releases of
hazardous substances from vessels and facilities. The Act
specifies an initial list of 696 hazardous substances.
The Act requires the person in charge of a vessel or
facility to notify the National Response Center immediately when
there is a release of a designated hazardous substance in an
amount equal to or greater than the reportable quantity for that
substance. The main purpose of the notification requirements is
to alert governmental officials of a release of hazardous
substances that may require rapid response to protect public and
environmental health.
Appendix A, Figure 2, at the end of this manual, is a list
published by EPA to satisfy the requirement of Section 306(a) of
CERCLA that all "hazardous substances," as defined in CERCLA,
shall be listed as hazardous materials under the Hazardous
Materials Transportation Act.
The CERCLA List also includes substances listed in the
Federal Water Pollution Control Act, the Solid Waste Disposal Act
and the Clean Air Act.
-------
E. CLEAN WATER ACT (1977)
The Clean Water Act (formerly the Federal Water Pollution
Control Act) (1972/1977) set forth comprehensive revisions of
previously existing water pollution control laws. Major
provisions of the Act, as amended in 1972 were:
o Standards for direct discharges into waters
o Standards for discharges into publicly owned treatment
works
o Provisions for responding to, preventing, and
penalizing spills of oil and hazardous substances
Regarding spills of oil and hazardous substances, EPA
designated a list of hazardous substances and defined what
constitutes a harmful discharge of both oil and each hazardous
substance.
The following are chemicals listed by EPA under Section
307(a) of the Clean Water Act. This list includes any toxic
pollutant or combination of pollutants which has been determined
hazardous due to the following criteria:
o Toxicity of the pollutant
o Resistance of the pollutant
o Degradability of the pollutant
o Its present or potential toxic effects on aquatic
organisms
Each toxic pollutant listed is subject to effluent
limitations resulting from the application of the best available
technology economically achievable. If determined by EPA,
effluent standards (which may include a prohibition) establishing
requirements for a toxic pollutant can be promulgated.
Toxic Pollutants List - For specific toxic pollutants, see
Appendix A, Figure 3, at the end of the manual.
F. CHEMICALS LIST BY EPA UNDER SECTION 112 OF THE CLEAN AIR ACT
o Benzene
o Mercury
o Radionuclides
o Vinyl chloride
8-8
-------
G. CHEMICAL TERMINOLOGY
1. Physical Properties
The successful use of health and safety rescue guides,
in addition to understanding definitions, requires knowledge of
the chemistry of the material. Chemicals by nature of their
intended use, react in a variety of ways and demonstrate a wide
degree of physical characteristics, many of which must be
understood if they are to if handled in a safe manner. One of
the most used information sources, the Material Safety Data Sheet
(MSDS) relies heavily on DOT definitions and the physical
properties of chemicals to diagnose potential hazards.
2. Density/Specific Gravity
The density of a substance is usually defined as mass
per unit volume or in somewhat less accurate but simpler terms,
the weight of a given substance divided by the volume of the
container it is being measured in. The density of 1000 gms of
water in a 1000 cm container is 1000 gms 1000 cm3 or 1 go per
cm3.
The significance of densities can be noted when
investigating or sampling a drum or tank with an open top. If
the drum has been open to the accumulation of rain water and the
substance in the drum is Benzene with a density of 0.879 gm per
cm3, then the Benzene is lighter or has less density than water
and will float on top. A sample taken from the top will most
likely include the Benzene. Since Benzene is highly flammable
and very volatile, and to some extent toxic, personnel working
near the container must be constantly on guard for explosion,
fire, or asphyxia.
If in the above example the substance were Carbon
disulfide with a density of 1.274 gm/cm it would be heavier than
water and would sink to the bottom of the container below the
water layer. A sampling device such as the Coliwasa would be
needed to take a true representative sample of the container.
Little or no danger from fire, explosion, or toxic fumes would be
present.
In sampling streams, sewers, or ponds, if the density
of the substance is greater than 1.00 gm per cm3, then it will be
found on the bottom of the water layer. If the density is less
than 1.00 gm per cm3, then it will be found on top. Table 8-2 is
a list of some common liquids and solids and their densities.
-------
TABLE 8-2
Densities of some common liquids and solids
Density Density
Substance ig/ca? at 20^9 (lb/ft3 at 68°F)
Acetone 0.792 48.42
Aluminum 2.70 168.48
Benzene 0.879 54.85
Carbon disulfide 1.274 79.50
.Chloroform 1.489 92.91
Diethyl ether 0.730 45.55
Ethyl alcohol 0.791 49.36
Gasoline 0.66-0.69 41.0-43.0
Kerosene 0.82 51.17
Lead 11.34 707.62
Mercury 13.6 848.64
Silver 10.5 655.20
Sulfur 2.07 129.17
Turpentine 0.87 54.29
Water (4%) 1.00 62.40
8 -
10
-------
3. Vapor Density
In most cases, liquids or solid density is compared to
water. In the case of vapors, density is compared to air at
standard atmospheric pressure and density, or if a direct
comparison of existing conditions of the ambient air. If the gas
being measured is heavier than air, it will have a tendency to
settle to the lowest physical point before eventually dispersing.
If, on the other hand the gas being measured is lighter
than the ambient air, it will rise and quickly disperse.
Gases with densities greater than air create three
hazards. First, if the vapor displaces enough air to reduce the
atmospheric concentration of oxygen below 16% (21% is normal)
asphyxia (death by suffocation) may result. Second, if the
vapor is toxic, then inhalation dangers are present. Third, if
the gas is explosive, explosive concentrations may accumulate in
depressions, ditches, wet wells sewers, etc., where they are
often overlooked or out of normal scrutiny. Table 8-3 is a list
of common gases that have been compared to air = 1. Normal
density of air at standard temperature and pressure (STP) is
.0012 gm per cm3.
TABLE 8-3
Vapor densities off some cowman gases
Density
Vapor Density
Gas
(g/1 at 0%)
(air » 11
Acetylene
1.16
0.899
Armenia
0.76
0.589
Carbon dioxide
1.96
1.52
Carbon monoxide
1.25
0.969
Chloride
3.17
2.46
Fluorine
1.70
1.32
Hydrogen
1.09
0.07
Hydrogen chloride
1.63
1.26
Hydrogen cyanide
1.21
0.938
Hydrogen sulfide
1.S2
1.18
Methane
0.714
0.553
Nitrogen
1.25
0.969
Oxygen
1.43
1.11
Ozone
2.14
1.66
Propane
1.96
1.52
Sulfur dioxide
2.86
2.22
8-11
-------
4. Vapor Pressure
Vapor pressure is defined as the pressure exerted by a
vapor against the sides of a closed container. The vapor pressure
of a substance is dependent on temperature and is specific to
that liquid. As temperature rises, the vapor pressure exerted on
a closed container increases, increasing the danger of rupture.
If the container is open, the vapor pressure is relieved by rapid
vaporization. There is a direct relationship between the lower
boiling point of a lower density liquid and the greater vapor
pressure it will exert on the container at a given temperature.
In somewhat simpler terms, the higher the evaporation rate of a
substance, the greater the chances of a build-up of pressure
inside a heated container.
Values for vapor pressure are most often given as
millimeters of mercury (mm Hg) at a specific temperature. Table
8-4 gives the vapor pressure of some common liquids.
TABLE 8-4
Vfapor pressures of some ommuu liquids
Temperature
I00)
Mater
(imi of Hg)
Ethyl Alcohol
(mm of Hg)
Benzene
(mm of Hg)
-10
2.1
5.6
15
0 4.6
12.2
27
10
9.2
23.6
45
20
17.5
43.9
74
30
31.8
78.8
118
50
92.5
222.2
271
75
289.1
666.1
643
100
760.0
1,693.3
1,360
8-12
-------
5. Boiling Point
The boiling point is the temperature at which a liquid
changes to a vapor. A major consideration with toxic substances
is how they enter the body. With high-boiling-point liquids, the
most common method of entry is by body contact. With low^-
boiling-point liquids, generally it is by inhalation.
6. Melting Point
The temperature at which a solid changes to a liquid is
the melting point. This temperature is also the freezing point.A
substance often exhibits marked differences in properties
depending on the phase it is in. Liquids may be explosive or
highly reactive, while solids may be relatively inert. Personnel
dealing with substances that may exhibit a phase change should be
aware of the dangers.
7. Solubility
Solubility is defined as the ability of a solid,
liquid, or gas to dissolve in a solvent. An insoluble substance
can be physically mixed or blended in a solvent fora short time,
but is unchanged when it finally separates. The solubility of a
substance is independent of its density or specific gravity, but
can be closely related to vapor pressure and boiling point.
Solubility is of particular importance when determining
the ability of a substance to disperse or migrate from one area
to another, and to the ability to locate, sample, or recover
hazardous materials. Insoluble liquids for example, can be
located in a stratified layer in a container or on the top or
bottom of a lagoon. Soluble materials, on the other hand, are
virtually impossible to locate, sample, or recover once they have
mixed with a solvent.
Although solubilities vary greatly, water is commonly
referred to as the universal solvent since nearly every
substance, at least to some degree, is soluble in it. Solubility
is measured in parts per million (ppm) 1 ppm = .0001 %,
approximately 1 mg/1.
Solubilities are often influenced by external factors
such as pH. Insoluble heavy metal precipitates often become
quite soluble in water when the pH is lowered. In some cases, pH
can be lowered by subsoil conditions.
8. Flashpoint
The definition of flashpoint is the minimum liquid
temperature at which a spark or flame causes an instantaneous
flash in the vapor space above the liquid.
8-13
-------
The relative flammability of a substance is based on
its flashpoint. An accepted relationship between the two is:
o High flammability - Flashpoint less than 100
degrees F.
o Moderate flammability - Flashpoint greater than
100 degrees F but less than 200 degrees F.
o Relatively inflammable - Flashpoint greater than
200 degrees F.
Table 8-5 relates the physical properties to the
combustion of Butyl alcohol and Xylene.
TABLE 8-5
Physical properties related to the coribustion of
Butyl Alcohol and Xylene
Boiling Flash Fire Autoignition Lcmer Upper
Point Point Point Tenperature Q
-------
9. Chemical Compatibility
The term chemical compatibility, at least on the
surface, appears to have a relatively straight forward
definition. If two chemicals in contact with each other do not
react in any way, they are said to be compatible. It should be
remembered however, that the speed of a chemical reaction is
dependent on factors such as temperature, concentration, and
physical state. Chemicals which appear to be compatible may in
fact simply be slow in reacting.
In the normal routine of Agency personnel in field
work, some mixing of chemicals is inevitable. It is critical for
personnel working with a variety of chemicals to know the
compatibility of these chemicals. The result of mixing of
incompatible chemicals could range from the formation of highly
toxic gas to violent fire or explosion Table 8-7 illustrates some
of the results of mixing incompatible chemicals.
TABLE 8-7
Hazards doe to cHadeal reactions (incompatibilities)
- Generation of heat - e.g., acid and water
- Fire - e.g., hydrogen sulfide and calcium hypochlorite
- Bqjlosion - e.g., picric acid and sodium hydroxide
- Toxic gas or vapor production - e.g.* sulfuric acid and plastic
- Flammable gas or vapor production - e.g., acid and metal
- Formation of a substance with a greater toxicity than the reactants -
e.g., chlorine and ammonia
- Formation of shock- or friction-sensitive compounds
- Pressurization of closed vessels - fire extinguisher
- Solubilization of toxic substances - e.g., hydrochloric acid and chromium
- Dispersal of toxic dusts and mists
- Violent polymerization - e.g., ammonia and acrylonitrile
8-15
-------
Understanding chemical compatibility must not be left
to chance. A wide variety of resources has been developed to
assist field personnel in this task. Table 8-8 shows some of
the possible incompatible combinations.
TABLE 8-8
Mon-ooepatible cheaicals
00 NOT GCMCM?
Alkali metals, such as calcium, potassium, and sodium with water,
carbon dioxide, carbon tetrachloride, and other chlorinated
hydrocarbons.
Acetic acid with chromic acid, nitric acid, hydroxy 1 containing
compounds, ethylene glycol, perchloric acid, peroxides and
permanganates.
Acetone with concentrated sulfuric and nitric acid mixtures.
Acetylene with copper (tubing), flourine, bromine, chlorine,
iodine, silver, mercury, or other compounds.
Ammonia, anhydrous with mercury, halogens, calcium hypochlorite or
hydrogen flouride.
Ammonium nitrate with acids, metal powders, flammable fluids,
chlorates, nitrates, sulphur and finely divided organics or other
combustibles.
Bromine with ammonia, acetylene, butadiene, butane, hydrogen,
sodium carbide, turpentine or finely divided metals.
Chlorates with ammonium salts, acids, metal powders, sulfur,
carton, finely divided organics or other combustibles.
Chromic acid with acetic acid, napthalene, camphor, alcohol,
glycerine, turpentine, and other flamnable liquids.
Chlorine with ammonia, acetylene, butadiene, benzene and other
petroleum fractions, hydrogen, sodium carbides, turpentine, and
finely divided powered metals.
Hydrogen peroxide with copper, chromium, iron, most metals or
their respective salts, flammable fluids, and other combustible
materials, aniline* and nitro-rnethane.
Hydrogen sulfide with nitric acid* or oxidizing gases.
8-16
-------
TABLE 8-8 (cont)
Aniline with nitric acid, hydrogen peroxide or other strong
oxidizing agents.
Iodine with acetylene or ammonia.
Mercury with acetylene, fulminic acid, or hydrogen.
Nitric acid with acetic, chromic and hydrocyanic acids, aniline,
carbon, hydrogen sulfide, flammable fluids or gases, and
substances that readily become nitrated.
Oxygen wil oils, grease, hydrogen, flammable, liquids, solids and gases.
Oxalic aiod with silver or mercury.
Perehloris acid with acetice anhydride, bismuth and its alloys, alcholol, paper,
wood and other organic materials.
Hydrocarbons, generally, withl fluorine, chlorine, bromine, chromic acid or
solium peroxide.
Phosphorus perntootide with water.
Potassium permangante with glycerine, ethylene glycol, benzaldetnde, or sulfuric
add.
Sodium peroxide with any caddizable substances, far instance: methanol, glacial
acetic acid, acetic anhydride, benzaldehyde, carbon disulfide, glycerine,
ethylene lyol, ettyl acetate, furfural, and so on.
Sulfuric acid with chlorates, perdUcrates, permanganates and water.
8-17
-------
In the case of unknown chemicals, chemical analysis by
a laboratory is the only way to determine, with some degree of
certainty, possible incompatibility. Care should be exercised
not to assume the results of a specific test are sufficient to
determine compatibility for an entire site.
Response personnel who must determine compatibilities
should refer to "A Method for Determining the Compatibility of
Hazardous Wastes (EPA 600/2-80 076)," published by EPA's Office
of Research and Development.
Field personnel may at times find it is impossible to
ascertain laboratory compatibility tests. In the absence of such
tests, as a minimum safeguard, simple field tests should be
performed. The following tests represent a minimum field testing
for compatibility.
H. CHEMICAL TESTS
1. Hater Reactivity and Solubility
a. Purpose
This method is designed as a qualitative test for
the reactivity and solubility of unknown liquid wastes with
water.
b. Summary
A small volume of liquid waste is mixed with water
and observed for miscibility, rise in temperature, precipitation,
and gas formation.
c. Sampling Procedure
The sample should be collected and tightly sealed
from atmospheric reaction. Tests should be performed as soon as
possible.
d. Apparatus
o Test tube
o Liquid thermometer
o 10 ml disposable pipets
o Glass stirring rods
8-18
-------
e. Procedure
o Pipet 10 ml of water into test tube. The
test tube should be clamped securely to a
stand at a 45 degree angle to prevent
splattering in the event of a violent
reaction.
o The temperature of the test solution and
water should be nearly equal.
o Insert a thermometer and record the
temperature.
o Slowly add 10 ml of test sample to the test
tube. The liquid should drain slowly down
the inside of the test tube any addition
should be stopped if an immediate reaction
occurs.
o Mix the sample with a glass stirring rod.
o Observe mixture for incompatibility signs
such as liquid/liquid phase separation, gas
or solids formation, color or temperature
changes.
f. Conclusion
Gases involved may be toxic or explosive.
Temperature rise is an indication of exothermic activity that
might lead to spontaneous fire or explosion. Color change or
phase separation is indicative of chemical incompatibility that
may have deleterious effects.
2. pH
a.
a solution.
b.
paper.
c.
Purpose
To determine the hydrogen ion concentration pH of
ftpp^yaty?
Small test tube or beaker and pH range testing
Sample Collection
Perform test immediately.
8-19
-------
d.
Procedure
o Approximately 10 mis of sample is placed in a
small beaker or test tube.
o The indicator strip of pH paper (hydrion
paper) is either immersed in the sample or a
drip of sample is placed on the test strip.
o The color developed on the test strip is
compared to the color chart supplied with the
test package.
e. Conclusion
Solution below pH 2.0 and above pH 12.5 should be
handled with care as acids and bases.
3. Compatibility of Liquid Waste/Liquid Waste
a. Purpose
This test is designed to determine the
compatibility of liquids of unknown composition at ambient
temperatures.
b. gampie HanflUnq
Samples should be collected in closed containers
prior to testing.
c. Apparatus
o Small glass beaker
o 10 ml disposable pipets
o Liquid thermometer
o Glass stirring rod
d. Procedure
Pipet 1 ml of the first unknown waste into a
beaker. Place thermometer in the liquid. Record temperature.
Add 1 ml aliquots of the other waste to be tested, stirring after
each addition. Note any rise in temperature gas bubbles, or
precipitation of solids as each aliquot is added.
8 — 20
-------
e. Conclusion
Gases evolved nay be toxic or explosive.
Temperature rise is an indication of exothermic activity that
might result in spontaneous fire or explosion. Solid
precipitation indicates chemical incompatibility that may be
deleterious effects.
I. INFORMATION RESOURCES
In approaching any chemical hazard, the single greatest
danger is the unknown. Safety precautions, protective gear, and
advanced planning all become a matter of trial and error, or just
plain luck if careful analysis of the hazards substance is not
undertaken.
As the result of public and regulatory pressure for
increased knowledge of the hazards of chemical compounds, an
abundance of informational resources has been developed. EPA
field personnel should be aware of the various resources
available, what information can be ascertained from them, and the
format used by each. The uniqueness of the format of many of
these resources requires prior exposure and practice to utilize
them to their fullest advantage in the shortest possible time.
The following list represents some of the data sources currently
available.
CHRIS: Chemical Hazard Response Information System,
developed by the U.S. Coast Guard. Access through the National
Response Center, telephone (800) 424-8802.
"Dangerous Properties of Industrial Materials," fourth
edition (1975), edited by N; Irving Sax, Van Nostrand Reinhold,
Co., 135 W. 50th St., New York, NY 10020.
"Condensed Chemical Dictionary," Gessner G. Hawley, Van
Nostrand Reinhold Co., 135 W. 50th St., New York, NY 10020.
"The Merck Index," ninth edition (1976), Merck and Co.,
Inc., Rahway, NJ 07065.
"NIOSH/OSHA Occupational Health Guidelines for Chemical
Hazards," U.S. Government Printing Office, Washington, D.C.
20402.
"Fire Prevention Guide on Hazardous Materials," National
Fire Protection Association (NFPA), Quincy, MA 02269.
1984 Emergency Response Guidebook; Guidebook for Hazardous
Materials Incidents. 1984, U.S. Department of Transportation,
Materials Transportation Bureau, DMT-11, Washington, D.C. 20036.
8-21
-------
"NIOSH/OSHA Pocket Guide to Chemical Hazards," U.S.
Government Printing Office, Washington, D.C. 20402.
Farm Chemicals Handbook. (1984), Richard T. Meister,
editorial director, Meister Publishing Co., 37841 Euclid Avenue,
Willoughby, OH 44094.
Materials Safety Data Sheets (MSDS): Department of Labor
Standardized Material Safety Data Sheets (MSDS).
"Documentation of the Threshold Limit Values (TLV)," fourth
edition (1980), ACGIH Publications Office, 6500 Glenway Avenue,
Building D-5, Cincinnati, OH 45221.
Registry of Toxic Effects of Chemical Substances. 1980
edition, two volumes, Richard J. Lewis, sr., and Roger L. Tatken,
editors, U.S. Department of Health and Human Services, Public
Health Sevice, Center for Disease Control, National Institute for
Occupational Safety and health, Cincinnati, OH 45226.
Emergency Handling of Hazardous Materials in Surface
Transportation. 1981, Bureau of Explosives, Association of
American Railroads, 1920 L Street, N.W., Washington, D.C. 20036.
HMIS: Hazardous Materials Information system, developed by
the Department of Defense, Defense Logistics Agency, Defense
General Supply Center, Richmond, VA 23297.
J. CHEMICAL HAZARD WARMING SYSTEMS
There have been many attempts to expedite or summarize vital
information found in the various data sources. Two systems that
have gained wide recognition and acceptance are the system of
hazardous material placarding and marking of large tanks and
trucks, devised by the Department of Transportation (DOT) and the
labeling system found on smaller tanks and containers, devised by
the National Fire Protection Association (NFPA).
K. DOT HAZARD EVALUATION SYSTEM
The DOT Hazardous Materials Transportation Administration is
responsible for the safe transportation of over 1,400 chemicals.
The system is based on a series of regulations summarized in the
Code of Federal Regulations 40 CFR. These regulations spell out
in definitive language the proper shipping names, warning labels
and placards that must be present to ship a hazardous material or
hazardous waste on the public highways. These warning devices
can prove extremely valuable in Agency personnel work. A summary
of these requirements is found in the Hazardous Material Tables
49 CFR 172.101.
8-22
-------
L. DOT MARKING AND LABELING
Under DOT regulations, containers up to 110 gallons must
have one of the 1,400 proper shipping names listed in the
Hazardous Material Tables. In addition, there must also be a 4"
x 4" diamond-shaped label that contains a warning of the hazards
present (see Figure 8-1).
FIGURE 8-1
DOT Hazardous Materials Warning Labels
yt\
<< mm w
\l*"<»¦ J'
Nir
•MlllOft I* «Mr
IWIIW fHW.
,/itx
({ rum \> << ^ >
(Jf
A
/\
\Z
/^V
•x ^ Vi
•:< iititur >;•
\ /'
•\j^'
v;' t*Pon
\yw.
*•»*
*•
C«|i *«eian
0«?
8-23
-------
taiVwll
'¦—¦i r
ot
TLerrt\,rr*-. J2j 2? .
Im J
>#l •
tow T* Yf-ltmm, l»1 »¦•»•: Oar
(*•••<( UtL'ii IX OC
n*i|» Llt-lj* w
MliOMiit^i
•now ll'l«lt»l
fia^HOT tftaalMI Oxxrt>» immj(M ¦ lr'T'a'4Baa H« M |fea Tat* II
Bo *«Ma l> Tit—« . fM* <1 .
0»»>< »H '' IV* M'SdA MM ¦«« ¦••a. '•» nr. Ipa It < ¦¦ ¦< . IM. CUt. «
81 nin i 'miw* Mam(*"*C*A> AM mmmOm Mat (mm* » ¦».
»•« lM •«» »» '¦*> IM W Kn^*.9 k| null H «W** *•• . I ¦ HI im m
¦nipfa HtmW'KK*
•** *000 I'lMVSf m ^ PWI I FV«ar
NA , Ma»m~W0f.& Ci. b.T<>»M>m> k«at »MnS
luymttmrndl*| naa.
aaaa >Ma«« OalmAw* At «im«i*w
C*imtktmt4t Omtpm. Barlhk «k ai. INI) ft 147. Pra.
4«cllaa tt pan I a nam rtiMk. ltd. OwW J», *.||
(mi). TatMiyt L Bra*aia|. TkaMijr W NmWhi ^
MmnuU Umna IDm. Na« Yark. INS) ft* )41
o
©«¦»• Mlgtlaii Ujljy RaamaUa ItaaU: (LhmiiMi
a
Ijr. laakaala. Humful tali aq b< ibwbri Iktaagb ikla.
UM Mtaal at mdWail MMti 4ym 9—4 mamr alv
"I"*" »aiii|>aaii4«. artllM laailiar. Hatlwai. all da«k
•••»l«aa «T«I|1««^ limm a* nlin lar xa«
»aiafc aSt. M*
ni«u» CAT «*«!*
The Merck Index
8-24
-------
BENZENE, Syns: brmol, phtnyl hydride, coal hoph-
ifia. Clear eolorlesi liquid. C4II4, tnw: 7S.11. mp:
3.41*. bp: S0.W-80.094*. Huh p: 12'K (CQ. d:
0 8794 <§> 20*. iuloign. lemp.: IqU'P. lei: 1.3%. Uel:
7.1%, vap. prttt: 100 (nirt @26.1". V4p. d: 2.77, Ulc:
95—100.
TllR " f'oiiorifnj occUrl taost comfnonljr through
Inhal 01 the vapor, though benzenfc eah penetrate
the lit in. ind poison irt that way. Locally, benzene
haJ I comparatively Uronj itt effect. producing
erylhemi tnd burning, ind. in htori ievere cam.
tdcmi Ind even blistering. Exposure (o high cone
of the vipor (3000 ppnt or higher) tniy result front
failurt of equipmtnl br ipillage. SUeh ex^oltire.
while fire in industry, tnay result lii fccute poison-
ing, characterized by the hateotie idioh of bentene
on thfc CSS. The anesthetic action of benzene li
timilar to that of other inesthetic gasei, consisting
of a preliminary ktage of txeilalioh followed by de-
pression Ind, if exposure it continued, death
through respiratory failure. The chronic, rather
than the kcule form, of benzenfc poifofting is im-
portant in induitry. It ii i recog leukemogen. {/A
}, ), i03J There is no ipecific blood picture occur-
ring in catci of chronic benzol poitoning. The boh£
marrow may be hypoplastic, normal, or hyper*
plastic, the changes reflected it) the peripheral
blood. Anemia, leueopenia, macroeytosis, reticulo-
cytosit. thromocytopenia, high color index, and
prolonged bleeding time may be present. Case! of
myeloid teuitemia havi been reported. For thi
Supervision of (lie worker, repeated blood examini-
tions are necessary, including hemoglobin determU
naliont, white Ind ted celt count! Ind differential
Jmtari. Where I worker shows A progressive drop
in either red or while cells, or where the while count
remains below 5.000 per eu mm ol the ted count
below 4.0 million per cu mm, ori two tuccesiive
monthly examination*, he should be immediately
removed from txposurt. following absorption of
benzene, elimination ts Chielly through the umg«,
when fresh air ii breathed. The portion thai it ib-
iorbed it oxidized, and the oxidation products ire
combined with iulruric and glycuronic acidi and
eliminated in the Urine, Thit may be used as a diag-
nostic lign. Benzene hxi I definite cumulative ac-
tiori, ind expoii/rc to relatively high cone is not
serious from-tht point of view of causing damage
to (hi blood-forming iystem, provided the expo-
lure St hot repeated. On the other hand, daily ex*
Posure lo Cone of 100 ppm or less will usually cause
damage if continued over i protracted period of
time. \fi icute poisoning, (he worker becomes con*
fused and dizzy, complaint of lightening of the leg
muselei and of pressure over the forehead, then
passes into i stage of excitement. If allowed lo re-
main In exposure, he quickly becomes stupefied and
lapsei into eomi. In non-fatal cases, recovery is
lisilally eotnplele knd no permanent disability oe-
ttlri. In chronic poisoning the onset is slow, with'
the iymptoms vague; fatigue, headache, dizziness,
hausea and lost of appetite, loss of weight and weak-
hesi are eommon eomplainti in early cases. Later,
pallor, hoseblcedr, bleeding gums, metrorrhagia,
petechial ihd purpura may develop. There is great
individual variation in the iignt and symptoms of
chronic benzene poisoning. Behzene is a common
lit cohtaminant
ftre tfatitrd: Dangerous, when exposed to heat or
flame; can reaet vigorously with oxidizing mate-
halt, lUch ki firf,, Cl,. CrOi, 0,NClO., 0«, O,.
perchloral'es, (AlClj + FCIO«), (HiSO« + perman-
ganates). kiOi. (AgCIOi + tcetic acid), Na,Ot.
Wu
Spont Heating: No.
Explosion Hazard: Mod, when its vapors are exposed
to flame. Uie with adequate ventilation.
biiaster Hatard:xbangerous, highly flam.
To Fight Fire: Foari, CO>. dry chemical.
Dangerous ProMrUes of Industrial MiUhals M. Irving Sax
8-25
-------
BENZENE • Skltt
c6Hj
25 ppm (Approximately flO hig/m^)
Benzene as an acute posion produces narcotic effects comparable to those of toluene. Chronic
lntoxicatlor by benzene Is by fit" the most ierious disease caused by the common hydrocat-bon
solvents, lit action is primarily on the bone marrow resulting In numerous blood changes and, In
sertoui casei, aplastic ant mil, with a frequently fatal outcome. It Is UnlqUl lhrtong the hydrocar-
bons as a myelotoxlcant, according to Gtfrarde(l). felklns(2) staled thai more than 140 fatal
cased ol benzene poisoning had been recorded prior to 1959. Vlglilhi and Salta(3) llslid 26
deaths from chronic benzene poisoning In two provinces in Italy between i960 ind 1963. Eleven
of these cases were diagnosed is leukemia, which frequently develops several year! after ces-
sation of exposure to benzene.
Many of the deaths from benzene hav# Resulted from exposures Of the ohdef of 200 ppm or
more. Bowdltch and Elkins(4) estimated that of eleven fatal cases, three resulted from concen-
trations !h excess of 200 ppm, four from cohcentratlons between 100 and 200 ppm, and three
from concentrations Judged to be below 100 fcpht (but Hot ftielsurtd). Greenburg et al.(S) de-
scribed nine eases, with one death, In the rotogravure printing Industry. Of 48 air analyses, 20
showed lesi than 100 ppm, and IS more than 200 ppm. Savllahtl(6) found that 107 of 14? workers
in a shoe factory revealed blood abnormalities. The source of the benzene wii fcetneht, and con-
centrations were reported to have tanged from 3l8 to 470 ppm (these seem high for shoe cement-
ing operations). One death occurred.
Wlnslow(7), however, reported blood changes In worker* where concentrations of benzene
vapor below 100 ppm were found. Helmann and Ford(8) found one death and three cases with blood
changes where air analysis for benzene showed a concentration of 109 ppm. WUson(9) reported
three fatal cases In a plant where the average concentration of benzene vapor was 100 ppm. Hardy
and Elkins(lO) recorded one death and several cases of blood changes In & plant where repeated
air analyses Indicated benzene vapor concentrations of about 60 ppm. '
Blaney(ll) found little evidence of benzene intoxication In a group of 90 workers regularly
exposed to benzene for about 13 years. Coneehtratloni wtri fcenirally to*, but urinary phenol
measurements indicated some exposures of the order of 25 ppm(12). Pagnotto et al.(13) found
rubber spreaders exposed to benzene vapor concentrations ranging for the most part between 6
and 25 ppm. A limited number of blood studies showed some abnormalities but no apparent cor-
relation with exposure. So far as Is known, hone of this group developed serious blood dyscraslas.
A TLV of 25 ppnt Is believed tow enough to prevent serious blood changes, but this limit should
be considered a ceiling and exposure to higher concentrations not permitted.
Other recommendations: Cook (1945) 50 ppm; Smyth (1956) 35 ppnl; ElklnS (1939) 25 ppm;
ANSI (1969) 10 ppm; U.5.S.R. (1967) 6 ppm; Czechoslovakia (1969) 16 ppm.
References;
1. Cerarde, H.W.: toxicology and Biochemistry of Aromatic Hydrocarbons, Elsevier Publish-
ing Co., New York (1960).
2. Elklns, H.B.: Chemistry of Industrial Toxicology, p. 103, Wiley & SonS* New York (1959).
3. Vlgllanl, E.C., Salta, G.: New Eng. J. of Med. 271, 672 (1964).
4. Bowditch, M.. Elklns, H.B.: J. Ind. Hyg. It ToxTJl, 321 (1939).
5. Greenburf, L., Mayers, M.R., Goldwater, L„ Smith, A.R.: J. Ind. Hyfc. Ir Tox. 21, 395 (1939).
6. Savllahtl, M.: Arch. Gewerbepath. u. Gewerbehyg. 15, 147 (1936).
7. Winslow, C.E.A.: J. Ind. Hyg. 9, 69 (1927).
8. Helmann, H., Ford, C.B.: N.Y.~!nd. Hyg. Bull. p. 224 (Nov. 1940).
9. Wilson, R.H.: J. Lab. Clin. Med. 22. 1511 (1942).
10. Hardy, H.L., Elklns, H.8.: J. Ind. Hyg. 6 Tox. 30, 196 (1948):
11. Blaney, L.: Ind. Med. & Surg. 12, 227 (1950).' ~~
12. Walkley, J.E., Pagnotto. L.D., Elklns, H.d.: Am. tnd. Hyg. Assn. J. 21, 362 (1961)
13. r- -itto, L.D., Elktns, lf.B., Brugseh, H.G., Walkley, J.E.: Am. Ind. Hyg. Assn. J. 22, 417
(19b 1).
8-26
-------
CJ<». tV»n«MK Sit »r4ct of tt!|k*voivml
eKtrnte^b produced in U.S. (I'M).
CM
-i y, o
CH
t tl
$
III IV
Structure I, CsmalaM rui| ikrm| ill ttenxM*.
It. SlMdirf nnt »Ko**«| doufctt WW( only.
IIL Sinph rinl «ikM double Mh »rlh
•mil in4isii«i| fniiim af otkos atomi tc
vkick nhiiiml eiome or ptafi may be al-
ImM Q • »nh*. ) • mii, 4 • fui|L
' IV. CiMniiid Mrueluro, nik twloiri cbcb Mrf
|ixiii| tlw nmm at thk awpwit
Thm flrucium im *Im itferiud t» m tlw bun
nucleua.
Ftopeniet: CiIkIm I* l<{Ht-y«fl«w, mobile.
Squid «f highly itfrmnnm miuiu; aromatic odor,
neon kwa wb tmoky Ikw; k.t. 10.1*0 u.
*f'C; 'f ¦» iiniA'py w/mI Hi *r£.
(nam wdn (n 20/D) 1.301 I0sTSh> ¦»wi fetoMd
cup) 12* F; nrfia tension JJ d rnts/jem. Avteifniiioa
Icmp. 1044* P. Miecifclc will aWohoJ ether. atttain.
carboa MneklwM, aim dtivlM*. mm «%
Ili|kllr to Inkle iii waler.
lkn«UM; (•) Hyd'adcalkyfctiwi tf latum or of
pjroiyia (q.*.k It) InwItikiiH af (oW-
cm kf
forming el fitnlnK (4) (factWaal dittifiaiioo «f
coal tar.
Oradcc: Crude; m« rotor, motor, Mistrial pom
g"Q: nitration (l*Os ikiofkM^m; N noli %:
99.U mok % naatfradc.
Contained: Oram*: lank can; karat*.
Hiui4: Flammable, 4ia|tron fire rill. Iitbu'w
| j "» '* h» •"'"'i Taiif in min;
i'— p*"''iiow. ai»d »fcin tbwMioo. Tohraacc. IS
Km in air. saitiy atia intti avaiSMe frmm Maoo-
:tarui| Omimui Asm., WaihiafiaN, O.C
War. Ethylbenvna (fe> npiia monomark
Wanne (for dcwrfraiik q(M«UM (far qto);
phenol; mtrohonmc (far anilrnej; makac anhydride;
^•dtntnRM; ckltlCtaRK kttM
hcsechloridc; bmiRae-eatfoaic aod; totoac tatl>
knock fasolitu.
Snipping Relations (Kail) Red labd (Air) Flt»>
ntable liquid laM.
Set alio aromatic.
Condensed Chemical Dictionarya GeJlner Kawtey
8-27
-------
INZ
BENZENE
U« i I p '
Fir*
Ixpotur*
WalM
MM Ion
»«<
c*u rot aiscu *»-
VSiSl
0 WHIIWII — ¦¦ ¦!!¦¦¦ mil I
t m
lww«
19 (¦
IS CM
"~
IMMM U
l wm i
IVU
I I I mm* («•«•»«¦ VtoMi
1 m MOM
• • taNM i|*»CC
' n-»n
i mm mnjmm
* •
llP'dl.WMl
V Hi' |i f I m>*m ••
ft 0
II mm+mtuw
««%***
i. oock «4crmvT
•«
I |«/% •«•
mcn
l sucni aMvracnmn
l C i
CmmmM N««fen«*U
| MptamCi
talfWifM
HmMMPII
j nun i ¦¦<•
» OIpMI ^
It. 1
«)*1
•»t
«*1
l}M
•> jrc
(*•«/• «•* i «•««•)«•« <+ i.i
• * lil|
mm^rnmmamm *mm in
uviud '»ti
8-28
-------
TABLE OF PLACARDS AND APPLICABLE RESPONSE GUIDE PAGES
CSB OHLT ~> MATERIALS CAKMOT SB SPECIFICALLY IDKKTDTtEO
THROCOH SHXPKNO PAPERS OB MAXKDK29.
Guide 48
8-29
-------
TABLE OF PLACARDS ANO APPLICABLE RESPONSE GUIDE PAGES
USE OWLr IF MATERIALS CAMMOT BE SPECIFICALLY IDENTIFIED
THBOOOH 3HZPPINQ PAPERS OR MARKINGS.
£
4lammabl$> <$flaMa*bl"e)>>
Guide 38 Guide 41
/N
' L %
\ OXIDIZED >
S /
\ /
\ '
\ /¦
\ /
V
Guide 47
A
/ ORGANIC \
\ PEROXIDES
v /
\ '/
Vx //
W/
V
Guide 52
Guide 95
Guide 59
QrrSRNATIONAlt
SfDFMMO
ONLY
Guide 37
Guide 41
8-30
-------
ID Guide
No. No.
Name of Material
ID Guide
No. No.
Name of Material
10SI 13 LiqUITTED NONFLAMMABLE
CAS eharftd with
NITROGEN, CARSON
DIOXIDE or AIR
1060 17 MCrHYL ACETYLENE,
mixed with 13* to 20V
PROPADIENE, stabilized
1061 19 METIIYLAMINE, anhydrous
10(1 It MONOMETIIYLAMINE,
anhydrous
1062 S3 METHYL BROMIDE
1063 16 METHYL CHLORIDE
1064 16 MET1IYL MERCAPTAN
1063 13 NEON, compressed
1066 13 NITROGEN, eompresaed
1067 10 NITROGEN DIOXIDE
1067 30 NITROGEN TETROXIDB
1061 16 N1TROSYL CHLORIDE
1070 14 NfTROUS OXIDE
1071 33 OIL GAS
1073 14 OXYGEN, eempresed
1073 33 OXYGEN, eryo(enle liquid
1073 33 LIQUIFIED PETROLEUM GAS
1075 33 LPG, liquified petroleum pi
107$ 33 PETROLEUM GAS,
liquified
1076 13 PHOSGENE
1077 33 PROPYLENE
107S 13 REFRIGERANT GASES, n.oj.
1079 16 SULFUR DIOXIDE
1060 13 SULFUR HEXAFLUORIDE
1061 17 TETRAf LUOROETHYLENE,
Inhibited
1093 17 TRIF^UOROCHLORO-
ETHYLENE
1063 19 TRIMETIIYLAMINE. anhydrous
1065 60 VINYL BROMIDE
1096 17 MONOCHLOROETHYLENE
1066 17 VINYL CHLORIDE
1067 17 VINYL METHYL ETHER,
inhibited
1066 36 ACETAL
1069 36 ACETALDEHYDE
1090 36 ACETONE
1091 36 ACETONE OIL
1093 30 ACItOI.KIN, inhibited
1093 30 ACRYLONfTRlt.E, inhibited
1093 36 ALCOHOL, denatured
1096 3f ALCOHOL, industrial
1096 3S ALLYL ALCOHOL
1099 39 ALLYL BROMIDE
1100 3S ALLYL CHLORIDE
1101 37 DISTHYLALUMINUM
CHLORIDE
1103 39 ALUMINUM TR1ETHYL
1103 3T ALUMINUM TRIMETHYL
1104 38 AMYL ACETATE
1109 3* AMYL ALCOHOL
1106 30 AMYL AMINE
1107 3t AMYL CHLORIDE
1101 38 AMYLENE
1109 38 AMYL FORMATE
1110 38 AMYL METHYL KETONE
1110 38 METHYLAMYL KETONE
1111 38 AMYL MERCAPTAN
1113 38 AMYL NITRATE
1113 38 AMYL NITRITE
1114 37 BENZENE
1114 37 BENZOL
1119 38 BENZINE
1116 37 BRAKE FLUID, HYDRAULIC
1130 38 BUTANOL
1130 39 BUTYL ALCOHOL
1133 38 BUTYL ACETATE
1139 39 BUTYLAMINE
MATERIALS IN IK3LD ORANGE may require bolatfon or evacuation from spill areas.
Find the materiel by name in the tables immediately following the Guide paces.
8-31
-------
Guide 2fr POTENTIAL HAZARDS^ • r ^
FIRE OR EXPLOSION
Will bum. May be ignited by heat, sparks and flames.
Flammable vapor may spread away from spill.
Container may explode in heat of fire.
Vapor explosion hazard indoors, outdoors or in sew*rs.
Runoff to sewer may create fire or explosion hazard.
HEALTH HAZARDS
Vapors may cause dizziness or suffocation.
Contact may irritate or bum skin and eyes.
Fire may produce irritating or poisonous gases.
Runoff from fir* control or dilution water may cause pollution.
EMERGENCY ACTION
Ke«p unnecessary people away.
Stay upwind: keep out of low areas.
Isolate hazard area and deny entry.
Wear seif-contained breathing apparatus and Ml protective clothing.
Isolate for 1/2 mile In all directions if tank or tankcar la Involved In fire.
FOR EMERGENCY ASSISTANCE CALL CHEMTREC (800) 424.9300.
Also, in ease of water pollution, call local authorities.
FIRE
Small F!raa: Ory chemical. C02. water spray or alcohol loam.
Large Fires: Water spray, tog or alcohol team.
Mova container from fire area if you can do H without risk.
Slay away from ends of tanks.
Cool containers that are exposed to flames with water from the side until well
after fir* is out
For maaafv* Are in cargo area, us* unmanned hose holder or monitor nozzles.
Withdraw immediately in caa* of riaing sound from venting safety device or
discoloration of tank.
SPILL OR LEAK
No Raree. smoking or llama* in hazard area.
Slop leak if you can do it without risk.
Us* water spray lo reduce vapors.
Small Spllla: Take up with sand, or other noncombuatibl* absorbent material.
then flush area win water.
Larg* Spllla: Oik* far ahead of spill tor later dtsposal.
FIRST AID
Mow vtctln to fresh air call emergency m*dlcal care.
If not breathing, give artificial respiration.
If breathing ia difficult giv* oxygen.
In caa* of contact with material, immediately Rush skin and ey*s with running
water tor at toast IS minutes.
Remov* and isolat* contaminated dothing and shoes.
8-32
-------
UNIT 9
HEALTH HAZARDS OF CHEMICALS
A. EFFECTS OF CHEMICALS IN THE BODY
Toxic chemicals can affect the body in many ways. The same
chemical can produce different effects simply by altering the:
o route of exposure (skin contact,inhalation, ingestion)
o amount of toxicant you are exposed to (dose)
o number of exposures (doses) and frequency
o length of each exposure (duration)
The effects caused by different chemicals in the body are
dependent upon not only the four factors mentioned above, but
also upon the site of action in the body (target organ).
B. ROUTES OF EXPOSURE
The primary routes of exposure that will be encountered by
field personnel are through inhalation and skin contact. To a
lesser degree, ingestion of contaminants and direct contact with
the blood (through accidental cuts, punctures, and scratches) can
also occur. These routes are discussed in detail in Unit 10.
C. DOSE, NUMBER OF DOSES, AND DURATION OF EXPOSURES
The size of a dose received at a field site can vary from
extremely small to extremely large. Not only does the quantity
of the dose affect the resulting toxicity, but also, and more
importantly, the relative size of the dose. By this, it is meant
that the more toxic or hazardous a substance, the less that can
be tolerated without any response. For example, if you are
exposed to two equal quantities of two chemicals, hydrogen
cyanide and 1,1,1 trichloromethane, the hydrogen cyanide is going
to be much more toxic than the 1,1,1 trichloromethane. Thus,
hydrogen cyanide is relatively more toxic than 1,1,1-
trichloromethane.
The length of exposure and length of manifestation of
effects are often subdivided into two categories:
o Acute - single exposures; or multiple exposures
occurring within 2 hours or less; effects which are
manifested very shortly after exposure
o Chronic - repeated or prolonged exposure to low
concentrations of toxicant; effects which are of long
-------
duration, frequent recurrence, or slowly increasing
seriousness. With some chemicals, effects will
reverse or lessen once exposure is stopped.
The effects caused by acute exposure are quite often
different from those caused by chronic exposure to the same
chemical. For example, acute exposure to lead produces colic
while chronic lead exposure leads to wrist drop.
If agents which you are acutely exposed to are rapidly
absorbed by the body, it is likely that toxic effects will be
noticed immediately. Also, it is quite possible that acute
effects will be produced with each addition to long-term, low-
level chronic exposure. Conversely, acute exposure to a chemical
may result in delayed toxicity or toxicity which resembles
chronic exposure effects. Chronic exposure to toxicants
generally results in chronic effects, such as those seen with
some cancers. Here, chronic exposures (low-level and long-term)
such as with cigarette smoking or asbestos exposure, not
manifested as cancer until after many years of continued
exposure.
Chemicals which produce acute effects are likely to be
noticed immediately and exposure discontinued (if possible).
These effects include:
o irritation of the skin, eyes,respiratory tract or
gastrointestinal (GI) tract
o immediate pain in the area of contact or an associated
area (such as a stomach ache after oral exposure to a
compound)
o dizziness, light-headedness, fainting
o immediate allergic reaction
If there is no immediate warning that you are being exposed
to a toxic chemical - no pain, irritation, odor, or other warning
or reaction - you more than likely will not try to stop or
discontinue your exposure. It is only after repeated exposures
or the surfacing of latent effects that you realize exposure has
occurred or that exposure you knew had taken place was harmful to
your health.
The effects caused by acute or chronic exposure can vary
greatly in severity. Some effects will be additive; some may
prove to be reversible once exposure is ceased; some may be
reversed after exposure to a different chemical or with medical
treatment; some may cause permanent, irreversible damage; some
may cause death.
9-2
-------
It is important to realize what chemicals you will be exposed to
at your work site and to learn the effects of these exposures.
Sources of known effects for various toxic substances are readily
available and will be covered in Unit 10.
D. LOCATION OF TOXIC ACTION
In the human body, toxic effects can be manifested virtually
anywhere. Chemicals can prove harmful at the molecular and
cellular level, the tissue and organ level, or the system level.
Even though the skin, respiratory tract, or GI tract may be the
site of contact and entry of chemicals into the body, toxicity is
expressed and measured at the particular chemical's target site.
If harmful effects of exposure to a chemical occur at the site of
contact, such effects are termed local effects. Examples include
inhalation of irritants, ingestion of caustics, and skin contact
with strong acids. Effects which are observed away from the site
of contact or entry are termed systemic effects. Systemic
effects require absorption and transport of the toxicant to a
site(s) away from the entry site. The majority of toxic
substances produce systemic effects.
Some chemicals exhibit both local and systemic effects. For
example, tetraethyl lead harmfully affects the skin at the point
of contact (absorption site) and is then transported to the
central nervous system (CNS) where further damage occurs.
The organ in which the majority of harm occurs is termed the
.target organ for a particular chemical. The target organ
generally is not the site of major storage for this chemical in
the body, however. For example, lead is concentrated in the
bone, yet toxicity occurs in the body's soft tissues. In the
case of polychlorinated biphenyls (PCBs), the storage site is
adipose (fat) tissue, while harmful effects are seen in the liver
and other organs.
The target organ involved most frequently in toxic reactions
is the central nervous system (CNS), especially the brain. Other
frequently affected systems, in order of toxicity, include the
circulatory system, blood & hematopoietic system and the visceral
organs (liver, kidney, lung, & skin). Target organs least often
used include muscles and bones.
E. AFFECTS ON BEHAVIOR AND PHYSIOLOGICAL PROCESSES
The primary exposure routes for toxic chemicals are, as
mentioned, skin contact, respiratory tract, and gastrointestinal
tract. Toxicity, however, is generally expressed elsewhere,
primarily at the biochemical or cellular level of organs and
organ systems. Life processes can be altered through the
effects of toxic chemicals at these sites of action including:
9-3
-------
o nerve irritability (ability to respond to stimuli)
o conductivity (of nerve impulses)
o muscle contractibility (ability to change form by
shortening)
o metabolism
o integration (the ability to coordinate activities by
accelerating or slowing activities)
o adaptation
o reproduction
Generally, systemic toxic effects are first recognized as
shifts in normal physiological or behavioral patterns. The
shifts may range from subtle to dramatic, and may be felt over
the whole organism. In many cases, modification in any of the
basic life processes will produce the first signs or symptoms
that an exposure to a toxic agent has occurred.
For example, exposure to chemical which reduce the normal
physiological levels of nerve irritability can cause decreased
sensitivity to touch, heat, and pain. Changes in muscle
coordination or reflex actions may result from alterations in
normal contractibility and conductivity (of muscles and nerves).
F. ADAPTATION TO TOXIC CHEMICAL
The human body has an extraordinary capacity to adapt to
environmental changes which it is faced with. This ability to
protect itself from environmental challenges is known as
adaptation. Natural defense mechanisms in the body react to such
external disturbances as inadequate nutrition and exposure to
foreign substances.
A breakdown in the adaptive capacity of an organism results
in the manifestation of toxic effects in the body. Alteration in
structure, function, or response of the organism results. These
harmful effects usually result from the body being over-taxed, or
overwhelmed by one or more stresses placed upon it. Evidence of
toxic responses to chemicals are often indicated by one of the
following conditions:
o change in organ function, such as increased kidney
output
o organ enlargement or morphological changes in cells and
tissues
9-4
-------
o physiological evidence of cell injury, such as
decreased respiratory rate
o biochemical changes such as in serum enzyme or cell
metabolite levels
6. INHALATION
The respiratory tract is in constant contact with the
environment. Surface area of the lungs ranges from 70 to 100
square meters, representing the largest exposed surface of the
human body. Lungs are exposed to toxicants by inhalation
(directly) and exhalation (of substances which entered the body
through skin absorption or ingestion).
The structure of the respiratory system is such that
particle size greatly determines depth of penetration. This
system is divided into three regions:
o Nasopharyngeal: Extends from the nose to the larynx.
Particles of 5 microns or larger are usually deposited
here due to filtering by special cells and mucous
glands. This region also is responsible for adding
moisture to inhaled air and moderating the temperature
of inhaled air.
o Tracheobronchial: Consists of the trachea, bronchi,
and bronchioles and serves as the conducting airway
deep into the lungs. Particles between two and five
microns are deposited here and are removed by the
upward movement of the mucous layer in ciliated
portions of this area. Coughing and sneezing rapidly
move these particles toward the glottis where they may
be swallowed and absorbed by the gastrointestinal
tract. These ciliated cells can be temporarily
paralyzed by smoking or use of cough suppressants.
o Pulmonary: Consists of alveolar portions of the lung.
Particles one micron and below penetrate to this area
which is the lung's basic functional unit and the
primary site of gas exchange with the blood. Particles
which reach this site will either be absorbed rapidly
by the blood or cleaned away by scavenging macrophages.
Gases in the alveoli equilibrate almost instantly with
blood passing through the lungs capillary beds. The
concentration of gas in the blood depends on its
solubility in blood. For example, chloroform has a
high solubility while ethylene has a low solubility.
For highly soluble compounds, respiration rate
determines the rate of toxicant absorption.
-------
For compounds of low solubility, heart rate determines
the rate of toxicant absorption (amount of blood flow
through the lung area).
Removal of toxic substances from the alveoli occurs by three
means:
o physical removal - through alveolar fluid moving
substances up eventually, to the glottis;
o phagocytosis - through the action of macrophages,
debris is engulfed by these cells and removed through
the mucociliar channels or lymphatics; and
o lymphatics - both free and phagocytized particles can
migrate via the lymphatic system to lymph tissue where
it can remain for a long time.
Not all particles which enter the alveoli are removed.
Silica and asbestos, for example, result in macrophage death and
fibrous lesion formation on the lungs. Alveolar dust plagues and
nodules can also result.
Substances which cause damage to the respiratory system when
inhaled are classified according to their affect on the
respiratory tract:
o Asphyxiants - gases which deprive body tissues of
oxygen
- Simple asphyxiants: At high concentrations they
displace air, leading to suffocation. Examples:
Nitrogen, Helium, Methane, Neon, Argon.
- Chemical asphyxiants: They prevent oxygen transfer to
tissues. Examples: Hydrogen sulfide, Carbon monoxide
(binds to hemoglobin more readily than oxygen), Cyanide
(prevents oxygen transfer from blood to tissues).
o Irritants - irritate air passages and constrict
airways. May cause edema and infection. Examples:
Hydrogen fluoride, Chlorine, Hydrogen chloride,
Ammonia, Sulfur dioxide, organic solvents.
o Necrosis producers - kill cells and cause edema.
Examples: Ozone, Nitrogen dioxide.
o
Fibrosis producers - kill normal lung tissue producing
scar tissue which may decrease lung capacity.
Examples: Silicates, Asbestos, Beryllium, Quartz.
-------
o
Allergens - cause allergic response of
bronchoconstriction and pulmonary disease. Examples:
Isocyanates, Sulfur dioxide.
o Carcinogens - cause lung cancer. Examples: cigarette
smoke, coke oven emissions, Asbestos, Arsenic.
o Effect on other organs - via the respiratory tract.
Examples: Solvents, Anesthetic gases, Lead, Mercury.
Table 9-1 gives examples of industrial toxicants which
produce respiratory tract disease.
-------
TABLE 9-1
Industrial Toxicants that Produce Disease of the Respiratory
Tract
Toxicant
Site of Action Acute Effect
Chronic Effect
Aluminum
Anronia
Arsenic
Asbestos
Beryllium
Boron oxide
Cadmium
oxide
Carbides of
tungsten*
titanium. 6
tantalun
Chlorine
Qiromium
(IV)
Cobalt
Hydrogen
chloride
Iron oxides
Upper airways Cough, shortness Fibrosis &
of breath, irri- enphysema
tation
Upper airways
Irritation,
edema
Upper airways Bronchitis.
irritation,
pharyngitis
Lung parenchyma
Alveoli
Alveoli
Alveoli
Upper, lower
airways
Upper airways
Nasopharnyx.
Upper airways
Lower airways
Upper airways
Bronchitis
Cancer.
bronchitis.
laryngitis
Fibrosis,
cancer
Edema, pneunonia Fibrosis.
ulceration
Edema,
hemorrhage
Cough, pneunonia ESiphysena
Hyperplasia, Fibrosis
metaplasia of
of bronchial cells
Cough# irrita-
tion , asphyxiant
Nasal irrita- Cancer
tion, bronchitis
Asthma
Irritation.
Alveoli,
bronchi
Cough
Fibrosis, inter-
stitial
pneumonitis
Benign pneumo-
coniosis
9-8
-------
TABLE 9-1 (cont)
Toxicant
Site of Action Acute Effect
Chronic Effect
Isocyanates Lower airvays,
alveoli
Manganese
Nickel
Nickel
car bony1
Nitrogen
Cbddes
Osmium
tetraoxide
Ozone
Phosgene
Phthalic
anhydride
Sulfur
dioxide
Tin
Toluene
Lower airvays,
alveoli
Nasal mucosa*
bronchi
Alveoli
Bronchi,
alveoli
Upper airways
Bronchi,
alveoli
Alveoli
Lohwr airvays,
alveoli
Upper airvays
Bronchioles,
pleura
Upper airvays
Vanadium Upper, lcuer
airvays
Bronchitis,
pulmonary edema,
asthma
Pneumonia, often Recurrent
fatal penunonia
Irritation
Cancer
Edema (delayed
syrrptcms)
Edema
Bronchitis,
bronchospasm
Biphysema
Broncho-
pneumonia
Irritation, Bnphysema,
edema, hemorrhage bronchitis
Edema
Bronchitis,
asthma
Bronchitis,
fibrosis,
pneumonia
Emphysema
Bronehoconstric- Bronchitis,
tion, cough, nasphyaryngitis
tightness in chest
Widespread nett-
ling of x-ray
without clinical
signs (benign
pneumonconios is)
Bronchitis,
edema, bronchospasm
Irritation, nasal Bronchitis
inflammation,
edema
Xylene
Lower airways Edema, hemorrhage
9-9
-------
Many factors influence the overall toxic effects of airborne
contaminants entering the body through the respiratory system,
including:
o Chemical concentrations in inhaled air
o Physical and chemical properties of the substance
o Deposition sites in the respiratory system and the
body's ability to defend against them through removal,
inactivation, detoxification or elimination
For gases and vapors, absorption rates within the
respiratory tract or into the blood stream depend upon:
o . Vapor pressure of the chemical (higher vapor pressures
cause increased evaporation, in turn causing increased
lung concentrations)
o Its concentration in inhaled air
o Its distribution coefficient across the alveolar-
capillary membrane (the higher the coefficient, the
more readily the vapors dissolve into the blood stream)
Distribution coefficients for common volatile solvents are
shown in Table 9-2.
TABLE 9-2
Common Solvents and Their Distribution Coefficients
Solvent Distribution Coefficient
Methanol
1700
Sthanol
1300
Acetone
330
Diethyl Ketone
157
Ethyl Ether
IS
Benzene
7
Carbon Disulfide
5
9-10
-------
H. INGESTION
Although the gastrointestinal (GI) tract is an important
entry route for xenobiohes into the body, it should not be of
primary concern to field personnel. As long as care is taken to
protect the hands and face area, and proper cleanup procedures
are followed, inhalation and skin contact should be of more worry
to personnel than ingestion.
Food chain contamination and direct ingestion of toxicants
(on foodstuffs, clothes, fingers, cigarette smoke, or gum) can
lead to absorption by the blood and distribution of these
chemicals to various body organs and systems where harmful
effects are manifested. Absorption of toxicants can take place
anywhere along the GI tract from the mouth to the rectum
depending upon the characteristics of the chemical. For example,
weak organic acids tend to be absorbed by the stomach, while weak
organic bases tend to be absorbed by the intestine.
Most chemicals simply diffuse across the GI tract wall to
the blood stream. Even particles can cross the GI tract walls to
the blood stream. Not all toxicants can survive the GI tract's
acidic pH, however. For example, proteins such as snake venom
are broken down by digestive enzymes and rendered harmless.
As with skin contact (and DMSO), certain agents enhance GI
absorption of chemicals. Ethylenediaminetetraacetic acid (EDTA)
a chelating agent used for treatment of lead poisoning is one
such substance which increases absorption of strong acids, strong
bases and neutral compounds.
Absorption of some chemicals can be altered by the presence
of other specific chemicals. For instance, cadmium decreases
absorption of zinc and copper; calcium decreases absorption of
cadmium; zinc decreases absorption of copper; magnesium decreases
absorption of fluoride; milk increases lead absorption; and
starvation enhances absorption of dieldrin.
Ingestion of hazardous substances by field personnel can
result from:
o mouth pipetting
o swallowing contaminated water (if one falls into a
contaminated water body)
o eating without decontaminating the hands and face
o drinking from contaminated containers
o smoking at the site or prior to decontamination
9-11
-------
It is important to try to prevent any oral contamination
through personal hygiene. Although this may be difficult in the
field, it is extremely important in order to ensure the safety
and health of field personnel.
I. ABSORPTION, DISTRIBUTION, STORAGE & ELIMINATION
The process by which toxic substances are able to pass
through membranes and enter the bloodstream is termed absorption.
The main routes of absorption are through skin contact, the
lungs, and the gastrointestinal tract, although other routes
exist (intraperitoneal, subcutaneous).
Once in the bloodstream, toxic substances are available for
distribution throughout the body. The distribution is usually
rapid, but depends on the rate of blood flow through each organ
as well as the ease with which the chemical crosses over the
capillary system into particular cells of each organ. Thus, the
affinity of a chemical for a particular organ or tissue
determines where a chemical is distributed.
Distribution of chemicals in the body is often complicated
and not a simple matter of equal distribution. Often, a toxicant
binds to a particular site such as fat, liver, or bone rather
than remaining in the plasma. Some chemicals concentrate at
their target site, or site of toxic action. Other chemicals
however, concentrate at sites other than the target organ. These
sites are storage sites. Lead, for example, exhibits its toxic
effects in the soft tissues, however is stored in bone. Storage
depots can be considered to protect organisms as no harmful
effects are manifested at these sites. If all of the toxicant
was in storage, no harmful effects would occur. This is not the
case, however, as toxicants in storage sites are always in
equilibrium with free toxicant in the blood plasma. As the
toxicant is metabolized (broken down by body functioning), more
is released from the storage site to equilibrate levels
circulating in the body.
The initial settling site of a chemical is primarily
dependent upon:
o blood flow to the area
o permeability of the tissue to the particular toxicant
o binding sites readily available
These sites are not necessarily permanent homes for
toxicants. Chemicals can later redistribute themselves to other
locals. An example of redistribution is seen with inorganic
lead. Immediately after absorption, lead localizes in
erythrocytes (red blood cells), the liver, and kidney.
9-12
-------
Later, the 18 lead is redistributed to the bone, taking the place
of calcium normally found here.
Toxicants can be totally removed from the body by methods of
elimination or excretion. The major route of excretion for
toxicants is through the kidneys. Other important excretory
routes include the liver and biliary system (for DDT and lead)
and the lungs (for carbon monoxide dimethyl ether and other
highly volatile liquids) . Also, excretion through the
gastrointestinal tract (as feces) occurs frequently, as does
secretion through milk, sweat, and saliva.
Figure 9-1 illustrates many of the popular routes that
foreign substances (xenobiotics) follow once inside the body.
9-13
-------
FIGURE 9—1
ROUTES OP ENTRY, ABSORPTION, DISTRIBUTION, AND ELIMINATION
ENTRY
Ingestion
ABSORPTION
Inhalation
Z
Gastrointestinal
tract
DISTRIBUTION
AND STORAGE
ELIMINATION
Respiratory
traet
Skin Contact
<
f
Dermis and Epidermis
Blood and Lymph
Extracellular
Fluid
I
Secretory
Structure*
Adipose)
tissue
(fat)
Organs
Expired air
Bone
Secretions
If you follow each route of entry, you can see possible
ways in which chemicals entering the body may reach different
parts of the body and be stored or eliminated.
9-14
-------
We will now look at several examples of the pathways that
chemicals follow upon entry into the body.
1. Carbon tetrachloride: This extensively used
chemical is a chlorinated hydrocarbon with a high vapor
pressure. Once inhaled, the vapors move quickly (within 2-4
hours) into the bloodstream where the kidney filters the chemical
and it is stored in the liver. Carbon tetrachloride (CC14) is
hepatoxic (causes liver damage) at low concentrations and, at
high concentrations, causes renal (kidney) damage. It is often
transformed in the liver from carbon tetrachloride to chloroform,
thus inducing more damage. (See Figure 9-2.)
9-15
-------
FIGURE 9-2
ABSORPTION, DXSZSUBOTZCK, and ELXMXHATXOt OP OWBCN TETBMSLDBUX
ENTRY
ABSORPTION
Ga«trointa«tinal
tract
OZSTRZBOTION
ANO STORAG*
ELIMINATION
9-16
-------
2. DDT (dichlorodiphenyl trichloromethane): This
pesticide was used intensively for years until it was found to be
a food contaminant and hazardous substance. DDT is inhaled and
nay produce lung irritation as well as kidney damage. Long-term
exposure affects the central nervous system. Delayed toxicity is
usually noted, as DDT is temporarily stored in adipose tissue
(fat cells). Eventually, DDT moves out of storage and causes its
toxic effects on nerve cells. (See Figure 9-3.)
9-17
-------
FIGURE 9-3
ABSORPTION, DISTRIBUTION, AND ELIMINATION OP DOT
ENTRY
ABSORPTION
DISTRIBUTION
AND STORAGE
ELIMINATION
If you follow each route of entry, you can see pcs?ible
ways in whieh chemicals entering the body may reach different
pasts of the body and be stored or eliminated.
9-18
-------
3. Arsenic - Arsenic and arsenic compounds exhibit a
wide range of toxic effects on the organs and systems of the body
including the gastrointestinal tract, respiratory system, skin,
blood, liver, endocrine system, and central nervous system.
Arsenic may be inhaled or ingested through contaminated drinking
water. It may be expired through the lungs, or eliminated
through the urine of affected persons. (See Figure 9-4.)
9-19
-------
FIGURE 9-4
ABSORPTION, DISTRIBUTION, AND ELIMINATION OF ARSENIC
ENTRY
ABSORPTION
Gastrointestinal
tract
Respiratory
tract
Skin Contact
'
Dermis and Epidermis
DISTRIBUTION
AND STORAGE
ELIMINATION
If you follow each route of entry, you can see possible
ways In which chemicals entering the body may reach different
parts of the body and be stored or eliaina.ed.
9-20
-------
Understanding the possible routes of absorption,
distribution, storage and elimination of toxic materials in the
body can lead to an appreciation of the need to prevent the
effects which can result from environmental exposures.
A person's exposure to chemicals can be evaluated by
measurement of concentrations of toxicants or metabolized by-
products in samples of blood or tissue, or in samples of feces,
urine, expired air or secretions. Such biological or medical
monitoring may provide evidence that exposure to a potentially
harmful chemical has occurred. These•measurements may be useful
for subsequent monitoring after an exposure to hazardous
substances, to aid in the treatment of toxic effects and to
evaluate the need to avoid or minimize future exposures.
An acute exposure can be represented by a concentrated dose
in a short time. The same quantity in a series of smaller doses
should represent the same exposure if there were no metabolism or
elimination of toxic materials. However, for most materials
there is a gradual reduction of the concentration within the
body.
To give you a better understanding of the time factor in
reduction of the quantity of toxic chemical in the body, let us
take a look at an example of the rate of elimination of ethyl
alcohol from the blood of a test animal.
The rate of elimination is usually characterized as having a
"biologic half-life," the period of time required for the
concentration to drop by half. The biologic half-life of ethyl
alcohol is about 20 minutes. Every 20 minutes the concentration
drops to half its previous value.
After about 120 minutes from the initial exposure the
concentration will have dropped nearly to zero. As long as the
dosage is not repeated more often than every 120 minutes, the
maximum concentration in the blood will not exceed the
concentration from a single dosage.
If the dosage is repeated before the initial exposure has
dropped to zero, the concentration will gradually build up. When
the dosage rate exceeds the elimination rate, the build up is
called "bioaccumulation." Bioaccumulation can occur with either
high or low levels of exposure, as well as with exposures by more
than one route of entry.
The adverse effects from exposure to a toxic chemical will
frequently depend on the time interval between exposures. if
there is sufficient time between exposures or doses, the chemical
has time to be detoxified or eliminated and there is less
likelihood of an overexposure.
9-21
-------
Recognition of the importance of time intervals between
doses or exposures includes:
o aspirin labels that recommend a limit on the number
taken in one day,
o advice on limiting the volume of alcoholic beverage
consumed with a certain number of hours in order to
prevent legal intoxication, and
o Threshold Limit Values for occupational exposure to
airborne contaminants.
Thus, many factors are involved in the determination of
toxic effects in the system by chemical agents. It is nearly
impossible to predict eventual harm to most chemical exposures
due to the complicated and intrinsic mechanisms of body
processes. An exception would be acutely toxic compounds, which
cause immediate death from even small exposures, such as with
cyanide.
9-22
-------
STUDENT EXERCISE
Inorganic lead has been known to cause harmful effects to
infants as well as adults for many years. While children often
ingest lead through peeling paint, adults are also exposed to
this metal, especially if working in lead smelters where lead
fumes and lead oxide dust present environmental hazards. Once in
the system, lead is absorbed into the blood stream and is rapidly
transferred to bone and soft tissues. Eventually, the lead is
redistributed to the liver and kidney where harm is done.
Secretion of lead occurs primarily through the bile and urine.
Use the above information to complete the diagram below for
lead. Circle all involved conponents in this Toxic system.
9-23
-------
ROUTES OF ENTRY, ABSORPTION, DISTRIBUTION, AND ELIMINATION
OF LEAD
ENTRY
Ingestion
Inhalation
Skin Contact
ABSORPTION
Gastrointestinal
tract
Respiratory
tract
Dermis and Epidermis
DISTRIBUTION
AND STORAGE
c
Blood and Lymph
y
QiverJ
Bile
Extracellular
Fluid
[Kidney] Lung ]]
/Adipose)
tissue
(fat)
gladder (Alveol j
Secretory
Structures
Organsj
Soft
tissue
Bone
ELIMINATION
Feces
Urine
Expired air
Secretions
If you follow each route of entry, you can see possible
ways in which chem'lcals enturing the body may reach different
parts of the body and be stored or eliminated.
9-24
-------
UNIT 10
EVALUATING HEALTH HAZARDS AMD TOXICITY
A. INTRODUCTION
The health and safety of Agency employees involved in
environmental incident response is at stake with each new field
activity. Each incident poses unique and special problems.
Personnel must be able to soundly evaluate these hazards and
effectively plan a course of action in response to these
incidents.
All incidents are potentially harmful to some segment of the
environment, workers or public. Many chemicals are combustible,,
toxic, reactive, flammable, explosive, corrosive, radioactive, or
biologically active, alone or when mixed together and pose a
potential threat to human health and the environment. Caution,
appropriate protective measures, and sound evaluation are all
essential ingredients to safe incident response.
B. PRACTICAL CONSIDERATIONS
For response personnel, protection of themselves and the
public is of immediate concern at an incident site. The
following factors must be considered during evaluation of the
situation:
o What toxic agent(s) is present?
o How will this agent enter the body?
o How will this agent affect the body?
o How toxic is this agent?
o Is the agent reactive? With air? Water?
o What are the incompatibilities of the agent?
Answers to these and similar questions dictate levels of
personnel protection to be employed, required monitoring, and
levels of public protection (e.g., warnings, evacuations, route
detours) to be instituted.
10-1
-------
C. NEEDS FOR SPECIFIC INFORMATION ON HEALTH HAZARDS FOR
CHEMICALS
In order to make rational and valuable decisions in choosing
protective equipment for site mitigation measures and public
health concerns, specific information on the health hazards of
involved chemicals is mandatory. Knowledge of specific chemical
hazards help you to:
o Determine hazards and degree of hazard for each
chemical.
o Make initial decisions concerning protective equipment/
monitoring devices, precautions to be taken and public
awareness needed.
o Determine potential exposures the workers and the
public, and whether these exposures need monitoring.
If so, is monitoring equipment available? Should
monitoring be done routinely through medical testing,
continuously at the site, or after-the-fact through
laboratory analysis?
o Determine specific protective equipment required. This
includes respiratory equipment, clothing, gloves,
boots, and face shields. Compatibility of the
chemicals with clothing materials must be known in
order to make sound judgments.
o Develop procedures and reaction strategies in response
to overexposures of the public and workers from
chemicals at an incident site.
o Determine incompatibilities of incident site chemicals.
This information is mandatory for containment and
cleanup procedures. If a chemical reacts violently
with water, air, absorbents, clothing material, or
other chemicals, this information must be known prior
to start-up of mitigation.
10-2
-------
D. ROUTES OF EXPOSURE
In determining exposure of humans to various chemicals, it
is important to consider the major routes by which chemicals
enter the body. Generally speaking, the effect (or rapidity of
effect) of a chemical on the body is a function of its mode of
entry into the body. At the site of a chemical incident, there
are three primary routes for chemicals to enter the body:
o through contact with skin, eyes, or hair
o through inhalation by breathing fumes, vapors, dusts,
or particles
o through ingestion by swallowing contaminated food,
placing contaminated objects in the mouth, by chewing
gum/tobacco, or by smoking
E. CONTACT
Skin consists primarily of two layers: a tough outer
epidermis and a more sensitive, sponge-like inner layer, the
dermis. Hair follicles penetrate both layers of skin. Located
in the sensitive dermis are sweat ducts and glands, sebaceous
glands, connective tissue, fat and blood vessels. These two
layers together form skin, acting as a barrier against the entry
of foreign matter into the body. The epidermis plays a major
role in preventing penetration of chemicals through the skin.
Due to its vast surface area (1.6 - 1.8 m2) the epidermis itself
is more susceptible to chemical exposure than hair follicles and
sweat glands which penetrate both layers of skin.
Despite its large surface area, intact skin is quite an
effective barrier against most chemical invasions when exposure
times are brief. Some chemicals, however, are much too toxic for
even short-term skin exposures such as:
o organic phosphates
o aniline
o phenol
o hydrogen cyanide
Brief exposures to these substances could cause serious or
fatal poisoning.
The ability of skin to resist chemical penetration is
primarily a function of one distinct portion of the epidermis,
the stratum corneum. This layer is comprised of dead cells
located on the outer surface of skin. Both the thickness of the
10-3
-------
stratum cornevun and the diffusivity of these cells determine the
permeability of skin to various chemicals. For example, although
the soles of the feet exhibit high diffusivity, the thickness of
the stratum comeum here makes it difficult for toxicants to be
absorbed at this site. On the other hand, areas such as the
face, eyelids, and armpits have such a thin stratum comeum that
chemicals can penetrate these regions rather easily.
Chemical properties of toxicants also influence diffusivity
of the stratum comeum. Fat and lipid-soluble compounds and many
organic solvents are able to readily penetrate this outer layer
of skin. Skin contact with solvents such as DMSO greatly
facilitates the passage of poisons into the body. Absorption
enhancement mechanisms are unknown, but the results can prove
extremely dangerous for the unsuspecting victim.
Intact skin has a number of natural defenses against"
xenobiotics (foreign substances). These include:
o epidermis: prevents chemical absorption and is a
physical barrier to most bacteria, primarily due to the
stratum comeum layer
o sebaceous glands: secrete fatty acids to inhibit
bacterial and fungal growth
o melanocytes (skin pigment): prevent damage from
ultraviolet (UV) rays sunlight
o sweat glands: regulate body heat
o connective tissue: provides elasticity which protects
against physical trauma
o lymph-blood system: provides protective responses to
infection
There are many factors which enhance the absorption of
xenobiotics through the skin, including:
o cuts or abrasions of the skin's epidermis
o increasing skin's moisture content (through sweating or
being wet)
o increasing skin temperature, causing increased blood
flow to the skin and opening of sweat cells, which
allows sweat to dissolve solids, thus increasing
absorption ability
o increasing the concentration of foreign substances
10-4
-------
o altering skin's normally mild acidity (pH = 5)
o decreasing substance particle size
o adding surface-active agents or organic chemicals such
as DMSO, which readily penetrates the skin carrying
practically any substance with it
o inducing ion movement with an electrical charge
Once skin contact with toxins has been made, and absorption
has taken place, effects of these toxins may be manifested.
Effects may be local or systemic. Local effects include
irritation of the skin, dermatitis, swelling, and cell death.
Examples of compounds causing local effects include:
o primary irritants which act directly on skin at the
site of contact such as sulfuric acid (battery acid) ^
acetone, benzyl chloride, carbon disulfide,"
chloroform, chromic acid, and other soluble chromium
compounds, ethylene oxide, hydrogen chloride, iodine,
methyl ethyl ketone, mercury, phenol, phosgene,
styrene, sulfur dioxide, picric acid, toluene and
zylene
o photosensitizers which cause skin irritation and
redness due to increased sensitivity to sunlight such
as creosote, tetracyclines, acridine, pyridine,
furfural and naphtha
o allergic sensitizers which cause allergic reactions
upon repeated contact, such as formaldehyde, phthalic
anhydride, ammonia mercury, nitrobenzene, toluene
disocyanate, chromic acid and chromates, cobalt, and
benzoyl peroxide
Contact by toxins is not only manifested through the skin,
but also the eyes. The eyes are harmfully affected by many of
the same chemicals that penetrate the skin, but eyes are much
more sensitive and readily absorb many xenobiotics. The eyes are
also extremely sensitive to direct contact by chemicals such as:
o Acids - damage depends on the strength of the acid and
the acid's protein-combining capacity
o Sulfuric acid - not only corrosive, but it removes
water from the clear membrane covering the eye and
generates heat simultaneously
o Hydrochloric acid - causes severe damage at pH 1, but
no effect at pH 3 and above
10-5
-------
o Picric acid and tannic acid - produce equal damage
throughout the entire acidic pH range
o Alkalies - damage appears mild initially but can lead
to ulceration, perforation, and clouding of the cornea
or lens
The pH of the alkaline substance and exposure time are
most important in determining damage potential to the
eyes. Problem alkalies include:
Sodium hydroxide
Potassium hydroxide
Ammonia (an extremely rapid eye penetrant)
Calcium oxide (lime) - dangerous because it
forms clumps upon eye contact and is
difficult to remove
Organic solvents - these substances dissolve
fat, induce pain, and dull the cornea; damage
is increased greatly when solvents are hot.
Examples include:
- Ethanol
- Toluene
- Acetone
o Lacrimators - these substances cause instant tearing at
low concentrations without damaging tissues. At very
high concentrations, chemical burns and cornea damage
can result. Examples include:
Chloroacetophenone (tear gas)
MACE
For some toxins which are ingested, inhaled, or absorbed,
the eye is the target organ for harmful systemic effects.
Examples include:
o Naphthalene - causes cataracts and retinal damage
o Phenothiazine, an insecticide - causes retina damage
10-6
-------
o Thallium - causes cataracts and optic nerve damage
o Methanol - causes optic nerve damage
F. EXPOSURE LIMITS
An important consideration in controlling exposures to
hazardous substances is knowing maximum allowable exposures if
such values have been set.
1. EXPOSURE THROUGH SKIM CONTACT AND INGESTION
No limits have been set for ingestion or skin contact
with toxicants. Precautionary labeling is not yet required for
industrial hazardous substances, but undoubtedly will be required
in the near future. Hazardous wastes, on the other hand, are
required to be labeled as such, and can be shipped only after
precautionary labels have been attached (such as "corrosive,n
"flammable," etc.). Many manufacturers place warning labels on
their hazardous substance packages. These precautions include
such terms as corrosive; irritating; rapidly absorbed through
skin; avoid contact with eyes; in case of contact, flush
immediately with water; use with adequate ventilation.
Manufacturing companies determine warning labels and use
restrictions based on toxicity tests prior to distribution for
sale. However, in order to assign exposure limits for contact or
ingestion, the exact amount and duration of exposure must be
accurately measured. These measurements would be nearly
impossible to obtain, especially under field conditions.
Overexposure thus would be determinable only through signs and
symptoms of toxic effects of chemicals.
2. INHALATION EXPOSURE LIMITS
Inhalation exposure limits for many industrial
chemicals (nearly 600) have been set by two major groups: The
American Conference of Governmental Industrial Hygienists
(ACGIH), and the Occupational Safety and Health Administration
(OSHA). These limits are based on inhalation exposure alone and
do not account for a combination of inhalation and any other
exposure route. Thus, total exposure is rarely taken into
consideration through these values.
Exposure limits are based on normal workdays for
average employees and are expressed as Threshold Limit Values
(TLVs). These TLVs refer to airborne concentrations of chemicals
under conditions believed to be representative of what all
workers may be repeatedly exposed to daily, without adverse
effects. Three categories of TLVs are defined by the ACGIH:
10-7
-------
o Threshold Limit Value - Time Weighted Average
(TLV-TWA) - The time weighted average
concentration for a normal 8-hour workday and 40-
hour workweek.
o Threshold Limit Value - Short Term Exposure Limit
(TLV STEL) - The concentration to which workers
maybe exposed continuously for a short time (15
minutes) without adverse health effects. The TWA
must not be exceeded.
o Threshold Limit Value - Ceiling (TLV-C) - The
concentration that should never be exceeded for
any length of time.
Threshold Limit Values are not to be used as an index
of toxicity. These values are primarily based on short-term
exposure tests on laboratory animals whose sensitivity is not
necessarily equal to that of humans. In addition, human exposure
data were mostly based on exposure to young males, who do not
represent the average worker.
Values set by OSHA are termed Permissible Exposure
Limits (PELs) and are based on an earlier edition of the ACGIH*s
TLVs. It must be realized that for TLVs and PELs, individual
susceptibilities vary, making TLV exposure levels too high for a
small percentage of employees. This small percentage of workers
may be seriously affected at levels at or below set TLVs.
6. AIR MONITORING INSTRUMENTS
Air monitoring instruments provide an integral portion of
the information necessary to determine the presence of
potentially harmful, hazardous substances. The purpose of this
section is to:
o List air monitoring instruments useful for hazardous
substance identification.
o Describe the operating theories and principles of these
instruments.
o Illustrate the proper interpretation and limitations of
the data obtained.
Used correctly, these instruments provide data that help
personnel determine:
o Potential or real effects on the environment
o Immediate and long-term risks to public health,
including the health of on-site workers
10-8
-------
o Appropriate personnel protection and respiratory
equipment to be used on-site
o Actions to mitigate the hazard(s) safely and
effectively
Many of the common types of monitoring and sampling
equipment discussed in this section of the manual are listed in
tabular form in Appendix I at the end of this unit.
1. Characteristics of Air Monitoring Instruments
To be useful in the field, air monitoring instruments
must be:
o Portable
o Able to generate reliable and useful results
o Sensitive and selective
o Inherently safe
All of these traits may or may not be present in any
one instrument.
a. Portability
A prime consideration that determines the
usefulness of a field instrument is portability. Transportation
shock resulting from the movement from one place to another,
together with unintentional abuse, ranks high in shortening the
usable life of an instrument. To reduce this trauma, instruments
should be selected that have reinforced shells or frames, shock-
mounted electronic packages, or padded containers for shipment.
Exposure to the elements and the test atmosphere
itself is of concern for those instruments repeatedly used in
adverse conditions or as long-term monitors. Anodized or coated
finishes, weather-resistant packaging and remote sensing are
effective in reducing downtime and increasing portability.
In short, a portable unit should possess ease in
mobility, the ability to withstand the rigors of use, quick
assembly, and short check out and calibration time.
b. Reliable and Useful Results
Response time, the interval between an instrument
"sensing" a contaminant and generating data, is important to
producing reliable and useful results in the field. Response
time depends on: test(s) to be performed, dead time between
10-9
-------
sample periods (the time for analysis, data generation, and data
display), and the sensitivity of the instrument. Response time
establishes the pace of the overall survey and the individual
tests.
Another consideration is that the instrument must
give results that are immediately useful. Instruments should be
direct reading, with little or no need to interpolate, integrate,
or compile large amounts of data.
c. Sensitivity and Selectivity
A third requirement of a good field instrument is
the ability to sample and analyze very low contaminant levels,
and, ideally, to discern among contaminants exhibiting similar
characteristics.
Sensitivity defines the lowest concentration an
instrument can accurately and repeatedly analyze. In the
strictest sense, it is a function of the detecting ability of the
instrument, and does not address the electronic amplifier, if the
unit has one. The operating range establishes the upper and
lower use limits of the instrument. It encompasses the
sensitivity limit at its lower end and the overload point at its
upper.
Selectivity establishes what contaminants will
elicit a response on the instrument. Additionally, selectivity
mandates which, if any, interferences may produce a similar
response. Selectivity and sensitivity must be reviewed and
interpreted together. Many devices have high selectivity but
widely varying sensitivities for a given family of chemicals, for
example aromatics, aliphatics, and amines.
Amplification, often used synonymously (and
incorrectly) with sensitivity, deals with an electronic
amplifier's ability to increase very small electrical signals
emanating from the detector. This capacity may be fixed or
variable. However, changing the amplification of the detector
does not change its sensitivity. For optimum field usefulness,
an instrument should possess high sensitivity, wide range, high
selectivity, and the ability to vary the amplification of
detector signals.
d. Inherent Safety
The portable instrumentation used to evaluate the
presence of hazardous substances must be demonstrated as being
safe to use in hostile environments. Electrical devices, such as
the monitoring instruments, must be constructed in such a fashion
as to eliminate the possibility of igniting a combustible
atmosphere. The sources of this ignition could be: an arc
10 - 10
-------
generated by the power source itself or the associated
electronics, and/or a flame or heat source inherent in the
instrument and necessary for its proper functioning.
Several engineering, insurance, and safety
industries have standardized test methods, established inclusive
definitions; and developed codes for testing electrical devices
used in hazardous locations. The National Fire Protection
Association (NFPA), a forerunner in this endeavor, created
minimum standards in its National Electrical Code (NEC) published
every 3 years.
This code spells out among other things:
o Types of controls acceptable for use in
hazardous atmospheres
o Types of areas in which hazardous atmospheres
can be generated and the types of materials
that generate these atmospheres
2. Hazardous Atmospheres
Depending upon the response worker's background, the
term "hazardous atmosphere" conjures up situations ranging from
toxic air contaminants to flammable atmospheres. For our
purposes, an atmosphere is hazardous if it meets the following
criteria:
o It is a mixture of any flammable material in air
(see Class and Group below) whose composition is
within this material's flammable range (LEL-LFL).
o A critical volume of the mixture is sufficiently
heated by an outside ignition source.
o The resulting exothermic reaction propagates the
flame beyond where it started.
Hazardous atmospheres can be produced by one of three
general types of materials:
o Flammable gases/vapors
o Combustible dusts
o Ignitable fibers
10 - 11
-------
Whereas the flammable material may define the hazard
associated with a given product, the occurrence of release, (how
often the material generates a hazardous atmosphere) dictates the
risk. Two types of releases are associated with hazardous
atmospheres:
o Continuous: Those existing continuously in an
open unconfined area during normal operating
conditions.
o Confined: Those existing in closed containers,
systems or piping, where only ruptures, leaks, or
other failures result in a hazardous atmosphere
outside the closed system.
There are six possible environments in which a
hazardous atmosphere can be generated. However, not every type
of control will prevent an ignition in every environment. To
adequately describe the characteristics of those environments and
what controls can be used, the National Electrical Code defines
each characteristic:
o Class is a category describing the type of
flammable material that produces the hazardous
atmosphere:
Class I is flammable vapors and gases, such as
gasoline, hydrogen. Class I is further divided
into groups A,B,C,and D on the basis of similar
flammability characteristics (Table 10-1).
Class II consists of combustible dusts like coal
or grain and is divided into groups E,F, and G.
Class III is ignitable fibers such as produced by
cotton milling.
o Division is the term describing the "location" of
generation and release of the flammable material.
Division 1 is a location where the generation and
release are continuous, intermittent, or periodic
into an open, unconfined area under normal
conditions.
Division 2 is a location where the generation and
release are in closed systems or containers and
only from ruptures, leaks or other failures.
Using this system, a hazardous atmosphere can be
routinely and adequately defined. As an example, a spray-
painting operation using acetone carrier would be classified as a
10 - 12
-------
Class I, Division 1, Group D environment. Additionally, an
abandoned waste site containing intact closed drums of methyl
ethyl ketone, toluene, and xylene would be considered a Class I,
Division 2, Group D environment. Once the containers begin to
leak and produce a hazardous atmosphere, the environment changes
to Class I, Division 1, Group D.
10 - 13
-------
TABLE 10-1
CLASS I CHEMICALS BY GROUPS
Group A Atmospheres
Acetylene
Group B Atmospheres
Butadiene
Ethylene oxide
Hydrogen
Manufactured gases containing more
than 30% hydrogen (by volume)
Propylene oxide
Group C Atmospheres
Acetaldehyde
Crotonaldehyde
Cyclopropane
Diethyl ether
Ethylene
Unsymmetrlcal dimethyl hydrazine
(UDMH, 1-, 1-dimethyl hydrazine)
Group 0 Atmospheres
Acetone
Acrylon1tr1le
Annonla
Benzene
Butane
1-Butanol (butyl alcohol)
2-Butanol (secondary butyl alcohol
2-Butyl acetate
n-Butyl acetate
Isobutyl acetate
Ethane
Ethanol (ethyl alcohol)
Ethyl acetate
Ethylene d1chloride
Gasol1ne
Heptanes
Hexanes
Isoprene,
Methane (natural gas)
Methanol (methyl alcohol)
3-Methyl-1-butanol (1soan\yl alcohol)
Methyl ethyl ketone
Methyl Isobutyl ketone
2-Methyl-l-propanol (Isobutyl alcohol
2-Methyl-2-propanol (tertiary butyl
alcohol)
Octanes
Petroleum naphtha
Pentanes
1-Pentanol (amyl alcohol)
Propane
1-Propanol(propyl alcohol)
2-Propanol (Isopropyl alcohol)
Propylene
Styrene
Toluene
Vinyl acetate
Vinyl chloride
Xylenes
Source: National Electrical Code. National F1re Protection
Association, 470 Atlantic Ave., Boston MA 02210 (1977).
10 - 14
-------
3. controls
Three methods exist to prevent a potential ignition
source from igniting a flammable atmosphere:
o Explosion-proof: Encase the ignition source in a
rigidly built container. "Explosion-proof"
instruments allow the flammable atmosphere to
enter. If and when an arc is generated, the
ensuing explosion is contained within the
specially designed and built enclosure. Within
it, any flames or hot gases are cooled prior to
exiting into the ambient flammable atmosphere so
that the explosion does not spread into the
environment.
o Intrinsically Safe: Reduce the potential for
arcing among components by encasing them in a
solid insulating material. Also, reducing th^
instrument's operational current and voltage below
the energy level necessary for ignition of the
flammable atmosphere provides equal protection.
An "intrinsically safe" device, as defined by the
National Electrical Code, is incapable "of
releasing sufficient electrical or thermal energy
under normal or abnormal conditions to cause
ignition of a specific hazardous atmospheric
mixture in its most easily ignited concentration.
Abnormal conditions shall include accidental
damage to any wiring, failure of electrical
components, application of over-voltage,
adjustment and maintenance operations and other
similar conditions."
o Purged: Buffer the arcing or flame-producing
device from the flammable atmosphere with an inert
gas. In a pressurized or "purged" system, a
steady stream of, for example, nitrogen or helium
is passed by the potential arcing device, keeping
the flammable atmosphere from the ignition source.
This type of control, however, does not
satisfactorily control analytical devices that use
a flame or heat for analysis such as a combustible
gas indicator (CGI) or gas chromatograph (GC).
National groups such as Underwriters Laboratories (UL),
Mutual (FM), and the American National Standards Institute
(ANSI) , together with NFPA, developed test protocols for
certifying explosion-proof, intrinsically safe, or purged devices
to meet minimum standards of acceptance.
10 - 15
-------
An electrical device certified under one of these test
methods, carries a permanently affixed plate showing the logo of
the laboratory granting certification and the Class (es),
Division(s), and Group(s) it was tested against.
Certification means that if a device is certified as
explosion proof, intrinsically safe, or purged for a given Class,
Division, and Group, and is used, maintained, and serviced
according to the manufacturer's instructions, it will not
contribute to ignition. The device is not, however, certified
for use in atmospheres other than those indicated.
Any manufacturer wishing to have an electrical device
certified by FM or UL must submit a prototype for testing. If
the unit passes, it- is certified as submitted. However the
manufacturer agrees to allow the testing laboratory to randomly
check the manufacturing plant at any time, as well as any
marketed units. Furthermore, any change in the unit requires the
manufacturer to notify the test laboratory, which can continue
the certification or withdraw it until the modified unit can be
retested.
A unit may be certified either by UL, FM or both. Both
laboratories follow test protocols established by NFPA and ANSI.
Therefore one certification is no better or worse than the other.
The important consideration is that the device is approved for
the Class(es), Division(s), and Group(s) it will be used in.
This mention of FM or UL in the manufacturer's equipment
literature does not guarantee certification. All certified
devices that are used in hazardous (flammable) locations must be
marked to show Class, Division, and Group, per NEC Table 500-
2(b).
Other organizations such as the Mine Safety and Health
Administration (MSHA), Canadian Standards Association (CSA),
National Electrical Manufacturers Association (NEMA), and the
U.S. Coast Guard (USCG) have developed their own testing and
certification schemes for electrical devices in hazardous
locations common to their jurisdiction.
MSHA tests and certifies electrical equipment to be
used in hazardous atmospheres associated with underground mining.
These atmospheres usually contain methane gas and coal dust;
hence the tests and certification are specific to those two
contaminants.
Often the same monitoring equipment is used in mines as
well as above ground and therefore carry more than one
certification, such as FM and MSHA.
To ensure personnel safety, it is recommended that only
approved (FM or UL) instruments be used on-site and only in
10 - 16
-------
atmospheres for which they have been certified. When
investigating incidents involving unknown hazards, the monitoring
instruments should be rated for use in the most hazardous
locations. The following points will assist in selection of
equipment that will not contribute to ignition of a hazardous
atmosphere:
o In an area designated Division 1, there is a
greater probability of generating a hazardous
atmosphere than in Division 2. Therefore, the
test protocols for Division 1 certification are
more stringent than those for Division 2. Thus, a
device approved for Division 1 is also permitted
for use in Division 2, but hot vice versa. For
most response work this means that devices
approved for Class I (vapors, gases). Division 1
(areas of ignitable concentrations). Groups
A,B,C,D should be chosen whenever possible. At a
minimum, an instrument should be approved for use
in Division 2 locations.
o An additional consideration is that all
instruments used in a methane environment should
be approved by the Mine Safety and Health
Administration (MSHA) as being safe in such
atmospheres.
o There are so many Groups, Classes, and Divisions
that it is impossible to certify an all-inclusive
instrument. Therefore, select a certified device
based on the chemicals and conditions most likely
to be encountered. For example, a device
certified for a Class II, Division 1, Group E
(combustible metal dust) would offer little
protection around a flammable vapor or gas.
4. Field Instruments
Four hazardous atmosphere conditions can occur: oxygen
deficient atmosphere; explosive atmosphere? toxic atmosphere; and
radioactive environments.
When first approaching a facility or site, the
potential hazards must be recognized and exposure risks
evaluated. This can be in the form of a preliminary site survey.
Information gained will most likely be limited but will provide
enough data to make some initial decisions. These might include
respirator and protective clothing selection or further
definition of the hazard by qualitative assessment.
10 - 17
-------
Once the plan of action, based on the initial survey,
is done, hazard evaluation is not over. No matter how passive
the situation appears, sites may be very dynamic. To ensure a
safe working environment, continuous or periodic monitoring of
the hazards must be performed.
To perform initial surveys and subsequent monitoring,
various portable instruments must be available. Such instruments
range from portable gas chromatographs to passive dosimeters.
The variety of instruments and operating principles is wide. New
instruments are introduced each year incorporating advances in
technology.
With such a variety of portable instrumentation
available, it follows that each serves a specific purpose. Some
display an immediate readout upon each sample taken manually.
Others monitor continuously and have built-in alarms to signal a
potential hazard. Many instruments are designed to sample over a
time period to determine a time-weighted average exposure. These
may be active or passive in design. There are instruments which
utilize unique components to determine the concentration of a
hazardous substance.
a. Oxvaen-Deficient Atmospheres
The oxygen content in a confined space is of prime
concern to anyone about to enter that space. Removal of oxygen
by combustion, reduction reactions, or displacement by gases or
vapors is a hazard which response personnel cannot detect.
Consequently, remote measurements must be made before anyone
enters a confined space.
Portable oxygen indicators are invaluable when
responding to hazardous material spills or waste sites. Terrain
variations in the land and unventilated rooms or areas may
contain insufficient oxygen to support life. In addition, oxygen
measurements are necessary when combustible gas indicator (CGI)
measurements are made, since the oxygen level in the ambient air
effects the accuracy of CGI's readout. When used properly the
portable oxygen indicator will read the percent oxygen in the
immediate atmosphere. The normal ambient oxygen concentration is
20.8%.
Most indicators have meters which display the
oxygen content from 0-25%. There are also oxygen indicators
available which measure concentration from 0-5% and 0-100%. The
most useful range for response is the 0-25% oxygen content
readout since decisions involving air-supplying respirators and
the use of combustible indicators fall into this range.
10 - 18
-------
(1) Theory
The oxygen indicator has two principle
components for operation. These are the oxygen sensing devices
and the meter readout. In some units air is drawn to the oxygen
detector with an aspirator bulb or pump; in other units, the
ambient air is allowed to equilibrate with the sensor. The
oxygen detector uses an electrochemical sensor to determine the
oxygen concentration in air. A typical sensor consists of: two
electrodes, a sensing and a counting electrode; a housing
containing a basic electrolytic solution; and a semipermeable
Teflon membrane.
Oxygen molecules (O2) diffuse through the
membrane into the solution. Reactions between the oxygen and the
electrodes produce a minute electric current which is directly
proportional to the sensors's oxygen content. The current passes
through the electronic circuit. The resulting signal is shown as
a needle deflection on a meter, which is usually calibrated to
read 0-10%, 0-25%, or 0-100% oxygen.
(2) Limitations
The operation of oxygen meters depends on the
absolute atmospheric pressure. The concentration of natural
oxygen (to differentiate it from manufactured or generated
oxygen), is a function of the atmospheric pressure at a given
altitude.
At sea level, where the weight of the
atmosphere above is greatest, more 02 molecules are compressed
into a smaller volume than at higher elevations. As elevation
increases, this compression decreases, resulting in fewer 02
molecules being "squeezed" into a given volume. Consequently, an
02 indicator calibrated at sea level and operated at an altitude
of several thousand feet will falsely indicate an oxygen-
deficient atmosphere (less than 19.5% as defined by HIOSH).
High concentrations of carbon dioxide (CO2)
shorten the useful life of the oxygen detector cell. As a
general rule, the unit can be used in atmospheres greater than
0.5% C02 only with frequent replacing or rejuvenating of the
oxygen detector cell.
Although several instruments can measure an
oxygen-enriched atmosphere (02 greater than 21%), no testing or
other work should ever be performed under such conditions because
a spark, arc or flame could lead to fire or explosion.
10 - 19
-------
b. Explosive Atmospheres
The combustible gas indicator (CGI) is one of the
finest instruments to be used to survey a site; typically, CGI
readings are taken concurrently with O2 level readings. It
measures the concentration of a flammable vapor or gas in air,
indicating the results as a percentage of the lower explosive
limit (LEL) of the calibration gas.
The LEL of a combustible gas or vapor is the
lowest concentration by volume in air which will explode, ignite,
or burn when there is an ignition source. The upper explosive
limit (UEL) is the maximum concentration. Above the UEL, there
is insufficient oxygen to support combustion so ignition is
impossible. Below the LEL, there is insufficient fuel to support
ignition.
(l) Theory
Most combustible gas indicators operate on
the "hot wire" principle. In the combustion chamber is a
platinum filament that is heated. The platinum filament is an
integral part of a balanced resistor circuit called a Wheatstone
Bridge. The hot filament combusts the gas on the immediate
surface of the element, thus raising the temperature of the
filament.
As the temperature of the filament increases
so does its resistance. This change in resistance causes an
imbalance in the Wheatstone Bridge. This is measured as the
ratio of combustible vapor present compared to the total required
to reach the LEL. For example, if the meter reads 0.5 (or 50,
depending upon the readout), this means that 50% of the
concentration of combustible gas needed to reach an unstable
flammable or combustible situation is present. If the LEL for
the gas is 5% then the meter indicates that a 2.5% concentration
is present. Thus the typical meter readout indicates
concentration up to the LEL of the gas.
If a concentration greater than LEL and lower
than the UEL is present, then the meter needle will stay beyond
the 1.0 (100%) level on the meter. This indicates that the
ambient atmosphere is readily combustible. When the atmosphere
has a gas concentration above the UEL the meter needle will rise
above the 1.0 (100%) mark and then return to zero. This occurs
because the gas mixture in the combustion cell is too rich to
bum. This permits the filament to conduct a current just as if
the atmosphere contained no combustibles at all.
10 - 20
-------
(2) Limitations
As with any instrument based on an
electrochemical reaction, all cgi's have several limitations:
(A) The reaction is temperature dependent.
Therefore, the measurement is only as accurate as the incremental
difference between calibration and ambient (sampling)
temperatures.
(B) Sensitivity is a function of physical
and chemical properties of the calibration gas versus those of
the unknown contaminant. Most combustible gas indicators are
calibrated to read accurately for methane or pentane, but not all
combustible gases and vapors will give the same response as the
calibration gas. Because of the variation in the relative
response of the flammable substance in the atmosphere to the
calibration gas (e.g. methane), the instrument may not give an
accurate indication of the flammable hazard — the reading (%LEL)
may be higher or lower than the actual concentration.
(C) There is no differentiation between
petroleum vaporsand combustible gases unless a charcoal pre-
filter is employed.
(D) The unit is intended for use only in
normal atmospheres, not ones that are oxygen enriched or
deficient. Oxygen concentrations are less than or greater than
normal may cause erroneous readings.
(E) Leaded gasoline vapors, halogens, and
sulfur compounds will foul the filament which decreases its
sensitivity. Compounds containing silicone will destroy the
platinum filament.
c. Toxic Atmospheres
(1) Photoionization Detector (PID)
(A) Theory
The light from the sun when passed
through a prism dispersed into the many colors that make up the
white light spectrum. The hues of colors from the deep reds
through the deep purples are a relatively small segment in the
overall electromagnetic (e-m) spectrum.
10 - 21
-------
The e-m spectrum covers long wavelengths
such as radio waves through the ultrashort wave gamma radiation.
As the wavelengths decrease in size (higher frequencies), the
wave energy increases. This relationship between energy and
frequency is based upon Planck's equation.
All atoms and molecules are composed of
particles: electrons, protons, and neutrons. Electrons,
negatively charged particles, rotate in orbit around the nucleus,
the dense inner core. The nucleus consists of an equal number of
protons (positively charged particles) as electrons found in the
orbital cloud. The interaction of the oppositely charged
particles and the laws of quantum mechanics keep the electrons in
orbits outside the nucleus.
The energy required to remove the
outermost electron from the molecule is called the ionization
potential. (IP) and is specific for any compound or atomic
species. IP is measured in electron volts (eV). High frequency,
radiation (ultraviolet and above) is capable of causing
ionization and is hence called ionizing radiation.
When a photon of ultraviolet radiation
strikes a chemical compound, it ionizes the molecule if the
energy of the radiation is equal to or greater than the IP of the
compound. Since ions are capable of conducting an electrical
current, they may be collected on a charged plate. The measured
current will be directly proportional to the number of ionized
molecules.
The photoionization process can be
illustrated as: RH + hnu -> RH+ + e-, where RH is an organic
or inorganic molecule and hnu represents a photon of XIV light
with energy equal to or greater than the ionization potential of
that particular chemical species to cause the emission of
electron e-.
Units which utilize photoionization
include the AID 580, the Photovac Model #10A10 (includes a gas
chromatographic mode), and the HNU P101 which is described below.
HNU P101 Photoionization Detector
The HNU P101 is typical of field
photoionization units now available. It consists of two modules
connected via a signal power cord.
o A readout unit consisting of a
4/1/2 in. analog meter, a
rechargeable battery, and power
supplies for operation of the
amplifier and the UV lamp.
10 - 22
-------
o A sensor unit consisting of the UV
light source, pump, ionization
chamber, and a preamplifier.
An electrical pump pulls the gas sample
past a UV source. Constituents of a sample are ionized,
producing an instrument response, if their ionization potential
(IP) is equal to or less than the ionizing energy supplied by the
instrument uv lamp being utilized. The radiation produces an ion
pair for each molecule of contaminant ionized. The free
electrons produce a current directly proportional to the number
of ions produced. The current is' amplified, detected, and
displayed on the meter.
Three probes are available with the HNU,
containing either an 11.7, a 10.2, or a 9.5-eV UV light source.
Species that have IP's greater than the lamp rating will display
a poor instrument response, or no response at all. Thus
employing the 11.7 eV lamp will ensure the greatest range of
detectable species; however, it requires constant maintenance and
frequent lamp replacement. For many applications, the 10.2-eV
lamp/probe can be used. It offers relatively high radiation
levels without frequent lamp replacement; and will detect many
species. One notable exception is the chlorinated aliphatics.
(B) Limitations
Although the HNU photoionization unit is
an excellent instrument for survey, there are very important
. limitations.
(i) The response to a gas or vapor may
radically change when the gas or vapor is mixed with other
materials. As an example, a HNU calibrated to ammonia and
analyzing an atmosphere containing 100 ppm would indicate 100 on
the meter. Likewise, a unit calibrated to benzene would record
100 in an atmosphere containing 100 ppm benzene. However, in an
atmosphere containing 100 ppm of each, the unit could indicate
considerably less or more than 200 ppm, depending on how it was
calibrated.
(ii) Radio frequency interference from
pulsed DC or AC power lines, transformers, high voltage equipment
and radio wave transmission may produce an error in response.
(iii) The lamp window must be
periodically cleaned to ensure ionization of the air
containments.
10 - 23
-------
(iv) Although the HNU measures
concentrations from about 1-2000 ppm, the response is not linear
over this entire range. For example, the response to benzene is
linear from about 0-600 ppm. This means the HNU reads a true
concentration of benzene only between 0 and 600. Greater
concentrations are "read" at a lower level than the true value.
The HNU can be used to help determine
the proper health and safety protocols when evaluating a
hazardous waste site or spill. However, the need to properly
interpret the HNU's data and to understand the limitations of
this instrument cannot be overemphasized. One particularly
important limitation is how the HNU responds toward mixtures of
chemicals. If only one chemical species is present, the HNU can
be set to quantitatively respond to that chemical. However, the
HNU will not quantitatively respond to a mixture unless the IP's
of all chemicals in the mixture are the same. This is because^
the HNU has a different sensitivity to compounds with different"
IP's. As a rule, the HNU is more sensitive to complex compounds
and less sensitive to simpler ones. In order of decreasing
sensitivity, measured on a scale of l to 10, the HNU responds to:
o Aromatics (e.g., benzene, toluene,
xylene) and aliphatic amine
hydrocarbons: 10
o Unsaturated chlorinated
hydrocarbons (e.g.,
trichloroethylene ,
dichloroethylene): 5-9
o Unsaturated hydrocarbons (e.g.,
propylene): 3-5
o Paraffinic hydrocarbons with 5 to 7
carbons (e.g., hexane, heptane):
1-3
o Ammonia and paraffinic hydrocarbons
with 1 to 4 carbons (e.g.,
ethane, propane): less than 1.
To compensate for this varying
sensitivity, the HNU incorporates a span pot (potentiometer),
which varies the gain on the amplifier. In the full clockwise
(CW) position at level 9.8, the HNU indicates the approximate air
concentration of all chemicals with a sensitivity of 10, for
example, aromatic hydrocarbons.
10 - 24
-------
In full counterclockwise (CCW) position at level 0, it indicates
the approximate concentration of ammonia or paraffinic
hydrocarbons. with the span pot positioned at any intermediate
point, HNU indicates the approximate air concentration of the
chemical whose sensitivity corresponds to that level.
When the span pot is set at 0 (fully
CCW) and the function switch to the 0-20 range, the scale on the
meter face reads 0-2 ppm. This expansion, which is valid only
for materials that have a high relative sensitivity (10), allows
measurements in the parts-per-billion range (ppb).
In most circumstances, using the HNU at
the lowest setting (span pot 9.8) provides adequate data to
determine the proper health and safety protocols for on-site
workers. Unfortunately, several chemicals, for example acrolein,
exhibit medium to low sensitivity (0-5), while their
toxicological effects place their threshold limit value (TLV) at
a very low level. If these chemicals are indicated by the HNIT
set to 9.8, for example, improper protective gear could be
chosen. Consider this scenario: The air in an unknown hazardous
environment must be sampled. Response personnel survey the site
with an HNU, which indicates 2.0 ppm (instrument span set to
9.8). Later, the air contaminant is found to be acrolein with a
TLV of 0.1 ppm (100 ppb) and an immediately dangerous to life or
health (IDLH) level of 5 ppm. Since acrolein has a low relative
sensitivity, its concentration probably was in excess to 5 ppm,
the IDLH value.
Thus, total reliance to the HNU data
without regard for the chemical makeup of the sample can be a
problem.
(2) Flame Ionization Detector fFIDl
(A) Theory
The FID uses ionization as the detection
method, much the same as in the HNU, except that the ionization
is caused by a hydrogen flame, rather than by a UV light. This
flame has sufficient energy to ionize any organic species with an
IP of 15.4 or less.
Inside the detector chamber, the sample
is exposed to a hydrogen flame which ionizes the organic vapors.
When most organic vapor burn, positively charged carbon-
containing ions are produced which are collected by a negatively
charged collecting electrode in the chamber. An electric field
exists between the conductors surrounding the flame and a
collecting electrode.
10 - 25
-------
As the positive ions are collected, a current proportional to the
hydrocarbon concentration is generated on the input electrode.
This current is measured with a preamplifier which has an output
signal proportional to the ionization current.
A signal conducting amplifier is used to
amplify the signal from the preamp and to condition it for
subsequent meter or external recorder display. An example of an
instrument using an FID is the Foxboro Organic Vapor Analyzer
(OVA), described below.
Foxboro Organic Vapor. Analyzer (OVA)
The Foxboro OVA consists of two major
parts: A 9-pound package containing the sampling pump, battery
pack, support electronics, flame ionization detector, hydrogen
gas cylinder, and an optional gas chromatography (GC) column. A
hand-held meter/sampling probe assembly.
The OVA is generally calibrated to
methane, but can be calibrated to the species of interest.
The OVA can operate in two modes:
(i) Survey mode: During normal survey
mode operation, a sample is drawn into the probe and transmitted
to the detector chamber by an internal pumping system. When the
sample reaches the FID it is ionized as described above and the
- xesulting signal is translated on the meter for direct-reading
concentration as total organic vapor or recorded as a peak on a
chart. The meter display is an integral part of the
probe/readout assembly and has a scale from 0 to 10 which can be
set to read 0-1D, 0-100, or 0-1000 ppm v/v.
(ii) Gas chromatography mode: Gas
chromatography (GC) is a technique for separating components of a
sample and qualitatively and quantitatively determining them.
The sample to be separated is injected into a column packed with
an inert solid; a carrier gas (hydrogen) flows through the
column. As the carrier gas forces the sample through the column,
the separate components of the sample are retained on the column
for different periods of time. The amount of time a substance
remains on the column, which is called its retention time, is a
function of its affinity for the column material, column
temperature, and flow rate of the carrier gas.
Under preset instrumental
conditions, each component elutes from the column at a different
but reproducible length of time. As the components elute from the
column, they flow into the detector. Since the output of the
detector is connected to a strip chart recorder, separate peaks
are recorded for each component. This readout is called a gas
10 - 26
-------
chromatograin. Since the retention times are reproducible, if the
retention tine of an unknown agrees with the retention tine of a
known, recorded under the sane set of analytical conditions, the
unknown is tentatively identified. In addition, the area under
each peak is proportional to the concentration of the
corresponding sample component. If these areas are compared to
the areas of standards, recorded under identical analytical
conditions, the concentration of the sample components can be
calculated. Note that if the "base" of the peak can be made very
narrow by varying the instrumental conditions, component
concentration is proportional to peak height, which can be read
directly off the chart.
As with the HNU Photoionizer, the OVA
responds differently to different compounds. Table 10-2 is a
list, provided by the manufacturer of the relative sensitivities
of the OVA to some common organic compounds. Since the
instrument is factory calibrated to methane, all relative
responses are given in percent, with methane at 100.
(B) Limitations
TABLE 10-2
Selection from Product Literature. Foxboro Analytical, by Foxboro
Analytical, copyrighted by Foxboro Analytical, reprinted wit.
permission of Publisher.
Compound
Relative Response
Methane
Ethane
Propane
n-Butane
n-Pentane
Ethylene
Acetylene
Benzene
Toluene
Acetone
Methyl ethyl ketone
Methyl isobutyl ketone
Methanol
Ethanol
Isopropyl alcohol
Carbon tetrachloride
Chloroform
Trlchloroethylene
Vinyl chloride
100
90
64
61
100
85
200
150
120
100
80
100
15
25
65
10
70
72
35
10 - 27
-------
Thus the identity of the chemical of
interest must be ascertained before its concentration can be
determined. In addition, the unit requires an individual trained
specifically to maintain and operate it. Experience in gas
chromatography is essential.
(3) Infrared Spectrophotometer
(A) Theory
The infrared spectrophotometer is a
compound specific instrument. Each compound being analyzed will
absorb at a discrete infrared wavelength. The unit measures how
much of the IR absorbed and indicates in ppm or per cent
absorbed.
The atoms of which molecules are
composed are held together by bonds of various types and lengths.
These arrangements, as in the classical ball and spring
configurations often presented in introductory chemistry,
establish finite locations and discrete movements for each atom
(ball) and bond (spring). These movements can be either
vibrational-rotational stretching or bending of the chemical
bonds. The frequencies of these movements are on the order of
infrared radiation (IR). A given bond movement can be initiated
by stimulating the molecule with IR of varying frequency. As the
bond moves, it absorbs the characteristic energy associated with
that movement. The frequencies and intensity of IR absorbed are
specific for a compound and its concentration, providing a
"fingerprint" which can be used as an analytical tool.
Foxboro, Perkin-Elmer, and Beckman are
producers of portable infrared spectrophotometers. The Miran IR
manufactured by Foxboro is discussed below.
Miran Infrared Spectrophotometer
The Miran (acronym for miniature
infrared analyzer) is a field IR spectrophotometer which uses a
variable length gas cell to measure concentrations of vapor in
ambient air.
Several movable mirrors permit repeated
passes, producing paths from several centimeters to several
meters.
10 - 28
-------
Field analysis presents problems not
normally encountered in spectrophotometry in the laboratory.
With lab instruments, the analyst can control the concentration
of material entering the sample cell. To analyze uncontrollable
gas the Miran must make repeated passes to achieve reliable
results. Liquid or solid samples are preferable to gas samples
because they possess more molecules than a gas of the same
volume.
Additionally, the spectra of analyses of
the same chemical in the liquid phase and gaseous phase are
markedly different. In the gaseous state, the molecules are free
to rotate, and intermolecular actions are at a minimum. The
liquid state "locks" the molecules in a given structure.
(B) Limitations
The Miran is designed for industrial
hygiene work in occupational settings where known types of
materials are generated and where 120-volt AC power is available.
At hazardous waste sites neither of these conditions is common,
making Mirans of questionable value. They also have not been
recognized by any approving agencies as being safe for use in a
hazardous location. Basically, the Miran is designed for
quantifying simple one or two component mixtures. They can be
used on a hazardous waste site with another analytical procedure
for confirmation such as gas chromatography. For use in unknown
situations, one of the more advanced units may be connected to a
computer which is capable of analyzing the readout through the IR
spectrum and can narrow the list of possible compounds to a
minimum resulting in identification of individual components.
(4) Direct-Reading Colorimetric Indicator Tubes
In evaluating hazardous waste sites, the need
often arises to quickly measure a specific vapor or gas. Direct-
reading colorimetric indicator tubes can successfully fill that
need. They are usually calibrated in ppm or % concentration for
easy interpretation. There are indicator tubes available for
continuous sampling over a longer period of time.
(A) Theory
The interaction of two or three
substances may result in chemical changes. This change may be as
subtle as two clear liquids producing a third clear liquid, or as
obvious as a colorless vapor and colored sol^-d producing a
differently colored substance. Detector tubes use this latter
phenomenon to estimate the concentration of a gas or vapor in
air.
10 - 29
-------
Colorimetric indicator tubes consist of
a glass tube impregnated with an indicating chemical. The tube
is connected to a piston cylinder or bellows type pump. A known
volume of contaminated air is pulled at a predetermined rate
through the tube. The contaminant reacts with the indicator
chemical in the tube, producing a stain whose length is
proportional to the contaminant• s concentration. Detector tubes
are normally species specific. In other words, there are
different tubes for different gases, e.g. chlorine detector tube
for chlorine gas, acrylonitrile tube for acrylonitrile gas, etc.
Some manufacturers do produce tubes for groups of gases (aromatic
hydrocarbons, for example).
A preconditioning filter may precede
indicating chemical to:
o Remove contaminants (other than the
one in question) that may interfere
with the measurement.
o React with a contaminant to change
it into a compound that reacts with
the indicating chemical.
o Completely change a non-indicating
contaminant into an indicating one.
Detector tubes and pumps are available
from MSA, Bendix, Drager, and Matheson/Kitigawa.
(B) Limitations
Several- different colorimetric
indicating tubes may be able to measure the concentration of a
particular gas or vapor, each operating on a different chemical
principle and each affected in varying degrees by temperature,
air volume pulled through the tube, and interfering gases or
vapors. The "true'1 concentration versus the "measured"
concentration may vary considerably among and between
manufacturers. To limit these sources of error, to control the
numerous types and manufacturers of tubes, and to provide a
degree of confidence to users, the NIOSH Testing and
Certification Branch has certified Detector Tube Units. The
certified unit includes the aspirating pump, detector tube, and
accessories. The certification implies that the unit must be
accurate within + or - 35% at 1/2 the PEL and + or - 25% at 1 to
5 times the PEL.
10 - 30
-------
A list of certified units (by tube) can be found in the NIOSH
detector tube Certified Equipment List. (Note: the NIOSH detector
tube certification program has been discontinued.) To improve
performance of all tubes, they should be:
o Refrigerated prior to use to
maintain shelf life of
approximately 2 years.
o Leak tested with the pump prior to
sampling and volumetrically
calibrated on a quarterly basis.
Undoubtedly the greatest source of error
is how the operator "reads" the endpoint. The jagged edge where
contaminant meets indicator chemical makes it difficult to get
accurate results from this seemingly simple test. A diligent and
experienced operator should be able to accurately read the
endpoint.
(5) other Gas Samplers and Monitors
There are several other gas monitors which
utilize electrochemical cells for detection. CO, H2S, and HCN
are three gases of interest. The principle is similar to the 02
meter previously described. Monitors of this type are typically
adjusted to sound an alarm when a particular contaminant level is
reached.
Probably the newest detector available is the
Mixed Oxide Semi-Conductor (MOS). It can be calibrated to a
variety of gases including chlorine, TCE, ammonia, N02. freon,
and toluene. It can be used in multiple detection units
incorporating several MOS detectors and an O2 cell.
Several instrument packages combine two or
more detectors. For example, a combined hot wire detector for
combustible gases and an oxygen sensor use a common pump,
battery, and electronic circuit. Normally, each detector
operates independently, thereby allowing one to be used even if
the other is not working properly.
Combination units afford response personnel
several advantages over single units, chiefly portability.
Additionally, combined instruments may incorporate an adjustable
alarm circuit that alerts the user to potentially hazardous
conditions. This capacity frees the user of the need to take
frequent meter readings and focuses attention on other hazards.
10 - 31
-------
(6) Programmed Thermal Desorber (PTD)
The programmed Thermal Desorber (Foxboro PTD-
132A) utilizes the principle of thermal desorption to extract
contaminants from charcoal or other detector tubes. The
instrument performs this function automatically, and, in
addition, has the ability to store the desorbed sample in a 300
ml chamber and to make replicate sample injections into a gas
chromatograph or other analytical instrument. it allows rapid
on-site analysis of collected air samples. Within the instrument
is a small oven which is used to heat the sorbent tube to
temperatures ranging from 100 - 350 C depending upon the
application. This heating has the effect of separating the
sample from the sorbent, thus freeing it to be carried by a flow
of clean carrier gas to the storage chamber. From there, the
sample is released in carefully controlled amounts into the
analytical instrument of choice. If the instrument is a gas
chromatograph, the chromatogram is recorded in the normal fashion
and the peaks qualitatively and quantitatively determined. The
calculations necessary to find the concentration of contaminant
in the original air are simply a volumetric ratio.
(7) References
National Electrical Code. Vol. 70, National
Fire Prevention Association, 470 Atlantic Ave., Boston, MA 02210
(1977).
Clayton, George D. (ed.). The Industrial
Environment - Its Evaluation and Control. 3rd ed., Public Health
Services Publication (1973).
Clayton, 6.D., and F.E. Clayton (ed.).
Patty's Industrial Hygiene and Toxicology, 3rd revised ed., Vol.
1: General Principles. John Wiley and Sons, New York, NY (1978).
Klinsky, Joseph (ed.). Manual of Recommended
Practice for Combustible Gas Indicators and Portable Direct
Reading Hydrocarbon Detectors. 1st ed., American Industrial
Hygiene Association, Akron, OH (1980)*
Conley, Robert, Infrared Spectroscopy. 2nd
ed., Allyn and Bacon, Inc., Boston, MA (1972).
10 - 32
-------
H. ODORS
If you should encounter unknown airborne contaminants, the
detection of familiar or unfamiliar odors may. alert you and your
coworkers to impending danger. Some irritating and toxic gases
and vapors can be easily detected by odor, while others cannot.
In addition, for some toxic gases, once their odor is detected,
it may be too late to escape harmful effects.
The olfactory system is designed to perceive odors
initially, then for only a short time after which the olfactory
nerves become fatigued and your ability to detect the odor
decreases or disappears. This may be a blessing near a garbage
bin, but it can prove quite harmful at hazardous waste sites and
plant sites. In addition, everyone does not have the same
ability to detect odors. It is important, therefore, to alert
everyone to odors that you perceive immediately, even if they are
unrecognizable.
Hydrogen Sulfide (K2S), for example, has the familiar aroma
of rotten eggs. This is detectable at concentrations of 0.025
parts per million (ppm). At 0.3 ppm, H2S is distinctly
recognized. It becomes offensive and intense at 3-5 ppm and
strong, but tolerable, at 20-30 ppm. (The TLV-TWA for a normal
workday is 10 ppm and the TLV-STEL is 15 ppm.) Above 200 ppm, the
offensiveness of H2S decreases and olfactory fatigue takes place
rapidly. Concentrations of 400-?00 ppm are dangerous after 30-60
minutes of exposure and as the concentration continues to climb,
unconsciousness and collapse can occur within seconds.
Hydrogen sulfide overexposure causes respiratory paralysis
which prevents further intake of H2S. Thus, immediate rescue by
persons wearing self-contained breathing apparatus can save a
life. However, without the proper protective gear, rescue
attempts most likely would prove fatal to all involved.
It is extremely important to warn others of detected odors
immediately. Identification of the odor, and its concentration
should be evaluated initially or the area should be evacuated
until this information is found, the gas is dissipated, or
appropriate protective gear is donned *
I. OVEREXPOSURE - SIGNS AND SYMPTOMS
When working in the field, you should be on the lookout for
signs of overexposure to your fellow crew members and aware of
your own symptoms of overexposure to yourself.
Signs are evidences which are observable by others, while
Symptoms are evidences which are not observable by others,
but are subjective.
10 - 33
-------
1. Inhalation exposure
a. Signs
o sneezing, or coughing indicates upper
respiratory tract irritation
o changes in breathing rate
o choking
b. Symptoms
o headache
o irritation of the eyes, nose and throat
o increased mucous secretion of the throat and
nose
o odors or tastes resulting from swallowed dust
and particulates
2. Skin Contact
a. Signs
o the skin on your hands may become dry and
whitened (due to defatting by solvents)
o cracked and red skin
o swelling
o itching, or rash
b. Symptoms
o burning sensation of contacted skin
o burning, or watery eyes
3. General Overexposure
Signs of overexposure can be obvious (as those
mentioned above) or subtle. You must stay on the alert to
recognize subtle signs such as:
o changes in normal behavior patterns
o dizzy spells
10 - 34
-------
o muscle spasms
o irritability
When ingestion is the route of exposure, symptoms may
not be manifested until hours or days later, when substances
reach their target organs. The rate of absorption of toxicants
through the stomach is often dependent upon stomach contents.
Substances are more rapidly absorbed if the stomach is empty.
The mouth, tongue or throat region may feel irritation or a
burning sensation upon ingestion or inhalation of some chemicals.
It is important to realize that you cannot possibly
monitor or be aware of every exposure you come into contact with.
Every situation will not call for respirators or full protective
clothing; therefore, it is essential that you be able to
recognize both potentially hazardous situations and signs and
symptoms of overexposure.
10 - 35
-------
J. AVAILABLE REFERENCES
If potential hazards can be recognized, or chemicals
identified, a number of information sources are available with
which to determine potential hazards of specific substance. This
information allows you to prepare yourself with proper protective
gear before coming into contact with toxicants. These
information references include:
o CHRIS: Chemical Hazard Response
Information System, developed by the
US. Coast Guard. Access is through the
National Response Center (800) 424-8802.
Although CHRIS consists of four manuals.
Volume 2 is most helpful in response to
hazardous waste spills and dump site
cleanup. It includes information on
chemical, physical and toxicological
properties of many chemicals allowing
you to quickly determine actions
necessary for safeguarding life,
property and the environment. (See
sanple)
o Documentation of the Threshold
Limit Values (TLVs),, fourth ed. (1980),
AOSIK Publications Office, 6S00 Glenway
Avenue, Building D-5,, Cincinnati, Ohio
45211. Literature sources used to
determine each TLV are given. Routes of
entry of toxic responses are defined for
limits given. Annual supplements
reflect recent research and TLV changes:
•TLVs: Threshold Limit values for
Chemical Substances and Physical Agents
in the work Environment with intended
gTianq*eS~Tor 1383-i9r4. (ACGIH TLV
Booklet), same address. TLVs and STELs
for chemical substances, mineral dusts,
nuisance particulates, some human
carcinogens and potential carcinogens,
heat stress, ionizing radiation, lasers
and noise are included. (See sample)
10 - 36
-------
o NIOSH/OSHA Occupational Health
Guidelines for Chemical Hazards# U.S.
Government Printing Q£fice, Washington,
DC 20402. This 3-volume guide gives
technical data for most substances
listed in the "NIOSH/OSHA Pocket Guide."
This information is detailed and
designed primarily for industrial
hygienists and medical personnel. This
guide*includes (in addition to the
"Pocket Guide" information) .medical
surveillance practices, air monitoring
and measurement procedures, personnel
sanitation, and spill and disposal
techniques. (See sample)
o Fire Prevention Guide on
Hazardous Materials, seventh ed.,
National Fire Protection Association
(NFPA), Quincy, MA 02269. Five manuals
are combined into one, giving much
information for pure chemicals, but not
mixtures. The subsections include:
1. Flashpoint of oils and nearly
9,000 trade-name chemicals,
manufacturers and principal uses.
2. Fire hazards of 1,300 flammable
liquids, gases and solids are given with
fire-fighting information. Flashpoint,
specific gravity, water solubility,
hazard identification and boiling point
for each are given.
3. Toxicity data on 416
chemicals.
4. Hazardous reactions of over
3,550 chemicals. A chemical is listed,
followed by those chemicals which can
cause a hazardous reaction.
5. Ibe NFPA labeling system which
rates chemicals according to their fire
hazards. (See sanple)
o The Merck Index, 10th ed.,
(1983), Merck and Company, Inc., Raway,
NJ 07065. It is designed to be
multipurpose and an extensive index, and
10 - 37
-------
cross-index make its use easy. It is
comprehensive and interdisciplinary,
containing information on a large number
of chemicals, drugs and biological
substances. It includes information on
the physical, chemical, and
toxicological properties of chemicals to
aid response personnel. (See sanple)
0 Dangerous Properties of Industrial
Materials, 4th ed., 11975), iHited by N.
Irving Sax, Von Nostrand Reinhold Co.,
135 W. 50th Street, New York, NY 10020.
Concise and descriptive, this book
provides information and technical data
for nearly 13,000 industrial and
laboratory chemicals. This information
is divided into three sections:
1. General information - synonyms,
description, formula, physical
constants. It is designed to expedite
hazard information retrieval.
2. Hazard analysis - toxicity,
fire hazard, explosive hazard
information.
3. Countermeasures - handling,
storage, shipping, first aid, fire-
fighting and personnel protection
information.
o Condensed Chemical Dictionary,
10th ed., (1981), Gessner G. Haw ley, Van
Nostrand Reinhold Co., 135 W. 50th
Street,, New York, NY 10020. This book
contains concise, descriptive technical
data on thousands of chemicals and
reactions. It is designed for quick and
easy use and can be very helpful in
assessing hazardous waste sites and
spills. The information given includes:
1. Technical descriptions of
confounds, raw materials and processes.
2. Expanded definitions of
chemical entities, phenomena and
terminology.
10 - 38
-------
3. Descriptions or identification
of many trade-name products used in the
chemical industry. (See sample)
o Farm Chemicals Handbook, (1984),
Richard T. Meister, editorial director,
Meister Publishing Co., 37841 Euclid
Avenue, Willoughby, OH 44094. This is
an annual publication listing
experimental, available, and
discontinued pesticides and products.
Trade names, common names, and chemical
names of products are listed. For each
pesticide, names of basic producers and
principal formulations are given.
o Registry of Toxic Effects of
Chemical Substances, (RTECS), 1980 edT7
2 volumes,, Richard J. Levis,, Sr., and
Roger L. Tatken, editors, U.S.
Department of Health and Human Services,
Public Health Service, Center for
Disease Control, National Institute for
Occupational Safety and Health,
Cincinnati, OH 45226 or Government
Printing Office, Washington, DC. This
book contains toxicity data on nearly
40,000 chemicals and lists over 145,000
chemical substances. Synonyms, mutation
data, toxicity data, ACGIH TLV values,
toxicological reviews, existing federal
regulations (EPA, OSHA, DOT), NIOSH
criteria document program standards, NCI
Carcinogens Testing Program and the
EPA/TSCA inventory are included. (See
sample)
o 1984 Emergency Response
Guidebook: GuT5ebook for Hazardous
Materials Incidents, 1984, U.S.
Department of Transportation, Materials
Transportation Bureau, DMT-11,
Washington, DC 20036. mis guidebook
vas developed for emergency situation
use by fire, police, first aid and civil
defense personnel. This guide is used
by cross-referencing either a chemical
substance name or UN/NA ID number to a
given emergency situation guide. These
guides present health* fire and
explosion hazard information and address
10 - 39
-------
spill, leak, and fire emergency action.
(See sample)
o Emergency Handling of Hazardous
Materials in Surface Transportation,
1981, Bureau of Explosives, Association
of American Railroads, 1920 L Street,
NW, Washington, DC 20036. This guide is
divided into two sections. The first
gives general information concerning
hazardous materials incidents, dealing
with general recommendations and each
DOT hazard class. The second section
presents commodity specific emergency
response information for each DOT-
regulated hazardous material. Two cross
reference indicies show DOT-required 4-
digit numbers and products, and 7-digit
standard Transportation Commodity Code
numbers (STCC).
o Handbook of Toxic and Hazardous
Chemicals, 1981, by Marshall Sittig,
Noyes Publications, Noyes Building, Park
Ridge, NJ 07656. This handbook combines
concise information on the health and
safety of nearly 600 hazardous
substances. Answers to the following
questions are covered for each chemical:
1.
vtiat is it?
2.
Where is it encountered?
3.
How nuch is tolerable?
4.
How is it measured?
5.
ttiat are the harmful effects?
6.
How do you protect yourself
against it?
(See sample)
o Toxic and Hazardous Industrial
Chemicals Safety Manual for handling and
disposal, with toxicity and hazard data,
1982. Published in Japan by the
International Technical Information
Institute. Available through lab Safety
10 - 40
-------
Supply (among others), P.O. Box 1368
Janesville, HI 53547-1368. TTiis Manual
covers handling and disposal: of over 700
chemicals, giving toxicity and hazard
data on each. Dangerous interchemical
reactions for nearly 300 chemicals are
also provided. (See sample)
A number of data bases are
available to EPA personnel through
either microfiche, manuals, or computer
print-outs. These include:
o OHMTAOS: Oil and Hazardous
Materials Technical Assistance Data
System (developed by EPA).
o HMIS; Hazardous Materials
Information System, developed by 000,
Defense Logistics Agency, Defense
General Supply Center, Richmond, VA
23297.
o MEDLARS
o TOXLIKE
o TOXBACK
o TOXBACK/ 65
In addition, Material Safety Data
Sheets (MSDS) are prepared and made
available by chemical manufacturers and
importers. Physical and chemical
information, known acute and chronic
health effects, exposure limits,
carcinogenicity, precautionary measures
and first aid procedures are covered by
the given information. Employers are
responsible for obtaining or developing
MSDS for each hazardous substance used
in their work, places. In addition,
employers must ensure that employees
have access to this information and are
informed as to the contents of the MSDS.
10 - 41
-------
APPENDIX 1
MONITORING EQUIPMENT AND SAMPLE MEDIA
USED FOR EVALUATION
Exposure/
Contanlnant
Hon1toring
Equipment.
Sample Collec-
lon Media
Type Of Sample
Analytical Method/
Equipment
Combustible
Gas/Vapor
Combustible
Gas .Indicator
N/A
Instantaneous
N/A (direct read-out)
Oxygen
Deficiency
Oxygen Meter
N/A
Instantaneous
N/A (direct read-out)
Ionizing
Radiation
1.
Gel ger-MuMer.
Counter
1. N/A
1. Instantaneous
N/A (direct read-out)
2.
F1 la-badge
Dosimeter
2. Film w/Three Filters
(1.e. A1. Cd. Pb) 9
2. Personal
2. Densitometer9
Organlcs
I.
Portable Gas
Chromatograph
With FID
1. N/A
1. Instantaneous
1. N/A
(direct read-out)
2.
Photo1on1z1ng
Detector
2. N/A
2. Instantaneous
2. N/A
(direct read-out)
3.
low-Flow
Sampling Pump
3. Charcoal Tube/
Silica Gel
'3. Personal/Area
3. Gas Chromato-
graph w/FID or
GC/Mass Spec-
trometry
4.
Piston/Bellows
Pump
4. Colorlmetrlc Tubes
4. Instantaneous
4. N/A
(direct read-out)
Pesticides/
Herbicides
Low-Flow
Sampling Pump
Flberglas Filter
Followed By SIHca Gel
Personal/Area
Sequential
Desorption10
-------
APPEND^ (CONTINUED)
MONITORING E0U1PMENT AND SAMPLE MEDIA
USEO FOR EVALUATION
exposure/
Contaminant
Monltoring
Equipment
Sample Collec-
lon Media
Type Of Sample
Analytical Method/
Equipment
Inorganics
(I.e. metals)
High-Flow
Sampling Pump
Cellulose Ester Fiber
Filter or Midget
Implnger and
Trapping Reagent
Personal/Area
Atomic Absorption
Spectrometry or
Chromatography
Particulates/
Aerosols
1.
Total Sus-
pended Parti-
cle Monitor
1. Membrane Filter
1. Area
1. N/A
(direct read-out)
2.
High-Flow
Sampling
Pump
2. PVC Membrane
Filter
2. Personal/Area
2. Gravimetric
Acids
1.
High-Flow
Sampling Pump
1. Midget Implnger w/
HjO or Alkaline
Reagent
1. Personal/Area
1. ColoHmetrlc/
Spectrophotom-
etry
2.
Piston/Bellows
Pump
2. Color1metric Tubes
2. Instantaneous
2. N/A
(direct read-out)
Alkalies
1.
High-Flow
Sampling
Pump
1. Midget Implnger w/
Acidic Reagent
1. Personal/Area
1. Color!metric/
Spectrophotom-
etry
2.
Piston/Bellows
Pump
2. Colorlmetric Tubes
2. Instantaneous
2. N/A
(direct read-out)
-------
APPENDIX I (CONTINUED)
MONITORING EQUIPMENT AND SAMPLE MEOIA
USED FOR EVALUATION
Exposure/
Contaminant
Monitoring
Equipment
Sample Collec-
tor* Media
Type Of Sample
Analytical Method/
Equipment
Noise
1. Sound Level
Meter w/Octave
Band Analyier
1. N/A
1. Instantaneous
2. Personal Noise 2. N/A
Dosimeter
2. Personal
1. N/A
(direct read-out)
2. N/A
(direct read-out)
Heat Stress
Uet-Bulb, Dry-
Bulb. and Globe
Thermometer
N/A
Instantaneous
N/A (direct read-out)
Reprinted from "Hazardous Materials and Waste Management", Jan./Feb., 1984, tilth permission of the publisher.
-------
STUDENT EXERCISES
Z. You have been sent to a hazardous waste site to clean up a
variety of chemicals buried 15 years ago. Included in the dump
are Benzene and Chlorine Trifluoride. Before you enter the site
for mitigation, answer the following questions for your safety:
1. What is the short term exposure limit for Benzene (ppm) ?
2. Is Benzene flaimable? Yes/No
3. Is Benzene a carcinogen? Yes/No/Suspected
4. For disposal of the Benzene found in the dump, what DOT
shipping label will be required?
that method should be used for final disposal?
S. Do speeial precautionary measures need to be. taken due
to the fact that drums of Chlorine Trif luoride are located
alongside druns of Benzene? Yes/Mo
Wry/Wiy not?
II. You have been assigned to work at a Superfund site which is
known to contain a large number of drums of Benzene. The site is
25 years old. What protective gear would you don prior to entry
into this area? (Airborne concentrations of Benzene at the site
are unknown)
Civet Eye wear:
Clothinqt
Respiratory Equipment; ______
Hand and Foot Protection:
III. You and six fellow workers have been working at a Superfund
site containing buried drums. The site is 8 years old and
consists of two cells which separate some wastes from others.
Cell "1" contains a large number of drums of Benzene. Cell "2"
contains leaking drums of Chlorine Trif luoride. After working in
Cell "2" for two hours, you are reassigned to Cell "1" to replace
a fellow employee who is complaining of a burning sensation on
his wrist and forearm (probably due to seepage of Benzene into
the cuff of his protective gear). There is one "decontamination"
10 - 45
-------
area set up and the Injured employee has been taken there. What
procedures will you follow prior to entering Cell "1?"
IV. Use the information in Table 1 to answer the following:
1. which listed chemicals are carcinogenic to the
respiratory tract?
2. Which listed chemicals are likely to cause asthma after
exposure?
10 - 46
-------
UNIT 11
HAZARDS OF FLAMMABLE OR EXPLOSIVE ATMOSPHERES OR MATERIALS
A. INTRODUCTION
Fire and explosion hazards are risks encountered in many EPA
field activities. To understand and react appropriately to these
risks it is necessary to be able to: recognize the risk and the
degree of hazard it represents; respond; control and — if
possible — prevent an emergency from occurring.
B. RECOGNITION
The single greatest danger faced by any agency personnel is
the unknown. Before entering a confined space or hazardous^
environment, take the time to carefully evaluate the dangers that
might possibly exist.
First, attempt to find out what substance you will be
handling. Shipping invoices, safety data sheets, labels,
manifests, company employees, markings and place cards can all be
extremely useful in determining the name of the product.
Once the name is known, consult hazard reference sources
such as those discussed in the unit on chemical recognition.
These reference sources offer an abundance of safety information.
Always check these sources before handling materials. Names such
as benzene and benzidine sound very similar but have distinctly
different hazards and degrees of hazards. Never try to simply
recall hazards. Always check and confirm.
Be sure that all personnel understand the information that
is given in the hazard reference source. The Chemical Hazard
Recognition Unit on the Chemistry of Hazardous Materials should
be reviewed to relate vapor pressure, flash point, combustible
material and flammable material to the data obtained on the
hazardous material to be handled.
C. DEGREE OF HAZARD
Information resources such as the Coast Guard's Chemical
Response Information System (CHRIS) provide valuable information
on possible hazards of chemicals. However, these systems cannot
define the specific degree of danger present at the individual
site. That evaluation must be done by you, based on your
observations.
11-1
-------
Substances may change their degree of hazard according to
the state they are in. Kerosene and diesel fuel in bulk
quantities, such as a drum, are not readily ignited by an
ordinary ignition source, such as a spark, match or cigarette.
These same substances volatilized, vaporized, sprayed or spread
over a large area, such as might be found in a spill, can become
highly flammable or explosive. As the surface area of the
substance is exposed to greater quantities of oxygen, the ability
to ignite increases. Seemingly harmless substances such as
flour, coal, or even metals such as. aluminum and iron, become
highly explosive when small particleis are heavily dispersed in
air. Sites such as coal handling facilities and flour mills have
a potential for devastating explosions. Solvents such as 1,1,1
trichloroethane, which is normally considered nonflammable,
becomes flammable when sprayed as a fine mist.
The same effect as spraying occurs when the material is
applied to a cloth or rag. Although kerosene in a drum will not
readily ignite, clothing covered with kerosene will easily
ignite. If a material is combustible, there is a excellent
chance that its flammability will increase as its surface area
exposed to oxygen increases.
Flashpoint is also discussed in the unit on chemical hazards
of hazardous materials. To review: the flashpoint of a liquid is
the temperature at which it will give off enough vapor to allow a
flame to travel or propagate through the vapor-air mixture.
The flashpoint of a material is important as an immediate
indication of the potential hazard of a material for producing a
flammable concentration. The lower the flashpoint or the higher
the immediate ambient temperature, the more hazardous the
material.
Kerosene has a flashpoint of 100 degrees F while gasoline
has a flashpoint of 45 degrees F. Normally we think of gasoline
as being much more hazardous than kerosene. In ambient
temperatures above 100 degrees F, they both represent high fire
or explosion hazards.
While these temperatures vary considerably from substance to
substance, many switches and motors, like cigarettes and matches,
cause sufficiently high temperatures to ignite most common
materials at their flashpoint. Another factor contributing to
the degree of hazard is the concentration of oxygen and the
concentration of the flammable material present in an atmosphere.
The following table represents flammable materials commonly
found in environmental field work.
11-2
-------
TABLE 11-1
FLAMMABLE MATERIALS
Flammable frigid?
Aldehydes
Ketones
Amines
Ethers
Aliphatic hydrocarbons
Aromatic hydrocarbons
Alcohols
Nitroaliphatics
Flammable Solids
Phosphorus
Magnesium dust
Zirconium dust
Titanium dust
Aluminum dust
Zinc dust
Water-Reactive Flammable Solids
Potassium
Sodium
Lithium
Pvrophoric Liquids
Organometallic compounds
Dimethyl zinc
Tributyl aluminum
It is necessary to have a proper fuel-to-air (oxygen) ratio
(% fuel in air) to allow combustion. There is a range of fuel
concentrations in air, at which each material can be ignited and
sustain combustion. This is called the Flammable or Explosive
Range. The lowest concentration of fuel in this range is the
Lower Flammable Limit (LFL) or Lower Explosive Limit (LEL).
Concentrations less than the LEL are not flammable because there
is too little fuel to support combustion. The highest ratio that
is flammable or explosive is the Upper Flammable Limit (UFL) or
Upper Explosive Limit (UEL), concentrations greater than the UEL
are not flammable or explosive because there is too much fuel
displacing the oxygen dr not enough oxygen to support combustion.
11-3
-------
Fuel concentrations between the LEL and UEL are optimum for
starting and sustaining fire. The LEL for benzene is 1.3% (13000
ppm). The UEL is 7.1 (71000 ppm) ? thus if an explosion meter
monitors a benzene concentration between 1.3% and 7.1% in an
atmosphere, fire or explosion is a possibility. Concentrations
below 1.3% do not represent an immediate threat of fire or
explosion, and concentrations above 7.1% do not represent an
immediate fire or explosion hazard; but they could nevertheless
represent a danger of asphyxiation from oxygen deficiency.
D. ATMOSPHERIC MONITORING INSTRUMENTS
Several field instruments are used to analyze ambient air.
Due to the limit of the scope of the Basic Field Activities
Course, only a few basic monitoring instruments will be
discussed. A greater variety of instruments will be covered in
greater depth in the intermediate and advanced safety courses.
At no time should EPA field personnel attempt to use or rely on a
reading taken from an instrument unless sufficient training and
practice have been completed.
1. Combustible Gas Indicators or Explosimeters
The combustible gas indicator should be one of the
first instruments used to analyze the danger of fire or
explosion. It measures the concentration of flammable vapor or
gas in the air, indicating the results as percent of the Lower
Explosive Limit (LEL) of the calibrated gas or vapor. For
accurate results it is necessary not only to calibrate this
instrument before use, but also to interpret the results
correctly using the chart of the calibration gas measured and the
gas present in the atmosphere.
Depending on the manufacturer and model, the meter
needle indicator of 1.0 or 100% reveals that the test atmosphere
contains a concentration of flammable material in the air at the
LEL. This environment could ignite or explode in the presence of
an ignition source. A meter reading of 0.5 or 50% indicates that
the air contains approximately one half of the LEL. Generally,
concentrations in excess of 0.25 or 25% of the LEL are considered
dangerous.
If the needle climbs to 1.0 (100%), passes it, then
falls to zero or below, it does not indicate the monitoring
device is malfunctioning or that the atmosphere contains no
vapors; instead, it indicates that the concentration of vapor a
gas-in-air exceeds the Upper Explosive Limit (UEL) of the
calibrated gas. Such a situation calls for rapid evaluation both
as to explosion danger and lack of oxygen.
11-4
-------
If the needle swings to 1.0 (100%) and remains in that
position, it means the Explosive limit is between LEL and UEL.
This is the optimum condition for explosion or fire and great
care must be exercised to evacuate the area.
2. Oxygen Meters
Explosimeters and oxygen meters must be used in
conjunction with each other. Explosimeter readings are based on
the assumption the normal 21% oxygen is present. Greater or
lesser amounts change the LEL and UEL of many gases, making the
reading on the explosimeter questionable. If possible, use a
combination meter that integrates the two readings. Never enter
an atmosphere with 02 reading below 19.5%. Table 11-2
illustrates the results of oxygen deficiency.
TABLE 11-2
PHYSIOLOGICAL EFFECT OF OXYGEN DEFICIENCY
% Oxygen (by volume)
At Sea Level Effects
21
Nothing abnormal
16-12
Increased breathing volume. Accelerated
heartbeat. Impaired coordination.
14-10
Very faulty judgement. Very poor
muscular coordination. Muscular
exertion brings on rapid fatigue that
may cause permanent heart damage.
Intermittent respiration.
<6
Spasmodic breathing. Convulsive
movements. Death within minutes.
E. OXIDIZERS
Most combustion must be supported by sufficient oxygen.
Glowing or smoldering may continue with oxygen reaching
concentrations as low as 8-10%. However, in some chemical
combinations, atmospheric oxygen may be completely absent but
combustion nevertheless supported by substance known as.
oxidizers. Such chemical substances are able to supply oxygen
chemically or to supplement oxygen with other substances that
support combustion. In many instances combustion is spontaneous,
rapid and often explosive.
11-5
-------
Agency personnel should be particularly careful when
handling substances that are identified or known to be strong
oxidizers. Fires supported by oxidizers are often extremely
difficult to control or extinguish. Of particular concern are
mixtures of oxidizers and organic compounds. In these
situations, combustion is usually spontaneous or requires no
ignition source to ignite. Table 11-3 is a list of common
oxidizers.
TABLE 11-3
COMMON OXIDIZERS
Nitrates
Chlorine
Perchloiates
Persulfates
Permanganates
Hypochlorites
Peroxides
Thiosulfates
Dichromates
Sulfuric Acid
Nitric Acid
Perchloric Acid
F. PREVENTION AND HAZARD REDUCTION
Prevention and reduction of fire and explosion hazards can
be accomplished by:
o Control of ignition sources, and
o Control of quantities & concentrations
1. Control of Ignition Sources
Where you cannot control fuel sources, you need to
control ignition sources as much as possible. Since many
chemicals and petrochemicals are highly flammable, ignition
sources should be excluded or carefully controlled during
sampling and when handling flammable samples.
Sources of ignition include matches and cigarette
lighters, electrical switches, electrical equipment, welding
sparks, engines, catalytic converters on motor vehicles, and
static electricity.
If you will be working in an industrial plant, it is
important to find out if there are areas where there may be
flammable concentrations of gases or vapors and where sources of
ignition are not permitted. (Many plants do not allow employees
or visitors to carry matches or lighters into the plant.)
11-6
-------
a. Instruments and Equipment for Hazardous Locations
There are some particularly important fire safety
requirements for any electrically-powered equipment that is to be
used in atmospheres containing flammable concentrations of dusts,
vapors, or gases. To prevent ignition and explosion, heating
elements, sparking motors or other ignition sources must be
protected from contact with the flammable atmosphere. All
electrical equipment, sampling apparatus, portable instruments,
and other possible sources of ignition must be safe for use in
such atmospheres. NOTE: Flash photography should not be used in
a flammable or explosive atmosphere.
The EPA and OSHA standard for a hazardous
atmosphere, based on extensive industrial experience, is an
atmosphere that contains a concentration of combustible gas,
vapor or dust greater than 25% of the Lower Explosive Limit (LEL)
of the material. Despite this standard, safe practices dictate
that unprotected ignition sources not be taken into any area with
a flammable atmosphere meter reading above zero.
To determine whether there is a need to take
special steps to prevent ignition of flammable vapors, gases, or
dusts in a potentially hazardous locations or atmospheres at a
plant, determine if the plant has identified hazardous areas and
specified precautions. If not, an assessment of the hazards must
be made and a decision reached as to whether ignition sources
need to be protected or kept out. In some situations, a test of
the atmosphere is necessary to find out if ignition sources must
be excluded.
Hazardous locations for ordinary electrical
equipment are those in which fire or explosion hazards may exist
due to concentrations of flammable gases, vapors, or dusts.
Hazardous locations are classified by the type of material
present, and by the likelihood that a combustible concentration
is present.
b. Enclosure and Ventilation
Electrically-powered field sampling equipment that
is not safe to use in hazardous atmospheres because of
unprotected ignition sources must be enclosed and ventilated.
o First, identify all points where electrical
connection, switches, motors, heaters, or
other devices may provide sufficient energy
to ignite flammable mixtures.
o Next, make a relatively tight enclosure
around the ignition sources.
11-7
-------
o Finally, provide fresh air ventilation or
inert gas purge in the tight enclosure, and
interlock the source of electrical supply
with the ventilation or purging flow, so that
if the flow is interrupted the equipment will
be disconnected.
c. Approved Equipment
Electrical equipment manufactured for use in
hazardous locations has a label specifying the Class and Group of
atmospheres in which the equipment can safely be used.
Electrical equipment tested and approved by Underwriters
Laboratories or Factory Mutual Laboratories is listed in their
publications of approved equipment. Each listing is specific,
and equipment cannot safely be used in atmospheres for which it
is not rated.
d. Certification
National groups such as Underwriters Laboratories
(UL), Factory Mutual (FM), and the American National Standards
Institute (ANSI), together with NFPA, developed test protocols
for certifying explosion-proof, intrinsically safe, or purged
devices to meet minimum standards of acceptance.
An electrical device certified under one of these
test methods carries a permanently affixed plate showing the logo
of the laboratory granting certification and the Class(es),
Division(s), and Group(s) it was tested against.
Certification means that if a device is certified
as explosion-proof, intrinsically safe, or purged for a given
Class, Division, and Group, and is used, maintained, and serviced
according to the manufacturer's instructions, it will not
contribute to ignition. The device is not, however, certified
for use in atmospheres other than those indicated.
Three methods exist to prevent a potential
ignition source from igniting a flammable atmosphere:
(1) Explosion-proof
Encase the ignition source in a rigidly built
container. "Explosion-proof" instruments allow the flammable
atmosphere to enter. If and when an arc is generated, the
ensuing explosion is contained within the specially designed and
built enclosure. Within it, any flames or hot gases are cooled
prior to exiting into the ambient flammable atmosphere so that
the explosion does not spread into the environment.
11-8
-------
(2) Intrinsically Safe
Reduce the potential for arcing among
components by encasing them in a solid insulating material.
Also, reducing the instrument's operational current and voltage
below the energy level necessary for ignition of the flammable
atmosphere provides equal protection. An "intrinsically safe"
device, as defined by the National Electrical Code, is incapable
"of releasing sufficient electrical or thermal energy under
normal or abnormal conditions to cause ignition of a specific
hazardous atmospheric mixture in its most easily ignited
concentration. Abnormal conditions' shall include accidental
damage to any wiring, failure of electrical components,
application of over-voltage, adjustment and maintenance
operations and other similar conditions."
(3) Purged
Buffer the arcing or flame-producing device
from the flammable atmosphere with an inert gas. In a
pressurized or "purged" system, a steady stream of, for example,
nitrogen or helium is passed by the potential arcing device,
keeping the flammable atmosphere from the ignition source. This
type of control, however, does not satisfactorily control
analytical devices that use a flame or heat for analysis such as
a combustible gas indicator (CGI) or gas chromatograph (GC) .
There are six possible environments in which a
hazardous atmosphere can be generated. However, not every type
of control will prevent an ignition in every environment. To
adequately describe the characteristics of those environments and
what controls can be used, the National Electrical Code defines
each characteristic:
(1) Class
Class is a category describing the type of
flammable material that produces the hazardous atmosphere:
(A) Class I is flammable vapors and gases,
such as gasoline, and hydrogen. Class I is further divided into
groups A, B, C, and D on the basis of similar flammability
characteristics (see Table 11-4).
(B) Class II consists of combustible dusts
like coal or grain and is divided into groups E, F, and G.
(C) Class III is ignitable fibers such as
produced by cotton milling.
11-9
-------
(2) Division
Division is the term describing the
"location" of generation and release of the flammable material.
(A) Division 1 is a location where the
generation and release are continuous, intermittent, or periodic
into an open, unconfined area under normal conditions.
(B) Division 2 - is a location where the
generation and release are in closed systems or containers and
only from ruptures, leaks, or other failures.
Using this system, a hazardous atmosphere can be
routinely and adequately defined. As an example, a spray-
painting operation using acetone carrier would be classified as a
Class T, Division 1, Group D environment. Additionally, aif
abandoned waste site containing intact closed drums of methyl
ethyl ketone, toluene, and xylene would be considered a Class I,
Division 2, Group D environment. Once the containers begin to
leak and produce a hazardous atmosphere, the environment changes
to Class I, Division 1, Group D.
11 - 10
-------
CI,
TABLE 11-4
Z Qtendcals By froupe
Group A Atmospheres
Acetylene
Group B Atmospheres
Acrolein (inhibited).
Arsine
Butadiene
Ethylene oxide
Hydrogen
Manufacturer gases containing
more than 30% hydrogen
(by volume)
Propylene cadde
Propylnitrate
Group C Atmospheres
Acetaldehyde
Allyl alcohol
n-Butyraldehyde
Carbon mcncBd.de
&otonaldehyde
Cyclopropane
Methyl ether
Diethylamide
Epichlorohydrin
Ethylene
Ethyleneimine 3*
Ethyl mercaptan
Ethyl sulfide
Hydrogen cyanide
Hydrogen sulfide
Msrpholine
2-Witxopropane
Tetrahydrofuran
Onsymmtrieal dimethyl hydrazine
(OEM!, 1-, 1-dijnethyl hydrazine)
Group 0 Atmospheres
Acetic Acid (glacial)
Acetone
Acrylonitrile
Ammonia
Butane
1-Butanol (butyl alcohol)
2-Butanol (secondary
butyl alcohol) •
n-Butyl acetate
Isobutyl acetate
di-Isabutylane
Ethane
Ethanol (ethyl alcohol)
Ethyl acetate
Ethylacrylate
(inhibited)
Ethyl diamine
Ethylene dichloride
Ethylene glycol
ncncmethyl ether
Gasoline
Isoprene
Zsopropyl ether
Hesityl oxide
Methane (natural gas)
Methanol (methyl alcohol)
Methyl-l-butanol
(isoamyl alcohol)
Methyl ethyl ketone
Methyl isobutyl ketone
2-Methyl-i-propanol
(isobutyl alcohol)
2-Methyl-2-propmo 1
(tertiary butyl alcohol)
Octanes
Fstroleum naphtha1
Pentanes
1-Pentanol (amyl alcohol)
Propane
1-Propanol(propyl
alcohol)
2-Propanol (isopropyl
alcohol)
Propylene
Pyridine
11 - 11
-------
TABLE 11-4 (cont)
Group 0 Atmospheres
Styrene
Toluene
Vinyl acetate
Vinyl chloride
xylenes
Source* National Electrical Code. Vol. 70. Table 500-2.
National Fire Protection Association, 470 Atlantic Avenue..
Boston, HA 02210 (1981).
1A saturated hydrocarbon mixture boiling in the rang* 20° - 135QC
(68° - 275°FJ. Also known by the synonyms enxine, ligroin,
petroleum ether, or naphtha.
2. Static Electricity
Because static electricity can ignite flammable
concentrations of gases or vapors, it is important to recognize
activities that can generate static electricity and to know what
can be.done to prevent accumulation and discharge of this energy.
Static electricity is generated by contact and
separation of materials, such as particulates moving though a
stack, gas issuing from a nozzle at high velocity, or poured or
sprayed nonconducting liquids or solids. Thus, static
electricity is generated when materials flow through pipes,
hoses, or ducts, when a belt runs over a pulley, and when a
person walks across a floor.
Static electricity accumulates higher voltages in
atmospheres with low humidity and during dry weather.
As examples of the hazards that can be caused by
development of static electricity, pouring solvents can, under
some circumstances, generate enough charge to ignite the vapors
present. A person can accumulate a static charge by walking or
working near a process that generates static electricity. (A
person can easily build up a charge of 100,000 volts, which could
release more than 40 times the energy needed to ignite
hydrocarbon gases and vapors, and more than 1000 times the energy
to ignite acetylene and hydrogen.)
11 - 12
-------
Practical measures to prevent accumulation or discharge
of static electricity in field activities include:
o Ground all probes used for stack sampling;
o Provide a bonding connection between metal
containers when flammable gases or liquids are
transferred or poured; and
o Wear footwear with adequate conductivity for the
hazardous conditions.
Conductivity is more critical in atmospheres which can
easily be ignited, such as those with flammable concentrations of
acetylene, hydrogen, ethyl ether, or hexane. If you are going to
be working in such atmospheres, try to find out more about the
hazards and the precautions needed. For example, rubber-soled
footwear may build up a charge of static electricity in the
wearer.
6. EMERGENCY PROCEDURES AND RESPONSES
In any field activity where there is a possibility of a
fire, you should be prepared to deal with the emergency to
protect yourself and other members of your crew. You need to
know what to do in case of a clothing fire, and when and how to
get quickly out of or away from the area. If the site you are
visiting has an emergency plan and procedures and an alarm
signal, find out before you begin work what the alarm signal
sounds like and what emergency procedures to follow.
Everyone should know the emergency procedure to follow in
case of a clothing fire. This is the procedure recommended by
the National Fire Protection Association:
1. Stop (do NOT run). Stopping prevents fanning the
flames and making injuries even more serious.
2. Drop (to the floor or other horizontal surface).
Dropping gets your face and nose out of the path of
smoke and hot gases, and prevents the flames from
spreading rapidly upward. Dropping will lessen (but
not prevent), injury from a clothing fire.
3. Roll (to smother the fire). Rolling helps snuff out
the flames and cool burning clothing.
Try to prevent anyone from running while on fire. If a fire
blanket is available, bring it to the victim; don't let them go
get it. If a safety shower is available, use it only after the
clothing has been removed.
11 - 13
-------
UNIT 12
SELECTION AND USE OP FIRE EXTINGUISHERS
A. INTRODUCTION
A fire is an oxidation process. It requires fuel and an
oxidant — usually the oxygen in the air. Usually, the fuel must
be in a gaseous state before it will combine with oxygen to
produce a fire. If the combustion produces enough heat to
vaporize more fuel, the fire will continue until either the fuel
or the oxidizer is gone, or until some other process intervenes.
We are most interested, in this unit, in the intervention
equipment, procedures, and mechanisms.
Even if fuel and a good oxidizer are present, a source of
ignition energy is usually required. Spontaneous combustion can
occur: that will be discussed in the unit on chemical hazards.
This unit is concerned with stopping the combustion process.
Once again, a fire needs enough heat to vaporize the fuel,
an oxidizer (usually oxygen in the air), and a source of
ignition. We can stop a fire if we cool the fuel below the
vaporization point, or if we separate the fuel vapor from the
oxidizer which happens if either the fuel or the oxidizer is all
used up.
B. CLASSES OF FIRES
There are four classes of fires:
o Class A: Ordinary combustible fuel such as wood, paper,
cloth, and rubber. The fire burns into the material,
but solids must be heated to the vaporization point for
the fire to continue.
o Class B: Flammable (combustible) liquids or gases such
as gasoline, kitchen grease, fuel oil, propane gas,
alcohol and many others. The fuel is vaporized and
burns above the surface of the liquid, or near the
point at which the gas escapes from a confinement.
o Class C: Electrical equipment. In addition to the
fire hazard, there is danger of an electrical shock,
until the current has been turned off or disconnected.
o Class D: Combustible metals that burn vigorously and
react violently with water or some other extinguishing
agent. Examples are sodium, potassium, magnesium,
titanium, and zirconium.
12 - 1
-------
C. TYPES OF FIRE EXTINGUISHERS
For class A fires, the most common method of putting out the
fire is to cool the fuel below its vaporization temperature.
Water works very well because such a lot of heat energy is used
up in converting the liquid water to steam. Usually, steam won't
burn, and the steam excludes oxygen, thus stopping combustion,
while the vaporization of the water cools the fuel. Dry
chemicals such as Halon 1211 or baking soda can also put out the
fire, but they are less effective than water as cooling agents.
Solid fuel may come in large chunks that get quite hot, and
even if the surface is cooled and the fire goes out, heat from
within may reheat the surface, evaporate any water, and reignite
the fuel. Fire departments soak Class A fires thoroughly, and
firemen often stay in a burned house for many hours, to put out
any fire that may reignite.
Class B fires bum above the surface of a liquid, or near
the point at which a gas escapes. They are extinguished by
excluding oxygen from the surface of a liquid fuel, or by
interrupting the jet of gas. Water may not work on burning
liquid. If the liquid is lighter than water, it will float on
top of the water and continue to burn. The water may only serve
to spread (float or splash) the fuel over a larger area.
Compressed carbon dioxide, dry chemicals, foam, Halon 1301 and
Halon 1211 often work well. In the case of a burning jet of gas,
even a hard blast of air may disperse and cool the fuel long
enough to stop the fire. However, if the fire has heated any
nearby surface, that hot surface may ignite the fuel again.
Many flammable liquids constantly release flammable vapors
even at normal temperature and pressure.
A Class C (electrical) fire results when the electric energy
is converted to heat (thermal) energy,, and that heat vaporizes
and ignites a handy fuel. The first step to extinguishing this
class of fire is turn off the electricity — unless the fire,
short circuit, etc., that caused the fire has already melted the
wires. In any event, you should turn off the current to avoid
touching a "live wire" and producing a dead person.
Your next concern should be the fact that much electrical
equipment is so massive that it can get very hot and stay hot for
a long time. Metal transmits heat very well, so the mass of
overheated equipment may be quite large. These fires can be
fought by excluding oxygen, by interrupting the flame reaction,
or by cooling the hot equipment, preferably with agents that
don't conduct electricity. Dry chemicals, C02 gas under
pressure, Halon 1301, and Halon 1211 all have been used
successfully to stop Class C fires.
12-2
-------
When you are sure the current is off, you can use water to
cool the hot equipment, but remember that water may cause further
problems when it is time to turn the electricity back on. Think
before you act.
Class D (burning metal) fires should not be doused with
water: that is likely to make matters very much worse. The
agents to use are called "dry powders" (as opposed to "dry
chemicals", which are different). Dry powders may include
graphite, sodium chloride, or special materials, all treated to
make them free flowing. You will need to know the combustion
characteristics of the burning agent and have the proper
extinguishing agent available. The use of water may cause an
explosion, and the use of C02 may accelerate the rate of
combustion.
If no proper extinguishing agent is available, try to
isolate the fire and let it burn itself out.
D. FIRE EXTINGUISHER IDENTIFICATION
Unfortunately, there are two systems in use to mark fire
extinguishers. You may find either one when you look at the
equipment.
The old system uses the letters, A, B, C, or D, to indicate
which type of fire the extinguisher is intended to put out, but
there is more than that.
Class A has "A" in a triangle, and the color green, with the
words "ordinary combustibles" written just below the symbol.
The new system uses pictographs. A Class A fire should be
fought with an extinguisher showing a burning wastebasket and a
bonfire. For pun>oses of this unit, we will simply say "New" to
indicate the pictograph system, and "Old" to indicate the
alphabetic system.
Class
A
Old:
triangle, green, "ordinary combustibles"
New:
Burning wastebasket and bonfire
Class
P
Old:
square, red, "flammable liquids"
New:
Container pouring liquid, and a fire
Class
C
Old:
circle, blue, "electrical equipment"
New:
Electrical plug and a receptacle with
flames
12-3
-------
Class D Old:
star, yellow, "combustible metals"
New: No pictograph.
The pictograph "New" system shows the types of fires on
which the extinguisher should NOT be used by a pictograph with a
red, diagonal slash through it: forbidden, just like the
pictographs in international traffic signals.
Fire extinguishers may have multiple ratings; for instance,
carbon dioxide (C02) extinguishers carry both "B" and "C" ratings
because they can be used safely on both types of fire.
It is important to know that there are several types of
Class D fire extinguishers, and any one type of Class D
extinguisher may not be suitable for all Class D fires. Choose
the fire extinguisher for an area where a burning metal fire
might occur with care and intelligence, and use it only for those
metal fires for which it is recommended.
E. PRECAUTIONS FOR FIGHTING FIRES
Before starting to extinguish a fire, the first step is to
warn others so that the area can be evacuated. Shout, turn in an
alarm, or both.
As the next step you must call the local fire department: if
you go ahead on your own, and then find that you can't put the
fire out with the equipment on hand, it may then be too late for
the local fire department to save the situation. Host areas now
have a 911 emergency system, so usually you can use the
telephone. Plan ahead to be ready to give them directions to the
fire.
The third task is to judge the situation and decide whether
you can fight the fire without endangering yourself. If you
decide to retreat, shut doors behind you — and don't try to go
back.
The fourth precaution is to contain the fire before you
fight it: prevent its spread, and then see if you can put it out
completely. This will increase the chances that it won't be out
of control when the firemen arrive.
If you decide you can fight the fire safely, here are some
safety considerations:
o The fire extinguisher should have the rating and size
for the fire. An extinguisher that's suitable for a
wastebasket won't help much if two whole rooms are on
fire.
12-4
-------
o Have someone back you up with a second extinguisher, in
case you get into trouble.
o Don't enter a burning building unless you are wearing
fire repellent clothing and self-contained breathing
apparatus. And you will need even more back-up
protection there if you get in trouble.
F. SELECTION AND USE OF A FIRE EXTINGUISHER
Once you have found the right sort of fire extinguisher and
taken it off the hook, or out of the cabinet, get the
extinguisher ready for use before you approach the fire: Pull
out the locking pin near the head of the extinguisher. If there
is a simple nozzle, aim it at the base of the fire. If there is
a hose or tubing in a holder, take it out of the holder and aim
the nozzle or horn at the base of the fire. If there is a horn
on a tube, raise it and then aim it at the base of the fire.
Test the extinguisher: Sgueeze the release trigger once
before you get too near the fire, to make sure it works, and to
see how much extinguishing material comes out and how far it may
shoot. If the fire extinguisher doesn't work, you will have to
decide again if you have time to find one that does.
With an ordinary fire hose, the stream of water will reach
about 30 feet. You should stand well back and aim the water at
the base of the fire. If you get too close, the force of the
stream might scatter the fire and spread it. A pressurized water
extinguisher is a smaller version of the same thing: you may be
able to shoot intermittent jets of water by working the trigger.
If the extinguisher is the old soda-acid type, turn it
upside-down to mix the chemicals and start it squirting. It will
tend to keep shooting out its stream until it is exhausted. If
you tip it back up, it may eventually stop.
The stream from a small aaueous-charqed extinguisher, if it
is not too powerful, may be spread into a fan shaped fine spray
with your finger.
A Dry Chemical Extinguisher ejects, a fine powder at high
speed. The powder is often sodium bicarbonate, which gives off
CO2 when it gets hot. This dry powder has much more fire-
fighting capacity than the compressed liquid carbon dioxide that
is often used in small fire extinguishers. Dry chemical
extinguishers are usually painted red (except for the label).
They usually have a hose and nozzle, and may have a gauge on the
top or a cartridge cover on the side. They are pressurized to
push the powder out in a high-speed spray. Dry chemical
extinguishers are usually rated "B" and "C," but some are rated
"A," "B," and "C."
12-5
-------
Shoot your powder at the base of the fire, using a sweeping
notion, from side to side. Cover a Class A fire with powder.
Start spraying a Class B fire at the side closest to you and work
away until the fire is out, then watch for possible reignition.
Don't get too close to a Class B fire; you night splash the
liquid around with the force of your high velocity spray.
Liquid cq£ Extinguishers discharge gaseous carbon dioxide at
low velocity. Expanding gas gets cold, so there nay be some
artificial snow in the discharge, too. The flow of cold gas past
the nozzle or horn will generate static electricity. It may also
get cold enough to freeze your hand, so hold the insulated handle
and keep your hands off the cold part.
The discharge has an effective range of only two to four
feet; you have to get close with liquid CO2, so don't use it on a
big fire.
Foam type extinguishers use a cartridge and mix in air to
discharge an agueous foam that covers the surface of burning
solvents to suppress vapors and keep away the air. It is
effective on Class B or A fires. They use lots of foam at
airports if a plane catches fire. Foam works well on fairly
large fires.
G. MORE PRECAUTIONS
These rules and methods should sound simple and obvious as
you read this. When you are choking on smoke, and being
blistered by heat, and the fire keeps reigniting as fast as you
put it out, it's hard to keep cool (figuratively and literally).
Take advantage of every opportunity to get some practical
experience before you fight your first real, unplanned fire. In
particular, you really need to practice with the different kinds
of fire extinguishers.
Review all the previous precautions, then note these too:
o If you are fighting, a fire outdoors, keep the wind at
your back; let it carry the smoke away from you and
carry the firefighting substance to the fire. Inside a
building, beware of drafts. If moving air is carrying
the fire toward you, inside or out, get out of there—
FASTI
o When you approach a fire, be sure you can retreat
rapidly, in a straight line, if the need arises. Don't
climb obstacles in an intrepid eagerness to get close
to the fire; they may slow your retreat.
12-6
-------
o Never turn your back on a fire, nor on the place where
the fire just was. It might reignite.
o Never use water on combustible metals, flammable
liquids, or on electrical fires while the current is
on.
The best fire fighting strategy is fire prevention; but if
you must fight a fire, do so safely.
12-7
-------
STUDENT EXERCISES
1. List and define the 4 classes of fires* and give 2 examples
of typical fuel for each type*
2. When you discover a fire, you should keep 4 precautions in
mind. List then.
12
-------
3. When you call the fire department to report a fire, you vill
be asked for the location of the fire. As a visitor to the site,
you may not know just where you arel What do you think you could
do, or should have done?
4. 9» wrong action is usually worse than no action in fighting
a fire. List three wrong actions that we mentioned, or that you
think tm should haws nwiticnadT
12
9
-------
UNIT 13
LEVELS OP PROTECTION
A. INTRODUCTION
Personnel must wear protective equipment when activities
involve known or suspected atmospheric contamination, when
vapors, gases, or particulates may be generated by site
activities, or when direct contact with skin-affecting substances
may occur. Full facepiece respirators protect lungs,
gastrointestinal tract, and eyes against airborne toxicants.
Chemical-resistant clothing protects the skin from contact with
skin-destructive and absorbable chemicals. Good personal hygiene
limits or prevents ingestion of material.
Equipment to protect the body against contact with known or
anticipated toxic chemicals has been divided into four categories
according to the degree of protection afforded:
o Level A: Should be worn when the highest level of
respiratory, skin, and eye protection is needed.
o Level B: Should, be worn when the highest level of
respiratory protection is needed, but a lesser level of
skin protection.
o Level C: Should be worn when the criteria for using
air-purifying respirators are met.
o Level D: Should be worn only as a work uniform and not
on any site with respiratory or skin hazards. It
provides no protection against chemical hazards.
The Level of Protection selected should be based on:
o Type and measured concentration of the chemical
substance in the ambient atmosphere and its toxicity.
o Potential for exposure to substances in air, splashes
of liquids, or other direct contact with material due
to work being done.
In situations where the type of chemical, concentration, and
possibilities of contact are not known, the appropriate Level of
Protection must be selected based on professional experience and
judgment until the hazards can be better identified.
13-1
-------
While personnel protective equipment reduces the potential
for contact with toxic substances, ensuring the health and safety
of responders requires, in addition, safe work practices,
decontamination, site entry protocols, and other safety
procedures. Together, these provide an integrated approach for
reducing harm to workers.
B. LEVELS OF PROTECTION
1. Level A Protection
a. Personnel protective equipment
o Supplied-air respirator approved by the Mine
Safety and Health Administration (MSHA) and
National Institute for Occupational Safety
and Health (NIOSH). Respirators may be:
pressure-demand, self-contained
breathing apparatus (SCBA)
or
pressure-demand, airline respirator
(with escape bottle for Immediately
Dangerous to Life and Health (IDLH) or
potential for IDLH atmosphere)
o Fully encapsulating chemical-resistant suit
o Coveralls*
o Long cotton underwear*
o Gloves (inner), chemical-resistant
o Boots, chemical-resistant, steel toe and
shank (depending on suit construction, worn
over or under suit boot)
o Hard hat* (under suit)
o Disposable gloves and boot covers* (worn over
fully encapsulating suit)
o Cooling unit*
o 2-Way radio communications* (inherently safe)
* Optional
13-2
-------
b. Criteria for selection
Meeting any of these criteria warrants use of
Level A Protection:
(1) The chemical substance has been identified
and requires the highest level of protection for skin, eyes, and
the respiratory system based on:
(A) measured (or potential for) high
concentration of atmospheric vapors, gases, or particulates
or
(B) site operations and work functions
involves high potential for splash, immersion, or exposure to un-
expected vapors, gases, or particulates of materials highly toxic
to the skin.
(2) Substances with a high degree of hazard to
the skin are known or suspected to be present, and skin contact
is possible.
(3) Operations must be conducted in confined,
poorly ventilated areas until the absence of substances requiring
Level A protection is determined.
(4) Direct readings on field Flame Ionization
Detectors (FID) or Photoionization Detectors (PID) and similar
instruments indicate high levels of unidentified vapors and gases
in the air.
c. Guidance on selection
Fully encapsulating suits are primarily designed
to provide a gas or vapor tight barrier between the wearer and
atmospheric contaminants. Therefore Level A is generally worn
when high concentrations of airborne substances are known or
thought to be present and these substances could severely effect
the skin. Since Level A requires the use of a self-contained
breathing apparatus, the eyes and respiratory system are also
more protected.
Until air surveillance data are available to
assist in the selection of the appropriate Level of Protection,
the use of Level A may have to be based on indirect evidence of
the potential for atmospheric contamination or other means of
skin contact with severe skin affecting substances.
13-3
-------
Conditions that may require Level A protection
include:
(1) Confined spaces: Enclosed, confined, or
poorly ventilated areas are conducive to build up of toxic
vapors, gases, or particulates. (Explosive or oxygen-deficient
atmospheres also are more probable in confined spaces.) Confined
space entry does not automatically warrant wearing Level A pro-
tection, but should serve as a cue to carefully consider and to
justify a lower Level of Protection.
(2) Suspected/known highly, toxic substances:
Various substances that are highly toxic especially through skin
absorption for example, fuming corrosives, cyanide compounds,
concentrated pesticides, Department of Transportation Poison "A"
materials, suspected carcinogens, and infectious substances may
be known or suspected to be involved. Field instruments may not
be available to detect or quantify air concentrations of these
materials. Until these substances are identified and
concentrations measured, maximum protection may be necessary.
(3) Visible emissions: Visible air emissions
from leaking containers or railroad/vehicular tank cars, as well
as smoke from chemical fires and others, indicate high potential
for concentrations of substances that could be extreme
respiratory or skin hazards.
(4) Job functions: Initial site entries are
generally walk throughs in which instruments and visual
observations are used to make a preliminary evaluation of the
hazards. In initial site entries, Level A should be worn when:
(A) there is a probability for exposure to
high concentrations of vapors, gases, or particulates.
(B) substances are known or suspected of
being extremely toxic directly to the skin or by being absorbed.
Subsequent entries are to conduct the many
activities needed to reduce the environmental impact of the
incident. Levels of. Protection for later operations are based
not only on data obtained from the initial and subsequent
environmental monitoring, but also on the probability of
contamination and ease of decontamination.
Examples of situations where Level A has been
worn are:
o Excavating of soil to sample buried
drums suspected of containing high
concentrations of dioxin.
13-4
-------
o Entering a cloud of chlorine to repair a
value broken in a railroad accident.
o Handling and moving drums known to
contain oleum.
o Responding to accidents involving
cyanide, arsenic, and undiluted
pesticides.
The fully encapsulating suit provides the
highest degree of protection to skin, eyes, and respiratory
system if the suit material resists chemicals during the time the
suit is worn. While Level A provides maximum protection, all
suit material may be rapidly permeated and degraded by certain
chemicals from extremely high air concentrations, splashes, or
immersion of boots or gloves in concentrated liquids or sludges.
These limitations should be recognized when specifying the type
of fully encapsulating suit. Whenever possible, the suit
material should be matched with the substance it is used to
protect against.
2. Level B Protection
a. Personnel protective equipment
o Supplied-air respirator (MSHA/NIOSH
approved). Respirators may be:
pressure-demand, self-contained
breathing apparatus
or
pressure-demand, airline respirator
(with escape bottle for IDLH or
potential for IDLH atmosphere)
o Chemical-resistant clothing (overalls and
long-sleeved jacket; hooded, one or two-piece
chemical-splash suit; disposable chemical-
resistant, one-piece suits)
o Long cotton underwear*
o Coveralls*
o Gloves.(outer), chemical-resistant
o Gloves (inner), chemical-resistant
13-5
-------
o Boots (outer), chemical-resistant, steel toe
and shank
o Boot covers (outer), chemical-resistant
(disposable)*
o Hard hat (face shield)*
o 2-Way radio communications* (intrinsically
safe)
* Optional
b. Criteria for selection
Meeting any one of these criteria warrants use of
Level B protection:
o The type and atmospheric concentration of
toxic substances has been identified and
requires a high level of respiratory
protection, but less skin protection than
Level A. These would be atmospheres:
with concentrations Immediately
Dangerous to Life and Health, but
substance or concentration in the air
does not represent a severe skin hazard
or
that do not meet the selection criteria
permitting the use of air purifying
respirators.
o The atmosphere contains less than 19.5%
oxygen.
o. It is highly unlikely that the work being
done will generate high concentrations of
vapors, gases or particulates, or splashes of
material that will affect the skin of
personnel wearing Level B protection.
o Atmospheric concentrations of unidentified
vapors or gases are indicated by direct
readings on instruments such as the FID or
PID or similar instruments, but vapors and
gases are not suspected of containing high
levels of chemicals toxic to skin.
13-6
-------
c. Guidance on selection
Level B does not afford the maximum skin (and eye)
protection as does a fully encapsulating suit since the chemical-
resistant clothing is not considered gas, vapor, or particulate
tight. However, a good quality, hooded, chemical-resistant, one-
piece garment, with taped wrist, ankles, and hood does provides a
reasonable degree of protection against splashes and to lower
concentrations in air. At most abandoned hazardous waste sites,
ambient atmospheric gas or vapor levels have not approached
concentrations sufficiently high to warrant Level A protection.
In all but a few circumstances (where highly toxic materials are
suspected) Level B should provide the protection needed for
initial entry. Subsequent operations at a site require a
reevaluation of Level B protection based on the probability of
being splashed by chemicals their effect on the skin, the
presence of hard-to-detect air contaminants, or the generation of
highly toxic gases, vapors, or particulates, due to the work
being done.
The chemical-resistant clothing required in Level
B is available in a wide variety of styles, materials, construc-
tion detail, and permeability. One or two-piece garments are
available with or without hoods. Disposal suits with a variety
of fabrics and design characteristics are also available. Taping
joints between the gloves, boots and suit, and between hood and
respirator reduces the possibility for splash and vapor or gas
penetration. These factors and other selection criteria all
affect the degree of protection afforded. Therefore, a
specialist should select the most effective chemical-resistant
clothing based on the known or anticipated hazards and job
function.
Level B equipment does provides a high level of
protection to the respiratory tract. Generally, if a self-
contained breathing apparatus is required for respiratory
protection, selecting chemical-resistant clothing (Level B)
rather than a fully encapsulating suit (Level A) is based on
needing less protection against known or anticipated substances
affecting the skin. Level B skin protection is selected by:
Comparing the concentrations of known or
identified substances in air with skin toxicity
data.
Determining the presence of substances that are
destructive to or readily absorbed through the
skin by liquid splashes, unexpected high levels of
gases, vapor, or particulates, or other means of
direct contact.
13 - 7
-------
- Assessing the effect of the substance (at its
measured air concentrations or potential for
splashing) on the small areas left unprotected by
chemical-resistant clothing. A hooded garment
taped to the mask, and boots and gloves taped to
the suit further reduces area of exposure.
For initial site entry and reconnaissance at an open
site, approaching whenever possible from upwind, Level B protec-
tion (with good quality, hooded, chemical-resistant clothing)
should protect response personnel, providing the conditions
described in selecting Level A are known or judged to be absent.
3. Level c Protection
a. Personnel protective equipment
o Air-purifying respirator, full-face,
canister-equipped (MSHA/NIOSH approved)
o Chemical-resistant clothing (coveralls;
hooded, one-piece or two-piece chemical
splash suit; chemical-resistant hood and
apron; disposable chemical-resistant
coveralls)
o Coveralls*
o Long cotton underwear*
o Gloves (outer), chemical-resistant
o Gloves (inner), chemical-resistant*
o Boots (outer), chemical-resistant, steel toe
and shank
o Boot covers (outer), chemical-resistant
(disposable)*
o Hard hat (face shield*)
o Escape mask*
o 2-Way radio communications* (inherently safe)
* Optional
13-8
-------
b. Criteria for selection
Meeting all of these criteria permits use of Level
C protection:
o Oxygen concentrations are not less than 19.5%
by volume.
o Measured air concentrations of identified
substances will be reduced by the respirator
below the substance's threshold limit value
(TLV) and the concentration is within the
service limit of the canister.
o Atmospheric contaminant concentrations do not
exceed IDLH levels.
o Atmospheric contaminants, liquid splashes, or
other direct contact will not adversely
affect any body area left unprotected by
chemical-resistant clothing.
o Job functions do not require self-contained
breathing apparatus.
o Direct readings are a few ppm above
background on instruments such as the FID or
PID.
c. Guidance on selection
Level C protection is distinguished from Level B
by the equipment used to protect the respiratory system, assuming
the same type of chemical-resistant clothing is used. The main
selection criterion for Level C is that conditions permit wearing
air-purifying respirators.
The air-purifying device must be a full-face
respirator (MSHA/NIOSH approved) equipped with a canister
suspended from the chin or on a harness. Canisters must be able
to remove the substances encountered. Quarter-or half-masks or
cheek-cartridge, full-face masks should be used only with the
approval of a qualified individual.
13-9
-------
In addition, a full-face, air-purifying mask can
be used only if:
(1) The substance has adequate warning
properties.
(2) The individual passes a qualitative fit-test
for the mask.
(3) The appropriate cartridge/canister is used,
and its service limit concentration is not exceeded.
An air surveillance program is part of all
response operations when atmospheric contamination is known or
suspected. It is particularly Important that the air be
thoroughly monitored when personnel are wearing air-purifying
respirators. Periodic surveillance using direct-reading instru-
ments and air sampling is needed to detect any changes in air
quality necessitating a higher level of respiratory protection.
Level C protection with a full-face, air-purifying
respirator should be worn routinely in an atmosphere only after
the type of air contaminant is identified, concentrations
measured and the criteria for wearing air-purifying respirator
met. To permit flexibility in prescribing a Level of Protection
at certain environmental incidents, a specialist could consider
using air-purifying respirators in unidentified vapor/gas
concentrations of a few parts per million above background as
indicated by a needle deflection on the FID or PID. However a
needle deflection of a few parts per million above background
should not be the sole criterion for selecting Level C. Since
the individual components may never be completely identified, a
decision on continuous wearing of Level c must be made after
assessing all safety considerations, including:
(1) The presence of (or potential for) organic or
inorganic vapors/gases against which a canister is ineffective or
has a short service life.
(2) The known (or suspected) presence in air of
substances with low TLVs or IDLH levels.
(3) The presence of particulates in air.
(4) Errors that may be associated with both the
instruments and monitoring, procedures used.
13 - 10
-------
(5) The presence of (or potential for) substances
in the air which do not elicit a response on the instrument used.
(6) The potential for higher concentrations in
the ambient atmosphere or in the air adjacent to specific site
operations.
The continuous use of air-purifying respirators
(Level C) must be based on the identification of the substances
contributing to the total vapor or gas concentration and the
application of published criteria for the routine use of air-
purifying devices. Unidentified ambient concentrations of
organic vapors or gases in air approaching or exceeding a few ppm
above background require, as a minimum, Level B protection.
4. Level D Protection
a. Personnel protective equipment
o Coveralls
o Gloves*
o Boots/shoes, leather or chemical-resistant,
steel toe and shank
o Safety glasses or chemical splash goggles*
o Hard hat (face shield)*
* Optional
b. Criteria for selection
Meeting any of these criteria allows use of Level
D protection:
o No contaminants are present.
o Work functions preclude splashes, immersion,
or potential for unexpected inhalation of any
chemicals.
Level D protection is primarily a work uniform.
It can be worn only in areas where there is no possibility of
contact with contamination.
13 - 11
-------
C. PROTECTION IN UNKNOWN ENVIRONMENTS
In all incident response, selecting the appropriate
personnel protection equipment is one of the first steps in
reducing health effects from toxic substances. Until the toxics
hazards at an environmental incident can be identified and
personnel safety measures commensurate with the hazards
instituted, preliminary measures will have to be based on
experience, judgment, and professional knowledge. One of the
first concerns in evaluating an unknown situation is atmospheric
hazards. Toxic concentrations (or potential concentrations) of
vapors, gases, and particulates; low oxygen content explosive
potential and, to a lesser degree, the possibility of radiation
exposure all represent immediate atmospheric hazards. In
addition to making air measurements to determine these hazards,
visual observation and review of existing data can help determine
the potential risks from other materials.
Once immediate hazards, other than toxic substances have
been eliminated, the initial on-site survey and reconnaissance,
which may consist of more than one entry, continues. Its purpose
is to further characterize toxic hazards and, based on these
findings, refine preliminary safety requirements. As data are
obtained from the initial survey, the Level of Protection and
other safety procedures are adjusted. Initial data also provide
information on which to base further monitoring and sampling. No
one method can determine a Level of Protection in all unknown
environments. Each situation must be examined individually.
D. ADDITIONAL CONSIDERATIONS FOR SELECTING LEVELS OF PROTECTION
There are several other factors which should be considered
in selecting the appropriate Level of Protection.
1. Heat and Physical Stress
The use of protective clothing and respirators
increases physical stress, in particular heat stress, on the
wearer. Chemical protective clothing greatly reduces body
ventilation and diminishes its ability to regulate its
temperature. Even in moderate ambient temperatures the
diminished capacity of the body to dissipate heat can result in
one or more heat-related problems.
All chemical protective garments can cause heat stress.
Somewhat less stress is associated with Level B or C when the
protective clothing does not require the use of a hood, tightly
fitted against the respirator face piece, and taped glove, boot,
suit interfaces, since more body ventilation and evaporation may
occur. As more body area is covered, the probability of heat
stress increases. Whenever any chemical-protective clothing is
worn, a heat stress recovery monitoring program must occur.
13 - 12
-------
Wearing protective equipment also increases the risk of
accidents. It is heavy, cumbersome, decreases dexterity,
agility, interferes with vision, and is fatiguing to wear. These
factors all increase physical stress and the potential of
accidents. In particular the necessity for selecting Level A
protection, should be balanced against the increased probability
of physical stress and accidents. Level B and C protection
somewhat reduces accident probability, because the equipment is
lighter, less cumbersome, and vision problems less serious.
2. Air Surveillance
A program must be established for routine, periodic air
surveillance. Without an air surveillance program, any changes
could go undetected and jeopardize response personnel.
Surveillance can be accomplished with various types of air pumps
and filtering devices followed by analysis of the filtering
media; portable real-time monitoring instruments located
strategically on-site; personal dosimeters; and periodic walk-
throughs by personnel carrying direct-reading instruments.
3. Decision-Logic for Selecting Protective Clothing
No adequate criteria, similar to the respiratory
protection decision-logic, are available for selecting protective
clothing. A concentration of a known substance in the air
approaching a TLV or permissible exposure limit for the skin does
not automatically warrant a fully encapsulating suit. A hooded,
high quality, chemical-resistant suit may provide adequate pro-
tection. The selection of Level A over Level B is a judgment
that should be made by a qualified individual considering the
following factors:
o The physical form of the potential contaminant.
Airborne substances are more likely for body
contact with personnel wearing non-encapsulating
suits, since they are not considered to be gas or
vapor tight.
o Effect of the material on skin:
highly hazardous substances are those that
are easily absorbed through the skin causing
systemic effects, or that cause severe skin
destruction. Skin contact with liquids are
generally more hazardous than vapors, gases
and particulates.
- less hazardous substances are those that are
not easily absorbed through the skin causing
systemic effects, or that do not cause severe
skin destruction
13 - 13
-------
o Concentration of the material - the higher the
concentration, the higher the risk of harm.
o The potential for contact with the material due to
work function and the probability of direct
exposure to the small area of skin unprotected by
Level B or C chemical-resistant clothing.
4. Chemicals Toxic to Skin
Chemicals have adverse skin effects ranging from
irritation to absorption into the body. Knowledge concerning the
presence or absence of these materials could be useful in
selecting the necessary Level of Protection. Therefore, a major
effort should be made to identify all substances.
5. Atmospheric Conditions
Atmospheric conditions such as stability, temperature,
wind direction, wind velocity, and barometric pressure determine
the behavior of contaminants in air or the potential for volatile
material getting into air. These parameters should be considered
in determining the need for and Level of Protection required.
6. Work in Exclusion Zone
For operations in an Exclusion Zone (area of potential
contamination), different Levels of Protection may be selected,
and various types of chemical-resistant clothing worn. This
selection would be based not only on measured air concentrations,
but also on the job function, reason for being in the area, the
potential for skin contact or inhalation of the materials
present, and ability to decontaminate the protective equipment
used.
7. Escape Masks
The use of escape masks is an option in Level C
protection. A specialist should determine their use on a case-
by-case basis. Escape masks could also, be strategically located
on-site in areas that have higher possibilities for harmful
exposure.
13 - 14
-------
E. VAPOR OR GAS CONCENTRATIONS AS INDICATED BY DIRECT-READING
INSTRUMENTS
Instruments such as the FID and PID can be used to detect
the presence of many organic vapors or gases either as single
compounds or mixtures. Dial readings are frequently referred to,
especially with unidentified substances, as total vapor and gas
concentrations (in ppm). More correctly they are deflections of
the needle on the dial indicating an instrument response and does
not directly relate to total concentration in the air. As a
guide to selecting Level of Protection, based on dial readings
response, the following values could be used. They should not be
the sole criteria for selecting Levels of Protection.
Dial Reading Level of Protection
Background to 5 ppm C
above background
5 ppm above background B
to 500 ppm above background
500 ppm above background A
to 1000 ppm above background
Vapor or gas concentration, as indicated by the readout on
instruments such as the FIDs or PIDs are a useful adjunct to
professional judgment in selecting the Level of Protection to be
worn in an unknown environment. It should not be the single
selection criterion, but should be considered with all other
available information. Total vapor or gas concentration as
selection criteria for Levels of Protection should only by used
by qualified persons thoroughly familiar with that information.
13 - 15
-------
UNIT 14
PROTECTIVE CLOTHING AND EQUIPMENT
A. INTRODUCTION
Protective clothing is a collective term that includes all
outerwear worn for the purpose of protecting the head, eyes,
ears, torso, and feet. In the normal demands of field work,
Agency employees will face a wide variety of hostile environments
and situations. The opportunity for injury ranging from minor
cuts and abrasions to major chemical burns, are numerous. It
should be evident that taking steps to evaluate these hazards and
provide for protection against them is in the very best interest
of EPA and the employee. Department of Labor statistics indicate
that over 60% of the work related injuries occur during routine
job assignments. In many of these injuries, lack of enforcement
by supervisors and lack of concern by the individual resulted in
accidents that either could have been avoided or minimized by the
wearing of correct protective clothing or equipment.
B. SELECTION OF PROTECTIVE CLOTHING
Agency employees faced with the necessity to select proper
protective equipment can be quickly overwhelmed with the vast
variety of equipment available. Unlike some areas of the work
environment, protective equipment has few regulations or
standards by which accurate judgement can be made. It is up to
the individual to exercise caution, good sense, and proper
judgement in making final determinations of worker protection.
C. RATIONALE FOR SELECTION
Personnel protection must never be left to guesswork. It is
imperative that the hazards to be faced are evaluated in every
way possible. A wide variety of safety data sheets, CHRIS
Manuals and the like are available to assist personnel in
selecting equipment. However, they all depend on knowing what
hazards the wearer is to face. It is the unknown or the
unexpected that can pose the greatest threat.
In all cases, review histories, talk to experienced
Personnel, check shipping papers, and test the testing or
monitoring equipment to help select proper equipment. When
facing an unknown, always prepare for the worst possible
situation.
Before leaving for a field site, check the available
inventories to be sure the correct type of equipment can be
procured. A last minute substitution of proper equipment can
leave personnel unprotected for the hazards at hand. If the
14 - 1
-------
proper equipment is not in Agency stock, attempt to borrow the
equipment from another Region or office. If the proper equipment
cannot be obtained, cancel the field activity until the proper
gear can be found.
Have all crew members fit-tested before leaving for the
activity. Equipment or clothing that is too large or too small
will not only make work difficult or uncomfortable, but may
neutralise the protection of the equipment or be dangerous.
D. TYPES OF PROTECTIVE CLOTHING
The types of protective gear that Agency field personnel
should wear is based on anticipated hazards to be faced. It is
important to stress that most accidents occur in routine work
when the individual least expects it. Whatever gear is selected,
it should be worn as a part of daily dress. Like seat belts in
an automobile, habits should be developed which when broken
leave the individual with a feeling of insecurity. It is no
chance of fate that most accidents occur to individuals not
wearing the proper safety gear.
1. Head Protection
Hard hats (or safety helmets) are designed to provide
protection against impact, flying particles and electrical
shock, and to provide shielding against the sun. Most hard hats
provided for EPA field personnel will withstand an impact of 40
foot pounds, as well as insulation against electrical shock from
voltages up to 2200. Hard hat standards of performance are set
by the American National Standards on hard hats Z89.1 - 1981 and
are tested by SEI or Safety Equipment Institute.
Hard hats should be used during field activities
whenever there is the possibility of impact from falling objects
or contact of the head with stationary objects such as pipes or
overhangs. It should be remembered that hard hats provide
limited protection. There can be no substitute for the precaution
of staying out from under areas where work is going on overhead.
A great deal of the protection afforded by the hard hat
comes from the separation of the head from the underside of the
hard hat. The head band or suspension strap should be adjusted
so that when worn there is about one inch separating the head and
the hat. The one-inch provides cushion from impacts with the
hat. Hard hats can also be equipped with insulating liners for
protection from the cold and chin strap to prevent wind from
blowing off hats or when leaning over.
14-2
-------
The common practice of carrying the hard hat in the
back window of a vehicle can be a detriment to the strength of
the hard hat. Plastic material may become brittle if allowed to
be exposed to the sun for long periods of time. Store the hard
hat out of the direct rays of the sun.
2. Eye and Face Protection
Eye and face protection should be worn in all field
activities where there is danger from flying or falling particles
or chemical splashes. Such eye and face protection should meet
the standards set by OSHA Z87.1-1981' and the American National
Standards for industrial eye protection. These vigorous
standards preclude standard glasses as a form of protection.
Although all prescription glasses sold in recent years
are required by FDA standards to resist some impact, glasses made
to those standards will not provide the impact resistance or
thickness requirements of the standards for industrial eye
protection established by ANSI and required by OSHA. Where eye
glasses are required by Agency personnel, safety goggles or face
shields covering the glasses or lenses placed in the goggles, or
prescription safety glasses meeting OSHA standards should be
obtained.
Safety glasses and eye protection which meet ANSI
standards for industrial eye protection will also have frames
designed to hold the lens in place against impact. If the frames
are not metal, the material will be slow burning. New safety
glasses will have the lenses and frames marked with the standard
number to show compliance with the ANSI standard.
Contact lenses have sometimes been considered a safety
hazard in activities where chemical dusts, vapors or gases may be
encountered; however, the only Federal prohibition is that they
must not be worn under any type of respiratory protection.
Hard contact lenses are not considered to provide
acceptable eye protection against impact. Hard contact lenses do
not seem to aggravate chemical splash injuries according to
information published in the Journal of Occupational Medicine.
Soft contact lenses are susceptible to absorption of
vapors and may aggravate some chemical exposures, particularly if
they are worn for extended periods. Manufacturers of soft
lenses generally recommend they not be used in certain
atmospheres.
14-3
-------
3. Foot Protection
Foot protection should be selected with the type of
protection in mind. The following types of protection should be
considered:
o toe or foot damage due to impact
o penetration of nails or other sharp objects
o contamination by chemicals
o ankle twists and sprains
o slippery surfaces
o cold
o static electricity
a. Toe or Foot Damage Due to Impact
Impact resistant footwear, such as safety shoes or
safety boots are recommended for any field activity in which
heavy objects (such as drums) may drop on the foot or injure the
toes. Such safety shoes may be required to enter industrial
plants.
Safety shoes or boots provide impact resistance by
the steel cap built into the toe of the footwear. The footwear
can be ordered in various degrees of protection depending on
expected hazards.
b. Penetration of Nails or Other Sharp Objects
Normal street shoes provide very little protection
from penetration of the soles by nails and other sharp objects.
Construction sites, landfills, and many industrial sites have a
wide variety of foot hazards. Agency personnel should never
enter sites without proper foot protection. Most industrial work
boots have reinforced soles or heavy rubber soles that will
resist penetration of sharp objects. If such sharp objects do
penetrate the foot, medical attention should be sought at once.
c. Contamination bv Chemicals
The type of footwear and the material it is made
of must be selected based on anticipated chemical hazards. No
other portion of the body is as likely to be contaminated with
chemicals as are the feet. Although leather is the most common
material in the manufacture of footwear, it is the least
14 - 4
-------
desirable where there is danger of chemical contact. Leather,
due to its absorption capacity, is almost impossible to cleanse
or decontaminate and most likely the footwear will have to be
disposed of.
If there is an obvious chance of contamination,
footwear worn over safety shoes should be selected. Such
footwear includes pull-over boots, shoe covers, booties, or
safety pull-on boots. Keep in mind that penetration of footwear
with a contaminated object such as a nail, may lead to rapid and
serious health effects.
d. Ankle Twists and Sprains
One of the most common injuries involving the feet
are ankle twists and sprains. When personnel are required to
work on hazardous footing such as are found in construction sites
or landfills, hightop industrial work shoes should be chosen.
This type of shoe laces up the ankle providing extra support
while walking. Such shoes, while not attractive, provide the
support that low top or street shoes do not give.
e. Slippery Surfaces
No other industrial accident is more frequent or
results in more disabling accidents than slipping and falling.
Sprains, dislocations, broken bones, contact with dangerous
machinery and drowning all are often attributed to unsure
footing. On many wet or slippery surfaces, leather or smooth
soles are treacherous.
Material and design of soles should be selected
with anticipated hazardous surfaces in mind. It is rare indeed
when shoes appropriate to office wear are appropriate for field
work.
Non-skid soles made of substances such as
reinforced rubber are generally the best choice. Where
particularly hazardous surfaces, such as those coated with ice
are encountered, clamp-on ice spikes may be used.
f. Cold
EPA field personnel are often required to spend
long hours in the field during cold weather. Footwear for this
type of work should be selected with high insulation ratings and
somewhat over-sized (1/2 size) to provide room for heavy thermal
socks. Cold weather is usually associated with ice, snow and
wind. Outer surfaces of footwear should be made of winter-proof
materials or treated to make the material impervious to water.
14-5
-------
Wet, cold feet can quickly lead to frost bite. Frost bite of the
toes is a serious condition and can result in disabling injuries.
(See Unit on Cold and Heat Stress.)
g. Static Electricity
Due to various conditions such as low humidity,
ribbing clothing, contact with certain surfaces, the body may
build up amounts of static electricity. Voltage in excess of
10,000 volts are not uncommon. Such high voltage results in the
shock common on cold, dry winter days. Such high voltage may
also provide the energy to trigger explosions or fires in areas
where these dangers exist. Rubber soled shoes act as an
insulator preventing the static electricity build up in the body
from escaping into the floor. When conducting surfaces are
touched, such as the rim of a metal barrel, a discharge of
electricity in the form of a spark is generated. In the right
conditions, such sparks could be disastrous.
Special non-insulating shoes are manufactured to
prevent static buildup. Devices that attach to the leg and
special soles worn over rubber soles shoes also prevent static
buildup. In some industrial settings such as the manufacture of
explosives, these shoes are required before entry is permitted.
4. Ear Protection
Hearing protection may be necessary at some field sites
to prevent temporary loss of hearing. Long-term exposure to high
levels of sound can cause permanent loss of hearing in many
frequency ranges as a result of nerve damage, and short exposures
can cause temporary loss.
A simple test you can make to see if you need hearing
protection is to try speaking to a person standing beside you.
If you have to shout to communicate, you need hearing protection
to reduce the amount of sound reaching your ears. Although
hearing protectors reduce the sound level in many frequency
ranges, they can actually improve speech communication under
noisy conditions by reducing the interference caused by the
noise.
Earmuff hearing protectors generally provide the most
effective protection. If glasses, sideburns or long hair prevent
effective use of earmuff protectors, the next best protection is
a set of earplugs. Earplugs provide varying degrees of sound
attenuation. The most effective earplugs are custom-molded to an
individual user, and the least effective consist of a small wad
of synthetic fibers which is shaped as it is inserted into the
ear canal. The effectiveness of ear protectors is reduced by
14-6
-------
loose fit and work activities which allow leakage of sound.
Actual protection seldom matches the rated protection recorded
under test conditions.
5. Hand Protection
The second most common area of probable chemical
contamination next to the feet and the most probable area for
injury are the hands.
A wide variety of glove types are manufactured that
provide protection against injury. When glove selection is to be
made, the following list of considerations should be consulted:
o Injury due to abrasion, bruises, lacerations,
splinters and other mechanical hazards
o Chilling, freezing or burns
o Chemical and biological contaminants
o Dirt, grease, oil
o Electrical shock
When a variety of conditions exists, it may be
necessary to select more than one pair of gloves to wear
together. Viton for example, is relatively impervious to
polychlorinated biphenyls but tears easily. A second pair of
highly durable gloves may be worn over the Viton gloves to
provide mechanical protection. Illustration 14-1 presents a few
of the available types. Table 14-1 provides information for the
type of material needed to resist chemical absorption.
14-7
-------
ILLUSTRATION 14-1
OPPOSABLE GLOVES
TfU-TOUOl AAA!I
AU-mWOJI Y1NYI
T*y-roucH*sxn* vinn
P0tT*0 " ^otrfTNruHl UNf
th§ 0OIY-O OLOVt arartta mm-mm wm
3lw
Ofe
1#
ia*«M
kiaot
in
¦ tM.L
¦i CMtmlm* 100 01
>ie
WttX*
VtNYl IMMICNATID
«¦« —4 pMh •
•t m I • I m «•<*¦
¦MO*
IMOl
• M«U
m 9U79
ttanwau
HoifnitKiurn rrrvsi
r4M
n«ii
**mm i
VIA
n-A
774091
*MW| (M.
•m
jr-mti
HMI
MONKSY CIIP viwn COattd
ImmHttf tmt my
IMOli ¦>. tw<« M>L
It-ICOl KWiHlb
¦Mill Stew* «W| MIL
ll.lSi Mwm Mum U
m Jt 9*
»l* 0*m
mi* •>«* d
mm «•* c
»i« *«*
GENERAL PURPOSE
GLOVES
.itaiijij.
.mir
W1JtX-UTV VINTV IA^t(CNAT1D
I m « J
HYNIT
Nil IMFVtGMATTD/KMir UNIO
.uarftMftU
' v* Wari m
COTTON - 30UTHEBM
M <• •
UM v~«. •» at.
AOVANCt PMfcUTlI*
aiovu
14-8
-------
TABLE 14-1
Glove Selector Chart
Csisrriir® >ha c.iemical or shysical
r»auirBrrsr>(9 c> ycuf job. E*acp0%'
•Mln« lD%/
•
«
a
a
a
«
C>'—¦«
t
0
a
1
« A.
4
fcWI«»/
»
a
a
0
a
ntwwyi
SMNKt hnW
'wimi ¦«•<•/
Cm> T«r 0*inlaw
a
1
•
r
t
•
a
a
«*
« a.
*
9
a
S>r^»
r
a
a
a
f
MiscuuiNtoua
y
%
« «.
9
UtlW r»mn«»
*
t
1
0
CvRHt OH
a»n»T «>t
1
¦
(
1
1
a
a
a
a
1
¦
a
p
a
a
f iicurtw
¦
1
a
a
9
t
tiailMH '**
I
¦
a
a
9
9
1
a
a
a
9
9
0*t
AMU »N
a
a
¦
t
a
a
a
a
a
a
a
a
a
a
a
a
t
<
a
a
f
c
c
9
t
«
«
a
t
4
S>N«
A«Mint
a
a
«
a
«
9
t
a
¦
' a
«
9
•M'WM 'V4
1
a
a
a
0
9
WHWI
a
a
a
a
9
9
CwiMi 0«
t
a
a
a
m.m.
•
W*« 0»«»OM
«
a
9
a
9
•
Cvwt
C/mnm
m.m.
0
»
¦*
0
9
a
a
a
0
9
0
••M t »»«¦<« lM«
f
*
*
r
t$A.
9
MSA 010*9
r=-
«•
•=
•—
S ; S
wf0*«f
a
8
*
a
1
3
* ; *
rvTwO* «C0*M**f
a
(
«
0
f
3
3 f
m*»*j.Tirnj*9
a
«
t
c
€
9
J 1 :
1
* A.
a
•
<
l • !
urattv
1
•ill.
0
$
*
1
• *
^11(919
VIMTU »U9Tie
t
M H.
a
9
3
C
t !
sun* njii«i9
m a.
VINH vine
a
a
t
« -
- I
l-faWK* q-q—« '-'w n.ni'wyww
tHa4 INM |>m< ¦«»"••••" •»
•• (OiOTt* Mcnn <»» «• •• »• :««¦•"» '
•¦MX*!* 'W4T. '« MMM« •« *•' *
> !M ». M) uuWacMrr.'
ouovi unoths chart
»«»> Cww KiManM
Cwm ««»«•••«
r««v cnm s*»* c«i>
iM t«m
»«*¦ C««w« Jm«i» e«"
01
ir o»
Mil
*¦*) C««M «•'»« WW
14-9
-------
Gloves should also be selected according to how they
fit and the dexterity needed to do the job. It may be necessary
to buy a variety of gloves to meet the needs of a field operation
or to replace those with tears or that have become contaminated.
E. DONNING AND DOFFING PROTECTIVE CLOTHING
Realizing complete benefits from protective clothing depends
on the techniques used for donning and doffing the clothing. In
general, care must be taken to avoid tearing or puncturing the
materials particularly when using gear such as SCBA units and
avoiding contaminating the inside of the garments.
One of the basic precautions for donning protective clothing
is to keep the inside of the clothing clean and uncontaminated
before putting the garment on and while it is being put on. If
protective clothing or equipment is stored where it can become
contaminated, it may contaminate rather than protect personnel.
It is a common habit to store all contaminated equipment in one
place, allowing cross-contamination between, for example, boots
and the inside of an encapsulating suit.
In a similar fashion, if the clothing or equipment becomes
contaminated in the process of putting the equipment on,
personnel wearing the gear may be in contact with the
contamination all the time they are wearing or using the
equipment.
Minimizing penetration of contamination into your protective
clothing can be accomplished by a number of techniques. It is
recommended that the pants of the protective clothing be pulled
down over the boots and taped or rubber band be placed around the
bottom. This procedure reduces the chance of contaminants
falling into the tops of the boots. Likewise, sleeves should be
tucked into cuffs of gloves and taped or pulled down over the
wrists and taped. This prevents liquids from dribbling down the
open sleeve when the arms are raised or falling into the tops of
the gloves.
Always have at least one assistant to help don the clothes.
Not only do they help in the actual work, but they can inspect
the suit and gear to quickly spot rips and tears. Complex and
bulky gear, a hot, sticky perspiring body, add up to a great deal
of stress and strain on the individual and equipment which can
lead to unforseen damage that may endanger the worker or abort
the mission.
14 - 10
-------
1. Using and Removing Gloves
Before putting on protective gloves, remove any jewelry
that may puncture the material of the gloves. If the material of
the gloves is fragile, it may be important to trim your
fingernails to avoid puncturing the gloves while you are putting
them on, using them or taking them off.
If you are going to be dealing with known hazardous
materials, try to obtain and use gloves made of a material that
will provide predictable resistance to damage or permeation by
the hazardous material.
If you are going to be dealing with unknown hazardous
materials, try to obtain and use gloves that will resist damage
or permeation by a wide range of materials and consider using two
pairs of gloves with different qualities. It may also help to
don gloves if the hands or gloves are sprinkled with talcum
powder.
Removing gloves without contaminating the hands takes a
technique that can easily be learned with a little practice.
o Loosen both gloves by pulling lightly on each
fingertip of the gloves.
o Be sure not to touch your skin with the outside of
either glove.
o Remove the first glove either by pulling on the
fingertips or by grasping it just below the cuff
on the palm side and rolling the glove off the
fingers.
o Remove the second glove by inserting the ungloved
fingers inside the cuff on the palm side without
touching the outside of the glove and pushing or
rolling the glove off the fingers.
2. Using and Removing Boots
Before putting on protective boots over shoes, be sure
the shoes do not have any sharp spots or adhering material which
may puncture or abrade the protective boots.
If only known hazardous materials are to be handled,
try to obtain and use boots made of a material that will provide
predictable resistance to damage or permeation by the hazardous
materials.
14 - 11
-------
If there is the possibility of dealing with unknown
hazardous materials, try to obtain and use boots that will resist
damage or permeation by a wide range of materials. Consider
using protective boot covers or a second pair of boots over the
first.
Removing boots without contaminating the hands or feet
requires an easily-learned technique which is similar to that
used for removing gloves.
o Gloves are needed to avoid contaminating the hands
unless the boots are very loose.
o Loosen the boots by pulling them lightly with the
gloved hands.
o Be sure not to touch bare skin with the outside of
either glove.
o Remove the first boot either by pulling on the
toe, or by grasping it at the heel and pulling it
off the foot with a gloved hand or a bootjack.
o Remove the second boot in the same way or by
inserting the ungloved fingers inside the boot and
pushing it off without touching the outside of the
boot.
3. Using and Removing Fully Encapsulating Suits
In atmospheres where there is a need for complete
protection of the body from splashes or contact by vapors or
gases, it is necessary to wear a fully-encapsulating suit over
self-contained breathing apparatus. Use of fully-encapsulating
suits requires special preparation for donning and doffing and
special precautions for safe use of the suits and breathing
apparatus.
Safe use of full protective equipment requires a team
of persons who are physically fit and who are trained and
practiced in use of self-contained breathing apparatus and use of
the complete suits.
The team must include standby personnel who are
equipped and prepared:
o to carry out an emergency rescue if necessary;
o to assist the wearers into the breathing apparatus
and the suits;
14 - 12
-------
o to decontaminate the outside of the suit before it
is removed, so that wearers are not exposed while
they are getting out of the equipment; and
o to assist the wearers out of the suits, both
routinely and in an emergency such as running low
on breathing air.
In preparation for use of fully-encapsulating suits,
all of the necessary gear should be assembled in a clean change
area. In addition to trained personnel to assist and observe,
use of fully-encapsulating suits requires:
o SC6A for the suit wearers and the standby
personnel;
o Fully-encapsulating suits for the team entering
the hazardous area;
o Extra protective clothing and equipment for the
team; and
o Protective clothing for the standby personnel,
such as gloves, boots and disposable suits or
coveralls.
Each suit and breathing apparatus should be thoroughly
inspected and checked to see that everything is in operating
order. Any suit which has holes, rips, malfunctioning closures,
cracked masks or other deficiency must not be used.
Since use of an encapsulating suit, use of self-
contained breathing apparatus, and gathering samples all require
physical exertion, the person wearing the equipment usually
should strip down to a minimum of clothing to reduce heat stress.
This is particularly important if the sampling takes place in the
sun or near hot equipment, or during warm weather or under high
ambient temperatures within an industrial plant. A light weight
suit of cotton should be worn to absorb the sweat and increase
the surface area that evaporation can take place on, thus
increasing natural cooling. The cotton garment also prevents
chaffing and clinging of the protective gear. A thorough dusting
of talcum powder will assist the donning operation and reduce
possible damage to protective clothing.
Donning a fully-encapsulating suit is a complex
procedure requiring the coordination and assistance of a team of
individuals. The following brief summary does not take the place
of more advanced training required for certification.
14 - 13
-------
Before attempting to don a fully-encapsulating suit, a
review should be made of what equipment is needed. The equipment
should be laid out within quick and easy reach of the team. A
check list and practice will assist a team in preparing for an
actual event.
o Cotton undergarments
o Encapsulating suit
o Anti-fog spray
o Boots
o Tape
o Talcum powder
o Stool
o Plastic clean sheet
o Plastic bags for disposal or storage
o Brushes for decontaminating sprayer for
decontamination
o Knife or other device for emergency opening of
suit
o Intrinsic Communication System Lifeline
o SCBA Units
o Buckets for decontaminating solutions
F. CONTROLLING THE SPREAD OF CONTAMINANTS
The first step in controlling the spread of contaminants is
to carefully plan and practice the field activities that can lead
to contact with contaminants. Lay out activities such as
sampling in a manner that will reduce or keep to a minimum,
contact with contaminated surfaces. Part of this technique
depends on planning your activities to limit the number of
objects you have to touch, and part depends on setting aside
specific areas for activities such as packaging samples and
changing out of protective clothing.
The degree of effort necessary to set up "clean areas," and
dirty change or contaminated area is a function or result of the
amount of work or contact with the contaminants and the degree of
hazard of the expected contaminants.
14 - 14
-------
In the more advanced field training courses offered by EPA,
detailed techniques will be covered which cover all situations
that night be faced by Agency personnel. In this unit a basic
program as would be needed for sampling will be covered. To
convey the basic principles of preventing contaminants from
leaving a work site and entering an Agency vehicle, consider what
would be necessary to prevent mud covered work overalls and boots
from soiling a clean, new automobile. It is quite obvious that
just removing boots or gloves would be insufficient, nor would
taking off outerwear and boots while standing in mud solve the
problem.
A better plan would be to find a clean, dry area free of mud
and remove all gloves, outerwear, and boots that have been
exposed to mud. Locate a pathway from this clean, dry area to
the automobile that does not require exposing the clean clothes
and footwear to mud. Prevent covering the trunk or back seat
with mud from the removed outerwear by cleansing the gear. A
second alternative would be to cover them or place them in a bag
or container that will isolate them from their clean
surroundings. A last precaution: hands must be thoroughly
scrubbed to remove mud and a visual inspection made of likely
areas of contamination such as knees, shoes, seat of the pants,
and elbows to ensure accidental contact has not been made. This
activity would also extend to any passengers that intend to ride
in the vehicle.
While chemical contaminants may not be so obvious as mud,
the procedure for preventing spread of these chemicals is based
on the same procedures.
Following are some basic steps to pontrol the spread of
contaminants:
o Place a clean plastic sheet closely adjacent to the
contaminated work area.
o Notify crew members or post warning signs as to the
intent of the plastic change area.
o Clearly establish ••dirty" pathways from the plastic
change or transition area to the work area, and "clean"
pathways from the plastic change area to the outside.
o To minimize traffic to the change area, carefully plan
and equip the area with tools samplers, containers,
decontamination equipment, safety gear, and disposal
containers before work begins. Arrange to have clean
equipment set on tables to lessen the chance of
contamination while cleaning or decontamination is
taking place. If decontamination is to be accomplished
by sprayers, set the clean equipment table upwind of
14 - 15
-------
the area to be used for spraying. Hake plans to
collect decontamination solutions so they do not run
into the clean area. All decontamination solutions and
gear, such as brushes and buckets, should be regarded
as hazardous waste and either disposed of on-site or
disposed of in the proper manner as a hazardous waste.
6. DECONTAMINATION
Personnel may become contaminated in a number of ways
including:
o contacting vapors, gases, mists, or particulates in the
air.
o Being splashed by materials while sampling or opening
containers.
o Walking through puddles of liquids or on contaminated
soil.
o Using contaminated instruments or equipment.
Protective clothing and respirators help prevent the wearer
from becoming contaminated or inhaling contaminants; while good
work practices help reduce contamination on protective clothing,
instruments, and equipment.
Even with these safeguards, contamination may occur.
Harmful materials can be transferred into clean areas, exposing
unprotected personnel. In removing contaminated clothing,
personnel may contact contaminants on the clothing or inhale
them. To prevent such occurrences, methods to reduce
contamination, and decontamination procedures must be developed
and established before anyone enters a site and must continue
(modified when necessary) throughout site operations.
Decontamination consists of physically removing contaminants
or changing their chemical nature to innocuous substances. How
extensive decontamination must be depends on a number of factors,
the most important being the type of contaminants involved. The
more harmful the contaminant, the more extensive and thorough
decontamination must be. Less harmful contaminants may require
less decontamination.
Combining decontamination, the correct method of doffing
personnel protective equipment, and the use of site work zones
minimizes cross-contamination from protective clothing to wearer,
equipment to personnel, and one area to another. Only general
guidance can be given on methods and techniques for
decontamination. The exact procedure to use must be determined
after evaluating a number of factors specific to the incident.
14 - 16
-------
In instances where protective gear is of the disposable
type, large double thickness plastic bags should be used to
contain the gear. The bags should be sealed with tape and a
hazardous waste warning sticker applied. These extra precautions
will discourage scavenging of contaminated gear that is awaiting
disposal.
1. Preliminary Considerations
a. Initial Planning
The initial decontamination plan assumes all
personnel and equipment leaving the Exclusion Zone (area of
potential contamination) are grossly contaminated. A system is
then set up for personnel decontamination to wash and rinse, at
least once, all the protective equipment worn. This is done in
combination with a sequential doffing of protective equipment,
starting at the first station with the most heavily contaminated
item and progressing to the last station with the least
contaminated article. Each piece procedure requires a separate
station.
The spread of contaminants during the
washing/doffing process is further reduced by separating each
decontamination station by a minimum of 3 feet. Ideally,
contamination should decrease as a person moves from one station
to another further along in the line.
While planning site operations, methods should be
developed to prevent the contamination of people and equipment.
For example, using remote sampling techniques, not opening
containers by hand, bagging monitoring instruments, using drum
grapplers, watering down dusty areas, and not walking through
areas of obvious contamination would reduce the probability of
becoming contaminated and require a less elaborate
decontamination procedure.
The initial decontamination plan is based on a
worst-case situation or assumes no information is available about
the incident. Specific conditions at the site are then
evaluated, including:
o Type of contaminant
o The amount of contamination
o Levels of protection required
o Type of protective clothing worn
14 - 17
-------
The initial decontamination plan is modified,
eliminating unnecessary stations or otherwise adapting it to site
conditions. For instance, the initial plan might require a
complete wash and rinse of chemical protective garments. If
disposable garments are worn, the wash/rinse step could be
omitted. Wearing disposable boot covers and gloves could
eliminate washing and rinsing these items and reduce the number
of stations needed.
b. Contamination Reduction Corridor
An area within the Contamination Reduction Zone is
designated the Contamination Reduction Corridor (CRC). The CRC
controls access into and out of the Exclusion Zone and confines
decontamination activities to a limited area. The size of the
corridor depends on the number of stations in the decontamination
procedure, overall dimensions of work control zones, and amount
of space available at the site. A corridor of 75 feet by 15 feet
should be adequate for full decontamination. Whenever possible,
it should be a straight path.
The CRC boundaries should be conspicuously marked,
with entry and exit restricted. The far end is the hotline - the
boundary between the Exclusion Zone and the Contamination
Reduction Zone. Personnel exiting the Exclusion Zone must go
through the CRC. Anyone in the CRC should be wearing the Level
of Protection designated for the decontamination crew. Another
corridor may be required for heavy equipment needing
decontamination. Within the CRC, distinct areas are set aside
for decontamination of personnel, portable field equipment,
removed clothing, etc. These areas should be marked and
personnel restricted to those wearing the appropriate Level of
Protection. All activities within the corridor are confined to
decontamination.
Personnel protective clothing, respirators,
monitoring equipment, and sampling supplies are all maintained
outside of the CRC. Personnel don their protective equipment
away from the CRC and enter the Exclusion Zone through a separate
access control point at the hotline.
14 - 18
-------
FIGURE 14-1
HEAVY EOUIPMENT
OECONTAMINATION
AREA
i ...... .J
EXCLUSION
ZONE
j— «-Sr«-0-'
< O
M 111 J
=*0°
PI
o
u
^ £ "~T~
EXIT
PATH
CONTAMINATION
REDUCTION
ZONE
o I o-SS-o 0 o 1 o
I—«
Z
igi
£§8
oK
LEGENO
_g HOTLINE
- _ CONTAMINATION
CONTROL LINE
<8>
ACCESS CONTROL
POINT • EXTRANCE
ACCESS CONTROL
POINT . EXIT
SUPPORT
ZONE
; ORESSOUT I
I AREA !
I J
REDRESS
AREA
i. I
ENTRY
PATH
CONTAMINATION REDUCTION ZONE LAYOUT
14 " 19
-------
2. Extent of Decontamination Required
a. Modifications of Initial Plan
The original decontamination plan must be adapted
to specific conditions found at incidents. These conditions may
require more or less personnel decontamination than planned,
depending on a number of factors.
(1) Type of Contaminant
The extent of personnel decontamination
depends on the effects the contaminants have on the body.
Contaminants do not exhibit the same degree of toxicity (or other
hazard). Whenever it is known or suspected that personnel can
become contaminated with highly toxic or skin-destructive
substances, a full decontamination procedure should be followed.
If less hazardous materials are involved, the procedure can be
downgraded.
(2) Amount of Contamination
The amount of contamination on protective
clothing is usually determined visually. If it is badly
contaminated, a thorough decontamination is generally required.
Gross material remaining on the protective clothing for any
extended period of time may degrade or permeate it. This
likelihood increases with higher air concentrations and greater
amounts of liquid contamination. Gross contamination also
increases the probability of personnel contact. Swipe tests may
help determine the type and quantity of surface contaminants.
(3) Level of Protection
The Level of Protection and specific pieces
of clothing worn determine on a preliminary basis the layout of
the decontamination line. Each Level of Protection incorporates
different problems in decontamination and doffing of the
equipment. For example: decontamination of the harness straps and
backpack assembly of the self-contained breathing apparatus is
difficult. A butyl rubber apron worn over the harness makes
decontamination easier. Clothing variations and different Levels
of Protection may require adding or deleting stations in the
original decontamination procedure.
(4) Work Function
The work each person does determines the
potential for contact with hazardous materials. In turn, this
dictates the layout of the decontamination line. For example,
observers, photographers, operators of air samplers, or others in
the Exclusion Zone performing tasks that will not bring them in
14 - 20
-------
contact with contaminants may not need to have their garments
washed and rinsed. Others in the Exclusion Zone with a potential
for direct contact with the hazardous material will require more
thorough decontamination. Different decontamination lines could
be set up for different job functions, or certain stations in a
line could be omitted for personnel performing certain tasks.
(5) Location of Contamination
Contamination on the upper areas of
protective clothing poses a greater risk to the worker because
volatile compounds may generate a hazardous breathing
concentration both for the worker and for the decontamination
personnel. There is also an increased probability of contact
with skin when doffing the upper part of clothing.
(6) Reason for Leaving Site
The reason for leaving the Exclusion Zone
also determines the need and extent of decontamination. A worker
leaving the Exclusion Zone to pick up or drop off tools or
instruments and immediately returning may not require
decontamination. A worker leaving to get a new air cylinder or
to change a respirator or canister, however, may require some
degree of decontamination. Individuals departing the CRC for a
break, lunch, or at the end of day, must be thoroughly
decontaminated.
b. Effectiveness of Decontamination
There is no method to immediately determine how
effective decontamination is in removing contaminants.
Discolorations, stains, corrosive effects, and substances
adhering to objects may indicate contaminants have not been
removed. However, observable effects only indicate surface
contamination and not permeation (absorption) into clothing.
Also many contaminants are not easily observed.
A method for determining effectiveness of surface
decontamination is swipe testing. Cloth or paper patches-
swipes - are wiped over predetermined surfaces of the suspect
object and analyzed in a laboratory. Both the inner and outer
surfaces of protective clothing should be swipe tested. Positive
indications of both sets of swipes would indicate surface
contamination has not been removed and substances have penetrated
or permeated through the garment. Swipe tests can also be done
on skin or inside clothing. Permeation of protective garments
requires laboratory analysis of a piece of the material. Both
swipe and permeation testing provide after-the-fact information.
Along with visual observations, results of these tests can help
evaluate the effectiveness of decontamination.
14 - 21
-------
c. Equipment
Decontamination equipment, materials, and supplies
are generally selected based on availability. Other
considerations are ease of equipment decontamination or
disposability. Most equipment and supplies can be easily
procured. For example, soft-bristle scrub brushes or long-handle
brushes are used to remove contaminants. Water in buckets or
garden sprayers is used for rinsing. Large galvanized wash tubs
or stock tanks can hold wash and rinse solutions. Children's
wading pools can also be used. Large plastic garbage cans or
other similar containers lined with plastic bags store
contaminated clothing and equipment. Contaminated liquids can be
stored temporarily in metal or plastic cans or drums. Other gear
includes paper or cloth towels for drying protective clothing and
equipment.
d. Decontamination Solution
Personnel protective equipment, sampling tools,
and other equipment are usually decontaminated by scrubbing with
detergent water using a soft-bristle brush followed by rinsing
with copious amounts of water. While this process may not be
fully effective in removing some contaminants (or in a few cases,
contaminants may react with water), it is a relatively safe
option compared with using a chemical decontaminating solution.
This requires that the contaminant be identified. A decon
chemical is then needed that will change the contaminant into a
less harmful substance. Especially troublesome are unknown
substances or mixtures from a variety of known or unknown
substances. The appropriate decontamination solution must be
selected in consultation with an experienced chemist.
e. Establishment of Procedures
Once decontamination procedures have been
established, all personnel requiring decontamination must be
given precise instructions (and practice, if necessary).
Compliance must be frequently checked. The time it takes for
decontamination must be ascertained. Personnel wearing SCBA's
must leave their work area with sufficient air to walk to CRC and
go through decontamination.
3. Decontamination During Medical Emergencies
a. Basic Considerations
Part of overall planning for dealing with chemical
incidents is managing medical emergencies. The plan should
provide for:
14 - 22
-------
o Team members fully trained in first aid and
CPR.
o Arrangements with the nearest medical
facility for transportation and treatment of
injured, and for treatment of personnel
suffering from exposure to chemicals.
o Consultation services with a toxicologist.
o Emergency eye washes, showers, and/or wash
stations.
o First aid kits, blankets, stretcher, and
resuscitator.
In addition, the plan should establish methods for
decontaminating personnel with medical problems and injuries^
There is the possibility that the decontamination may aggravate
or cause more serious health effects. If prompt life saving
first aid and medical treatment is required, decontamination
procedures should be omitted. Whenever possible, response
personnel should accompany contaminated victims to the medical
facility to advise on matters involving decontamination.
b. Physical Iniurv
Physical injuries can range from a sprained ankle
to a compound fracture, from a minor cut to massive bleeding.
Depending on the seriousness of the injury, treatment may be
given at the site by trained response personnel. For more
serious injuries, additional assistance may be required at the
site or the victim may have to be treated at a medical facility.
Life Saving care should be instituted immediately
without considering decontamination. The outside garments can be
removed (depending on the weather) if they do not cause delays,
interfere with treatment, or aggravate the problem. Respirators
and back pack assemblies must always be removed. Fully
encapsulating suits or chemical resistant clothing can be cut
away. If the outer contaminated garments cannot be safely
removed, the individual should be wrapped in plastic, rubber, or
blankets to help prevent contaminating the inside of ambulances
and medical personnel. Outside garments are then removed at the
medical facility. No attempt should be made to wash or rinse the
victim at the site. One exception should be if it is known that
the individual has been contaminated with an extremely toxic or
corrosive material which could also cause severe injury or loss
of life. For minor medical problems or injuries, the normal
decontamination procedure should be followed.
14 - 23
-------
c. Heat Stress
Heat-related illnesses range from heat fatigue to
heat stroke, the most serious. Heat stroke requires prompt
treatment to prevent irreversible damage or death. Protective
clothing may have to be cut off. Less serious forms of heat
stress require prompt attention or they may lead to a heat
stroke. Unless the victim is obviously contaminated,
decontamination should be omitted or minimized and treatment
begun immediately.
d. Chemical Exposure
Exposure to chemicals can be divided into two
categories:
o Injuries from direct contact, such as acid
burns or inhalation of toxic chemicals.
o Potential injury due to gross contamination
on clothing or equipment.
For inhaled contaminants treatment can only be by
qualified physicians. If the contaminant is on the skin or in
the eyes, immediate measures must be taken to counteract the
substance's effect. First aid treatment usually is flooding the
affected area with water? however, for a few chemicals, water may
cause more severe problems.
When protective clothing is grossly contaminated,
contaminants may be transferred to treatment personnel or the
wearer and cause injuries. Unless severe medical problems have
occurred simultaneously with splashes, the protective clothing
should be washed off as rapidly as possible and carefully
removed.
4. Protection for Decontamination Workers
The Level of Protection worn by decontamination workers
is determined by:
o Expected or visible contamination on workers.
o Type of contaminant and associated respiratory and
skin hazards.
o Total vapor/gas concentrations in the
contamination reduction corridor.
14 - 24
-------
o Particulates and specific inorganic or organic
vapors in the CRC.
o Results of swipe tests.
a. Level C Use
Level C includes a full face, canister type air-
purifying respirator, hard hat with face shield (if splash is a
problem), chemical-resistant boots and gloves, and protective
clothing. The body covering recommended is chemical-resistant
overalls with an apron, or chemical-resistant overalls and
jacket.
A face shield is recommended to protect against
splashes because respirators alone may not provide this
protection. The respirator should have a canister approved for
filtering any specific known contaminants such as ammonia,
organic vapors, acid gases, and particulates.
b. Level B Use
In situations where site workers may be
contaminated with unknowns, highly volatile liquids, or highly
toxic materials, decontamination workers should wear Level B
protection. Level B protection includes SCBA, hard hat with face
shield, chemical resistant gloves, and protective covering. The
clothing suggested is chemical-resistant overalls, jacket, and a
rubber apron. The rubber apron protects the SCBA harness
assembly and regulator from becoming contaminated.
5. Decontamination of Equipment
Insofar as possible, measures should be taken to
prevent contamination of sampling and monitoring equipment.
Sampling devices become contaminated, but monitoring instruments,
unless they are splashed, usually do not. Once contaminated,
instruments are difficult to clean without damaging them. Any
delicate instrument which cannot be easily decontaminated should
be protected while it is being used. It should be placed in a
clear plastic bag, and the bag taped and secured around the
instrument. Openings are made in the bag for sample intake.
a. Decontamination Procedures
(1) Sampling devices
Sampling devices require special cleaning.
The EPA Regional Laboratories can provide information on proper
decontamination methods.
14 - 25
-------
(2) Tools
Wooden tools are difficult to decontaminate
because they absorb chemicals. They should be kept on site and
handled only by protected workers. At the end of the response,
wooden tools should be discarded. For decontaminating other
tools, Regional Laboratories should be consulted.
(3) Respirators
Certain parts of contaminated respirators,
such as the harness assembly and leather or cloth components, are
difficult to decontaminate. If grossly contaminated, they may
have to be discarded. Rubber components can be soaked in soap
and water and scrubbed with a brush. Regulators must be
maintained according to manufacturer's recommendations. Persons
responsible for decontaminating respirators should be thoroughly
trained in respirator maintenance.
(4) Heavy Equipment
Bulldozers, trucks, back-hoes, bulking
chambers, and other heavy equipment are difficult to
decontaminate. The method generally used is to wash them with
water under high pressure and/or to scrub accessible parts with
detergent/water solution under pressure, if possible. In some
cases, shovels, scoops, and lifts have been sand blasted or steam
cleaned. Particular care must be given to those components in
direct contact with contaminants such as tires and scoops. Swipe
tests should be utilized to measure effectiveness.
b. Sanitizing of Personnel Protective Equipment
Respirators, reusable protective clothing, and
other personal articles not only must.be decontaminated before
being reused, but also sanitized. The inside of masks and
clothing becomes soiled due to exhalation, body oils, and
perspiration. The manufacturers instructions should be used to
sanitize the respirator mask. If practical, protective clothing
should be machine washed after a thorough decontamination;
otherwise it must be cleaned by hand.
c. Persistent Contamination
In some instances, clothing and equipment will
become contaminated with substances that cannot be removed by
normal decontamination procedures. A solvent may be used to
remove such contamination from equipment if it does not destroy
or degrade the protective material. If persistent contamination
is expected, disposable garments should be used. Testing for
persistent contamination of protective clothing and appropriate
decontamination must be done by qualified laboratory personnel.
14 - 26
-------
6. Disposal of Contaminated Materials
All materials and equipment used for decontamination
must be disposed of properly. Clothing, tools, buckets, brushes,
and all other equipment that is contaminated must be secured in
drums or other containers and labeled. Clothing not completely
decontaminated on-site should be secured in plastic bags before
being removed from the site.
Contaminated wash and rinse solutions should be
contained by using step in containers (for example, child's
wading pool) to hold spent solutions. Another containment method
is to dig a trench about 4 inches deep and line it with plastic.
In both cases the spent solutions are transferred to drums, which
are labeled and disposed of with other substances on site..
H. STORAGE OF EQUIPMENT
Everyone has experienced the frustrating task of putting
something back into its original package. In the case of
expensive protective gear, the investment in time and frustration
of storing gear properly will undoubtedly result in longer life,
reduced maintenance and increased availability of critical gear.
In many cases, proper storage eliminates and transporting gear,
reduces the change of cross-contamination with contaminated gear,
and punctures and tears from gear stored near by.
14 - 27
-------
STUDENT EXERCISE
Using tables, illustrations, and data included in this Unit,
select the proper protective clothing for the job described.
A series of 55-gallon barrels have mysteriously shown up at
a sanitary landfill. They were uncovered by heavy equipment
leveling a pile of trash. Some of the barrels may have been
damaged. Workmen report the following names on the barrels:
Freon, Methyl Acetate, and Benzyl Alcohol. All work has stopped
until the wastes can be sampled and the hazards of the contents
can be ascertained. Heather conditions are sleet mixed with
rain; temperature at 32°F; winds at 5-10 mph.
Body Protection
Rationale
Head Protection
Rationale
Hand Protection
Rationale
Foot Protection
Rationale
Eye and Face Protection
Rationale
14 - 28
-------
UNIT 15
RESPIRATORY PROTECTION
A. INTRODUCTION
In the day-to-day field activities under EPA jurisdiction,
Agency employees are confronted with a vast variety of varying
and sometimes hostile conditions. Few conditions are so
immediately potentially dangerous as hazardous atmospheres.
While it is the policy of EPA to avoid sending personnel into
life threatening conditions, there are times when such danger
cannot be anticipated or avoided. The objective of this unit is
to provide Agency personnel with the basic information needed to
make intelligent decisions as to when, where and how to use
respiratory protection devices.
B. RECOGNIZING POTENTIALLY HAZARDOUS ATMOSPHERES
Respiratory protection is needed if personnel must enter any
area in which there may be either a deficiency of oxygen or a
high concentration of hazardous material in the air. In such
atmospheres, life or health may depend on using respiratory
equipment which can provide a supply of breathing air.
Respiratory hazards may exist at spill scenes, in the
vicinity of discharge or emission sites, within industrial
plants, and at hazardous waste sites. EPA policies require
respiratory protection when there has been a release of toxic
gases or vapors, when there is a high potential for a sudden
release of such material, or when it is necessary to enter an
environment where toxic airborne contaminants are either known to
be present or are likely to be present.
Not all dangerous atmospheres are obvious. Some toxic gases
have no odor nor visible sign of their presence. The need for
respiratory protection may not be apparent.
The behavior of others may not be a good indication of the
need for respiratory protection. For example, if you make a walk
through inspection of a plant, do you need to wear a respirator
if the company representative does not wear one? The company
representative who guides the Agency personnel may or may not be
a good example to follow. He or she may not be aware of or
believe there are hazards that require respiratory protection, or
may not be willing to acknowledge that there are dangerous
concentrations of toxic materials in the air.
15-1
-------
Even if hazards are recognized, if personnel plan to spend
considerable time in the plant taking samples or making
observations, they may need respiratory protection where others
are not wearing it.
Some employees may have developed a tolerance to irritating
materials, and others may have developed allergies and been
transferred to other work areas. The reaction of EPA personnel
to a particular atmosphere may be different from the reaction of
employees who work there regularly.
Agency personnel may also need respiratory protection
because the areas where they will be working may have higher
concentrations of airborne toxic material than areas where
employees work routinely.
Personnel in the sampling routine may experience many
different varieties of toxic materials compared to someone who
works in only one place.
C. RESPIRATORY HAZARDS
1. oxygen Deficiency
When it is necessary to enter a confined space, one of
the most important considerations is whether there is sufficient
oxygen in the atmosphere to enter and work safely in the space.
An oxygen deficiency and high concentration of hazardous
materials may occur in unventilated and confined spaces such as
the interiors of tanks, vats, pits, trailers, sewers, grain
elevators, unventilated rooms and abandoned buildings.
Oxygen deficiency can occur if vapors or gases displace
part of the air in pits and open tanks, or in other types of
confined spaces. Oxygen deficient atmospheres can occur when air
is displaced by gases and vapors, or were the oxygen is removed
by oxidation processes such as fire, rusting, or aerobic
microbial action. The effects of oxygen deficiency on a person
can range from minor to extremely serious. (Table 15-1.)
15-2
-------
TABLE 15-1
Physiological effects of oxygen deficiency are not
apparent until the concentration decreases to 16%. The various
regulations and standards dealing with respirator use recommend
that percentages ranging from 16-19.5% be considered indicative
of an oxygen deficiency. Such numbers take into account
individual physiological responses, errors in measurement, and
other safety considerations. For hazardous response operations,
19.5% oxygen in air is the figure that decides between air-
purifying and atmosphere-supplying respirators. EPA standards
require special respiratory protection for entry in any
atmosphere containing less than 19.5% oxygen.
2. Aerosols
Aerosol is a term used to describe fine particulates
(solid or liquid) suspended in air. Particulates include dust
and other minute particles such as found with coal and asbestos,
mists, fogs, smoke fumes, and sprays. The effect of aerosols
range from irritation and inflammation to systemic poisons.
15-3
-------
3. Toxic Materials
Gases or vapors containing toxic materials may have
immediate or delayed health affects on the individual.
Inhalation of certain toxic gases may have acute and deadly
effects with as little as a few short breaths. No danger is more
immediate nor effect more persistent, than the action of toxic
materials that enter by way of the respiratory tract. The
following list gives the chemical classification of dangerous
toxic substances that may enter through the respiratory track:
o Acidic: substances that are acids or react with
water to form acids.
o Alkaline: substances that are bases or react with
water to form bases.
o Organic: carbon compounds which may range from
methane to chlorinated organic solvents.
o Organometallic: organic compounds containing
metals.
c Hydrides: compounds in which hydrogen is bonded
to another metal.
o Inert: no chemical reactivity.
Groups of these substances, based on physiological
(toxicological) activity include:
o Irritants: corrosive substances which injure and
inflame tissue.
o Asphyxiants: substances which displace oxygen or
prevent the use of oxygen in the body.
o Anesthetics: substances which depress the central
nervous system, causing intoxication or a loss of
sensation.
o Systemic poisons: substances which can cause
pathology in various organ systems.
4. Measurements of Respiratory Hazards
Two values are used to describe respiratory hazards.
The first, the Threshold Limit Value (TLV), is a time-weighteJ
average concentration for a particular substance. Almost all
workers can be exposed to this level 40 hours a week without
15-4
-------
suffering adverse health effects. The TLV is recommended by the
American Conference of Governmental Industrial Hygienists
(ACGIH). Table 15-2 illustrates a summary of TLV's of some
common hazardous materials.
15 - 5
-------
TABLE 15—2
SELECTED IOLH l> 1984-63 TLV VALUES
CffOfiSUQd
IQUi
ppm
ppm
acataldahyda
10000
100
acatic acid
1000
10
acatie anhydrida
1000
S C
aeatona
20000
730
aerylenitrlla
4000
2 akin
ammonia
S00
25
araina
6
0.03
banzano
2000
10
-------
The second value, Immediately Dangerous to Life and
Health (IDLH), can be based not only on toxicity, but also on
other characteristics such as flammability. An atmosphere which
is within the flammable or explosive limit of the contaminant is
also considered IDLH. EPA has further defined or simplified the
meaning of IDLH as: "Any atmosphere that poses an immediate
hazard to life or produces immediate irreversible effects on
health that will be debilitating."
D. RESPIRATOR USE
1. Requirements
The Occupational Safety and Health Administration
(OSHA) is the policy formulating regulatory agency for worker
respiratory protection. The source of OSHA's policy is found in
29 CFR Part 1910.134 and is summarized as follows:
o Written standard operating procedures governing
the selection and use of respirators shall be
established.
o Respirators shall be selected on the basis of
hazards to which the worker is exposed.
o The user shall be instructed and trained in the
proper use of respirators and their limitations.
o Where practical, the respirators should be
assigned to individual workers for their exclusive
use.
o Respirators shall be cleaned and disinfected
regularly. Those issued for the exclusive use of
one worker should be cleaned after each day's use,
or more often if necessary. Those used by more
than one worker shall be cleaned and disinfected
thoroughly after each use.
o Respirators shall be stored in a convenient,
clean, and sanitary location.
o Respirators used routinely shall be inspected
during cleaning. Worn or deteriorated parts shall
be replaced. Respirators for emergency use such
as self-contained devices shall be thoroughly
inspected at least once a month and after each
use.
15-7
-------
o Appropriate surveillance of work area conditions
and degree of employee exposure or stress shall be
maintained.
o There shall be regular inspection and evaluation
to determine the continued effectiveness of the
program.
o Persons should not be assigned to tasks requiring
use of respirators unless it has been determined
that they are physically able to perform the work
and use the equipment. The local physician shall
determine what health and physical conditions are
pertinent. The respirator user's medical status
should be reviewed periodically (for instance,
annually).
It is EPA policy to provide appropriate respiratory
protective devices for EPA employees, and to require use of such
protective devices whenever they are necessary to protect
employee health. Employees are entitled to wear respiratory
protection if they are irritated by any material even though the
concentrations of material may not be expected to cause any
adverse health effects, and even though the concentrations do not
seem to effect others nearby in a similar way.
EPA policy requires use of respiratory protection in
four situations:
o When there is a high potential for a sudden
release of toxic gases or vapors or there has been
such a release.
o When preparing to enter hazardous environments or
locations such as waste or spill sites, where it
is known, or there is a reasonable belief, that
toxic airborne contaminants are present.
o When preparing to enter confined spaces, such as
manholes and unventilated buildings where there
may be an oxygen deficiency.
o During infrequent but routine operations where it
is not feasible to limit concentrations of toxic
material to safe levels by engineering controls.
15-8
-------
2. General Guidance
a. Selection and Use
Approved respiratory protective equipment must be
selected to provide protection against the hazards to which the
user may be exposed.
If possible, respirators should be assigned to
individual employees for their exclusive use. This will be
important particularly for air purifying respirators in which a
good tight fit of the facepiece has a greater effect on the
protection factor than it does for air supplying respirators
which operate in the continuous flow or positive pressure-demand
mode.
Hazardous conditions in the work area must be kept
under surveillance, and the degree of employee exposure or stress
must be observed and kept to safe levels. When work areas have
or may have an oxygen deficiency or other exposure which is
immediately dangerous to life or health, EPA policy and other
Federal standards require standby personnel on the scene who are
trained and equipped to carry out a rescue immediately.
Surveillance and ready assistance are also necessary if EPA
personnel are using air purifying respirators in areas which
contain concentrations of hazardous material above the
Permissible Exposure Limits (PEL). Close observation of
employees working in hazardous conditions is important for
limiting their exposure to hazardous materials by skin contact
and for minimizing any adverse effects of heat stress.
Standard operating procedures for typical field
activities must be developed by each working group. These
procedures for selection and use of respiratory, protective
equipment must be in written form and must be implemented so that
EPA employees will have effective protection from respiratory
hazards. Standard operating procedures are needed particularly
for entry into atmospheres which are immediately dangerous to
life or health.
Work in dangerous atmospheres requires development
of a standard operating procedure that will be understood and
used by everyone entering or working in atmospheres which are
dangerous to life or health. Working safely in such atmospheres
also requires thorough training, and the presence of a buddy and
a backup. It is important to recognize that the actual duration
of protection provided by the breathing apparatus may to
considerably less than the rated capacity because of heat stress,
work rate, body weight and the wearer's training and ability to
control his or her breathing rate.
15-9
-------
Selection of adequate respiratory protection for
field activities depends on the:
o nature of the hazardous operation or process;
o contaminant, type of hazard, concentration,
and effects on the body activities to be
conducted in the hazardous area;
o length of time that respiratory protection
will be needed;
o time required to get out of the hazardous
area to the nearest area having respirable
air; and
o specific characteristics of the respiratory
protective devices that are available within
the Agency or than can be purchased.
The initial step in selecting adequate respiratory
protection for a particular activity is to consider the nature of
the activity and the type of respiratory hazard that will exist
or that is likely to exist. There are three basic types of
hazards for which respiratory protection is needed:
(1) Oxygen Deficiency
The choice of respirators is very limited if
the working atmosphere is oxygen deficient. If an oxygen
deficiency exists or is possible, the choice of adequate
respiratory protection is limited to:
o Self-contained breathing apparatus, or
o Air-line respirator with an auxiliary
self-contained air supply.
(2) Flammable Gas, Liquid or Dust
It is EPA policy to measure flammable
concentrations of gases and vapors before entering an area where
such material may be present in hazardous amounts, and not to
enter any area which has in excess of 25 percent of the lower
explosive limit of any material present. However, unexpected
spills or leaks may make entry of such hazardous areas necessary
for rescue or other emergency reasons.
15 - 10
-------
If it is ever necessary to approach or enter
areas in which flammable vapors or gases are present or possible
in high concentrations, the respiratory protection must be
either:
o Self-contained breathing apparatus, or
an
o Air-line respirator with an auxiliary
self-contained air supply.
(3) Toxic Contaminant Exposures
Exposure to toxic contaminants can be divided
into three broad categories, depending on the degree of hazard.
These three degrees of hazard are related to the concentrations
of toxic materials which are present.
(A) Concentrations Immediately Dangerous to
Life or Death
There are several definitions of what
atmospheres are considered "Immediately Dangerous to Life or
Health." The NIOSH/OSHA Pocket Guide to Chemical Hazards
describes IDLH as a concentration from which one could not endure
for 30 minutes without any irreversible health effects.
The Federal standard on respiratory
protection defines IDLH as conditions that pose an immediate
threat to life or health or severe exposure to contaminants which
are likely to have adverse cumulative or delayed effects on
health.
EPA has defined "immediately dangerous
to life or health" as "any atmosphere that poses an immediate
hazard to life or produces immediate irreversible effects on
health that will be debilitating."
If an atmosphere is or may become
"immediately dangerous to life or health," the choice of adequate
respiratory protection is limited to:
o self-contained breathing apparatus,
or
o air-line respirators with an
auxiliary self-contained air
supply.
15 - 11
-------
(B) Concentrations Above Permissible
Exposure Limits but Below IDLH
Approved respiratory protection is
required for exposures to hazardous materials in airborne
concentrations which are above the Permissible Exposure Limits.
The Permissible Exposure Limit for a hazardous material is the
maximum concentration believed to cause no adverse effect in most
people if inhaled during regular five-day work weeks.
Respiratory protection is also required
for exposure to hazardous materials in concentrations which may
be expected to cause chronic toxic effects after repeated
exposure, or acute adverse physiological symptoms after prolonged
exposure.
(C) Concentrations Below Permissible
Exposure Limits (and Below IDLH)
When concentrations of hazardous
material are below the Permissible Exposure Limits or judged to
be at concentrations below such limits, respiratory protection is
not required. However, respiratory protection may be needed or
desired to prevent physical discomfort, irritation,
sensitization, or other adverse health effects.
b. Respiratory Protection for Concentrations Not
Immediately Dangerous
Since air purifying respiratory are lighter, less
cumbersome and less expensive to use than air supplying
respirators, air purifying respirators will usually be considered
first for protection against hazardous material concentrations
not immediately dangerous to life or health. If there is no
approved air purifying respirator that will provide the
protection needed, it will be necessary to use an air supplying
respirator.
Selection of an air purifying respirator for
protection against hazardous atmospheres is limited to those in
which the identity and concentration of material are known to be
within the purification limits of the respirators. For safety
and health reasons the concentration must be determined before
and during use of the type of respirator. This basic limitation
is EPA policy as well as a Federal standard.
15 - 12
-------
c. Summary of Factors for Selection of Type of
Respiratory Protection
The first steps in selection of air purifying
respirators are to:
o Identify the contaminant or contaminants
which are present,
o Determine the Permissible Exposure Limit,
warning properties and whether the warning
properties are adequate, and
o Determine the maximum concentration present
in the working area.
The next steps in the selection of a respirator
are based on the concentration and warning properties of the
contaminants present.
o If the concentration is below the Permissible
Exposure Limit respirator use is optional.
o If the concentration is above the Permissible
Exposure Limit respirator use is required.
o If the contaminant has adequate warning
properties, an approved air purifying
respirator may be worn. Select a respirator
with a filtration system which will provide
adequate protection and time for the
concentration measured in the working
atmosphere.
o If the material has no warning properties or
inadequate properties, an air supplying
respirator is required.
o If the concentration is above the level
considered IDLH, a self-contained breathing
apparatus is strongly recommended.
3. Respirator Selection
Before selecting a respirator for use, check to ensure
it has been approved by a recognized agency such as the Mine
Safety and Health Administration (MSHA) or the National
Institute for Occupational Safety and Health Administration,
(NIOSH). Approvals for respirators are based on tests conducted
at the National Institute for Occupational Safety and Health
Testing Laboratory.
15 - 13
-------
All respirators built to the same specifications will
have an approval designation displayed on the respirator or its
container. The designation will consist of the letters TC (for
Testing and Certification) and two groups of numbers which
indicate the type of equipment and the specific approval. The
approval label will also include the names of the certification
agencies.
Respirators that meet Federal design and test standards
will have an approval designation showing joint approval by the
Mine Safety and Health Administration,(MSHA) and NIOSH, and the
respirators will be included in the NIOSH Certified Equipment
List.
If a respirator is approved and listed for protection
against organic vapors, remember that the approval is only for
organic vapors with adequate warning properties.
Recently approved cartridges and canisters will show
MSHA and NIOSH on the approval label.
(Note: Older respirators may show the Mining
Enforcement and Safety Administration (MESA) or the Bureau of
Mines as the approval agency.)
A listing of all approved respirators and respirator
components is available in the NIOSH Certified Equipment List.
Editions and supplements are issued periodically. Chemical
cartridge or canister respirators do not provide reliable
protection against organic vapors without adequate warning
properties, and such respirators must not be used for protection
against such vapors.
The only organic vapors for which an air purifying
respirator is approved or acceptable are those which provide a
reliable odor or a noticeable irritation at a concentration which
is at or slightly below the permissible exposure limit. Organic
vapors are not considered to have adequate warning properties if
they cause olfactory fatigue, or if they cannot be detected until
their concentration exceeds the permissible exposure limit. They
are also not considered to have adequate warning properties if
they can be detected at extremely low concentrations, so that
they are detected long before their concentration presents any
hazard.
15 - 14
-------
Periodically, NIOSH publishes a list of all approved
respirators and respirator components. The list is entitled the
NIOSH Certified Equipment List. Respiratory apparatus can be
divided into two general types which are discussed in detail
later in this unit:
o Air-purifying - those that filter out
contaminants, and
o Air-supplying - those that supply air by means of
a cylinder of compressed gas or oxygen or by an
air line.
All respirators are composed of two main components,
the facepiece and the device which supplies or purifies air. The
facepiece comes in three configurations which relate to the
amount of protection the respirator affords:
o Quarter Mask (Type B - Half Mask) — fits from the
nose to the top of the chin, and utilizes two- or
four-point suspension.
o Half Mask (Type A - Half Mask) — fits under the
chin and over the nose, and must have four-point
suspension.
o Full Facepiece - covers all of the face from under
the chin to the forehead. It provides the best
protection because it is more easily fitted on the
face.
4. Respirator Fit-Testing
One of the most important requirements of respiratory
protection is proper fit-testing of respirators. Not all
respirators fit everyone, so each individual must find out which
facepiece fits best. To be approved, a respirator must be fit-
tested utilizing acceptable fit-test media and procedures. There
are two types of fit-tests, quantitative and qualitative.
The quantitative test is an analytical test which
measures the concentrations outside and inside the facepiece.
The relative difference between concentrations, termed the
Protection Factor (PF), is used in conjunction with the
acceptable Threshold Limit Value (TLV) to determine the maximum
concentration the user may be exposed to while wearing the test
respirator.
Table 15-3 lists all types of respirators and the PF's.
15 - 15
-------
TABLE 15-3
Selected respirator protection factors
Type of Respirator PF (Qualitative Test)
Air-purifying
quarter-mask
Half-mask
Air-line
quartermask
half-mask
Hose mask
full facepiecs
SCBA, demand
quarter-mask
half-mask
10
10
10
10
10
10
10
Air-purifying
full facepiece
Air-line, demand
full facepiece
100
100
SCBA, demand
full facepii
100
Air-line, pressure-demand*
with escape provision
full facepiece (no test required) 10,000*
SCBA, pressure-demand or
positive pressure
full facepiece (no test required) 10,000*
The following example using PF information indicates
the degree of difference between half-face masks and full-face
masks:
If a respirator passes the qualitative test, it can be
worn in concentrations determined by the assigned
Protection Factor (PF). The maximum concentration is
calculated by multiplying the TLV of the contaminant by
its PF. PF's for cartridge and canister respirators
are:
o Half-face mask, 10%
o Full-face mask, 100%
Example: Protection (ppm = PF x TLV (PF = 10; TLV =
10 ppm)
= 10 x 10
= 100 ppm
15 - 16
-------
Thus, for substance x with a TLV of 10, the half-mask
respirator provides protection up to concentration of
100 ppm of the substance.
E. FITTING A RESPIRATOR AND TESTING THE SEAL
Each person who may be expected to wear an air purifying
respirator (or a demand type of air supplying respirator) for any
field activity should have an opportunity before going into a
field situation to find a facepiece that provides a good tight
seal with his or her face. This requires trying on facepieces to
find one that seems to fit, and then testing the seal to be sure
the fit is adequate.
1. Fitting A Respirator
Not all sizes and shapes of faces can be fitted with a
respirator facepiece that will provide the tight seal necessary
for protection. Each person should be allowed to choose the most
comfortable facepiece that provides a satisfactory fit.
Respirators should be assigned to individual employees for their
exclusive use, if possible. If a person cannot find a facepiece
that fits tightly the only way to get respiratory protection is
to use equipment which provides a continuous flow of air or a
positive pressure.
Each time a person puts on an air purifying respirator,
the fit of the facepiece should be checked to be sure that the
seal will provide as much protection as possible.
A tight seal is difficult or impossible to achieve if
there is anything which gets between the facepiece and the skin,
such as parts of eyeglass frames, long hair, long sideburns, a
beard or beard stubble. (In one EPA operation, standard
procedures specified that male personnel had to shave every day
to assure optimum fit of the facepiece.) A tight seal is also
difficult to achieve if a person chews gum or tobacco, or is
missing one or both dentures.
2. Testing The Seal
Testing the fit of the facepiece seal is required with
all negative pressure respirators every time they are used.
Negative pressure respirators include all air purifying
respirators except those that are powered. Any air supplying
respirator that is operated in the demand mode should be tested
for fit each time it is used. Three tests should be used to get
maximum protection from a respirator.
15 - 17
-------
Either the negative pressure test or the positive
pressure test is required every time a negative-pressure
respirator is used. The qualitative fit test is required only
before the initial use of each different type of negative-
pressure respirator and again annually.
To prepare for testing the fit of a respirator, place
the respirator over the face and draw up the straps, one at a
time, beginning first with the bottom straps. The straps are
drawn up so that the facepiece fits securely, without being so
tight that it causes discomfort.
a. Negative Pressure Test
The purpose of the negative pressure test is to
see if the facepiece is tight enough to maintain a negative
pressure without leakage.
Close off the cartridge or canister inlet with the
palm of your hand.
Inhale gently for about ten seconds so that the
facepiece is drawn against your face.
If you feel a flow of air along the edge of the
facepiece, the inward air flow indicates leakage.
If you have leakage, tighten the straps and try
the test again.
If the leakage continues, get another type of
facepiece or another type of respirator.
If you are testing the fit of an air supplying
respirator, such as an SCBA, close off the facepiece hose with
the palm of your hand before you connect the hose to the
regulator. Inhale gently to feel if there are any leaks of air
into the facepiece along its edges. This test is optional if the
apparatus will be operated in the positive pressure-demand mode.
b. Positive Pressure Test
The positive pressure test will determine whether
the facepiece is tight enough to maintain a positive pressure.
Take a breath and hold it briefly while you take
the next step.
Close off the exhalation valve with the palm of
your hand.
15 - 18
-------
Exhale gently for about ten seconds to build a
positive pressure within the facepiece.
If a positive pressure cannot be built up and
there is an outward flow of air, there is leakage.
If you have leakage, you can tighten the straps
and try the test again.
If the leakage continues, get another type of
facepiece or another type of respirator.
On an air-purifying respirator, the exhalation
valve is usually the bottom valve. It opens when you exhale.
The upper valve is the inhalation valve, which closes when you
exhale into the facepiece.
c. Qualitative Fit Test
The qualitative fit test determines whether the
fit is tight enough to prevent leakage of a detectable odor in
through the seal. Respirators with particulate filters are
tested by exposure to an irritant such as smoke, and those with
chemical sorbent filters by exposure to an odorant such as
isoamyl acetate (banana oil) .
The test material is released close to the edges
of the sealing surfaces of the facepiece, to find out if the
wearer is able to detect any odor. First the leakage is tested
with the wearer remaining sedentary for about a minute; then the
wearer performs head and face movements that might occur
naturally.
If leakage is detected, tighten the straps and
retest.
If the leakage continues, get another type of
facepiece or another type of respirator.
A variation of the qualitative test uses a test
chamber, consisting of a special plastic bag or tent-like hood
which can be filled with a concentration of the test material,
and into which the wearer can insert her or his head while
wearing the respirator. Leakage is tested first with the wearer
remaining sedentary for about a minute; then the wearer performs
exercises simulating work, such as bending over and running in
place.
Qualitative fit tests are recommended annually,
and whenever EPA personnel are going to be entering particular!,
hazardous atmospheres.
15 - 19
-------
F. RESPIRATOR TYPES
1. Air-Purifying Respirators
a. Introduction
Any respirator is used because the concentration
of a contaminant is high enough to cause some type of health
effect. This may range from respiratory irritation through
systemic damage to death. The guidelines used to decide the need
for a respirator are the Threshold Limit Values. & concentrat ion
greater than the TLV requires respiratory protection. If the
concentration is within the concentration use limits of an air-
purifvina respirator, then that type mav be used. If it is
greater. then an atmosphere supplying apparatus must be worn.
Air-purifying respirators can be used only under
the following circumstances:
o The identity and concentration of the
contaminant are known.
o The oxygen content in air is at least 19.5%.
o The contaminant has adequate warning
properties.
o Approved canisters or cartridges for the
contaminant and concentration are available.
o The concentration does not exceed the IDLH.
Individuals who use air-purifying respirators must
wear a respirator which has been successfully fitted to their
faces. Most individual respirators will fit only 60% of the
working population. But with the variety of respirators
available, at least one type should be found to fit an
individual. An improperly fitted respirator delivers little of
the protection promised.
b. Reguirements for Respirator Selection
(1) Identification and Measurement
Before the appropriate air-purifying device
can be selected, the contaminant must be identified and measured.
This requires sampling and analysis. Selection of a device is
based on the highest possible concentration of the contaminant.
15 - 20
-------
Once a respirator has been selected and worn
in the contaminated environment, the atmosphere must be monitored
periodically. Otherwise, increased contaminant levels may
present a hazard the respirator is not capable of handling.
(2) Oxygen Content
The normal atmosphere contains approximately
21% oxygen. The physiological effects of reduced oxygen begin to
be evident at 16%. Without regard to contaminants, the
atmosphere must contain a minimum of 19.5% oxygen to permit use
of an air-purifying respirator. This is a legal requirement of
30 CFR Part 11 and a recommendation of ANSI Z88.2 - 1980. Below
19.5% oxygen, atmosphere-supplying respirators must be used.
(3) Warning Properties
A warning property is a sign that a cartridge
or canister in use is beginning to lose its effectiveness. At
the first such signal, the old cartridge or canister must be
exchanged for a fresh one. without a warning property,
respirator efficiency may drop without the knowledge of the
wearer, ultimately causing a health hazard.
A warning property can be detected as an
odor, taste, or irritation. Most substances have warning
properties at some concentration. A warning property detected
only at dangerous levels — that is, greater than TLV — is not
considered adequate. An odor, taste, or irritation detected at
extremely low concentrations is also not adequate because the
warning is being given all the time or long before the filter
begins to lose its effectiveness. In this case, the wearer would
never realize when the filter actually becomes ineffective.
The best concentration for a warning property
to be detectable is around the TLV. Table 15-4 lists odor
thresholds for a number of substances and their respective TLVs
(shown under the "adopted values TWA" column). For example,
toluene diisocsocyanate has a TLV of 0.005 ppm. The odor
threshold 2.14 ppm, is over 400 times the TLV, obviously not an
adequate warning property. An odor threshold of 4.68 ppm for
benzene, versus a TLV of 10 ppm, is an adequate warning property.
Dimethylformamide has a TLV of 10 ppm and an odor threshold of
100 ppm. An odor threshold 10 times greater than the TLV is not
adequate.
If a substance causes olfactory fatigue (that
is, the sense of smell is no longer effective), its odor is not
an adequate warning property. For example, upon entering an
15 - 21
-------
atmosphere containing hydrogen sulfide, the odor is quite
noticeable. After a short period of tine, it is no longer
detectable.
TABLE 15-4
Odof Thtaiholdt In Air »¦ Cwnpind la Threshold Limit Vilwi (1979)
Arfoptad Tan (¦(<«•
Vitot Valuaa
TWA STIL
b*mpim4 m** Mw DncWpdan fpm m§/m ppm m|/m]
AtMUiMt
0.21
6rm >«M
100
190
ISO
zzg
AmiIimM
1.0
Saur
10
29
19
37
Matmm
100.0
ClMmil iwttl. pvn^ant
7(0
1790
1000
237S
Act «Ma
an
lurnt mm turret*
at
029
0.3
0
Avytanitrila
2M
Ontan-garHc »u»«t«i«y
<•>
ANHCMarida
0*7
GfHc aniaw fgn(«ncy. ytw
1
2
2
9
AmImAmM
0.047
FW»r
10
If
—
—
Amtm. mawamatful
0.021
Fhfir. pwiee*
—
—
-
Amliii, TriMOKd
0.00021
W«hy. pimf m
—
—
—
—
Awiiwwla
49.9
Pwnfa**
29
19
39
37
AjmILm
1.0
PimtaM
2
10
9
20
liimwi
ill
10M
—
' —
_
0.047
•WW*
1
9
—
_
.MliNlMt
0.0021
Suffldy
—
—
—
—
Oramfcw
0.047
ftaacfi rung**
0.1
a7
0.3
2
IwittOmW
0.001
Savr
—
—
_
•
a2t
ViiwMiM
10
30
_
ClfttA WvmMivMv
lehNHiwile* «l CS4'
21.4
l«M punfant
SIM
30
20
12J
khWiwiw af CtU
100.0
CMMt
0.047
1«M
—
—
_
CNtHiw
asu
BUmK iiurgim
1
2
3
9
Ww ill >IiwwiiiM»
49.9
Amina. fcumt a*y
10
»
19
SO
ObMtfiy"arflM«ni#t
1000
n*hr. JvfifwW
10
30
20
SO
OinwtM (wIMa
0.001
VafaaMatutfM•
_
_
_
(pvrfum* ftdd
ai
_
—
—
—
Olptivnyl nHUl
aoo*7
Burr* rnbbTf
—
— -
_
—
trtwnat lrr"ih«def
1010
tnill
—
—
_
_
fiMMnMw
0.00047
Mat iriaarit, aanhv
1
20
29
too
ftM mmniw
0.001
Cant*. auMldy
0.9
1
2
3
FwmeidehHe
1.0
Hay (W m llll||yn|ii<
310
2
—
—
Hr*racMartc *4d «aa
iao
•.
•
_
—
Mydrogan lUWi (fr«n Ni>fl
0.0047
(nrnMa
10
19
19
27
IMnimi idM |M
0.000*7
-»
100.0
a-Mt
cMarida 1
MM 10p«"4
90
109
too
209
MllUjllw fWoMl
214 0
100
390
900
1700
MatfM «ttM IMM
iao
200
S90
300
999
mmm
a4t
100
410
129
910
Mthyl win—IW
0.0021
Suffdy.
as
1
—
—
m«m wwimn'w
0.21
him«in mnmv
100
410
129
910
wwhln^iwiiM
a2i
wwwwin inpn vm
_
•
_
..
. MkMnnt
0.0047
Shaa paflan.
1
9
2
10
0.001
Tar-Mai »w«a«
—
—
—
..
famiw
a47
(¦Ml
—
—
—
fw«Miw»nkiw
4.M
CWartwatad «a*»a«i
too
970
ISO
1000
MM
15 - 22
-------
TABLE 15-4 (cont)
Odor thratholrfa In Air ¦< Comp»r»d to Thrathold limit Vatuvi (11791 (eon'tf
Adoa9*erlptba
W"
ml/M1
ppm
mf/mf
«anal
6.047
tffefidnsl
1
1*
to
38
1.0
tUHM
0.1
04
¦ —
^NpMnt
0031
bniawy. mwataftf
03
04
t
I
*idim
0031
lunH. pvnf*. lamina
•
IS
to
30
r«ana NAM
0.1
SahwntV. ruMery
rrtxa MMiiMa4
0.047
Safcanfv. rubbery, phslkr
•0
311
too
jl!u» ir
_
_
>trltm anal»
3.14
M «4fca<«4 band«|a. mm am
0.000
0.04
003
0 IS
•cffaraatMana
114
to
170
ISO
•OS
I Human tmiiSu6*itnct matnM li l«a»a ea»t
-------
also considered IDLH. If the concentration is at an IDLH level
for any reason, and still within the use limits approved for the
cartridge, no air purifying respirator can be worn. only an
approved positive pressure self-contained breathing apparatus is
.allowed.
c. Types of Air-Purifvinq Devices
Basically, respiratory hazards can be broken down
into two classes: particulates, '• and vapors and gases.
Particulates are filtered by mechanical meanst while vapors and
gases are removed by sorbents that react chemically with them.
Respirators using a combination of mechanical filter and chemical
sorbent will effectively remove both hazards.
(1) Particulate-Removing Filters
Particulates can occur as dusts, fumes, or
mists. The particle size can range from macroscopic to
microscopic, and their toxicological effects range from severe or
innocuous. The hazard posed by a particulate can be determined
by its TLV. A nuisance particulate will have a TLV of 10mg/m3,
while a toxic particulate may have TLV well below 0.05 mg/m3.
Mechanical filters are classified according
to the protection for which they are approved under schedule 21C
of 30 CFR Part 11. Most particulate filters are approved only
for dusts and/or mists with TLV's equal to or greater than 0.05
mq/m3. These dust are usually considered to produce
pneumoconiosis (chronic fibrous reaction) and fibrosis, but are
not toxic. Such filters have an efficiency of 80-90% for 0.6
millimeter (mm) particles.
Respirators approved for fumes are more
efficient, removing 90-99% for 0.6 mm particles. This type of
respirator is approved for dusts, fumes and mists with TLV's
equal to or greater than 0.05 mg/m3.
Finally there is a high efficiency filter,
which is 99.7% effective against particles 0.3 microns in
diameter. It is approved for dusts, mists and fumes with a TLV
less than 0.05 mg/m3.
Mechanical filters load up with particulates
as they are used. As they do they become more efficient, but
also become more difficult to breathe through. When a mechanical
filter becomes difficult to breathe through, it should be
replaced.
15 - 24
-------
(2) Vapor- or Gas-Removing Cartridges
Sorbents are manufactured to remove a
specific chemical or group of chemicals. In contrast,
particulate removing filters remove particulates regardless of
their composition. Sorbents are available to remove specific
organic vapors, acid gases, and ammonia, among others. Each
sorbent has a maximum concentration use limit for that specific
contaminant. Once a sorbent has been filled up with the
contaminant, it will "break through" — that is, it will allow
the full ambient concentration of the contaminant to enter the
facepiece. Again, in contrast, particulate-removing filters
become more efficient (but harder to breathe through) as they
fill up. There is no breakthrough.
Chemical sorbents also vary in their ability
to remove contaminants (Table 15-5). For example, vinyl chloride
takes only 3.8 minutes to reach a 1% breakthrough — that is, for
1% of the ambient concentration to enter the facepiece. in
comparison, it takes 107 minutes for chlorobenzene to reach 1%
breakthrough. Thus, chlorobenzene is removed much more
efficiently than vinyl chloride. Cartridge efficiencies should
also be considered when selecting air-purifying respirators.
Studies of cartridge efficiencies are referenced in the Appendix
at the end of this manual.
15 - 25
-------
TABLE 15-5
Effect of Solvent vapor on Respirator Cartridge Efficiency*
Time to Reach It Breakthrough (10 ppnf
Solvent Minutes2
Aroma ties
Benzene 73
Toluene 94
Ethyl benzene 84
m-Xylene 99
Qjnene 81
Hesitylene 86
Aleohols^
Methanol 0.2
Ethanol 28
Isopropanol 54
Allyl alcohol 66
n-Fcopanol 70
sec-Sutanol 96
Butanol US
2-Methoxyethanol 116
Zsoanyl alcohol 97
4-Methyl-2-pentanol 75
2-Ethoocyethanol 77
Amyl alcohol 107
2-Ethyl-l-butanol 76.S
Monochlorides^
Methyl chloride 0.05
Vinyl chloride 3.8
Ethyl chloride 5.6
Allyl chloride 31
1-Chloropropane 25
1-Chlorofcutane 75
Chlorocyclopentam 78
Qilorobenzene 107
1-Oilorohexane 77
o
-------
TABLE 15-5 (cont)
Time to Reach II Breakthrough (10 ppm)
Minutes 2
Solvent
Trichlorides3
Chloroform 33
Methyl chloroform 40
Ttichloroethylene 55
1.1.2-Trichloroethane 72
1.2.3-Trichloropropane ill
Tetra- and Pentachlorides3
Carbon tetrachloride 77
Perchloroethylene 107
1,1,2,2-Tetrachloroethane 104
Pantachloroethane 93
Acetates3
Methyl acetate 33
Vinyl acetate SS
Ethyl acetate €7
Isopropyl acetate 65
Isopropenyl acetate 83
Propyl acetate 79
Allyl acetate 76
sec-Duty 1 acetate 83
Butyl acetate 77
Xsopentyl acetate 71
2-Methoacyethyl acetate 93
1,3-OiflethyLbutyl acetate 61
Aityl acetate 73
3-gthuxyelhyl acetate 80
Hexyl acetate 67
Kfetoma 4
Acetone 37
2HButanen« 82
2-Pentanone 104
3-Pentanone 94
4-Methyl-2-pentansne 96
Mssityl oxide 122
Cyclopentanone 141
3-Beptanone 91
2-Heptanone 101
Cyclohexanont 126
5-Methyl-3-heptanone 86
3-Methy Icyc lohesanone 101
Dlisobutyl ketone 71
4-Methylcyclchexanone 111
15
- 27
-------
TABLE 15-5 (cont)
Time to Reach It Breakthrough (10 pcm)
Solvent in Minutes2
Alkanes4
Pentane 61
Hexane 52
Methylcyelopentane 62
Cyclohexane 69
2,2,4-ltirnethyl pentane 68
Heptane 78
Methylcyclohexane 69
5-Ethy 1 idene-2-norbornene 87
Nonane 76
Decane 71
Amines4
Methyl amine 12
Ethyl amir* 40
Isopropyl amine 66
Propyl amine 90
Diethyl amine 88
Butyl amine 110
Triethyl amine 81
Dipropyl amine 93
Diisopropyl amine 77
Cyelohexyl amine 112
Oibutyl amine 76
Miscellaneous materials4
Aczylonitrile 49
Pyridine 119
1-Nitropropane 143
Methyl iodide 12
Dibromomethane 82
1,2-Oibromoethane 141
Ate tic anhydride 124
Bromobenzene 142
1 Nelson* G.O., end C.A. Harder. Respirator Cartridge
Efficiency Studies* University of California* Liventere. 1976.
2 Cartridge pairs tested at 1000 ppm* 50% relative humidity* 22°
C* and 53.3 liters/minute (equivalent to a moderately heavy work
rte). Pair cartridges preconditioned at room temperature and 50%
relative humidity for at least 24 hours prior to testing.
~ Mine Safety Appliances Cartridges.
4 American Optical Cartridges.
15 - 28
-------
Chemical sorbent cartridges and canisters
have an expiration date. They may be used up to that date as
long as they were not opened previously. Once opened, they begin
to absorb humidity and air contaminants whether or not they are
in use, and their efficiency and service life decrease. A
cartridge should be discarded after it is used.
Cartridges are selected for the particular
chemical they remove by a color coding system outlined in 29 CFR
19.0.135 (see Table 15-6).
TABLE 15-6
15 - 29
-------
d. Respirator Construction
The facepiece is one of two major components of an
air-purifying respirator (the air-purifying device being the
other). Essentially four types of facepieces and devices may be
used:
o Half-mask with twin cartridges,
o Full-face mask with twin cartridges,
o Full-face mask with chin-mounted canister,
and
o Full-face mask with harness-mounted canister
(gas mask).
The facepiece is the means of sealing the
respirator to the wearer. Attached to the facepiece is the lens
(in the case of the full-facepiece) and the suspension for
holding the mask to the face. An adapter is attached to the
cartridge or canister. With the adapter and the mask is an
inhalation check valve, which prevents exhaled breath from coming
back through the cartridge or canister. An exhalation valve
permits the exhaled breath to be exhausted and prevents air from
entering it during inhalation. Some respirators provide an
integral speaking diaphragm which is air tight. Each respirator
has different ways of assembling and attaching parts. This
prevents hybridizing two different makes into one, which
immediately voids its approval.
The recommended facepiece to use with cartridges
or canisters is the full-facepiece. It provides eye protection,
is easier to fit, and has a Protection Factor of 100X. The half-
mask has a Protection Factor of 10X. Cartridges and canisters
used in conjunction with the full-facepiece vary mainly in the
sorbents and the concentration of atmospheric contaminant that
can be removed. (See Tables 15-7a and 15-7b at the end of this
unit.)
Organic vapors can be removed by appropriate
cartridge, chin canisters, or the larger harness-mounted
canisters. Cartridges are approved for use in atmospheres up to
1,000 ppm (0.1%) of organic vapors, chin style canisters up to
5,000 ppm (0.5%), and harness-mounted canisters up to 20,000 ppm
(2.0%). Keep in mind that no air-purifying device is permitted
in IDLH atmospheres. Using a cartridge or canister at lower
concentrations effectively increases its service life.
The wearer should be familiar with the respirator
to be used. The parts should be easily identified by function,
which also is important in maintenance and cleaning.
15 - 30
-------
e. When to Use an Air-Purifvinq Respirator
Air purifying respirators mav be used under the
following conditions:
o The concentration of oxygen in the hazardous
atmosphere is known to be 19.5 percent or
more (but not more than 25 percent); and
o The concentration of airborne toxic material
is not immediately dangerous to life or
health; and
o The concentration of airborne toxic material
does not exceed the capacity of the filter or
cartridge/canister unit as marked on the unit
or the respirator approved; and
o The airborne toxic material does have
adequate warning properties (irritation or
odor) to signal failure of the
cartridge/canister or filter unit. Some
materials which do have adequate warning
properties are ammonia, chlorine and sulfur
dioxide.
2. Air Supply Respirators
Air supply respirators provide from five minutes to
several hours of breathing air. The amount of protection
provided is based on two factors: the type of facepiece, and its
mode of operation. The full-face mask provides the best
protection. Of the three modes of operation — continuous,
demand, and pressure-demand — the pressure-demand mode provides
the best protection.
a. Modes of Operation
(1) Continuous
In the continuous mode, air is constantly
flowing to the respirator user, usually from an air compressor or
compressed air tank. The flow must be regulated so that the, user
gets as much air as he needs.
(2) Demand
In the demand mode, a negative pressure is
required inside the facepiece to open a valve and permit air to
enter the respirator. The negative pressure may draw
contaminated air through any gaps in the facepiece-to-face seal.
This mode uses less air than the continuous mode.
15 - 31
-------
(3) Pressure-demand
The pressure-demand mode establishes a
positive pressure inside the facepiece. Any leaks around the
facepiece allow good air to enter from the tank. It continues to
flow until a high positive pressure is built up by exhaling.
When the internal pressure drops, more good air is admitted.
Some positive pressure is always present inside the facepiece.
This mode also conserves air because with a proper seal only the
air that is exhaled is replaced.
b. Types Of Devices
On the basis of construction, there are four types
of atmosphere-supplying respirators: oxygen-generating, hose
mask, airline, and self-contained breathing apparatus.
(1) Oxygen-generating
The oldest respirator is the oxygen-
generating respirator, which utilizes a canister of potassium
superoxide. The chemical reacts with exhaled C02 and water vapor
to produce oxygen. Oxygen generating respirators have been used
in the military and for escape purposes in mines.
(2) Hose mask
The hose mask uses a maximum 75-foot long,
large-diameter hose to transport clean air from a remote area.
The user breathes the air in, or it is forced in by a blower.
The user can over-breathe this source.
(3) Airline Respirators
The airline respirator is similar to the hose
mask, except that the air is compressed. The mode of operation
may be any one of three previously described. The air source
must not be depletable. No more than 300 feet of airline is
allowed.
(4) Self-contained Breathing Apparatus
The self-contained breathing apparatus (SCBA)
allows the wearer to carry a cylinder of compressed air or oxygen
without the restriction of a hose or airline.
Depending upon the source of air, the SCBA
can be either open or closed circuit. Closed-circuit devices mix
pure oxygen from a small cylinder with exhaled breath (C02
removed) to provide breathing air. This type of device, also
referred to as a rebreather, is approved only as demand-type
respirators.
15 - 32
-------
Open-circuit SCBA's are approved as either
demand or pressure-demand. Demand SCBA's are being phased out of
production because of the greater protection afforded by
pressure-demand apparatus.
An escape SCBA must have at least five
minutes of breathing air stored in a small cylinder or coiled
stainless steel tube. Some devices on the market have 15 minute
air supplies.
Under no circumstances are escape devices to
be used for entry into hazardous atmospheres.
(A) Modes of Operation of the SCBA
(i) Demand
In the demand mode, a negative
pressure is created inside the facepiece and breathing tubes when
the wearer inhales. This negative pressure draws down a diaphragm
in the regulator in an SCBA. The diaphragm depresses and opens
the admission valves, allowing air to be inhaled. As long as the
negative pressure remains, air flows to the facepiece.
The problem with demand operation
is that the wearer can inhale contaminated air through any gaps
in the facepiece-to-face sealing surface. Hence, demand
apparatus is assigned a Protection Factor of only 100, the same
as for a full-face air purifying respirator.
(ii) Pressure-Demand
An SCBA operating in the pressure-
demand mode maintains a positive pressure inside the facepiece at
all times. The system is designed so that the admission valve
remains open until enough pressure is built up to close it. The
pressure builds up because air is prevented from leaving the
system until the wearer exhales. Less pressure is required to
close the admission valve than is required to open the spring-
loaded exhalation valve.
At all times, the pressure in the
facepiece is greater than the ambient pressure outside the
facepiece. If any leakage occurs, it is outward from the
facepiece. Because of this, the pressure demand SCBA has been
assigned a Protection Factor of 10,000.
15 - 33
-------
(B) Types of SCBA Apparatus
(i) Closed-Circuit
The closed-circuit SCBA, commonly
called the rebreather, was developed especially for oxygen-
deficient situations. Because it recycles exhaled breath and
carries only a small oxygen supply, the service time can be
considerable greater than an open-circuit device, which must
carry all of its breathing air.
The air for breathing is mixed in a
flexible breathing bag. This air is inhaled, deflating the
breathing bag. The deflation depresses the admission valve,
allowing the oxygen to enter the bag. There it mixes with
exhaled breath, from which carbon dioxide has just been removed.
Most rebreathers operate in the
demand mode. Several rebreathers are designed to provide a
positive pressure in the facepiece. The approved schedule 13F
under 30 CFR Part 11 for closed circuit SCBA makes no provisions
for testing "demand" or "pressure-demand" rebreathers. The
approved schedule was set up to certify only rebreathers that
happen to operate in the demand mode. Thus, rebreathers designed
to operate in the pressure-demand mode can be approved strictly
as closed-circuit apparatus. Since regulations make no
distinction, and selection is based on approval criteria,
rebreathers designed to maintain a positive pressure can only be
considered as a demand-type apparatus.
Rebreathers use either compressed
oxygen or liquid oxygen. To assure the good quality of air to be
breathed, the oxygen must be at least medical grade breathing air
which meets the requirements set by the "U.S. Pharmacopeia."
(ii) Open-Circuit
The open-circuit SCBA requires a
supply of 21% oxygen and 78% nitrogen breathing air. The user
simply inhales and exhales. The exhaled air is exhausted from
the system. Because the air is not recycled, the wearer must
carry the full air supply, which limits a unit to the amount of
air that the wearer can carry easily. Available SCBA's can last
from five to 60 minutes. Units which have 5-to-15 minute air
supplies are only applicable to escape situations. The wearer
must have at least 30 minutes of air to enter a hazardous
atmosphere.
The air used in open-circuir
apparatus must meet the requirements in the Compressed c i ;
Association's Pamphlet G-7.1, which calls for at least "Grade D."
Grade D air must contain 19.5 to 23.5% oxygen with the balance
15 - 34
-------
being predominantly nitrogen. Condensed hydrocarbons are limited
to 5 mg/m3, carbon monoxide to 20 parts per million (ppm) and
carbon dioxide to 1,000 ppm. An undesirable air is also
prohibited. Air quality can be checked using an oxygen meter,
carbon monoxide meter, and detector tubes.
(C) When to Use an SCBA
Air supplying respirators must be used
to be sure of adequate protection when one of.these five special
conditions exists or may reasonably be expected to exist:
(i) the concentration of oxygen in the
hazardous atmosphere may have been reduced from the normal
concentration of about 21% to 19.5% or less; or
(ii) the concentration of airborne toxic
material exceeds a concentration which would be immediately
dangerous to life or health; or
(iii) the concentration of airborne toxic
material exceeds the limited ability of the filter or
cartridge/canister unit, as marked on the unit or the respirator
approval; or
(iv) the concentration of airborne toxic
material is not known to be less than the limited ability of the
filter or cartridge/canister unit, as marked on the unit or the
respirator approval; or
(v) the airborne toxic material does
not have adequate warning properties (irritation or odor) to
signal failure of the cartridge/canister or filter unit. Some
examples of materials which do not have adequate warning
properties are methyl bromide, dimethylformamide and phosgene.
6. CLEANING, INSPECTION AND STORAGE OF RESPIRATORS
Obtaining dependable protection from respirators requires
cleaning, inspection and storage to maintain them and prevent
damage or deterioration.
1. Cleaning
Respirators must be cleaned and disinfected after each
day*s use and more often if necessary. They must be cleaned and
disinfected before they are used by another person.
In general, the cleaning procedure is to disassemble
the respirator (without using tools), wash the facepiece and
breathing hoses in cleaning and sanitizer solution mixed in warm
water, rinse completely and dry in a clean area.
15 - 35
-------
Most respirator manufacturers distribute cleaner-
sanitizer material for cleaning their equipment. A mild
detergent will usually do a satisfactory job, either with or
without a mild bactericidal agent.
2. Inspection
Part of the maintenance of respirators is regular
inspection. Respirators must be inspected during cleaning, and
worn or deteriorated parts must be replaced. Each person using a
respirator should inspect the respirator before each use to be
sure that it is in working condition.
Respirators for emergency use must be inspected after
each use, and at least once a month between uses.
3. Storage
Storage for respirators must be in a convenient, clean,
and sanitary location, or in a container which will keep them
clean. If they are packaged in tight plastic bags and
transported on field trips, protect the bag from being abraded or
punctured. The respirators should also be protected against
temperature extremes and exposure to direct sunlight for
prolonged periods.
H. TRAINING REQUIREMENTS FOR RESPIRATORY PROTECTIVE EQUIPMENT
EPA standards require six hours of initial training for
users of respirators, and two to four additional hours annually
after the initial training. Records of training and fit testing
of employees are to be maintained by the supervisor.
Safe use of respiratory protective equipment depends on
thorough training. Every employee who may use a respiratory
needs to know: when it is needed, which type is needed, and the
capabilities and the limitations of the equipment for specific
exposures.
Every user of respiratory protective equipment needs to
learn how to put on the equipment to be used, how to adjust it
for a comfortable fit, and how to test the seal between the
facepiece and the face to see that the equipment fits tightly
enough to provide needed protection.
In addition, every user needs to have the opportunity to
wear the equipment in normal air for a period of familiarization,
and then to wear the equipment in a test atmosphere.
15 - 36
-------
The final selection of respirator type is based on a number
of factors including the protection factor (PF), the Threshold
Limit Value (TLV), the Immediate Danger to Life and Health (IDLH)
and Agency Policy. The condensed charts in Tables 15-7a and 15-
7b on the following two pages will provide some assistance in
helping field crews select the proper respirator type.
15 - 37
-------
TABLE 15-7a
Selection of Respirators for Emergency or Short-Term Use
on ihc Baiis of Haxsrd and Expected Concentration (Cues and Vapors)
Twboty Expected Concentrations of Gases or Vapon
Two to fl««
Fl*« to tea
Above tai
Oaygen deft-
(ton TLV or
times TLV'or
(fane* TLV or
doxy, emer-
op le 1000 ppm
1000-3000
3000-20,000
gency or abovt
ppm
ppm
20,000 pp«n
Law
So respiritor,
Canister cm
Cuiistv pi
Self-contained
or chemical
muk
mask or sir*
air or o«nm
cutridie needed
dm rapin(ar
Medtrata
Otemicai cm-
Canister p*
Air-iim or
Self-contained
trid«o
mask or air*
setf-conuinod
airor o«rtca
line respirator
ttf Of 0l^|0l
H!«b
Caftisto' pa
Air-line ro>
Seif-eontsincd
Self-contained
muk
piratar
air or oxyfea
air or osyscn
Nora:
(1) TLV nftn lo the TlnMd LMt Valwi for a nntv of nhuira pwWisM bf
the Ananas Conference of OuMiiaiNwal (adoBrial H) puiu (ne Saiian ( and
¦etionlQ.
(2) Sao Settfw I and X far a diseunran of (artery rump and (Mr rtktioa w TLV.
(J) Winn am void* We condition! Mcsawte wig rtspffiton for long* p«Sods (tbe*
I how), om equipment in a Mgiw pwteuiw cauporr than thoim tbam.
(4) SubfBt to BnaiiationfTaMoLt), hoa»qrparvpirator»may bemdia ptaceof ait
15 -
38
-------
TABLE 15-7b
Selection of Respirators for Emergency or Short-Term Uie
on th« Bui* of Haxird and Expected Concentration (Particulates)
Toxicity
Expected Concentrations of Particulate Metier
(Dusts, Fumes and Mtsu)
Two to Ave
Five to twenty
A bo>a twenty
Oxygen defl-
timet TLV
timet TLV
times TLV
eieni, craer-
lency. highly
conceive
Law
Respirator aot
Fitter
Filter or air-
Whseopo-
nullify needed
tine rapirator
rare it to
Filter or air*
eunmety
Moderate
Filter
Air- line or
con BMW
or Higfe (ton-
liae respirator
self-contained
dusts or to
icity no
ear or oxygen
dusts ia ea
greater
oxypea defi-
tbaa lead)
cient atffloa-
phere, a self-
Extremely
Filter or air*
Air-One ra»>
Self-contained
contained eir
High (toxicity
One respirator
ptraior
air or oajgut
or oxygen
¦renter
respirator
Uiaa tad)
must be used.
(1) TLV rtftn to tlie Threefold Llofc Valuae for a man bar of mbnence* pabiished br the
Amnion Cwfeew of Gum iiwwal [aduariai Myperaett (Sections I, t2).
(2) See Sactiorn I and 2 for • diaeuniaa of loudly ratine end their relation io TLVt
(3) Expvted concmrat ions of particulate matter ha* ben itova enlr ee multiples of the
threshold limit value*. When then veiuee «rt not available, the Mlowinf concentrations
mar be oed ee a foide:
MfanlDw
2 to J (TLV) opto JOmppcf*
iioSCTLV) JO io 1000 mppcf•
Above 20 (TLV) above 1000 mppcf*
(4) Wfcea enevoidable conditions aaentan u»n« itiimon for tofifs period* (above I
how),
-------
STUDENT EXERCISES
The following exercise has been developed to provide
practical axperiencs for field crew selection of respirator and
cartridge type. Students shculd refer to charts and tables found
in the unit.
An EPA crew has been sent to a now defunct solvent recycling
company. A number of samples from a variety of environments must
be taken. Determine the respirator type, cartridge if
applicable# and rationale used for each selection.
I. Building A
Building A was used for storage and recyling of the
nonchlorinated solvent acetone. Air monitoring indicates the
oxygen level to be 20.lt, with the LEX. for acetone at .30 or 301.
A. Air-purifying type respirator (rationale)
B. Cartridge type (rationale)
C. Bqpected breakthrough tine (rationale)
0. PF of type selected
E. Maximum ppm this respirator is good for
Calc.
F. Degree of warning properties - odor
G. Air-supplyuing respirator (rationale)
II. Building B
Air monitoring indicates ammonia to be present at SO ppm,
oxygen to be 19.8%.
A. ___
B .
C. '
15 - 40
-------
D.
E .
F .
G .
H .
IZ. Building C
Air monitoring indicates perchlorothylene at 93 ppm, oxycen
at 19.0t.
A .
B .
C .
D .
E .
P.
G .
H .
15 - 41
-------
UNIT 16
INSPECTION AND SAMPLING IN INDUSTRIAL PLANTS
A. INTRODUCTION
EPA field personnel who do inspection and sampling in
industrial plants will have to enter different types and sizes of
plants with a wide variety of potential hazards. The length of
exposure to such hazards may vary depending on whether you are in
the plant for a brief walk-through inspection or whether you are
there for a detailed inspection or a 24-hour sampling program.
To accomplish your job safely, you and other crew members
will need to know what type of hazards may exist in the plant,
how to protect yourselves from these hazards, what special safety
equipment you may need to take with you, and what to do in case
of an emergency that may result from you sampling activities or
from plant operations.
The main emphasis of this unit is on finding out as much as
possible about plant hazards before you visit, planning your
safety procedures, and gathering and taking with you all of the
safety equipment you may need.
B. HAZARDS AND PRECAUTIONS IN INDUSTRIAL PLANTS
As you prepare for inspection or sampling in an industrial
plant, it is important to know as much as possible about the
types of hazards that you may encounter there.
If you have been in any type of factory you realize there
are the usual hazards of machinery, conveyors, moving vehicles,
hot pipes electrical equipment, solvents and chemicals..
This section will describe details of some of the hazards
that you may find in industrial plants, as well as some special
precautions that may be necessary. This is only a partial list
of possible hazards, a brief summary of some problems that you
may face in an industrial plant. In all likelihood you will
encounter others and will have to define them and find out what
precautions are needed.
Adequate preparation for sampling and inspection includes
recognition of hazards along the route to the sampling site and
at the site, as well as hazards which are above or below the
sampling area where they may endanger the crew. In addition to
identifying these "usual" hazards, thorough preparation requires
recognition of hazards which can occur to cause an unusual, large
scale incident.
16-1
-------
1. Working Alone
Working alone can be dangerous if the person working
alone has safety problems, is hurt or is in an area of the plant
which has an unexpected fire or chemical emergency. It is always
best to visit or sample at a plant site with another person.
When this is not possible, it is important to establish
communication or a system of checking regularly with someone else
in the crew or in the plant.
2. Vehicles in Plants
When it is necessary to walk through plant areas, it is
important to follow designated aisles to avoid getting in the
path of moving equipment. Even within the proper walking areas
crew members must be especially alert for powered industrial
trucks and fork lifts which may travel the same aisles. Drivers
usually have a limited view of the passageways and may not expect
to encounter pedestrians.
It is particularly important to wear safety shoes or
boots in plants where there are heavy vehicles and moving loads.
Some plants with such hazards may not only require safety shoes
(to prevent toes from being crushed), but also instep protectors
(to protect the metatarsal arch).
a. Cranes
Overhead cranes which are carrying materials can
be a hazard because the crane operators may not be aware of
pedestrians in the working area and may not be able to see you if
you walk into the path of a moving load. These cranes may be
located inside a plant as well as outside.
Gantry cranes can also be a serious hazard if you
need to work near one of the crane rails. Gantry crane operators
have a limited viewing area from the cab of the crane and they
are not able to see anyone in a position close to the crane
rails.
Anyone who gets caught in the narrow clearance
between a gantry crane and the supporting structure is almost
certain to be crushed.
b. Trains
Trains in an industrial plant can be a hazard,
particularly if the train is remotely-controlled and the operator
cannot see you. If it is necessary to pass in front of any
train, even a stopped one, you should do so at with at least
seventy-five feet of clearance. Never walk between railroad
cars. Trains may start to move without giving any signal.
16-2
-------
3. Noise
Noise from industrial machinery and processes can
interfere with verbal communication and can cause temporary
hearing loss. Repeated or prolonged exposure to excessive noise
can cause permanent hearing loss.
Ear plugs or ear protectors should be used to prevent
both temporary and permanent hearing loss. (Use of ear plugs or
protectors can actually improve the ability to hear voice
communication in noisy areas because they attenuate interfering
frequencies much more than voice frequencies.)
If the work area is extremely noisy and verbal
communication is difficult, you may need to use ajradio, visual
signals or a horn to communicate™
4. Thermal Hazards
Sampling crews may encounter five types of thermal
hazards in industrial plants: heat stress from ambient exposures
and work activities, hot production or process equipment, hot
materials, hot samples and high-pressure steam.
a. Heat Stress
Sampling personnel can be affected by heat stress
from:
o radiant energy from hot equipment
o high ambient temperatures
o protective clothing that prevents evaporative
cooling
o strenuous exertion in activities such as
lifting or climbing
Since the effects of heat can be very serious, it
is important to recognize exposures which may cause heat stress,
take preventive measures to control the stress, and be prepared
to recognize and treat the effects if they occur. (See the unit
on heat and cold for further information.)
b. Hot Equipment
Many plants will have hot production or process
equipment and ducts or pipe lines with surfaces or discharges
which may be extremely hot. If it is necessary to work near such
heat sources, the hazards of burns can be reduced by wearing
insulating gloves and insulating or reflective clothing.
16-3
-------
c. Hot Material
Working in a plant which produces molten materials
can be hazardous if you are splashed or exposed to the radiant or
convection heat they produce, or if you have to move through
areas where such materials are conveyed or transported.
Taking samples from process lines can be hazardous
because of the heat at the sampling point, the heat of the
sample, and the possibility that the material to be sampled may
spurt from the sampling valve.
d. High-Pressure steam
Steam is used widely in chemical manufacturing
plants and it can be piped at a wide range of pressures and
temperatures. Steam and steam-heated lines and equipment are
obvious thermal hazards, but steam at high pressure can have
unexpected hazards because it may not be visible. For example,
many people have been severely burned by walking into a mass of
hot steam (from an accidental release) because they could not see
it and they had not heard the release. Super-heated high
pressure steam is clear, colorless and odorless, and does not
form an identifiable cloud of vapor. A massive release of high
pressure steam can remain in a large mass for some time after
release, and the mass can remain extremely hot.
High pressure steam is steam at 600 pounds per
square inch gauge pressure (psig). Saturated steam at 600 psig
is at a temperature of 486 degrees F or 252 degrees C.
Temperatures of superheated steam at 600 psig can range from 700-
1100 degrees F or 372-593 degrees C.
Because of the unexpected hazards of high pressure
steam, stay out of any plant area where a steam release has been
reported. Do not expect to see a cloud of steam where a release
has occurred, and do not feel it is safe to go into such an area
just because you do not see any evidence of steam.
5. Flammable Hazards
Since many chemicals and petrochemicals are highly
flammable, ignition sources should be carefully avoided during
sampling and handling of flammable samples.
Sources of ignition include matches, cigarette
lighters, burning tobacco, electrical switches, electrical
equipment, welding sparks and engines catalytic converters on
motor vehicles.
16-4
-------
It is important to find out if there are areas in a
plant where there nay be flammable concentrations of gases or
vapors and where sources of ignition are not permitted.
If extension cords, radios and electrically-powered
equipment used in sampling operations could spark, heat or
otherwise ignite flammable vapors and gases, such equipment must
not be used unless it can be modified or protected so that it
will be safe in such atmospheres. (For detailed recommendations
and procedures refer to the unit on fire and explosion hazards
and consult with Agency and plant safety personnel.)
Many plants do not allow employees or visitors to carry
matches or lighters with them in the plant to prevent anyone from
igniting flammable vapors or gases when lighting a cigarette.
6. Chemical Hazards
In addition to the chemicals you may be monitoring,
most plants will have many other chemicals which may be hazardous
in case of contact or inhalation. Such chemicals may be used
throughout the plant for cleaning, coating, treatinig,
fabricating, or formulating.
As long as toxic chemicals remain confined (within
bags, barrels, pipes, ducts, process equipment and other
containers), they will not be a hazard to you. However, as part
of your preparation for inspection and sampling in an industrial
plant you should find out whether large quantities of hazardous
chemicals are used or produced in the plant, by conducting a file
review.
Chemicals can become hazardous to you if they splash
from equipment or open vessels, leak from pipes or ducts, blow
into the air or spill out of containers or equipment. In some
large manufacturing plants, particularly in chemical plants,
there may be massive and unexpected releases or leaks of gases or
liquids which will require immediate emergency action on your
part.
Rubber boots should be worn when walking through
puddles or other areas that may be wet, particularly in chemical
plants, because liquids in the wet area may be corrosive or
otherwise harmful. While leather safety shoes and boots provide
protection against impact, they are not impermeable. Many
chemicals can pass through the leather and contact the skin.
Chemicals which corrode or penetrate leather and canvas footwear
may cause immediate injury, and they can cause delayed injury if
they cannot be removed from the material of the footwear. Some
chemicals such as nitriles cannot be cleaned from leather, and
once leather goods are contaminated they must be discarded.
16-5
-------
Any clothing which becomes contaminated should be
removed as soon as possible and cleaned or discarded. if any
material drips or splashes on your exposed skin, immediately wash
the material off your skin with copious amounts of water (to
avoid chemical irritation or other injury).
7. Weather conditions
If you are working outdoors, weather conditions can
affect your safety and health. Wind, rain, snow, ice, sun, and
temperature are likely to increase the hazards of your sampling
operation and the corresponding need for protective measures.
Wind can blow dust or chemical vapors toward you and
high winds can damage equipment and endanger any activity that
requires working at heights.
Direct sunlight, high temperatures, and strenuous work
can cause safety and health hazards separately and in
combination. For example, a long exposure to direct sunlight can
cause sunburn and can also heat metal to temperatures that will
burn unprotected skin. High ambient temperatures or direct
sunlight can cause samples to volatilize and pressurize sample
containers, with increased risks of leakage, container rupture
and exposure to the sample.
Rain, snow and ice are likely to increase the hazards
of walking, driving, and climbing outside. Moisture (from rain,
melted snow or ice) may short circuit electrical equipment and
increase the hazards from such equipment and from wires with
defective insulation.
Low temperatures may freeze lines and cause sampling
equipment to malfunction, and may interfere with safe performance
and the health of the crew.
Sampling personnel need to be aware of the symptoms of
frost bite and hypothermia, and wear warm, dry clothing to
prevent discomfort and any injury from cold. (See the unit on
heat and cold stress for more details.)
C. GATHERING INFORMATION TO PREPARE FOR PLANT VISITS
1. Using a Safety checklist to Record and Summarize
Information
The information you will need can be recorded by use of
a safety checklist. The benefits of a well organized safety
checklist are to help insure that necessary information is
obtained and to have a concise summary of information that may be
needed in case of emergency.
16-6
-------
Valuable information can often be gathered by reviewing
EPA files on previous inspections, by talking to other field
personnel who have inspected or sampled in the plant and by
talking to plant personnel who are familiar with plant hazards
and general precautions. They may be able to provide specific
information about hazards in plant areas where you will be
sampling or inspecting.
If it is possible to do a preliminary survey at a
sampling site before scheduling work, determine what hazards may
be present, what safety support may be available from the plant,
and what special protective equipment and clothing will need to
be provided for sampling personnel.
If no previous information is available, evaluation of
process and site conditions will be necessary to identify
equipment needed to protect test personnel, monitor exposures,
facilitate tests, and communicate for routine testing and
emergencies.
2. Access to Sampling Sites
If detailed information about sampling sites can be
obtained before going to the plant (or during a preliminary
survey), it will be easier to assure that all necessary sampling
and safety equipment will be taken to the site for access.
Equipment may include personal protective equipment and equipment
that may be needed to transfer sampling equipment and/or
personnel (such as rope, slings, harnesses, baskets, or carts.)
Many sampling sites are difficult to reach. They may
be surrounded by hot pipes or be located at the top of a tower or
in the middle of a muddy, untraveled field. Special equipment
may be needed to take samples adequately and safely.
3. Exposure Monitoring
Try to find out if the plant has monitored employee
exposure to chemicals produced or used at the plant site. This
information may be useful in determining what respiratory
protection is needed by sampling crews and whether exposures
should be monitored.
4. Information on Plant Layout and Processes
Before entering a large industrial plant, find out as
much as possible about the plant layout and processes, and any
unusual hazards in the plant. Find out if there are exposed high
voltage lines, high temperature or toxic gas streams, flammable
atmospheres, or remote-controlled equipment operating in areas
where the team will be walking or working.
16-7
-------
Plant layout or site maps should be obtained if they
are available, or the necessary information on process flow
should be sketched to show the flow of fluids and gases in pipes,
tanks, and reactors. Process flow information is essential for
determining sampling points and for understanding the nature and
hazards of the samples to be taken.
Sampling is often done when plant production is high
and emissions may be the greatest. During the pre-sampling
survey, or early in the initial visit, a member of the sampling
crew should determine or estimate the most extreme conditions
that might occur during sampling and should alert sampling
personnel so that they can be prepared.
5. Personal Protective Equipment
In addition to the safety apparel and safety equipment
that you need for protection from the hazards of you own sampling
operations, it is important to have personal protective equipment
for the hazards you may encounter in a manufacturing plant. Some
of these hazards, as we pointed out earlier, occur under normal
operating conditions, and some may occur suddenly in case of
plant emergencies. Preparation before the visit is essential so
you can take with you all the protective equipment and apparel
you will need to work safely.
6. Plant Emergencies
Most plant safety rules require all visitors and
employees to wear certain personal protective equipment in the
plant. The minimum required is usually a hard hat and safety
glasses. (Many plants will have hard hats and non-prescription
safety glasses available to lend to visitors who are unprepared.)
Some plants require safety shoes or other safety footwear.
Many plants have areas where additional protective
equipment is required. For example, cover goggles or face
shields are often required where corrosive chemicals are handled
and respirators may be required in areas where chemicals are
loaded and unloaded.
Many industrial plants do not allow contact lenses to
be worn in the plant. Some allow contact lenses when cover
goggles are worn over them. Contact lenses should generally not
be worn when the wearer is exposed to chemical fumes, or vapors
or might be splashed.
7. Special Requirements for Sampling
Personal protective equipment should be taken to
plant in preparation for the potential hazards which may
encountered and for the types of work which will be done. For
16-8
-------
example, splash protection apparel will be needed in case of
exposure to corrosive liquids and respiratory protection will be
needed for concentrated exposures to dust, fumes, vapors, and
gases.
Since sampling personnel will frequently be closer to
sources of concentrated exposure for longer periods and under
more adverse conditions than plant personnel, sampling personnel
will probably need more protection than plant personnel normally
use.
D. PLANT EMERGENCIES
Emergencies during sampling operations in an industrial
plant may be either of two types: an emergency that results from
plant operations, and an emergency that results from sampling
operations. If you observe either type of emergency, you need to
know how to communicate the emergency to the plant (pull an alarm
or use a phone) and how to get help where you need it.
In both types of emergencies you need to know how to react
to the emergency. Emergencies resulting from sampling operations
are likely to be relatively minor but plant emergencies can be
large-scale and very serious. In a plant-wide emergency, the
sampling crew needs to know the plant emergency signals and what
to do (when to run, which way, how fast, and where).
1. Emergency Signals
Industrial plants usually have an emergency alarm that
consists of both audible and visual alarms such as colored
flashing lights. Often these alarms are coded so that
information about the nature and location of the emergency is
identified.
For example, fire and spill alarms are often sounded
with an air horn, with the blasts on the horn grouped to give
code for the location. A signal with two blasts, followed by a
pause and five blasts, would indicate Code 2-5, which would mean
that the emergency was in the Loading Building. A long blast may
mean "All Clear," and repeated long blasts may mean "Evacuate."
Other alarms could be given by means of bells, or whistles, or
different kinds of horns.
2. Emergency Procedures
If a plant-wide emergency occurs while you are sampling
or on the site, follow plant safety guidelines for emergency
procedures. Normally, all smoking material should be
extinguished and motor vehicles in the plant should pull over and
stop. Visitors and employees should assemble at the checkpoint
16-9
-------
location designated for their area and wait there to receive
further information on whether additional emergency action is
needed( such as evacuation.
If you are in an area that must be evacuated because of
a spill or release of toxic material, you should evacuate at
right angles to the wind, or upwind of the incident. Never go
downwind of any accident or spill.
There are several ways to determine the direction of
the prevailing wind: by observation of a wind sock or a flag, or
by observation of smoke plumes or vapor clouds. Buildings and
other obstructions create eddy currents which may make it very
difficult to tell which way the wind is blowing. It is important
to look above the buildings and other structures to try to see a
flag or vapor cloud which will show you which way it is blowing.
If it is necessary to evacuate the area of the plant in which you
are working, it will be important that all crew members meet at a
pre-arranged location so that you can be sure that everyone did
get out of the area and is safe.
If it is not possible to meet at a pre-arranged
location, you must have some method of checking with each other
to see whether you are all safe.
16 - 10
-------
STUDENT EXERCISE 1
After observing the industrial scene in Figure A, describe the
safety hazards that are present. (Hint: There are at least 15.)
2
3.
4
5
6--
7
8._
9
10.
12.
13 v
14.
15.
16 - 11
-------
-------
UNIT 17
HAZARDS OF STACK SAMPLING
A. INTRODUCTION
Stack sampling and source inspection present some safety and
health problems that may not be encountered in other sampling
environments. Stack sampling and source inspection often take
place in complex industrial environments with many unexpected
dangers, and sampling often requires working at heights. Stack
sampling operations can also create hazards which may endanger
plant personnel as well as sampling personnel.
This Unit will emphasize the hazards of working at heights,
particularly in industrial environments, and the procedures and
precautions that can and should be followed for safety.
B. RESPONSIBILITIES
As the first step for preparing to work in an industrial
environment, sampling crew members need to find out what hazards
in the plant may endanger them and what the crew can do to
protect themselves. (Some recommendations for gathering
information on industrial plant hazards are discussed in detail
in another unit of this manual.)
Many industrial plants will provide safety and health
information on request, and many have taken measures to guard and
control hazards in their plants. However, you cannot rely upon
industrial plants to provide safe working conditions for sampling
personnel, even though plant management is responsible for
providing a place of employment which is free of recognized
hazards that are likely to cause serious physical harm. Sampling
crews may have to work in plant areas that are not used by plant
employees or that have unrecognized hazards, and crews may have
to work in areas that have hazards that are not controlled or
guarded. Therefore, sampling crews may have to take more
precautions and use more personal protective equipment than plant
employees do.
Sampling crews also have an important responsibility to
organize and conduct sampling operations so that they do not
endanger crew members or plant employees, or cause damage to
sampling equipment or plant property.
The sampling crew should provide control of any hazards thit
may be created as part of the sampling operation or sour
inspection, including hazards that may endanger plant employees
17-1
-------
or property. For example, the sampling team should rope off or
barricade any area where tools or equipment may fall when they
are being hoisted or used.
If any construction work has to be done to meet sampling
requirements, such as erection of a scaffold or cutting a
sampling port in a duct, an effort should be made to see that the
work is done in ways that make subsequent sampling as safe as
possible. For example, if a railing must be cut to provide for
access of the sampling probe, the sampling organization should
provide specifications for guarding the new openings in the
railing with chain, rope, or strong temporary railings. If a new
platform roust be built or scaffolding erected, the new
construction should have standard height guard railings,
toeboards, and other safety features.
If you are assigned to be a project officer for stack
sampling operations that are done by a Federal contractor, you
will have a responsibility to see that the sampling is done
according to the contract. since all Federal contracts require
compliance with Federal safety regulations and OSHA Standards,
part of your responsibility is to advise the contractor
informally if safety precautions are not being followed and the
contractor does not seem to be in compliance with Federal safety
regulations. However, as a project officer you must not give
directions to the contractor because any directions about
contract performance must come only from EPA contract officers
(otherwise you may become liable for the cost of the work done at
your direction).
C. LADDERS AND CLIMBING
Since almost any source inspection or stack sampling
activity will require crew members to climb fixed or portable
ladders, this section begins with basic information on inspecting
ladders for safety. Next is important information on how to
climb ladders safely, and how to place them for safe climbing.
1. Inspection of. Ladders
All ladders should be in good repair without any cracks
or damage that will weaken the ladder. Fixed ladders attached to
a structure should be securely fastened to the structure, and
portable ladders should be positioned safely for use. All ladder
rungs or cleats should be sound, securely fastened to the rails,
and evenly spaced.
If ladder rungs and cleats are not evenly spaced, the
ladder will be hazardous to climb. An even climbing rhythm
depends on even spacing of rungs. Uneven spacing of rungs may
17-2
-------
cause a misstep which can result in loss of balance or grip and
the possibility of falling. Climbing ladders with unevenly
spaced rungs will require extra attention to avoid injury.
2. Climbing Ladders
Persons who are going to climb ladders should wear
sturdy well fitted gloves, sturdy boots in good repair, and
clothing that is snug enough so that it is not likely to catch on
the ladder.
Climbing and descending should be done facing the
ladder. The foot should be placed on the rung so that the front
edge of the heel is against the rung to prevent slipping,
particularly on wet, oily or slippery rungs. The hands should
firmly grasp the rungs, not the rails. Gripping the rungs for
climbing, as fire fighters are trained to do, provides greater
control and less chance of slipping than gripping the side rails
of a ladder; the climbing rhythm followed so that at any time one
had has a firm grip on a rung while the other is reaching for the
next rung up or down.
Safe climbing requires both hands to be free for
gripping the rungs of the ladder. Nothing should be carried in
the hands while climbing. If tools and small equipment cannot be
hoisted, they should be carried up ladders only in backpacks, on
shoulder straps, or on belts. Care should be taken to prevent
tools or equipment (in backpacks, in pockets, or on tool belts)
from catching on a rung or rail and throwing the climber off
balance, or from becoming dislodged from the pack and falling to
a lower surface.
Portable ladders should be checked for total weight
capacity. Never have more than one person climbing the ladder at
one time. Check that there are no bows, bends, cracks, or rotted
wood in the ladder. Never use a make-shift ladder constructed on
site. Never use ladders as scaffolding or bridges to cross open
areas. Ladders are designed to have part of the weight
distributed in downward compression on the rail members. Use of
a ladder as a scaffold or bridge may exceed its design strength.
Use only ladders that have cleated, non-skid feet or
bottom pads. The single most frequent accident involving
portable ladders is the bottom slipping outward away from the
vertical support surface. Make sure the bottom cleated pads rest
on a non-slip, level surface. Beware of gravel, grass, smooth
wet concrete, or oily slippery surfaces.
Before climbing a portable ladder, position a crew
member at the foot of the ladder to stabilize the bottom while
climbing is taking place.
17-3
-------
Make sure the ladder is perfectly vertical before
climbing. Never attempt to shift or move a ladder while still on
it. Remove all equipment hanging from the rungs before shifting
position of the ladder. When moving a ladder, position one crew
member on each side to firmly grasp and stabilize it. Position
the ladder with the base a safe distance from the vertical
surface it is up against. If the base is too close to the
vertical surface, there is the danger of the weight of the
climber causing the ladder to fall backwards. If the base is too
far from the surface, there is increased strain on the structural
members of the ladder and a tendency for the bottom to slip away
from the vertical surface. Table 17-1 gives recommended distances
for given lengths of ladders.
Make sure the length of the ladder is adequate for the
job. Reaching from a ladder that is too short is a prelude to
disaster.
17-4
-------
TABLE 17-1
PITCH OF FIXED LADDERS
Fixed ladders shall be considered as substandard if they are
installed within the pitch range of 60 and 75 degrees with the
horizontal. Substandard fixed ladders are permitted only where
it is found necessary to meet conditions of installation. This
substandard pitch range shall be considered as a critical range
to be avoided if possible.
Pitch Greater Than 90 Degrees Ladders- have a pitch in excess of
90 degrees with the horizontal and are prohibited.
Maintenance — All ladders shall be maintained in a safe
condition. All ladders shall be inspected regularly, with the
intervals between inspections being determined by use and
exposure.
SAFETY REQUIREMENTS FOR SCAFFOLDING
General Requirements for all Scaffolding — Scaffolds shall be
erected in accordance with this standard for persons engaged in
work that cannot be done safely from the ground.
The anchorage for scaffolds shall be sound and capable of
carrying the maximum intended. Unstable objects shall not be
used to support scaffolds.
For wood scaffolds, guard rails should all be 2 x 4 inches,
installed no less than 36 inches or no more than 42 inches high,
with a midrail, when required, of 1 x 4 inch lumber. Supports
should be at intervals not to exceed ten feet. Toeboards shall
be a minimum of 4 inches in height.
Scaffolds shall be capable of supporting 4 times the maximum
intended load.
Scaffolds shall not be altered or moved horizontally while they
are in use or occupied.
Any scaffold damaged or weakened from any cause shall be
immediately repaired and shall not be used until repairs have
been completed.
Scaffolds shall not be loaded in excess of the working load for
which they are intended.
17-5
-------
D. WORK PLATFORMS
1. Protecting Areas Belov Work Platform
Areas in the "impact zone" below sampling operations
and hoisting operations should be roped off or barricaded to keep
people out of the area where parts or equipment may fall.
2. Flooring of Work Platforms
Open-grating platforms used for stack sampling should
be floored (with plywood) to prevent small tools and parts from
falling through the grating. (This will help keep all the gear
together, as well as keeping it from falling onto persons or
equipment below.) If tools, equipment or hardware fall from a
ladder or platform, the impact can cause damage or injury. If
solid flooring and toeboards cannot be provided, tool belts and
other devices should be used to prevent material falling from
sampling areas.
To minimize tripping hazards in elevated locations, the
flooring should be flat and level, and tape, tools, and small
objects should be stored so that they do not clutter the work
platform. Umbilicals and wires should be run so that they are
kept out of the working path. Tripping hazards that cannot be
eliminated should be minimized and marked to help reduce their
danger.
3. Toeboards
Toeboards should generally be provided as curbs around
the edges of working platforms to prevent equipment, small tools,
and other gear from being pushed or kicked over the edge.
Toeboards are not required if nothing in use can be dropped or if
no one can walk under the platform or close enough to the "impact
zone" to be hurt.
Toeboards should generally be four inches in height
from the top edge of the toeboard to the top of the working
surface. Lumber that is 1" x 4" or 2" x 4" nominal is acceptable
for toeboards.
4. Tools
It is important to prevent tools and other work
material from falling off of elevated work platforms both for
safety and for working without unnecessary interruption.
Although toeboards and solid flooring will help, other measures
may be needed.
17-6
-------
If tools or other equipment are used beyond the edge of
the working platform, it is advisable to take special precautions
to prevent them from falling. In some- situations, it may be
desirable to tie tools to the platform or other superstructure.
For example, a tie line should definitely be attached to any
wrench used to loosen a tight plug in a sampling port, in case
the wrench slips and falls.
5. Protection Against Falls from Heights
Working platforms and scaffolds usually are built with
standard guard railings, but roofs and temporary working surfaces
seldom have any sort of railing. This section describes the
standards for permanent and temporary guard railings, where
railings are needed, and situations where safety lines may be
needed.
Working platforms and elevated walkways should have
guard railings high enough to prevent workers from falling off
the elevated surfaces. If you find that the height of a guard
railing is below your waist level or center of gravity, you will
need to be aware of that deficiency and use extra caution while
you are working on the platform.
If you find that you have to work on a scaffold or
platform that does not have a guard railing, you should find a
way to get a temporary railing installed or use some other method
to protect yourself, such as a fall-protection harness.
a. Standards for Guard Railings
Standard guard railings are generally required for
any walking and working surfaces that are four feet or more above
another level. Standard guard railings have a top rail that is
42 inches above the working surface, and a midrail that is about
21 inches above the working surface. (Midrails are intended to
prevent workers from falling under the guard railings.)
Guard railings should be able to with stand a 200
pound force applied in any direction at any point on the toprail,
in order to provide reliable protection. If a guard railing
appears too weak to support you if you fall against it, do
something to strengthen, supplement or replace the railing before
you begin work on the platform or scaffold. If you decide to
test a railing for any reason, try NOT to do it so that you fall
if the railing fails.
b. Openings in Guard Railings
If sections of existing guard railing must be
removed to provide access to sampling ports for long probes,
there should be some alternative guarding of the opening in the
17-7
-------
railing. One alternative would be a temporary railing above and
below the path of the sampling train.
Another alternative would be a protective railing
that projects out beyond opening and provides protection against
falls. If you encounter an unprotected opening in a guard
railing, you should protect yourself by making a temporary
railing with rope or other material.
If guard railings have openings for hoisting,
stairs, or ladders that are near areas used for sampling
operations, try to close the openings with a snap chain, rope or
other temporary barrier to falling.
Since sampling operations must often be carried
out in locations not designed for protection of work operations,
existing railings may need to be augmented and temporary
protection of openings may need to be added to prevent falls.
c. Temporary Guard Railings
There is frequent need to walk or work near the
unprotected edge of roofs or other elevated surfaces, a temporary
guard railing can be installed to prevent falls. Such a railing
can be provided by tightly-strung rope or cable at 21 and 42
inches above the surface. If rope or cable is used as a
temporary guard railing, the rope or cable should have less than
six inches of sway under a 200 pound force and no more than three
inches of sag between supports, strong vertical supports should
be installed (safely) at intervals that do not exceed eight feet,
so that the rope or cable can provide reliable protection.
On some high surfaces it may be desirable to
provide a temporary guard railing or rope even if sampling
personnel do not plan to work near the edge. If the surface
slopes or is rough or slippery, there is need for a safety guard
railing or rope or a safety line. In such hazardous situations,
the 21 inch high mid-rail is particularly important to prevent
someone from slipping or sliding under the 42-inch high rope or
guard railing.
d. Alternatives to Guard Railings
Although guard railings are usually required for
walking and working surfaces that are four feet or more above
another level, there are some situations where the risk -f
falling does not seem to justify the expense and hazards f
erecting a temporary railing. For example, consider a one-stc:,
flat roof where sampling operations are twelve feet or more f r -
the edge. Although sampling personnel can walk over to the ed ;«
they will usually be working far enough away so they would not
likely to fall from the roof.
17-8
-------
During set-up and take-down operations when the
crew is hoisting equipment over the edge of the one-story roof,
the hazard of the height is likely to be so obvious that the crew
will pay great attention to the hazard and take precautions to
avoid falling over the edge. However, if extra attention alone
does not seem to provide great enough safety, some additional
protection will be needed. If providing a temporary railing is
hazardous, inconvenient or expensive, or if it interferes with
hoisting operations, some other safety measure may be needed.
Under some extreme conditions, where guard rails
or guard ropes cannot be provided for the work area and where
fall distances could cause serious injuries, personnel should
wear safety harnesses connected to well-rigged safety lines.
Safety harnesses that provide protection against falls are the
type with loops around the shoulders, legs and waist. Safety
lines for fall interruption must be equipped with shock-absorbing
devices to prevent serious or fatal injury from the impact of a
sudden stop at the end of the rope.
E. SCAFFOLDING
If you are going to work from scaffolding> this section will
list some important things to check before you go up on the
scaffold. This section is also intended to give you some
specifications and recommendations if you are responsible for
supervising scaffold erection or contracting for it.
1. Inspection of Scaffolding
Portable scaffolds should be erected so that they are
secure enough to minimize horizontal movement and to prevent them
from tipping over due to wind, load, or working stresses.
Scaffolds over twenty feet high should be secured or tied off at
least at every twenty feet of elevation.
Working surfaces on scaffolding should obviously be
strong enough to support personnel and equipment. If the floor
of the platform is built of boards or sheets of plywood, they
should not slide or fall off of the supports. If the floor is
built of planks that overlap, they should overlap at least 12
inches or be nailed down or secured against movement. It is
important that all plywood and planking be secured against wind
forces which may move or lift them.
Before using a scaffold, use this safety checklist for
the condition of the scaffold:
o Are barricades or signs needed to prevent the
scaffold from being struck by vehicles, and are
they provided?
17-9
-------
o Is the feel of the scaffold stable and firm?
o Is there an access ladder that is either built-in
and continuous, or a temporary ladder lashed
firmly?
o Are all other connections made firm, either with
pins, bolts, or nested construction?
o Are there secure cro.ss braces to prevent the
scaffold from tipping?
o Are the scaffold platforms wide enough to allow
safe testing?
o Are the scaffold platforms secured against
teetering and being blown off by the wind?
o Do the platforms have 42-inch high guard rails
with midrails, or does the cross-bracing give
equivalent protection?
o Do the platforms have toeboards?
o Are the toeboards of sufficient height (3-1/2
inches or more) to prevent tools and equipment
from falling?
2. Erection of Scaffolding
Scaffolds should be cross-braced and erected on solid
footings of sufficient size to avoid sinking into the ground or
into the roof. Cross-braces serve the important function of
keeping the scaffold erect by preventing it from tipping over or
collapsing. Most sections of scaffolding should have the cross-
braces connected, and the connections should be secured to keep
the braces in place.
Scaffolds should be erected so the vertical sections
are at right angles to each other to provide a rectangular area
for the platform and greater strength.
Scaffolds with built-in ladder sections should be
erected so that all the ladder sections are in a straight run.
This will facilitate use of the ladder and prevent injuries which
may occur if personnel are unaware of, or forget shifts in the
position of ladder sections.
If the scaffold is erected where it may be struck by
vehicles, barricades and signs should be installed.
17 - 10
-------
If you are responsible for erection of scaffolding, use
the above checklist as part of the specifications. The checklist
can also be used as informal safety information for anyone who
may erect scaffolds Agency personnel may have to use.
F. HOISTING
Stack sampling usually necessitates raising equipment and
replacement probes and supplies up to sampling sites, and
lowering equipment and other material after the tests. Hoisting
and lowering stack sampling equipment safely requires: rope,
gloves, a clear path, a reliable method of stopping or
controlling the rate of descent, a pulley or block and tackle for
lifting heavy equipment, support for the hoisting device, methods
of attaching loads¦, and reliable hooks and ropes. This section
will discuss these requirements and the advantages provided by
block and tackle.
Safe use of rope requires sturdy gloves for protection of
the hands and for getting a secure grip on the rope. Gloves
which have leather palms are effective.
Hoisting and lowering loads safely also requires
communication and coordination between the person hoisting the
load and the person guiding or receiving the load. If distances
are great and ambient noise levels are high, the crew may need to
have both visual and audible signals.
1. Clear Path
Hoisting equipment up to a sampling site requires a
clear vertical path that is unobstructed and wide enough for safe
passage of the equipment that has to be hoisted. If there is no
clear path that can be used for hoisting, it will take a lot more
effort to carry equipment up to the sampling site without risk of
damage. As preparation for hoisting equipment and supplies up
the sampling site, find out if there is a clear path for hoisting
or what route will have to be followed. This information should
be obtained as soon as possible, either during the initial visit
or as a part of a pre-sampling or preliminary survey.
2. Hoisting Procedure
Before lifting any loads up to the sampling site, the
hoisting area should be roped off or marked to warn passersby.
Access to the hoisting area should be limited to the crew members
doing the hoisting or guiding the load, who should definitely be
wearing hard hats.
(The rope or signs should be removed after the hoisting
has been completed and there is no danger of tools or equipment
falling, or after the sampling has been completed. You may have
17 - 11
-------
to remove the signs and barricades around the hoisting area right
after you complete the hoisting if the plant needs to use the
area for work or for traffic.)
No one should be directly under a load being hoisted,
even if block and tackle are being used.
If possible, when loads are lifted, the hoisting line
should be directly above the load so that the load is lifted
straight up from its resting position. Pulling a load sideways
as it is being lifted nay cause it to swing and damage the load.
To keep loads from swinging or blowing while they are
being hoisted, a tail line or guide line is recommended for
control. The tail line or guideline is controlled by the crew
member on the lower level at the hoisting site.
3. Controlling the Rate of Descent
Controlling the rate of descent of a load is important
to prevent damage to the load or injury to personnel. If
equipment is lowered directly on rope by hand or over a simple
pulley, personnel could lose their grip and drop the load or burn
their hands on the rope as the load accelerates downward.
Although the rate of descent can be controlled best by use of a
power-driven hoist or a block and tackle, a load can be lowered
safely on a rope if the controlling end of the rope is looped
around a support so that friction can be used for braking.
If equipment is going to be lowered directly, it is
possible to provide excellent control by looping the rope around
a railing or post.
Control of the pull on the running end of the rope can
control the friction of the rope around the railing or post and
make it easy to lower the load gradually and safely with very
little effort. (If a capstan or a capstan-like device is
available to loop the rope over, it has the advantage that a loop
may be thrown over the capstan without having to find the end of
the rope.)
4. Pulleys, Block and Tackle
Although hoisting without pulleys has been common in
stack sampling work, use of one or more pulleys is recommended.
Using a pulley for hoisting a load will usually reduce the
strength required for hoisting, and may allow the person hoisting
the load to work from a safer position. Pulleys and rigging
should be standard equipment for stack sampling crews.
17 - 12
-------
Sites over fifty feet high and those which are sampled
regularly should have a pulley support installed. Some companies
have installed gallows frames and pulleys permanently in such
locations.
The condition of frames and supports should be checked
before using them, particularly in corrosive atmospheres.
A block and tackle is a combination of rope and two
pulleys used to reduce the amount of force needed for lifting.
If heavy loads need to be lifted to stack sampling sites, or
controlled carefully on long lifts, the job can be done with less
stress on the crew by use of block and tackle. The reduction of
force required to lift a load with block and tackle is offset by
the need for longer rope and the time to pull it through the
pulleys.
Rigging block and tackle is done by placing the blocks
or pulleys close together in the same relative position as they
will be used, and threading the end of the coiled rope through
the pulleys to the connecting point on one of the pulleys. Then
the blocks can be pulled apart as needed without kinking or
tangling the line. The recommended storage procedure for rope
used in block and tackle is to pull the blocks together, coil the
rope, and store the coiled rope with the end on the bottom and
the block and tackle on top. With this procedure, the block and
tackle are ready to use without tangling or kinking of the rope.
5. Hooks and Other Devices for Attaching Loads
Hoisting ropes should be provided with hooks to be used
for attaching loads. All hooks used for hoisting should have
safety catches to keep loads attached to the hook until the
safety catch is released. The safety catch is designed to
prevent the load attachment or supporting eye or line from
slipping out of the eye of the hook.
The hook used for hoisting loads should be strong
enough to hold the load without bending out of shape. As a rule
of thumb, the load in tons that can be carried safely by a hook
is equal to the square of the inside diameter (in inches) of the
eye. As a rough estimate, a hook with a half-inch diameter eye
could safely carry a one-quarter ton load, and a hook with a one-
inch diameter eye could carry a one-ton load safely.
Loads to be hoisted should have well-attached
connections (such as an eye or sturdy handle) for the hoisting
hook or the hoisting line.
If loads do not have connections, or if a half-hitch is
not employed, the loads should be supported in slings or be
lashed so that the load will not shift or drop during the
17 - 13
-------
hoisting and lowering. When hois-ting probes or other equipment
without a specific attachment point, it is safer to provide a
separate sling or binding rope than to use the hoisting rope to
wrap or tie the load. The most commonly used sling is composed
of two lengths of rope with a galvanized ring spliced into each
end of each rope. To use the sling, one length is passed under
each end of the load and the four ring eyelets are hooked onto
the tackle hook of the hoisting line.
If a connecting device such as a shackle or clevis is
used in the sling,the safe load in tons is estimated to be the
diameter of the pin in 1/4-inches squared and divided by three.
For example, a half-inch diameter clevis pin is two quarter-
inches, and two squared and divided by three is 4/3 or 1-1/3
tons.
These rules of thumb are not suggested as a substitute
for accurate tables and reference material from manufacturers of
hooks and connecting devices, but they may be useful as a safety
check while in the field.
6. Rope
Rope needs to be strong enough to support the load to
be lifted, and large enough in diameter to allow a firm grip for
the load to be lifted. For example, rope that is 1/4-inch in
diameter is not large enough to allow a firm grip for a heavy
load; 1/2-inch or 3/4-inch diameter rope will allow a firm and
comfortable grip.
The estimated safe load for manila rope not larger than
one-inch in diameter, in tons of weight-bearing capacity, is
obtained by squaring the diameter of the rope in inches. For
example, a one-inch rope could safely carry a load of one ton,
and a 1/2-inch rope could carry a load of 1/4 ton. Sisal rope
can carry only one-third the safe load of manila rope.
Care should be taken to avoid kinking or damaging rope,
getting it wet, or dragging it in the dirt. If rope gets dirty,
it should be hosed off and then loosely coiled to dry. If rope
must be passed over sharp corners or edges, the sharp corners or
edges should be padded or protected (with chaging gear) to
prevent damage to the rope.
Rope should be routinely inspected for wear, breaks or
other defects either prior to each use or after each use (to save
time when the rope is needed). Manila sisal rope may need to be
replaced every year if used often or wetted frequently.
Rope that is rotten, frayed, or severely worn is not
reliable and should not be used.
17 - 14
-------
G. ELEVATORS AND MANLIFTS
1. Elevators
Passenger elevators are usually well maintained and
regularly inspected where the passenger load and frequency of use
are great, as in office and commercial buildings. However, small
industrial elevators and hoists may seldom be used or inspected
regularly and may be poorly maintained. Before a hoist or small
elevator is going to be used for access to tall stacks, the
sampling crew should test the operation of the hoist or elevator
and test the alarms and phones to see if they work and if someone
will respond to them. The crew should also check out what escape
routes may be available if the elevator or hoist stops during
use. Before performing these tests, notify plant personnel.
If the hoist or elevator seems to be unreliable, the
sampling crew should see what maintenance or emergency assistance
can be provided. If alarms do not work, or phones are not
reliable, the crew should carry a radio or other signaling device
so that assistance can be obtained if the hoist or elevator stops
between landings. If there is the possibility that the hoist or
elevator may stop between landings, find out whether it is
possible to get out of the car and whether there is any safe way
to get to a ladder or other route to the ground.
2. Manlifts
Manlifts are vertical conveyor belts for moving people
from floor to floor in less space and time than required by
stairs. Manlifts are old fashioned, dangerous and not designed
to move equipment or freight. Do NOT use a manlift unless it
cannot be avoided.
At the top of any manlift there should be two automatic
safety devices which cut off the power and set the brake if the
person does not step off the manlift at the top platform. (If
there were no safety devices and you did not let go, you would go
up over the top pulley and down the other side.) At the platform
there should be a grab bar to permit the rider to swing free and
on to the top landing If the emergency stops fail to operate at
the top of the manlift.
Before riding a manlift, check to be sure that:
o the emergency stop at the top of the manlift
operates,
o the emergency stop rope or rod beside the manl i! *
operates,
17 - 15
-------
o there is a permanent ladder accessible at the side
of the manlift,
o the underside of the floors or platforms and cone-
shaped guards to guide the ascending person
through the floor opening,
o there is sufficient illumination to see the
platforms and stops,
o there are instructions posted on each landing,
o the belt has not been spliced and does not show
wear, and
o the top landing has a sign designating it as the
top landing and to get off.
To ride a manlift safely:
o Never carry tools or objects in your hands or
protruding from your pockets or belt—they may
catch in the floor openings.
o Face the belt and get ready to grab the handhold
and place your feet on the step quickly.
o Do not leap to catch a step that has passed the
floor landing.
o Hold on to the handholds firmly with both hands.
o Put both feet squarely on the step, quickly.
o Be ready to get off quickly at the floor level you
want.
o Step away quickly to make room for the next person
getting off the lift.
H. ELECTRICAL HAZARDS
Electrical hazards in stack sampling operations can come
from three major sources: current leakage from line-powered
electrical equipment, static electricity, and lightning.
1. Current Leakage From Equipment
Sampling personnel may be exposed to serious shock
hazards from line operated electrical equipment which does not
have a safe and effective grounding connection.
17 - 16
-------
Ungrounded electrical equipment can be deadly because
exposed metal parts will be "hot" (at line voltage) if the "hot"
side of the line has short circuited to the case or other exposed
metal parts. If sampling personnel were to touch these exposed
metal parts at the same time they touched a grounded metal object
such as a pipe, they could be electrocuted. The hazard is
insidious because such a short circuit will not necessarily keep
the equipment from operating.
If the metal case or exposed parts are connected to a
grounding circuit, any internal short-circuit will trip the
circuit breaker rather than injure someone. If grounding
circuits cannot be provided, or if tests by the crew show that
the grounding connection is not grounded, the crew should use a
portable ground fault circuit interrupter (6FCI).
If any sampling apparatus has a noise-filtering
capacitor, the apparatus will not operate on a circuit with a
Ground Fault Circuit Interrupter (GFCI) because the capacitor
will trip the GFCI. If you have this type of apparatus, a
grounded circuit or connection to ground must be provided for
safety.
2. Static Electricity
Sampling personnel may also be exposed to shock hazards
if they are sampling a process stream which carries a significant
charge of static electricity from particulates in the process
stream or from an electrostatic precipitator. Sampling probes
should be grounded to remove static electricity and prevent
shocks to sampling personnel.
Shocks from static electricity may cause discomfort or
injury, or may startle sampling personnel and cause them to jump
back and fall from an elevated platform.
3. Lightning
Sampling personnel working on stacks or other elevated
structures are exposed to increased hazards from lightning,
particularly if they are working with grounded electrical
equipment. Personnel in such situations should be alert to
approaching storms, since lightning may strike in advance of a
storm. Sampling operations should be discontinued when there is
a hazard of lightning. In order to anticipate lightning hazards,
sampling personnel should use a portable a.m. radio to monitor
local weather reports and listen for static interference which
may indicate lightning discharges in the vicinity.
17 - 17
-------
I. COMMUNICATIONS
There are three types of communication that are important
for safe stack sampling operations: communications between
members of the sampling crew, a communications link with plant
personnel, and a portable receiver to monitor local stations for
weather reports and for static which may indicate approaching
storms.
If sampling sites are in locations where there may be
flammable concentrations of gases or vapors, electrical equipment
and radios should not be taken in without first finding out from
plant personnel that they are safe or can be adapted to work
safely in hazardous atmosphere.
1. Communication Between Members of the Crev
Rapid and effective communication is needed between
members of sampling teams for routine operations and for
emergency and safety-related messages. Delay or confusion in
communication during setup and breakdown or during hoisting
operations can result in damage to equipment and injury to
personnel. Good communication is especially important for safe
and effective operations that are not routine, that are carried
out or assisted by another crew, or that require close
cooperation between people who may not be used to working
together.
Radios are recommended for communication between
sampling team members, for carrying out routine monitoring tasks,
and for communicating about safety problems that arise* Radio
communication is effective for conveying special directions
during setup and breakdown, and for describing emergencies and
the type of help needed. EPA field experience has been that FM
radios are needed, because CB channels are used so much that it
is difficult to communicate quickly and without interference.
It may be possible to communicate effectively in
sampling operations by means of shouting, if distances are not
too great, winds are not too high, and noises in the sampling
area are not too great. However, voice communication is easily
interfered with by equipment noise, passing trains and other
vehicles, and concentration on the work. Hand signals and
gestures can be used for simple messages such as "move the
probe," but usually some audible signal is needed to attract
attention to the visual message.
Inexpensive whistles, horns or bells can be used eitf-' •
to call attention to visual signals or send audible signa*. •
Where distances or ambient noise levels are too great for ah
bell or mouth-powered whistle or horn to carry clearly, there •
Halon-powered hand-held horns that can be used effectively.
17 - 18
-------
2. Communication Between the Crew and the Plant
It is also desirable to have a means of communicating
with plant personnel in case of any emergency. In some cases it
may be possible to borrow a radio that is on the plant frequency.
If an emergency occurs in or near the sampling
operations (such as observation of lightning, or high winds, .or
damage to equipment, or injury to personnel) sampling personnel
need to have some means of communicating this emergency and
obtaining the help that is needed.
In case of a plant emergency, such as a fire, tornado
warning, or unexpected release of toxic chemicals, it is
imperative that sampling personnel know the plant emergency
signals and how to respond promptly and correctly.
3. Communication for Weather Information
It is desirable to have a portable receiver to monitor
local stations for weather reports and for static which may
indicate approaching storms.
J. PROTECTIVE AMD EMERGENCY EQUIPMENT
1. Protective Equipment for Routine Hazards
Stack sampling personnel should be sure to have the
personal protective equipment that may be needed for exposures in
sampling operations. The equipment will include the personal
protective and safety equipment for the routine exposures
expected, and it may include emergency breathing equipment as a
special precaution.
Under some conditions, stack sampling personnel may
need air purifying respirators, and under other conditions they
may need self-contained breathing apparatus.
Approved air-purifying respirators provide acceptable
protection only for exposures to irritating or toxic gases and
vapors in concentrations that are known to be within the limits
of protection provided by the respirators.
2. Emergency Equipment
Emergency equipment should be provided at the working
elevation for the types of emergencies which may occur there,
because there will be a delay in emergency response from
personnel at a different elevation. For example, if corrosive
chemicals can be splashed in the eyes or on the skin, or if heat
stress is severe, a supply of emergency water is needed a£ the
working elevation. Adhesive bandages may be needed for minof
17 - 19
-------
cuts, and emergency lighting may be needed in case of power
failure during night operations or operations inside of
windowless buildings.
Approved self-contained breathing apparatus or air-line
respirators must be provided and be within immediate reach of the
crew if there are hazards of exposure to concentrations that are
either unknown or beyond the limited capacities of filter-type
respirators. Such breathing apparatus should also be provided if
there is the possibility of release of high concentrations of
deadly gases such as hydrogen sulfide, hydrogen cyanide, or
hydrofluoric acid.
If unique hazards such as hydrogen sulfide, hydrogen
cyanide, or hydrofluoric acid may be present in high
concentrations, the sampling crew may need to have special
protective and emergency medical equipment.
K. WEATHER HAZARDS
Snow, rain, and dust storms are likely to interfere with
communication and cause other problems that will prevent safe
sampling operations. Such storms may also reduce visibility and
mobility and increase hazards to the extent that sampling
operations will need to be stopped. If ladders, stairs,
platforms and other walking and working surfaces are covered with
ice or snow, or are icing up from a freezing rain, there should
be qo climbing (except to "retreat") and no work at elevations.
Weather conditions can also affect sampling equipment and
personnel working outside and increase the hazards of the
sampling operation and the needs for protective equipment.
1. Heat
Hot weather and direct sunlight can contribute to the
heat load from process equipment and from physical activity, so
that it may be necessary to monitor for signs of heat stress.
High temperatures may also cause samples to volatilize and to
pressurize sample containers so that there is risk of a leak or
spray from the container. Metal in direct sunlight may become
hot enough to cause thermal burns to unprotected skin. Heat
stress may require special protective clothing, extra drinking
water or other fluids, and monitoring of personnel for sunburn or
symptoms of heat exhaustion or heatstroke.
2. Cold
Cold weather, wet clothing and wind can cause
frostbite, hypothermia, or other adverse effects. Low
temperatures may also freeze lines and cause sampling equipment
to malfunction.
17 - 20
-------
STUDENT EXERCISE 1
Examine Figure 1. List as many safety violations as can be
found. (Hint: There are at least 10.)
1._
2._
3
4._
5._
6._
7._
8*_
9._
10.
17 - 21
-------
-------
STUDENT EXERCISE 2
a. Will a hook with an eye of 1/2" safely support a load of
1,000 lbs?
b. Will a 1/4" clevis pin safely support a load of 1,000 lbs?
c. Will a manila rope of 3/4" diameter carry a load of 1,000
lbs?
17
- 23
-------
UNIT 18
HAZARDS OF FIELD SAMPLING
A. INTRODUCTION
Field sampling represents one of the largest
responsibilities of EPA field crews. As such, the probability of
facing a hazardous condition is large. The diversity of
environments, equipment used, personnel awareness and training
all to a large extent, play a role in the type and severity of
the hazard.
It is not possible to prepare field personnel for every
eventuality. Crews must depend on alertness, planning and common
sense for the unexpected.
This unit will help sharpen the backgrounds of personnel to
enable them to have confidence in preparing and preventing
accidents while sampling. Two major areas will be covered:
1. Physical Hazards of the Sampling Environment
2. Hazards of Sampling
The specific topic of sampling drums is covered in the unit
on hazardous waste sites.
B. PHYSICAL HAZARDS OF THE SAMPLING ENVIRONMENT
1. Sampling Equipment Instructions
Sampling equipment is manufactured in an endless
variety of sizes and shapes. In some cases, equipment has been
modified or even built by Agency personnel. The Coliwasa has for
many years been the mainstay for sampling liquids. Yet until a
few years ago, there were no commercial manufacturers of the
Coliwasa and units had to be built in-house.
Manufactured equipment usually comes with precise
instructions as to procedures for safe set up and operation. It
should become common practice to thoroughly read these
instructions before attempting to use the equipment.
Instructions should be placed in clear plastic covers to protect
them from inclement weather, chemicals, dirt and wear. if
possible, the sheets should be taped to the inside covers of the
carrying cases or if in multiple sheets or booklet, attached to
the equipment by a light chain or durable string.
18-1
-------
In the event of modifications to manufactured
equipment, special use for which the equipment was not originally
designed or in-house designed equipment, Standard Operating
Procedures (SOP) should be developed before the equipment is
authorized for field use. Copies of the SOP should be protected
and attached to the equipment or carrying case. SOP should also
be sent to all personnel that may have use for the equipment.
The SOP should make special note of limitations or hazards that
might exist. In some obvious cases, special note be made on the
outside of the carrying case to alert the individual of important
hazards. Examples of these hazards are:
o The carrying case contains hazardous chemicals.
o There exists breakable parts or containers inside.
o There is the danger of shock or explosion if used
improperly or in certain hazardous conditions or
atmospheres.
o Improper use or mixing may generate a dangerous
condition.
2. Carrying Equipment
Injuries to the back and abdominal muscles from lifting
heavy loads is one of the most common injuries reported. Such
injuries can range from relatively mild strains to major
permanently disabling injuries. Lifting heavy equipment should
be approached with thought as to:
o Overall weight
o Distribution of weight
o Unwieldiness or awkwardness
o Distance to be carried
o Obstacles to be negotiated such as slippery banks,
rocking boats and ladders
o Conditions such as wind, snow, ice and slippery
surfaces
o Visibility
18-2
-------
Whenever possible, assign two individuals to carry
equipment. Simply the weight alone should not be the only
consideration. A large sheet of plywood may not be particularly
heavy but is awkward, blocks the view of the person carrying it(
and can be extremely hazardous in high, gusty winds. Two
individuals carrying two sheets together is a much safer practice
than two individuals each carrying one sheet apiece. The
incidence of individuals being blown from roofs and ladders while
carrying large sheets is all too frequent.
Before lifting a case, check to see if equipment stored
inside is secure. A sudden shift in weight while the case is
being carried may throw the individual off balance and result in
a dangerous fall.
Experimentally lift a corner of the equipment to be
carried to determine its approximate weight. Check to see if
carrying handles are fastened securely to the container and are
in good condition. Check to see that tops, drawers, etc., are
securely fastened closed. Never lift equipment by makeshift
strings or ropes. If equipment seems heavy, request help
before lifting. Strains and hernias are usually caused during
the initial strain of lifting. If passing a heavy piece of
equipment to another individual, warm them of the approximate
weight before handing them the equipment. Strains and hernias
are often caused by improper position or stance, rather than by
sheer weight.
Heavy equipment should be lifted by using the power of
the leg muscles, rather than the back, stomach, or arm muscles.
Approach the container so as to have it evenly balanced. Never
bend over when lifting. The back should be kept straight and the
arms nearly vertical with the body. The knees should be bent to
grasp the load. Lifting should be by straightening the legs,
with the back remaining in a nearly vertical position. Setting
down the load is the reverse of lifting.
Never climb ladders while carrying a heavy load.
Ladders require the use of both hands. Loads not only tie up the
hands, but unbalance the body. Loads should be lifted by winch
or pulley. Never attempt to lift a heavy load from a small boat
with only one person. The unstability of the boat along with the
shifting weight, may result in the boat tipping over or a severe
strain of the bodies of the lifters. Likewise, never attempt to
lift a heavy weight over a dock down into a boat. Not only is
the strain severe, but the uneven weight may cause the individual
to fall headlong into the boat or water. Heavy equipment should
be set on the side of the dock within reach of personnel in the
boat. Two individuals in the boat should grasp the equipment
while steadying the boat. Be sure the boat is securely tied at
both ends to prevent the boat from pushing away from the dock
while equipment is being lifted.
18-3
-------
3 c Compressed Gas Cylinders
Compressed gas cylinders are frequently used for
analytical equipment or for recharging SCBA air tanks. These
tanks represent a multitude of hazards. The empty tanks
themselves are extremely heavy and due to their elongated shape,
easily tipped over. Tanks should be carried on special dollys
designed to hold cylinders. These dollys have a saddle to hold
the tanks and an adjustable strap to prevent the tank from
tipping forward when the dolly is lifted upright.
Never move or transport a tank without the protective
threaded cap or top being in place. When full, the tanks are
under extreme pressure, striking the valve at the top of the tank
may shear off the valve assembly, venting the pressurized gas.
In addition to the potential of fire or explosion, the velocity
of the existing gas may propel the cylinder at extremely
hazardous speeds.
When transporting the tank or when setting the tank up
for use, securely chain or fasten the tank in an upright position
to prevent shifting or falling over. In some cases such as
acetylene, it is dangerous to lay the tank on its side. Such a
practice may cause a separation of the acetone, acetylene
mixture.
Always check tanks for pitting and misting. Any sign
of deterioration should be reported immediately and the tank
removed from service. Never assume that the color of the tank
indicates the contents. Color schemes are strictly the
prerogative of the company that moves the cylinders.
Never add adaptors or other gear to a regulator to make
equipment fit. Often special threads and sizes are put on
regulators to forewarn or prevent certain types of equipment from
being used or attached to the tanks. These precautions should be
carefully heeded by field personnel.
Threads on tanks are often reversed from the normal
directions used in common equipment. Never attempt to force
threads or nuts. If a thread won't give, stop and analyze the
direction you are attempting to turn the nut. In most cases, the
threads will turn off in the opposite direction. Never store
tanks in direct sunlight or near excessive heat. Non-flammable
gas such as carbon dioxide may rupture with a force equal to or
greater than that of flammable gases.
18-4
-------
C. THE SAMPLING ENVIRONMENT
Before setting up and using sampling equipment, attempt to
determine the type of environment you will be testing. In many
cases, this is best done by contacting a plant representative
such as a safety officer. Explain fully the nature of the test
and exactly the type of sampling equipment to be used. Make
sure the type of equipment is approved for the environment that
you will be in. In most cases, electrical sampling equipment is
approved for certain types of environments.
1. Certification of Electrical Sampling Equipment
National groups such as Underwriters Laboratories (UL),
Factory Mutual (FM), and the American National Standards
Institute (ANSI), together with NFPA, developed test protocols
for certifying explosion-proof, intrinsically safe, or purged
devices to meet minimum standards of acceptance.
An electrical device certified under one of these test
methods carries a permanently affixed plate showing the logo of
the laboratory granting certification and the Class (es),
Division(s), and Group(s) it was tested against.
Certification means that if a device is certified as
explosion-proof, intrinsically safe, or purged for a given Class,
Division, and Group, and is used, maintained, and serviced
according to the manufacturer's instructions, it will not
contribute to ignition. The device is not, however, certified
for use in atmospheres other than those indicated.
Three methods exist to prevent a potential ignition
source from igniting a flammable atmosphere:
a. Explosion-proof
Encase the ignition source in a rigidly built
container. "Explosion-proof" instruments allow the flammable
atmosphere to enter. If and when an arc is generated, the
ensuing explosion is contained within the specially designed and
built enclosure. Within it, any flames or hot gases are cooled
prior to exiting into the ambient flammable atmosphere so that
the explosion does not spread into the environment.
b. Intrinsically Safe
Reduce the potential for arcing among components
by encasing them in a solid insulating material. Also, reducing
the instrument's operational current and voltage below the energy
level necessary for ignition of the flammable atmosphere provides
equal protection. An "intrinsically safe" device, as defined by
the National Electrical Code, is incapable "of releasing
18-5
-------
sufficient electrical or thermal energy under normal or abnormal
conditions to cause ignition of a specific hazardous atmospheric
mixture in its most easily ignited concentration. Abnormal
conditions shall include accidental damage to any wiring, failure
of electrical components, application of over-voltage, adjustment
and maintenance operations and other similar conditions."
c. Purged
Buffer the arcing or flame-producing device from
the flammable atmosphere with an inert gas. in a pressurized or
"purged" system, a steady stream of, for example, nitrogen or
helium is passed by the potential arcing device, keeping the
flammable atmosphere from the ignition source. This type of
control, however, does not satisfactorily control analytical
devices that use a flame or heat for analysis such as a
combustible gas indicator (CGI) or gas chromatograph (GC).
There are six possible environments in which a
hazardous atmosphere can be generated. However, not every type
of control will prevent an ignition in every environment. To
adequately describe the characteristics of those environments and
what controls can be used, the National Electrical Code defines
each characteristic:
a. Class
Class is a category describing the type of
flammable material that produces the hazardous atmosphere:
(1) Class I is flammable vapors and gases, such
as gasoline, and hydrogen. Class I is further divided into
groups A, B, C> and D on the basis of similar flammability
characteristics (see Table 18-1).
(2) Class II consists of combustible dusts like
coal or grain and is divided into groups E, F, and G.
(3) Class III is ignitable fibers such as
produced by cotton milling.
b. Division
Division is the term describing the "location" of
generation and release of the flammable material.
(1) Division 1 is a location where the generation
and release are continuous, intermittent, or periodic into an
open, unconfined area under normal conditions.
18-6
-------
(2) Division 2 is a location where the generation
and release are in closed systems or containers and only from
ruptures, leaks, or other failures.
Using this system, a hazardous atmosphere can be
routinely and adequately defined. As an example, a spray-
painting operation using acetone carrier would be classified as a
Class I, Division 1, Group D environment. Additionally, an
abandoned waste site containing intact closed drums of methyl
ethyl ketone, toluene, and xylene would be considered a Class I,
Division 2, Group D environment. Once the containers begin to
leak and produce a hazardous atmosphere, the environment changes
to Class I, Division 1, Group D.
18-7
-------
TABLE 18-1
Class Z Qvnicals By Cioups
Grcup A Atmospheres
Group 0 Atmosphere
Acetylene
Group B Atmospheres
Acrolein (inhibited)
Arsine
Butadiene
Ethylene oxide
Hydrogen
Manufacturer gases containing
rare than 301 hydrogen
(by volume)
Propylene aad.de
Prapylnitrate
Group C Atmospheres
Acetaldehyde
Ailyl alcohol
n-Butyraldehyde
Carton monoxide
CTotonaldehyde
Cyclopropane
Diethyl ether
01 ethyl amine
Epichlorohydrin
Ethylene
Ethyleneimine
Ethyl mercaptan
Ethyl sulfide
Hydrogen cyanide
Hydrogen sulfide
Morpholine
2-Hitropropene
Tetrahydrofuran
Uhsynmetrical dimethyl hydrazine
(OEM!,. 1-, 1-dimethyl hydrazine)
Acetic Acid (glacial)
Acetone
Acrylonitrile
Ammonia
Butane
1-Butanol (butyl alcohol)
2-Butanol (secondary
butyl alcohol)
ft-Butyl acetate
Zsabutyl acetate
di-Isobutylene
Ethane
Ethanol (ethyl alcohol)
Ethyl acetate
Ethylacrylate
(inhibited)
Ethyl diamine
Ethylene dichlorlde
Ethylene glycol
moncmethyl ether
Gasoline
Heptanes
Isoprene
Zsoprcpyl ether
Mesityl oxide
Methane (natural gas)
Methanol (methyl alcohol)
3-Methyl-l-butanol
(isoaayl alcohol)
Methyl ethyl ketone
Methyl isobutyl ketone
2-Methyl-l-propanol
(isobutyl alcohol)
2-Methyl-2-propano1
(tertiary butyl alcohol)
Octanes
Petroleum naphtha1
Pentanes
1-Pentanol (amyl alcohol)
Propane
1-Propanol(propyl
alcohol)
2-Propanol (isoprapyl
alcohol)
Propylene
pyridine
18-8
-------
TABLE 18-1 (cont)
Group 0 Atmospheres
Styrene
Toluene
Vinyl acetate
Vinyl chloride
Xylenes
source: National Electricai Code, vol. -70, Table 500-2.
National Fire Protection Association# 470 Atlantic Avenue*
Boston* MA 02210 (1981).
1A saturated hydrocarbon mixture boiling in the range 20° - l3pC
(68° - 275°P). Also known by the synonyms enzine, ligroin,
petroleum ether, or naphtha.
2. Electrical Hazards
Sampling often requires Agency personnel to reach
remote or inaccessible places. In many cases such areas may
contain electrical wires or transformers. Great caution should be
exercised in these areas. Where practical, power should be cut
to remove the danger. Where this is not possible, highly
conductive equipment such as aluminum ladders, metal probes, and
other metal sampling gear should be avoided if possible.
Electrical insulating protective gear such as hard hats and
gloves should be worn.
Of particular danger are overhead wires. Before
raising or carrying ladders, check to see that equipment will
clear. If there is danger of contact, do not attempt to enter
that area.
A great deal of sampling equipment requires a source of
electrical power to operate it. It some cases, an electrical
power outlet may be some distance away. If possible, arrange for
the company to provide power. Long extension cords may be a
source of potential overheating and fire if a proper cord size is
not selected.
a. Guidelines for Selection of Extension Cords
If an extension cord is needed to bring power to
field sampling equipment or lights there are important guidelines
for selecting a cord that will be safe and serviceable.
Extension cords should have three wires, two for powex^ and one to
provide a separate grounding circuit for safety. The wires need
18-9
-------
to be large enough in diameter to carry the needed power over the
length of the cord without either significant voltage drop or
overheating.
A long extension cord should have large enough
diameter wires so that resistance in the cord will not lower the
voltage more than 3 percent over the length or the extension
cord. If the voltage supplied by the cord is too low, your
analytical results may not be accurate and your equipment may not
operate safety. Motors can burn oiit if the supplied voltage
drops too low.
The other important requirement for wires is that
they be of adequate size to carry the current drawn by your
equipment, so that the cord does not overheat, damage the
insulation, and possibly start a fire. (The current required by
your equipment could overload the current-carrying capacity of an
extension cord having wires of inadequate diameter without
tripping the circuit breaker to which your cord is connected. In
such a case the circuit breaker will not protect the extension
cord from damage.)
Localized overheating can also occur if there is
too small an area of contact between any plug blade and its
socket connection. The effectiveness of surface contact areas
can be estimated by use of a device with tests the tension
provided by the contact blades within an outlet.
The procedure for selecting an extension cord will
depend on whether you will use a cord that is available, or
whether you are going to have an extension cord made up for a
particular sampling activity.
In both cases you will need to know how much
power is required by the equipment you will be using, what the
voltage will be at the power source, and how far your equipment
will be from a power outlet.
The basic steps for assessing or specifying an
extension cord are as follows:
o First find the total number of watts required
for all of the equipment and lights that you
plan to connect to the extension cord.
o Find the lowest line voltage that can be
expected at the outlet to which the cord will
be connected during the time personnel will
be working. Personnel can inquire, test the
voltage, or make a rough estimate.
18 - 10
-------
If there is no data and the actual voltage
cannot be measured on a line with a nominal
voltage of 110 or 115, use the value of 100
volts for the calculation of the amperage the
wires must carry.
o Next, find out how many amperes the cord will
have to carry by dividing the total number of
watts of the equipment to be used by the line
voltage expected at the outlet. Watts
divided by volts equals the number of amperes
of current to be carried by the cord.
o Find out how long an extension cord will be
needed to reach from an available outlet to
the location of the equipment. Be sure to
allow enough length so that the cord can go
over or around obstructions or passageways.
b. Precautions for Use of Electrical Equipment
If personnel will be using any electrically-
powered equipment, there are two precautions you should follow.
The first is to see that there is no damage to the electrical
insulation of the equipment or its cord, and the second is to be
sure that you cannot touch uninsulated electrical conductors or
metal parts which may be nhotn or energized.
There are four important requirements for
electrical cords. The first is that electrical cords should have
no breaks in the insulation.
Second, cords should be inspected periodically,
with the cord disconnected from the power source.
Third, electrical cords should have plugs which
keep the terminals insulated and which assure safe connection of
wires to the terminals.
The fourth important requirement for electrical
cords is continuity of the grounding wire. If equipment with a
grounding wire and a workable three-prong plug is connected to a
two-wire extension cord, the grounding wire cannot perform its
safety function.
18 - 11
-------
c. Portable Electrical Equipment
With portable electrical equipment there are three
practical steps that can be taken to prevent touching "hot" or
energized metal parts. Any one of these steps will provide
protection against electrical shock from the equipment:
o Be sure that all exposed metal parts of
electrical equipment are connected to an
effective grounding circuit, or
o Provide a Ground Fault Circuit Interrupter in
the line, or
o Use power tools which are "Double Insulated"
to prevent any exposed metal surface from
providing contact with a "hot" wire.
d. Grounding Exposed Metal Parts of Electrical
Equipment
If personnel connect electrical equipment to an
effective grounding circuit, they must be sure they are grounding
all exposed metial parts.
Ungrounded electrical equipment with only a two-
wire electrical cord will usually continue to operate even if the
hot wire comes into contact with the metal shell or exposed metal
parts. If such equipment is held by a person who is also in
contact with the earth or some grounded metal object, the
individual could be shocked seriously and perhaps fatally.
If a hot wire in a piece of electrical equipment
touches metal parts that are grounded (by connection to the green
grounding wire), there will be a direct short circuit which will
trip the circuit breaker and de-energize the electrical
equipment. Electrical equipment will not continue to operate if
there is a short circuit from the hot wire to metal parts that
are grounded.
To assure that exposed metal parts of
electrically-powered equipment cannot become electrically "hot"
as a result of damage to the insulation of the hot wire, it is
necessary to have a separate connection between exposed metal
parts and the ground. This is usually accomplished by usinq
equipment which has a third wire connecting the metal shell
through the cord to a grounding connection in the electricil
outlet. As an extra precaution you can check electricii
equipment for leakage currents between the metal parts and <
grounded conductor.
18 - 12
-------
In addition to having all of the equipment
provided with a connection to the grounding wire, personnel must
have a three-wire cord with a three-prong plug. It is also
necessary that the grounding connection in the electrical outlet
be attached to a ground. Outlets should be tested before use to
see whether they do have an effective connection to ground or
whether an alternative grounding method must be used.
e. Ground Fault Circuit Interrupters
If it is not possible to provide effective
grounding portable electrical equipment, Ground Fault Circuit
Interrupters can prevent injury if someone makes contact with a
hot wire and the ground. When the device detects unbalanced
current in a circuit, it will interrupt the current flow within a
few milliseconds and prevent further flow of an injurious amount
of current.
Portable ground fault circuit interrupters (GFCI)
are available for field use. They are recommended particularly
in wet locations where the hazard of current flow to the ground
is great. (Ground fault circuit interrupters do have the drawback
that they will interfere with operation of any apparatus which
uses a capacitor across the line as a noise filter.)
f. Double Insulated Electrical Tools
Electrically-powered tools are available with
"Double Insulation" designed to prevent any exposed metal part
from becoming energized and causing a shock to the user.
Electrically-powered tools identified by the
manufacturer as being " Double Insulated" are considered
reasonably safe to use in locations where the user may contact
either the ground or grounded equipment. Such tools should be in
good condition with undamaged parts. As an additional
precaution, such equipment should be checked to see that use or
repairs have not damaged insulation and allowed exposed metal
parts to come into contact with hot wires.
If personnel ever have to work on or enter
electrically-powered equipment, be sure the power is shut off and
the shutoff switch is locked so that no one can inadvertently
turn the power on.
3. Sampling
Hever open containers, tanks, mixers, etc., without
first seeking the advice or approval of plant personnel. In many
cases such containers may be under pressure or have extreme
temperatures.
18 - 13
-------
Drums should be moved only after careful observation of
their condition. A normal filled drum weighs close to 500
pounds. Steel-toed shoes should be worn and equipment such as
dollys, or fork lifts used to lift or tote barrels. A barrel
tipped on its edge is highly unstable and difficult to control.
A shift in its contents may cause the barrel to go out of control
causing personal injury and increasing the risk of leaks, fire
or explosion. Never stand or walk on containers to reach remote
containers. If containers that must be sampled are not
accessible, have company employees clear a path or move barrels.
Generally laboratories require very small quantities of
samples. Take only the amount of sample needed to complete
analysis. Containers of samples represent hazards. The larger
the sample size, the greater the hazard.
Sample containers must be checked for compatibility
with the material sampled. Flammable liquids, corrosives and
other highly hazardous materials should not be placed in glass
containers unless the containers have special coatings to prevent
shattering. Bakelite or PVC tops should be used in place of
metal tops. Before the samples are removed from the sampling
site, a check should be made to insure the tops are correctly and
securely fastened. Decontaminate the outside of the sample
container thoroughly before packing for transit. Never carry
sample containers in Agency vehicles without securing them from
rolling or bumping. A case designed for this purpose or a stout
container filled with an inert packing absorbent such as
vermiculite will prevent breakage, bumping or rolling about while
in transit. If the material is to be shipped, special
precautions must be exercised. (See unit on Sample Labeling and
Shipping.)
Sampling procedures often require chemical reagents.
Reagent bottles should be packed in absorbent, cushioning
material to prevent bumping and leakage. Labels for reagents
should be of indelible material and care taken to separate
incompatible chemicals. in many cases, the reagent chemicals
themselves represent a more serious threat of harm than the
materials sampled. SOP's outline test procedures, as well as
sampling hazards and chemical incompatibilities should be
included with testing chemicals. In cases where reagents must be
measured out, equipment contamination such as pipettes must be
solved by disposables or decontaminating solutions.
Reagents such as concentrated acids and bases are
hygroscopic (attract water). Small drops on the outside of
bottles will quickly dilute, running down the sides of bottles
and pooling at the bottom. Such pools can lead to unknowing skin
contamination or eye burns.
18 - 14
-------
STUDENT EXERCISES
Bcercise Z
Locate as many safety hazards as visible in the following
diagram:
18 - 15
-------
Exercise II
A piece of electrical sampling equipment draws 120 volts and
uses 280 watts. The electrical source is 90* away. What size
wire is needed?
Exercise III
Sampling is to be done in a closed environment that normally
contains acetone. What type of approval must the equipment have
to be safe in this type of environment?
Is the following Znstrunent approved for this environment?
/VISA
Combustible Gas and 0t Alarm
mM 219 m m. 441189
Pentane „
MOST II OPtMTO III ACCOROMCI WIT* IMTWCTIOil
MPO. •*
MNE SAFETY APPUANSS COMMIT
ottolmh mwnwo. hia. mm
wm m i i& m ¦* tMtm www ¦
18 - 16
-------
UNIT 19
INSPECTION SAFETY FOR WATER AND WASTEWATER PLANTS
A. INTRODUCTION
The safety and health of agency employees entering water and
wastewater plants can be best analyzed by examining the overall
hazards that exist at these plants. In the routine of a thorough
inspection of such plants, agency personnel face, on a limited
basis, all the potential dangers encountered by daily operations
personnel.
Operational techniques used by various systems such as
trickling filter plants or activated sludge plants pose unique
hazards. It is not within the scope of this course to single out
particular plant types. The possible hazards present at each of
these types of plants will be handled collectively. As routine
inspections will most likely include a wide variety of plant
types. Inspectors should thoroughly acquaint themselves with all
the hazards that may be encountered.
B. TYPES OF ACCIDENTS AND FREQUENCY
The following is a summary of the types and locations of
accidents and hazards routinely reported in water and wastewater
plants (see Figure 19-1).
19-1
-------
FIGURE 19-1
19-2
-------
Table 19-1 indicates a reversal in accident rates. Prior to
1983, the industry was recording a gradual decline in accident
rates. The year 1983 saw the rate beginning to climb.
Statistics indicate that at the present accident rate, one in
every 10 workers will receive an injury requiring lost work time.
In the last year seven fatalities were reported as a result of
job related accidents at water and wastewater facilities.
19-3
-------
TABLE 19-1
1983 Personnel injuries in wastewater works
U.S. and Canada (as determined from WPCF 1984 Safety Survey),
Collection systems only
< 10
255
1175
692
846.76 32
37.79 247.2
291.9
0
> 10 to
25
141
2346
676
1182.14 51
43.14 407.0
344.3
0
> 25 to
100
157
7654
1560
3111.58 241
77.45 3319.2
1066.7
1
> 100
48
18503
2550
4819.24 347
72.00 4553.0
944.8
0
Total
601
29676
5498
9959.72 671
67.37 8526.4
856.1
1
Treatment plants only
< 10
341
1692
1140
2137.94 51
23.35 525.2
245.7
0
> 10 to
25
212
3605
1593
3281.88 79
24.07 1090.0
332.1
0
> 25 to
1U0
192
9632
3664
7303.56 294
40.25 3723.5
509.8
2
> 100
76
32510
6899
13806.66 769
55.70 7676.2
S56.0
3
Total
821
47339 13296
26530.04 1193
44.97 13014.9
490.6
5
Others-resorted only as collection
and treatment
< 10
299
1116
1054
1713.18 54
31.52 488.5
285.1
0
> 10 to
25
70
1169
639
1264.65 45
35.58 619.5
489.9
0
> 25 to
100
59
2886
1468
2900.23 139
47.93 1423.0
490.7
0
> 100
39
31531
10295
19818.41 1007
50.81 15276.6
770.8
1
Total
467
36702
13456
25696.47 1245
All systems
48.45 17807.6
693.0
1
< 10
700
3002
2886
4697.88 137
29.16 1260.8
268.4
0
> 10 to
25
304
5070
2908
5728.67 175
30.56 2li6.5
369.5
0
> 25 to
100
262
14000
6711
13316.38 674
50.62 8405.8
635.8
3
> 100
122
68104
19744
38444.31 2123
55.22 275C5.8
715.5
4
Total
1408
90176
32249
62186.24 3109
49.99 39348.9
632.8
7
A: Population Size Group (X 10"^I *
B: NUmber of Reports
C: Population Served (X 10~3)*
0: Total Number of Siployees
E: Total Man-hours (X 10^)
F: Total Disabling Injuries
G: Injury Frequency per 10° Man-hours
H: Total Days Lost
I: Severity Hate (days lost from work per 1Q6 man-hours)
J: Fatal Cases
•Population served is partly composed of industrial waste population
equivalents'
•Totals do not add up because of duplication in above-groups
•A fatality represents 150 days lost as recommended in the National Safety
Council's "1983 Accidents Facts" manual
19-4
-------
It is evident from reported statistics that water and
wastewater plants represent a persistently dangerous workplace.
Table 19-2 summarizes personnel disabling injuries in 1983, for
wastewater works by U.S. EPA Region.
TABLE 19-2
1983 Personnel disabling injuries in wastewater works by 0-S. ETA Region
A
B
C
D
E
F
G
H
I
J
I
96
2629
1279
2519.195
155
66.50
2954
ii?2.i
0
11
178
12099
3513
6719.333
342
50.90
3641
541.9
0
III
153
9242
4038
8079.715
293
36.26
4517
559.1
1
IV
113
6512
3820
7591.865
368
48.47
4054
534.0
2
V
411
24836
9180
17888.014
873
48.80
10917
610.3
1
VI
77
4607
1990
3958.465
238
60.12
2952
745.7
1
VII
107
524S
1902
3505.581
173
49.35
2058
587.1
2
VIII
S2
3119
934
1788.352
69
38.58
750
419.4
0
IX
70
16880
3800
6871.774
452
65.78
5508
801.5
0
X
46
3285
1076
2075.527
79
38.06
1207
581.5
0
Dotal
1302
88454
31532
60997.821
3052
50.03
38558
632J.
7
As ffA Region
8: Nunber of Reports
C: Population Served IX 10~3)
0: Total NUrrber of Employees
Es Total Man-hours
-------
Statistics also indicate that the severity of injury
increases as the size of the plant increases; even though studies
also indicate that the larger the plant is, the more likely it is
to have safety equipment available and safety programs in place.
Increased personnel and opportunity for accident are the most
probable causes for this disparity.
Figure 19-2 and Table 19-3 are summaries of the types of
injuries suffered by personnel in the wastewater industry. Since
the frequency of exposure of agency personnel to some of these
types of injuries is less than others, concentration will be made
on the following areas representing the most immediate threats:
1.
Grit chambers, screens and comminutors
2.
Clarification and aeration facilities.
3.
Disinfection
4.
Lagoons and ponds
5.
Sampling
6.
Laboratory
7.
Confined spaces (digestors), wet wells
8.
Chemical hazards
9.
Aerosols and microorganisms
10.
Gases and vapors
19-6
-------
FIGURE 19-2
Parcantaga (No. Injurlaa) Raportad by Typa of Injury
Ho. Si*l*mai 144> , tnwmbgmmnn
No. InJuHaai 3118
t.rmsi
ntoinmy 1.1* (Tfl
imtMwitnnei
in no
ter**«ntoav
M%n*n
TABLE 19-3
Inddanco of disabling injury by causa of acridant.
No.
Disabling
%
Ciitn of Acddant
ln/uri«s
Total
Sprain (train in lifting, putting, or pushing
773
248
obtaets
Sprains rutins caused by cwtAward position
546
17 5
or sudden twist or slip
Struck agsinst stationary or moving objact
284
85
Struck by (ailing or dying obftcts
259
83
FaQs on samo lavai to working surfseo
2S0
80
Fills to diffarant lavai bom platform. laddor.
243
78
sum. ate.
Struck by sharp « Mint objoct
183
S9
Caught in. undar. or bocwaan obfocts
169
54
Contact with radiations, caustics, toxie. or
157
50
iwdmi substancas
Occupational iBnaas (vaccinaOoa raaction.
67
2.1
typhoid, ate.)
Contact with tamparatuto axtramaa (Bra.
55
18
frostbita. scalding, ate.)
Bub bod or abradad
S3
17
Motor wahtcta
91
18
Animal or insoct bitas
40
13
Contact with alacuic currant
8
03
Total
3117
19-7
-------
C. GRIT CHAMBERS, SCREENS AND COMMINOTORS
1. Volatile Gases and Oxygen Deficiency
Grit chambers, screens and comminutors generally serve
the same purpose of reducing or removing objectionable material
in raw wastewater. Depending on plant hydraulics and design, the
devices are located In buildings often under ground, with limited
ventilation. In extensive collection systems serving large
metropolitan areas, wastes often arrive in a septic state
containing industrial volatiles such as gasoline. The conditions
prevailing in the housing building may be identical to wet wells
or other confined space entry structures. The dangers and
precautions discussed in the previous section on Confined Space
Entry, should be followed in detail.
2. Physical Hazards
In addition to dangerous gas and oxygen deficiency,
grit chambers, screens, and comminutors also present additional
hazards. Generally, these areas remain constantly wet, with
large amounts of grease and oil present. The combination of oils
and greases with ladders, rails, and open fast moving machinery
present formidable safety hazards.
3. Flammable Liquids
Due to the construction design of grit chamber inflow
channels, oils and greases often accumulate in these areas prior
to entering the main plant. In the case of gasoline, fuel oil,
or other flammable materials that have been dumped or leaked into
the drains, dangerous accumulations may be present at the grit
chamber channels, with little or no evidence at other parts of
the plant. Agency personnel are cautioned to be particularly
alert and observant during these emergencies. Flow channels are
usually designed to decrease incoming wastewater velocity by
widening the channel. It is at this point that volatiles usually
accumulate.
4. Safety Precautions
As a minimum, the following safety precautions and gear
should be adhered to before entering grit chambers, screens and
comminutors:
o Confined area should be checked for appropriate
ventilation
o Confined area should be monitored for explosive
gases, toxic fumes, oxygen deficiencies. (See
section on Confined Spaces Entry.)
19-8
-------
o Entry, work, and inspection areas should be
checked for missing ladder rungs, hand rails, poor
lighting, missing machine guards, overhead
conveyor belts, standing water, or grease.
As a minimum, the following safety gear should be worn:
o Hard hat
o Safety splash goggles
o Rubber gloves
o Rubber soles, steel toed boots
If conditions warrant further protections;
o Close fitting slicker or water repellent outerwear
(loose or floppy fitting rain gear with
drawstrings should be avoided when entering areas
containing moving machinery)
o Knee-high rubber safety boots
o Dust or organic vapor respirator
D. CLARIFICATION AND AERATION FACILITIES
1. Flammable Liquids
The open design of clarifiers and aeration tanks
generally precludes the dangers of confined space entry.
Flammables and other volatiles may, however, be present in
sufficient quantity to explode or ignite. Sources of ignition
such as cigarettes, matches, or lighters should be prohibited in.
these areas, particularly in times of known spills.
2. Physical Hazards
The open nature of these tanks should be guarded by
extensive hand rails. Life poles, life jackets, and life rings
should all be present when entering these areas. Sample
collections or D.O meter reading in the tank area should include
the wearing of a life vest and the presence of a second person.
19-9
-------
3. Safety Precautions
As a minimum, the following safety equipment should be
worn by agency personnel entering into the clarifier or aeration
areas:
o Hard hat
o Rubber gloves
o Rubber soled safety boots
o Splash goggles
In the case of sampling:
o Life vest
Particular caution should be exercised during the
winter months. Inclement weather may result in treacherous
conditions on the walk-ways above clarifiers and aerators.
Personnel are often heavily dressed for warmth during these
times. The shock of cold water during a fall into a tank, coupled
with the weight of wet clothes could result in disaster.
E. DISINFECTION
Storage Facilities - The use of gaseous liquids, or solid
chlorine as a disinfectant and odor suppressant is common place.
For most facilities over cylinders containing one ton of chlorine
and having an accumulative weight of 3,700 lbs. Such large
amounts of a highly toxic and reactive chemical pose problems in
storage and safety. Stored cylinders should be kept under roof
away from direct contact with liquids. When chlorine gas comes
in contact with moisture, it forms highly corrosive hydrochloric
acid. Such acid is not only a threat to the worker and the
inspector, but can accelerate the rate of leakage by further
eroding the structural integrity of the cylinder.
F. CHLORINATION ROOM SAFETY
Chlorine as a gas is heavier than air and as a result, will
accumulate at floor level or in manholes or depressions.
Chlorination rooms should be separate from other facilities.
Before entering such rooms, agency personnel should examine the
exterior for floor level ventilation and power exhaust systems.
If windows are available, a visual examination of the interior
may provide evidence of the yellowish appearance of leaking
chlorine gas. Many facilities have chlorine warning systems or
instruments that can detect chlorine at 0.5 mg/1. Full face
respirators should be found near the entrance to the chlorinator
building. Never enter a chlorinator building alone. After
19 - 10
-------
satisfying oneself that ventilators are present, power exhaust
systems are working, and no visual signs of chlorine can be seen,
one person should enter the room and the other remain outside for
rescue purposes until the all-clear has been reported. Exposure
to even minute quantities of chlorine generally can be detected
by smell and watering and irritation to the eyes and nose. Any
such occurrence should be cause to exit the room immediately.
Minute leaks can often be detected visually by checking for
droplets of moisture on the underside of connections and valves.
Chlorine's affinity for water usually results in moisture
accumulation near the leak.
2. Safety Precautions
At a minimum, after exercising all previously discussed
precautions, Agency personnel should wear the following safety
gear when entering a chlorinator room:
o Hard hat
o Rubber gloves
o Safety glasses
o Rubber soled safety shoes
If chlorine in any amount is detected, no entry should
be attempted. Rescue attempts should be made with a full face
SCBA.
G. SLUDGE DIGESTION
Anaerobic sludge digestors represent a formidable safety
hazard. During the normal operations of the digestor, sludge is
converted to, among other products, methane and carbon dioxide.
Methane, when combined with oxygen at a ratio of 5:1 to 20:1, is
highly explosive. Entry into an active digestor requires
specific training and certification in confined space entry. The
scope of this course does not allow specific detailed description
of this type of training.
19 - 11
-------
H. LAGOONS AND PONDS
1. Physical Hazards
Agency personnel in the normal inspection procedure,
visit the sites of lagoons and ponds. All such ponds should have
a protective fence surrounding the immediate area. Safety rings,
life preservers, life poles and boats should be found adjacent to
these structures. When sampling, precautions should be taken to
prevent slipping and falling down banks. Inclement weather,
animal burrows and other such hazards may provide unstable
footing. Wastewater ponds range from 4 feet to 10 or more feet
deep. Such ponds represent a real threat to drowning as well as
the ever present exposure to pathogens. When sampling is
necessary, a second backup person should be present to effect a
rescue if necessary.
2. Safety Precautions
As a minimum, agency personnel should wear the
following safety equipment:
o Hard hat
o Splash goggles
o Rubber gloves
o Knee high rubber safety boots
I. LABORATORY HEALTH AND SAFETY
1. Chemical Hazards
Agency personnel involved in water and wastewater plant
inspections will normally be required to enter laboratories.
Such laboratory visits do not normally require agency personnel
to perform laboratory work. Even so, certain hazards are present
by nature of the presence of the inspector in the laboratory
environment. Routine laboratory analysis requires a wide array
of chemicals, many of which pose certain hazards. The names and
formulas of certain common acids should be known:
o Hydrochloric Acid - HC1
o Sulfuric Acid - H2SO4
o Nitric Acid - HN03
o Chromic Acid - H2SO4 + KjC^Oy
o Phosphoric Acid - H3PO4
19 - 12
-------
Not all acids react at the sane speed; exposed
personnel should not procrastinate if an accident occurs. Eyes
exposed to acid splashes should be rinsed in an emergency eye
wash for a minimum of 15 minutes. Acid splashes on skin or
clothing should be counteracted by first removing all
contaminated clothing and thoroughly flushing the skin with
water. Never attempt to neutralize acids splashed on the body
with bases or other chemicals.
Bases are also corrosive and readily react with acids,
organic solvents, clothing and skin. Frequently, skin contact
with bases is not immediately noticed by the individual until
significant damage is done. As with acids, exposure of the skin
or eyes to bases should be countered with continuous flushing
with clean water.
The names and formulas of common bases are listed
below:
o Sodium Hydroxide NaOH
o Potassium Hydroxide KOH
o Ammonium Hydroxide NH4OH (ammonia)
o Sodium Carbonate Na2C03 (soda ash)
o Soduim Bicarbonate NaHCC>3
o Calcium Hydroxide Ca(0H)2 (slaked lime)
o Calcium Oxide CaO (quick lime)
Although there are many chemicals that are commonly
found in a water and wastewater laboratory, only one other group
shall be discussed as representing a significant hazard to Agency
personnel, that of a group identified by the family name as
oxidizers.
Oxidizers by nature react with organic substances such
as skin, clothing, and organic solvents. The speed and intensity
of the reaction depend on the specific combination of oxidizer
and organic material, and the physical conditions surrounding the
site.
19 - 13
-------
The reaction can be quite violent with spontaneous combustion or
explosions resulting. By law, labels must clearly identify
oxidizers. As a rule, oxidizers should be kept separate from any
contact with organics. Listed below are some of the common names
and formulas of oxidizers frequently used in water and wastewater
analysis:
o Potassium dichromate K2Cr207
o Soduim Thiosulfate Na2S203
o Calcium Hypochlorite Ca (001)3
o Chlorine Cl2
o Sodium Persulfate Na2S20g
o Nitric Acid HN03
o Sulfuric Acid H2SO4
o Perchloric Acid HCIO4
2. Physical Hazards
To the visitor or inspector, physical hazards to be
found in the laboratory are generally classified as chemical
splashes or contact, cuts from glassware, slips or falls.
Be cautious of liquids in unmarked glassware. Always
assume its an acid or other hazardous chemical. Stay clear of
glassware such as flasks and test tubes that are being heated.
They have a tendency to suddenly spurt their contents out in the
direction they are pointed. Assume any wet spot on a lab surface
or on the outside of a reagent bottle to be hazardous. Many
reagents such as basses, are as slippery as soap. Be cautious of
slippery when laboratory floors are Wet. When entering a
laboratory, make note immediately of the location of safety
showers, eye washes and other safety devices.
3. Safety Precautions
Agency personnel entering a laboratory should, as a
minimum, wear the following safety equipment:
o Splash goggles
o Rubber soled safety shoes
19 - 14
-------
. If the inspection will require close proximity to
active experiments, the following safety gear should be added:
o Full face splash shield
o Rubber apron
o Rubber gloves
For other information regarding chemical properties and
hazards, see units pertaining to Chemical Hazards and on Chemical
Safety and Evaluation.
J. CONFINED SPACES
1. Definition
A "confined space" is defined as any enclosed or semi-
enclosed space that has limited openings for entry and exit, that
is not intended for continuous employee occupancy, and that does
not have sufficient natural or mechanical ventilation to prevent
the build-up of a hazardous atmosphere. Typical confined spaces
in the. wastewater industry are manholes, sewers, metering
stations, valve or siphon chambers, pump stations, empty tanks,
pits, or any other area in the system that has direct contact
with wastewater, sludge, or sludge gas, or conduits carrying
these substances.
As wastewater is collected and treated, chemical and
biological process changes take place, releasing or increasing
the concentrations of toxic and combustible gases. Even when
toxic or combustible gases are not present in concentrations high
enough to cause physical harm, the biological or chemical changes
may use up the oxygen in the atmosphere, creating an oxygen
deficiency which will cause asphyxiation.
2. Potential Hazards
Since confined space entry has resulted in more deaths
and injury that any other source in the wastewater industry, it
is essential to recognize the dangers and carefully evaluate the
situation prior to entry. The following list comprises the most
serious hazards encountered in confined space entry:
o Explosive gases
o Toxic gases
o Oxygen deficiency (asphyxiation)
19 - 15
-------
o Falling
o Bumping into obstructions
o Vehicular traffic
o Suffocation
Safety precautions exercised before entry into a
confined space are dependent upon the conditions that exist in
that space. Oxygen level, flammability and toxicity all must be
measured before any decisions can be intelligently made. Over
protection limits the type, amount of work, and time a worker may
remain in the space. Under protection, of course, endangers the
health and safety of the worker. Table 11-4 describes the
minimum preparation required for three classes of confined space
entry. Where information on the table coincides with the actual
work environment, the recommendations should be followed
carefully. If the conditions in the space have the potential to
change, monitoring must be done frequently and changes in safety
and health requirements changed with the conditions.
19 - 16
-------
TABLE 19—4
Confined space classification table
Parameter - Class A
Characteristics:
Immediately dangerous to life-rescue procedures require the entry
of more than one individual fully equipped with life support
equipment—communication requires an additional standby person
stationed at the confined space
Oxygen
16% or less
(a) 16.3 kPa (122 mm Hg) or greater than 25%
(b) 25.3 fcPa (190 rri Hg)
Flammability Characteristics
20% or greater of LH
Toxicity :
(b) IDLH
Paraneter - Class B
Characteristics
Dangerous, but not immediately life threatening—rescue
procedures require the entry of no more than one individual fully
equipped with life support equipment; indirect visual or auditory
communication with workers
19 -
17
-------
TABLE 19—4 (cont)
Oxygen
lb.lt tc IS.4%
(a) 16.J-19.6 kPa (122-147 mm Hg)
21.7-25.3 kPa (163-190 mm Hg)
or 21.5% to
25%
Flaramability Characteristics
10%-9% LEL
Toxicity
Greater than contamination level.
Sub Part Z (GSHA)—less than (b)
referenced
IOC*
in 29 CFR Part 1910
Paramptgr - Class C
Characteristics
Potential Hazard—requires no modification of work procedures;
standard procedures; direct communication with workers from
outside the confined space
Oxygen
19.5% to 21.4%
(a) 19.7-21.7 kPa
(148-163 mm Hg)
Flammability Characteristics
10% LEL or less
Toxicity
less than contamination level referenced in 29 CFR Part 1910 Sub
Part Z (GSHA)
(a) Based upon a total atmospheric pressure of 100 kPa (769 mm
Hg) (sea level)
(b) Immediately Dangerous to Life or Health (IDIM)—as referenced
in NIOSH
Registry of Toxic and Chemical Substances, Manufacturing
chemists data sheets industrial hygiene guides or other
recognized authorities.
19 - 18
-------
Routine often results in carelessness. Plan every
confined space entry with rescue in mind, even if the entry is to
be a brief inspection. Asphyxiation or the effects of toxic
gases require only seconds to render an inspector unconscious.
Rescue procedures should be designed for each entry. If a
confined space has an A or B classification from Table 19-4,
there should be a trained standby person with a fully charged,
positive pressure, self-contained breathing apparatus (SCBA) at
hand. Additional duties of the standby person are to maintain
unobstructed life lines and communications to all employees
within the confined space and to summon rescue personnel if
needed. Under no circumstances should the standby person enter
the confined space until he is relieved and is assured that
adequate assistance is present.
It is evident that safe confined space entry is highly
dependent on instrument monitoring of ambient air quality. See
the unit of this manual which provides an overview of monitoring
equipment availability and function.
All sewers and underground structures should be
considered dangerous until they are adequately tested. Tests
should be taken of the ambient air quality in the manhole before
removing the cover. Most manhole lids have small openings in the
cover to allow an instrument probe to be inserted. The principal
tests are oxygen deficiency, explosion range and toxic gases. If
Agency personnel are to remain in the hazardous environment for a
prolonged period of time, continuous monitoring will be required.
There have been instances, such as the arrival of spill material,
when the nature of the atmosphere has changed quickly in a
hazardous condition.
If a hazardous atmosphere is found, determination or
correction of the source is mandatory before entry, or if the
confined space has already been entered, exit must be undertaken
immediately.
Entry into a confined space should not be attempted
when tests indicate the concentration of flammable gases in the
atmosphere is greater than 25% of the lower flammable limit
(LFL), such as found in anaerobic digestors and some sewer
conditions. It is necessary to determine the oxygen level prior
to measuring the range of flammability to make necessary
corrections in the flammability measurements. It is absolutely
necessary that personnel be completely familiar with the
operation, maintenance, calibrations, and limitation of equipment
before using it to test life threatening environments.
19 - 19
-------
The percentage of oxygen for entry into a confined
space should be no less than 19.5% or greater than 25% at 100 kPa
(760 sun Hg). At sea level, the normal atmospheric pressure for
air [20.9% 02 + 78.1% N2 + 1% Ar + trace amounts of other gases)
is 100 kPa [14.7 psi or 760 mm Hg) absolute. The partial
pressure of oxygen (p02) at sea level will be approximately 21.3
kPa (160 mm Hg); p02 can be reduced by reducing the 02 level in
air.
Oxygen deficiency resulting in anoxia is an insidious
killer. The initial effects result in a psychological attitude
that is manifested by the feeling of lassitude and well being and
that will generally result in the inability of the victim to
discern the need for help. At any indications of lassitude
symptoms like those of intoxication, or decrease in alertness,
the victim should be removed from the area immediately.
Not all manholes are vented or have holes for probes.
In some cases, monitoring equipment does not have probes.
Manhole covers should be lifted with care to avoid any sparks.
When the cover has been removed, further testing of the
atmosphere for combustible gases and or toxic gases and oxygen
deficiency must be made, particularly at the lower levels where
gases with densities greater than air will accumulate.
Before entering a confined space, inspect the access
ladder for missing rungs, accumulations that will make footing
and grasping difficult, obstructions that might interfere will
passage and mechanical equipment without proper guards.
Remember, wet wells may accumulate flammable liquids on their
surface. Never enter any type of confined space with cigarettes,
matches or a lighter. Be sure there is adequate lighting
available, and, if entering a street manhole, that adequate
traffic control has been instituted.
3. Safety Precautions
Confined space entry is one of the most hazardous
priorities to be encountered in a wastewater plant. Advanced
planning and training are absolute prerequisites before
attempting entry. It is only within the scope of this course to
give the basic fundamentals of confined space entry. Further
training and certification is required before agency personnel
should attempt entry.
19 - 20
-------
At a minimum, the following safety gear should be
available for agency personnel:
o Atmospheric-testing equipment to guard against
oxygen deficiency and combustible gases and toxic
hydrogen sulfide (H2S) gas
o Self-contained air breathing apparatus for each
person going underground and for the standby
rescue crew
o Protective clothing, including rubber boots,
gloves, rain gear, hard hats with chin straps, and
face shields or goggles
o Explosion-proof lights
o Communication equipment if the scope of the work
makes it necessary
o First aid kit (including amylnitrite capsules for
H2S exposure)
o Harness and individual life lines for each person
going underground and for the standby crew above
ground
Table 19-5 is a summary of considerations for entry in
confined spaces as described by Table 19-4.
19 - 21
-------
TABLE 19-5
Check list of considerations for entry.
working in.
and exiting
confined a
paces
I ten Class A
Class B Class C
Permit
X
X
X
Atmospheric testing
X
X
X
Monitoring
X
0
0
Medical surveillance
X
X
0
Training of personnel
X
X
X
Labeling and posting
X
X
X
Preparation
Isolate/lockout/tag
X
X
0
Purge and ventilate
X
X
0
Cleaning processes
0
0
0
Requirements for special
equipment/ tools
X
X
0
Procedures
Initial plan
X
X
X
Standby person
X
X
X
Corniunications/observation
X
X
X
Rescue
X
X
X
Wbrk
X
X
X
Safety equipment and clothing
Head protection
0
0
0
Hearing protection
0
0
0
Hand protection
0
0
0
Foot protection
0
0
0
Body protection
0
0
0
Respiratory protection
0
0
Safety belts
X
X
X
Life lines, harness
X
0
Rescue equipment
X
X
X
Recordkeeping/ exposure
X
X
0 - Indicates determination by the qualified person
Class A-Atmosphere immediately dangerous to life-oxygen
deficiency, explosive, toxic, flammable.
Class B-Could cause injury or illness that can be protected
against-not immediately dangerous to life or health.
Class C-Confined space hazard requiring no work procedure modification.
19 - 22
-------
K. CHEMICAL HAZARDS
Normally, wastewater should not contain any significant
amounts of hazardous chemical materials. If significant levels
are found, they usually originate from normal industrial
discharge, accidental spillage or illegal dumping.
The types of chemicals, chemical compounds and chemical
mixtures that may be present in wastewater are endless.
Wastewater plants serving industrial communities have a much
greater probability of significant chemical content that do
others. As industrial pretreatment standards come into effect,
agency personnel may increasingly be exposed to a host of
chemicals at the industrial treatment facility. Two of the most
common exposures are to corrosive and solvent wastes.
1. Corrosive Wastes
Pretreatment facilities that are treating their wastes
for pH often receive the wastes in a potentially harmful state of
below pH 5.0 or pH above 9.0. Strong chemicals such as
hydrochloric acid (HC1) and sodium, hydroxide (NaOH) are used to
neutralize these wastes. High or low pH solutions are not only
hazardous due to their corrosive effects on human tissue, but
also are often responsible for the release of toxic gases such
as hydrogen cyanide, ammonia and chlorine. The neutralization
process itself is an exothermic process (gives off heat) and can
result in local eruptions and splattering.
Small spills of should be treated with a buffering
substance such as sodium bicarbonate. Never attempt to
neutralize an acid with a base or vise-versa. The neutralizing
is very exothermic and often results in splattering.
2. Solvent Wastes
Nearly all common solvents can be linked to some form
of health hazard. Chlorinated solvents such as trichlothylene
have been identified as suspected carcinogens. Highly volatile
solvents such as xylene and acetone can burn, explode,
asphyxiate, or emit poisonous vapors. In addition, most
flammables have a defatting effect on the skin that removes the
protective oil film and leaves it susceptible to attack by
weather, bacteria, or other chemical agents. Before entering any
confined space such as wet wells, pump stations, grit or
comminutor rooms, a thorough check, of ambient air quality should
be undertaken. In the case of the anticipation of spilled
material arriving at a plant, air monitoring should be
continuous.
19 - 23
-------
L. GASES AND VAPORS
Gases and vapors are the normal products of bacterial action
on waste products as well as a result of industrial discharge of
entrained gases into the treatment system. Of particular concern
to agency personnel is that of significant levels of gases that
are found in confined spaces, that exhibit the properties of
explosiveness, flammability or toxicity. Due to the physical
design of wastewater plants such as wet wells, as well as
physical processes such as aeration, uncommonly high levels of
these gases and vapors may be found. Table 19-6 lists the
characteristics of gases common to the wastewater industry.
19 - 24
-------
TABLE 19-6
Characteristics of gases ccmiun to the wastewater injustzy
Gas and chemical formula
Ammonia NHj
Specific gravity
0.59
Explosive limits - LEL UEL
16 25
Maximum safe 60-min exposure (t vol. in air)
0.03
Maximum safe 8-hr exposure (% by vol. in air)
0.01
Cdmnon properties
Colorless, sharp, and pungent
Physiological effects
Irritates eyes and respiratory tract; toxic at 0.01%
Location of highest concentration
Op high
Most ccwiun sources
Sewer gas
Slrrplest and safest method of testing
Oxygen deficiency indicator; odor
Gas and chemical formula
Carbon Dioxide C02
Specific gravity
1.53
Bqplosive limits - LEL us,
Honflanrable
Maximum safe 60-min esqsosure (% vol. In air)
4.0-6.0
Maxirrun safe 8-hr exposure (% by vol. in air)
0.5
Comnon properties
Colorless, odorless, nonflammable; may cause acid taste in
large quantities
Physiological effects
Acts on respiratory nerves; lot cannot be endured for more
than a few minutes
Location of highest concentration
Dawn law but may rise if heated
Most cowwon sources
Sludge, sewer gas, combustion carbon and its confounds
Sinplest and safest method of testing
Oxygen deficiency indicator
Gas and chemical formula
Carbon Monoxide CO
Specific gravity
0.97
19 - 25
-------
Explosive limits - LEX, UEL
12.5 74.2
Maximum safe 60-min. exposure (% vol. in air)
4.0
Maximm safe 8-hr exposure (% by vol. in air)
0.005
Conmon properties
Colorless, odorless, tasteless, non-irritating; flammable,
explosive, poisonous
Physiological effects
Combines with hemoglobin of blood causing oxygen starvation;
fatal in 1 hr. at 0.11; unconsciousness in 30 min. at 0.251
and causes headaches in a few hours at 0.02%
Location of highest concentration
Up high specifically if in presence of illuminating gas
Most coiumn sources
Manufactured fuel gas, flue gas, confcustion and fires
Simplest and safest method of testing
00 indicator
Gas and chemical formula
QUorine Clj
Specific gravity
2.49
Dqplosive limits - LB, UEL
Nonflammable
Maxiitun safe 60-min. exposure (I vol. in air)
0.0004
Maximum safe 8-hr exposure (t by vol. in air)
0.0001
Cannon properties
Yellow-green color; irritating, pungent odor; nonflammable
and supports combustion
Physiological effects
Irritates respiratory tract, causes irritation and burning
of the skin, coughing and pulmonary edema in small
concentrations
Location of highest concentration
Down low
(tost caiman sources
Qilorine cylinder and feed line leaks
Simplest and safest method of testing
Qilorine detector
Gas and chemicil formula
Ethane C2H$
Specific gravity
1.0S
&plosive limits - X2, UQ,
3.1 15
19 - 26
-------
Maximum safe 60-min. exposure (% vol. in air)
No limit provided oxygen percentage (at least 12%) is
sufficent for life
Conron properties
Colorless* odorless, tasteless, flammable, e^losive, non-
poisonous
Physiological effects
Acts mechanically to deprive tissues of oxygen; does not
support life
Location of highest concentration
Down low
Most common sources
Natural gas
Sinplest and safest method of testing
Combustible gas indicator, oxygen deficiency indicator
Gas and chemical formula
e Gasoline C5H12-C9H20
Specific gravity
3.0-4.0
Explosive limits - IS, DEL
1.3 7
Maxljiun safe 60-min. exposure (t vol. in air)
0.4-0.7
Maximum safe 8-hr exposure (% by vol. in air)
Varies
Common properties
COlor, flanrable, explosive, odor noticeable at 0.03t concentration
Physiological effects •
Symptoms of intoxication when inhaled, difficult breathing
and convulsions; fatal at 2.43%
Location of highest concentration
Dcwn low
Most coiiiion sources
Service stations, storage tanks and dry cleaning operations
Sinplest and safest method of testing
Contoustible gas indicator; oxygen deficiency indicator
Gas and chemical formula
Hydrogen Sulfide HjjS
Specific gravity
1.19
Explosive limits - LEL UEL
4.3 46
Maximum safe 60-tni. exposure (I vol. in air)
0.02-0.03
Maximum safe 8-hr. exposure (% by vol. in air)
0.001
Conron properties
Rotten egg odor in small concentrations; colorless,
flammable and e^losive
19 - 27
-------
Physiological effects
Paralyzes the respiratory system; lessens the sense of smell as
concentration increases; rapidly fatal at 0.2%
Location of highest concentration
Down lew; can be higher if air is hot and humid
Most conmon sources
Coal gas, petroleum, sewer gas and sludge gas
Sijnplest and safest method of testing
Lead acetate paper, lead acetate ampoules, H2S detector
Gas and chemical formula :
Methane 014
Specific gravity
O.SS
Btplosive limits - IS. UEL
5 IS
Maximum safe 60 min. exposure (« vol. in air)
No limit providing sufficient oxygen (at least 12%) is present
Gormen properties
Colorless, odorless, tasteless, explosive, flammable, and
non-poisonous
Physiological effects
Deprives tissues of oxygen; does not support life
Location of highest concentration
At top# increasing to certain depth
tost conmon sources
Digestion of sludge
Simplest and safest method of testing
Combustible gas indicator; oxygen deficiency indicator
Gas and chemical formula
Nitrogen N2
Specific gravity
0.97
Bcplosive limits - LEL UEL
Nonflaimable
Conmon properties
Colorless, tasteless, odorless, and nonflammable
Physiological effects
In very high concentrations, reduces oxygen intake; does not
support life
Location of highest concentration
Op high and sometimes in low areas
Most cairoon sources
Sewer and sludge gas
SLnplest and safest method of testing
Oxygen deficiency indicator
Gas and chemical formula
Oxygen (in air) 02
Specific gravity
1.11
Bqplosive limits - LEL US.
19 - 28
-------
Nonflanrable
Connor. properties
Colorless, odorless, tasteless; supports combustion
Physiological effects
Normal air contains 20.93% 02. Below 19% considered
deficient; 131 dangerous; below 54-7% fatal
location of highest concentration
Variable at different levels
Most common sources
Oxygen deficiency from poor ventilation and chemical
combustion of Oj
Sinplest and safest method of testing
Oxygen deficiency indicator
Gas and chemical formula ¦
Sludge gas
Specific gravity
varies
Explosive limits - LEL UEL
5.3 19.3
Maximum safe 60-min. exposure (% vol. in air)
Varies with composition
Common properties
Flanrable, practically odorless, and colorless
Physiological effects
Will not support life
Location of highest concentration
Up high
Most common sources
Digestion of sludge
Simplest and safest method of testing
Combustible gas indicator, oxygen deficiency indicator
M. PATHOGENIC HAZARDS
1. Aerosols
Aerosols and mists generated at wastewater treatment
facilities can be responsible for the spread of a host of
diseases caused by viruses, bacteria, (see Tables 19-7 and 19-8)
and fungi (see Table 19-9).
19 - 29
-------
TABLE 19-7
Diseases Associated with Human Fecal Waste
Bacterial infections
Typhoid fever
Paratyphoid fevers
Cholera
Shigellosis (bacillary dysentery)
Viral infections
Poliomyelitis
Coxsackie infection
Infectious hepatitis
(very many other enteric viruses exist)
Potozoal.infections
Entamoeba histolytica
Helminthiasis
Fish tapeworm
Beef tapeworm
Pork tapeworm
Pinworm
Roundworm
Whipworm
Hookworm
TABLE 19-8
Diseases Associated with Animal Fecal Waste
Salmonellosis
Infection from pig intestinal protozoan
(Balantidium coil)
Helminthiasis
Pig ascaris
Animal tapeworms
Hydatid worm
19 - 30
-------
TABLE 19-9
Fungus Diseases (Mycoses) Associated with Solid Vfastes
Coccidioidomycosis
Sporotrichosis
Histoplasmosis
Candidiasis
Workers can be infected directly by inhalation or
indirectly by droplets settling on clothing. Sources of aerosols
include aeration tanks, weirs, and flumes, spray and irrigation
sites. Indoor areas where aeration occurs are likely to have the
highest aerosol concentrations.
Table 19-10 lists factors that nay affect bacterial and
viral survival in aerosols. By understanding the conditions for
increased survival, Agency personnel may be better able to
protect themselves.
19 - 31
-------
TABLE 19-10
Factors that affect the survival and dispersion of bacteria and viruses
in wastewater aerosols
Factor
Remarks
Relative humidity
wind speed
Sunlight
Temperature
C£en air
Bacteria and most enteric viruses
survive longer at high relative
humidities, such as those occuring
during the night. High relative
humidity delays droplet evaporation
and retards organism die-off.
Low wind speeds reduce biological
aerosol transmission.
Sunlight, through ultraviolet
radiation# is deleterious to
microorganisms. The greatest
concentration or organisms in aerosols
from wastewater occurs at night.
Increased temperature can also reduce
the viability of organisms in aerosols
mainly by accentuating the effects of
relative humidity. Pronounced
temperature effects do not appear
until a temperature of 80 degrees F
(26 degrees C) is reached.
It has been observed that bacteria and
viruses are inactivated more rapidly
when aerosolized and when the captive
aerosols are exposed to the open air
than when held in the laboratory.
Much more work is needed to clarify
this issue.
19 - 32
-------
N. PARASITIC DISEASES
Parasitic diseases such as hookworm and ringworm can also be
spread by contact with contaminated material and ingestion
through the mouth, usually while eating or smoking, or contact
with exposed skin.
O. SAFETY PRECAUTIONS
Use of proper protective equipment such as rubber gloves and
washable or disposable coveralls -will prevent contact with
contaminated surfaces. Washable coveralls should not be washed
with other non-work related clothing or in the family washer. A
washer dedicated to contaminated work clothes should be made
available at Agency headquarters. Disposable clothing should be
placed in a plastic disposable trash bag and sealed before being
disposed of. Boots, gloves, and other non-disposable equipment
should be thoroughly scrubbed in a strong soapy solution
containing a bactericide such as tincture of Roccal or Wescodine.
Above all, care must be taken to institute a comprehensive
program of personal hygiene. After contact with wastewater or
inspection of a wastewater facility, agency personnel should
shower before leaving for home. Never eat, drink, or smoke
before thoroughly scrubbing hands. In high aerosol areas wear
gauze-type respirators to reduce inhalation of pathogens. Always
launder reusable clothes after each day of contact. Never wear
disposable cloths more than once. Dispose of these clothes
properly. Report any illness or infection promptly to your
supervisor. Receive medical check-ups regularly.
19 - 33
-------
STUDENT EXERCISE 1
Directions:
The following exercise is broken into four sections. Each
section corresponds to a specific location in a typical wastewater
facility. The student is to examine the given information (drawings
and descriptions) and complete the exercise pertaining to that
section's information. A list of available equipment is given at the
beginning of the exercise.
General Description:
The plant to be inspected is a typical 3.0 mgd activated sludge
plant located in Eau Claire, Wisconsin. The plant serves a small city
of 100,000 with a fairly large manufacturing base consisting of
electrical appliance manufacturers, rubber tire manufacturers, leather
product manufacturers and breweries. The outfall is a large river.
The plant was built in the 1930's, with some improvements since. The
date is late February, with a large accumulation of snowfall but very
little melt-off.
Available Equipment:
30-minute airpack (S3A)
Organic vapor respirator
Full face shield
Splash goggles
Safety goggles
Rubber safety boots
Rubber soled safety shoes
Hard hat
Rubber gloves
Rain gear (coat and hood)
Disposable water resistant overalls
Safety line and harness
2-way portable radio
Ttotally enclosed acid suit
HjS monitoring equipment
O2 meter
Explosive gas monitor (LEC meter)
First aid kit
Flashlight
Denim work overalls
Leather gloves
Disposable gauze face mask
Leather soled vrerk shoes
19 - 34
-------
STUDENT EXERCISE 2
A. After examing Figure 19-3, list at least 10 safety hazards
that can be spotted.
1 .
2 . ;
3 . •'
4 . ;
5 .
6. _
7 .
8 .
9 .
10.
B. List at least 3 hazards that may be present but cannot be
seen.
1.
' 2.
3.
c. What safety precautions would you follow before entering an
area similair to the one diagrammed?
1 .
2 . ; '
3 .
D. At a minimun, what safety equipment would you take before
entering into an area similair to the one diagrammed?
1 .
2 .
3 .
4 .
19 - 35
-------
-------
u>
I
u
-------
STUDENT EXERCISE 3
A. After examing Figure 19-4/ chlorine disinfection room, list
at least 10 safety hazards that can be spotted.
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
B. For each of the hazards listed above, list in the
corresponding number what should be done to eliminate the hazard.
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
19 - 38
-------
STUDENT EXERCISE 4
A. After exaraing Figure 19-5, list at least 10 different safety
hazards than can be seen.
1 .
2 . ;
3 . __
4 .
5 . ;
6 . ;
7 .
8 . ;
9 . ;
10.
B. Explain your actions if the following laboratoy accidents
were to occur:
1. Acid is spilled on you:
2. A chemical gets into your eyes:
3. Acid is spilled on the floor:
19 - 39
-------
)
I
1
II II 11 1
JL
_L
1
_L
_JL_
1
11
IteEiwH _7m—"
^RstM
=" aid n 3
l\#y
II
1
II
w
JaOa)
i. -!
-if—
Ci
» 1 1
~l
;<
1.
H
O
u>
I
U1
II
0
0
J
D
D
0
-------
-------
STUDENT EXERCISE 5
Examine Figure 19-6. An industrial site upsteam is suspected of
dumping a lage quantity of toxic, highly volitile, chemicals into
the sanitary sewer.
A. Using appropriate informal resources, determine if this
situation is a Class A, B or C confined space.
Answer
B. Give the rationale for your choice in A:
C. List 10 safety precautions that should be taken before
entering the manhole:
1 .
2 .
3 .
4 .
5 .
6 .
7 .
8 .
9 .
10.
D. List the appropriate safety equipment that should be
available before entering this Class of confined space:
19 - 42
-------
UNIT 20
MIME SAFETY
A. INTRODUCTION
Both surface and underground nines are regulated very
strictly to assure the safest practical working conditions. EPA
personnel who need to enter and inspect a mine should have
comprehensive. awareness of the dangers, and the rules,
procedures, and equipment that are used to make this dangerous
environment safer.
If you know what a well-run mine should look like, and know
how to look for commonly occurring dangers, you will have a good
basis for judgment about whether the mine is operated with safety
in mind. If you have as much concern for the attitudes of
management as for specific environmental problems, it will be
helpful to you to know what to look at in a mine.
The mine operator must inform workers, and visitors of any
need for special clothing or safety equipment and must provide
safety orientation to tell all visitors (and employees) about the
mine*s safety precautions. The mine operator must provide the
necessary special clothing and equipment for the employees. The
mine management may lend you the clothing and equipment needed,
but the management is not required to do so. Ask, in advance, if
the mine operator will provide personnel with what is needed. In
any event, personnel should provide their own hard hat, safety
glasses, and safety footwear, even if the mine provides the other
necessary items.
The hazards in mining include the possibility of earth
slides or cave-ins, toxic gases, the use of explosives, a
possible inadequacy of oxygen, and proximity to powerful
machinery, including narrow gauge railroading, massive earth
moving equipment, elevators and hoists.
B. MOVING VEHICLES AND MACHINERY
Mining regulations stress equipment safety. Moving
equipment must have safety and warning devices. All equipment
operators and their supervisors must be trained people, and they
must use signals before putting the equipment in motion.
Equipment maintenance or repair may take place only after
power has been shut off and the equipment has been blocked to
prevent movement. All machinery must be inspected regularly and
maintained in safe condition. Loading and hauling equipment must
be inspected before each use. Defective equipment or machinery
may not be used until it has been repaired.
20-1
-------
Underground nine tunnels must serve both hauling equipment
and people. There must be at least inches of clearance between
the sides of the hauling equipment and the walls, or else shelter
holes at least four feet wide, with 40 inches of clearance must
be provide, and they must be marked clearly with lights,
reflectors or luminous paint.
In coal mines the shelter holes must be at least 4 feet
wide, 5 feet deep, and 6 feet (or the height of the seam,
whichever is less) high, and located every 105 feet. The
elevators and hoists are inspected daily, in underground coal
mines, and the safety catches are tested bi-monthly.
In other underground mines, hoists and elevators are
inspected, tested, and maintained systematically, and records
must be retained for three years.
Underground shuttle cars and mining equipment must have
strong canopies or cabs to protect the operators from anything
that might fall. All air compressors and boilers must be
inspected and maintained to meet the national safety standards.
Finally, good housekeeping is required in all mines. Loose
material, garbage, and unneeded gear must be kept away from
machinery and equipment, and must be regarded as a hazard to be
kept away from the work areas.
C. HAZARDS FROM UNSTABLE SURFACES
A Federal regulation requires that inspections and testing
of mine surfaces, in all mines, must occur as often as necessary
to insure safety. The mine operators must examine and test
potentially dangerous surfaces before any work may begin or any
machinery be started. Nevertheless, falls of rock from unstable
mine surfaces (face, roof, and ribs) are the primary cause of
injuries and deaths in mines.
In a mine, the ceiling is called the roof or back. The
walls may be called walls, ribs, pillars, or the face. The face
is the surface being mined, sometimes called the working face.
The floor is called the floor, but it may also be the roof of the
level below. In a coal mine, the roof directly (closest)
overhead is called the "immediate roof" and the rock bed or beds
above that are the "main roof." The immediate roof and the beds
above are the "strata" (of layers of sedimentary rock in which
the material being mined is found), and the material above the
(coal, ore, etc., bearing) strata is called the "overburden."
If the immediate roof is not supported, its own weight
(possibly enhanced by the weight above it) may cause the
immediate roof to sag, crack or collapse. When that happens,
methane gas may escape, or a space may be created where water can
collect to weaken the roof further.
20-2
-------
Coal mines use three systems to port the roof: bolting, in
which roof bolts are the only supports; conventional, in which
posts, timbers, jacks, cribs, sills, or beams are used in various
combinations; and the combinations system which uses roof bolts
plus other means of support. Roof control plans are required,
but we will not take time to consider all the possible variations
that can be employed.
Temporary supports must be installed before attempting the
installation of permanent supports. No one should go beyond a
temporary support unless it is within five feet of a permanent
support, and only workers installing temporary supports may go
beyond the last permanent support. Only experienced workers
should attempt to recover roof supports during retreat mining and
pillaring, and roof supports should be left in place if there is
any sign of roof weakness.
Visual inspection of supports may reveal undue load on the
supports (and thus roof weakness) if any of the following can be
observed:
o bending or decayed timbers, posts, or crossbars
o small chips or bark broken from supporting timbers
o roof bolts showing stress
o caps squeezed down and over many posts
Other danger signs are: slips, fractures, cleavages, or
crumbling of coal, rock or ore; changes in the rock texture; or
any moisture appearing in the roof after supports have been
installed; or any wetness in a spot that previously was dry.
The roof may be tested audibly by striking it. A solid,
clear, ringing tone signals a sound, solid roof. A drum-like
sound results when rock layers have separated and the roof is
loose. A loose thud signals loose rock or coal, and reveals a
very dangerous condition that must be corrected immediately.
An experienced worker will:
o test while standing under a supported roof
o be sure there is a safe line of retreat
o never turn away from the ribs, but always face them
20-3
-------
o always wear goggles
o never assume someone else tested the roof
o examine the roof frequently during the working shift
The most frequent falls come, not from roof, but from ribs
or walls, when the roof pressure above causes pieces of coal, ore
or rock to break off and fall or roll. Eternal vigilance might
be the best motto for the miner. When "ground falls," or falls
of material from the roof, are discovered, it is obvious that a
dangerous situation exists. It must be corrected before work can
continue in that part of the mine.
In surface mining, you will encounter some of the largest
earth-moving equipment developed by our race. Pit design is an
important consideration. The sides must not be so steep that the
walls might slide or collapse, even in a torrential rain storm.
Benches (level areas) may be incorporated in the walls, to
provide roads on which equipment can enter or leave the pit. If
the movement of material might occur and present a hazard,
barriers should be provided.
Loose and unconsolidated material must be moved back
(stripped) at least 10 feet from the top of the pit (or quarry
walls). Overhanging material, or hazardous banks, must be taken
down so that nothing can fall on the workers (or visitors).
As a visitor, avoid dangerous banks or other possible unsafe
ground, and don't walk between pit walls or banks and pieces of
equipment—where you might be trapped in case of a fall or slide.
D. HAZARDS FROM BLASTING OPERATIONS
Drilling and blasting are hazardous operations. Explosives
are used only by miners who have been trained to use them.
Explosives must be packed into blast holes and then non-
combustible stemming (packing) material must be tamped in place.
If the charge is not packed properly, a shot may blow out, and
dust or gasses may ignite and explode — a much larger explosion
than was planned. If the blasting material burns instead of
exploding, toxic gases may form and be circulated by the
ventilation system. The toxic gases may include:
o Carbon monoxide (CO), a very poisonous gas and
o Nitric oxide (NO) , a toxic gas generated when
explosives burn. When NO reacts with oxygen (0^) in
the air, nitrogen dioxide (NO2) is formed, and it is
potentially fatal when inhaled.
20-4
-------
Explosives must be kept dry, and the detonators must be
stored well away from the explosives. They all should be stored
in secure containers until just before use.
When explosives are taken to the site where they will be
used, they are to be transported in closed containers of
nonconductive material. In underground coal mines, explosives
are moved on belts in locomotive- or rope-towed cars, in shuttle
cars, or in specially designed safety equipment. In other
underground mines and surface coal mines, explosives are moved in
separate vehicles and are separated from the detonators by at
least four inches or hardwood or its equivalent.
A few words about explosives may be helpful. TNT
(trinitrotoluene) is an excellent military explosive. It is
powerful, but a Corps of Engineers blasting cap is required to
make it explode. A common form consists of quarter-pound blocks,
like hard plastic blocks. You can shoot at TNT with a rifle
bullet going 3000 ft/sec, chop TNT with an axe, pound it to
powder with a hammer, burn it in a fire, or explode black powder
next to it; none of these will make it explode. It will seldom
explode, by accident. Nitroglycerine, in contrast, is a liquid
that may explode if you drop the vial. Nitroglycerine was made
safer by soaking it into sawdust; that form is called dynamite.
Fresh dynamite is quite safe, but if dynamite is stored for a
long time, the nitroglycerine may drain to the bottom,and old
dynamite is about as unstable as plain nitroglycerine. Dynamite
is used frequently by miners and well diggers. A new favorite
explosive is ammonium nitrate, present in some fertilizers (e.g.,
Scott's Turf Builder). In quantities of a few pounds, it is
extremely safe, unless it is mixed with heavy oil. That slurry
will conform to the shape of an uneven blast hole, and a blasting
cap will set it off. Many miners and demolition men use ammonium
nitrate. A very large quantity of ammonium nitrate can be
exploded by a spark, even without the oil, but small quantities
are quite safe, until the oil is mixed in. There are many other
explosives. These are simple examples that may aid your
understanding of explosives and their uses, advantages, and
dangers.
Only explosives handlers may ride in a vehicle carrying
explosives, and then only if they are specifically needed. No
other material may be carried in the vehicles that are
carrying explosives, and those vehicles should be identified
clearly and never left unguarded.
20-5
-------
Regulations on explosives include the following:
o The areas around explosives must be cleared, guarded,
barricaded, and marked clearly to warn miners and mine
visitors.
o A warning must be given before any explosive is
detonated.
o Smoking is prohibited within 25 feet of explosives or
detonators.
o After blasting, searches must be made for fires and
undetonated charges.
Smoking is always prohibited in coal mines and gassy mines
(those with methane). Underground coal mines require special
precautions:
o Methane tests must be made in underground anthracite
mines before blasting; the methane level must be below
one percent; and
o Combustible material must not be used to stem the blast
holes.
E. HAZARDS OF MIME GASES
The presence of toxic gases and the absence of sufficient
oxygen are the twin hazards for those breathe the atmosphere in
an underground mine.
The list of Dangerous Gases is usually headed by methane.
Methane is flammable in air at concentrations from 5 to 15
percent, and it explodes very readily. Any mine in which methane
can be detected is a "gassy mine," and the maximum allowable
concentration is one percent. If methane exceeds one percent in
any area, several things must happen (or NOT happen).
o No electrical equipment may be energized, operated, or
taken into the mine.
o No blasting is permitted.
o No pillar recovery or intentional roof fall is
permitted.
o Ventilation must be increased. Air used for ventilation
may not contain more than 0.25 (one-quarter] percent
methane.
o Power must be shut down.
20-6
-------
Coal nine operators must conduct tests for methane three
hours (or less) before each shift and at least once during each
shift, in every work sector.
Gassy Mines: As stated earlier, any mine in which methane
is found is a "gassy" mine, and all coal mines are considered to
be gassy. Smoking is prohibited in all gassy mines. Welding
requires continuous methane testing before and during the welding
job. Correct door positions (Open or Closed) during ventilation
must be identified clearly. Methane monitors are required on the
mining equipment. And, all working areas must be tested for
methane within three hours before a new work shift enters the
mine.
If the methane concentration exceeds one percent within 12
inches of the back, face, or rib, work must stop; and all
equipment must be shut down until the methane concentration is
reduced below one percent. If the methane concentration reaches
1.5 percent, or if the ventilation fans stop, the miners must be
evacuated from the area, and all electrical power must be shut
down.
In coal mines, methane monitors on such equipment as
continuous miners, longwall and face cutting equipment, and
loading machines must be as close to the working surface as
possible, and they should be set to give an automatic warning if
the methane concentration should reach one percent, and to shut
off the equipment automatically if the methane reaches two
percent or if the monitor malfunctions.
Other dangerous gases may occur:
o Carbon monoxide (CO) results from blasting, fires, or
incomplete combustion or oxidation. It binds to
hemoglobin and prevents blood from carrying oxygen; it
produces headache, nausea, weakness, confusion and
death. It also burns. The Permissible Exposure Limit
(PEL) is 50 ppm.
o Nitric Oxide (NO) was discussed under blasting. It can
be fatal. PEL = 25 ppm.
o Nitrogen dioxide (NO2) comes from gasoline or diesel
engines, welding, blasting, or electrical discharges.
PEL = 5 ppm.
o Carbon dioxide (C02) is formed in fires and explosions,
and released by the action of acid on carbonate rocks.
It is mainly dangerous if its formation removes too
much oxygen from the air and thus causes suffocation.
The PEL ¦ 5000 ppm.
20-7
-------
o Hydrogen (H^) is extremely flammable, with a lower
explosive limit (LEL) of 4 percent, and an upper
explosive limit (UEL) of 75 percent. it is released
when storage batteries are charged, and in some high
temperature reactions.
o Hydrogen sulfide (H2) has the smell of rotten eggs, and
it is very deadly. PEL = 20 ppm. It also will burn.
Welding may release, or cause the formation of, toxic metal
fumes (from zinc), arsenic, or phosgene. Good ventilation is
important to safe welding.
Oxygen deficiency is considered to exist if the oxygen drops
from the normal value of about 21 percent in air to 19.5 percent
or lower. Oxygen can be consumed by combustion (fires, liquid
fuel engines, etc) or can be displaced by various other gases
such as carbon dioxide, methane, or hydrogen. Mine operators are
required to test for oxygen frequently, and to stop work and take
corrective action if the concentration should drop below 19.5
percent.
Personal protection involves the use of proper clothing and
equipment, and the availability of suitable respirators or masks
to permit survival in a toxic atmosphere.
Even mine clothing is regulated by Federal Law. Hard hats
are mandatory wherever falling objects may threaten the safety of
workers or visitors. If deep water exists within a mine, life
jackets or safety belts must be available. Seat belts must be
used if there is a possibility for a vehicle to turn over, and
where roll-over protection is provided. Snug clothing must be
worn around machinery or equipment that moves. Wherever special
hazards of radiation, chemicals, mechanical irritants, or toxic
or corrosive materials may occur, suitable protective clothing
or equipment must be worn or used. Miners in underground mines
must wear personal cap lamps and carry portable electric lamps.
Respiratory protection is an absolute necessity if people
are to escape from dangerous atmospheres.
Self-rescue devices have a filter that reacts with carbon
monoxide and will protect for one hour against CO concentrations
up to one percent. A self-rescuer will enable a miner (or
visitor] to get out of a mine that is contaminated with carbon
monoxide. It will not supply oxygen nor protect against other
toxic gases.
20-8
-------
A self-contained breathing apparatus (SCBA) with a tank of
compressed air will protect against any dangerous atmosphere (but
will not, of course, prevent an explosion). Another version is
the self-contained oxygen-generating breathing device. It
provides a 60-minute supply of oxygen.
Abandoned mines will, obviously, present a wide range of
possibly unsafe conditions. Toxic gases or inadequate oxygen are
obvious possibilities, and weakened roof supports are another
danger. If you must enter an abandoned underground mine, take
SCBA equipment, atmosphere monitors, especially explosive gas
detectors, and don't go alone. Proceed with great caution, while
a rescue team waits outside, or well back, to get you out if
danger overtakes you.
F. MIME COMMUNICATIONS
A mine operator must always know the location of every miner
and visitor in the mine. Every mine worker must be able to
contact any, or all, of the others. The surface (of an
underground mine) must have communication with all parts of the
mine, and the connection(s) above ground must be attended at all
times, and they should be located within 500 feet of the mine
entrance. The communication system should have its own power
source, independent of the electrical system for the mine.
Hoists and elevators require two signalling systems; one
must be a telephone or speaking tube. Trolleys and railroads may
have two-way radios or trolley phones. They may need their own,
independent, power source. Some mines use time clocks or boards
to record people entering (and their destination) and leaving.
Other mines use two metal tags for each person entering; the
worker keeps one tag and leaves the other with the cage man.
Surface mining communications needs are simpler, but any
miner working in a hazardous area must be able to communicate
with others. Federal regulations define other communication
needs according to conditions.
Mining is a dangerous occupation, and underground mines are
dangerous places to enter and inspect. Use this presentation as
a beginning of understanding, and pay close attention to the
orientation that will explain the safety precautions in any mine
you may need to enter.
20-9
-------
STUDENT EXERCISES
1 (a) You are looking at the roof support in a 5-year-old mine
tunnel* to see if the roof is sound. What should you look for?
1 (b) If the roof, walla, and supports look goed, ycu can still
make an audible test. Describe that test, the possible results,
and their meaning and significance.
20 - 10
-------
2. Which dangers of underground mining are absent from surface
mining or quarrying?
3. What do you think are the three greatest hazards of surface
mining?
20 - 11
-------
4. When blast holes were drilled into a mine face, some methane
seeped out, but the methane monitor was acting very erratic, and
the methane concentration was unknown. The new blasting expert,
who started work a day earlier, said, go on and blast, becausse
the blast would disperse that "little bit" of methane, and the
ventilation system would carry it away. Discuss this situation.
20 -,12
-------
5 (a) In an underground coal mine, a gasoline-powered generator
for welding is running badly and making bad smells. Monitors
show 20 ppm of carbon monoxide and 10 ppm of nitrogen dioxide,
measured one foot from the exhaust pipe. Should the welding job
be finished before the generator is sent "up" for repair?
Explain your answer (no credit for a lucky guess).
5 (b) Can welding continue for another half hour if all the
workers wear "self-rescue" masks? Explain why.
20 - 13
-------
UNIT 21
SAMPLING AT HAZARDOUS WASTE SITES
A. INTRODUCTION
It is the opinion of many that sampling at a hazardous waste
site represents the most dangerous environment faced by field
crews. Often crews are faced with a multitude of unknowns, in
various physical states, often in highly concentrated amounts and
in a variety of containers in dubious or poor condition.
Such combinations of threats and unknowns must be met with
proper planning, training, and practice.
It is fitting to say that nearly every unit in this manual
can be put to use when preparing to enter and sample a hazardous
waste site.
B. PLANNING AND PREPARATION
Planning and preparation for an investigation at a hazardous
waste site may in some cases take more time than the
investigation itself. There are three essential activities in
planning work at a site. They are:
o Obtain information about hazards at the site.
o Decide on the personal protection needed in different
areas.
o Define the boundaries of contaminated and
decontamination areas.
As preparation for an investigation of a hazardous waste
site, personnel need to:
o Prepare safety procedures and equipment.
o Gather all needed equipment.
o Provide training and practice in use of equipment and
procedures.
o Conduct a preliminary survey to get the detailed
information.
21-1
-------
The number of field personnel that should be assigned to a
hazardous waste site investigation depends on the number needed
for safe use of protective equipment, the length of time each
person can work under the particular stresses of the job, and on
the time available for the investigation.
For example, a team of at least three people is required for
safe and effective use of respiratory protection and a team of
five persons for use of encapsulating suits, because of the
requirements for teamwork and stand-by assistance. Working in
air supplying respirators will require a compressed air supply,
and extra cylinders or a special compressor. Rest periods are
also required to reduce fatigue and heat stress that are
generated by the work and by the use of the protective equipment
afid clothing. The amount of working time is also limited by the
activities of getting into and out of protective equipment and
decontaminating it.
1. Planning
a. Obtaining Information
The first step in a waste site investigation is
obtaining information about the hazard expected at the site and
about off-site sources of emergency assistance and supplies.
(1) Information About Site Hazards and Conditions
Planning begins with gathering as much
information as possible about the materials dumped at a site.
The effort may include a long search through records, and
interviews with former employees and people living near the site.
After information is gathered on the identity of materials
dumped, it may be necessary to find out what is known or
suspected about the characteristics and hazards of those
materials.
Information about physical conditions at the
site should include geologic and topographic maps, road maps,
and aerial photographs if available. Data on the prevailing wind
and weather conditions expected at the site can be very important
for carrying out the investigation safely.
Information should also be gathered about
conditions at the site, which may present safety and sampling
problems, such as soft or marshy areas, large or unstable piles,
and heaps of building materials or large pieces of reinforced
concrete.
21-2
-------
(2) Off-Site Emergency Assistance and Resources
Obtain information concerning off-site
emergency assistance and resources at a hazardous waste site
before the investigation begins.
Find out if emergency medical assistance is
available, such as an ambulance service or a fire department
paramedic team. Find out how to request assistance and how to
identify your location.
Find out which nearby hospital has Emergency
Room service, and whether there are laboratories nearby that can
perform useful tests in case of a chemical exposure emergency.
If there is any possibility of fire at the
site, find out which fire department will respond (if any), how
to contact the fire department that will respond and how to
identify the site so that they know where to respond.
Call all emergency numbers to find if they
are accurate and current, since hazardous waste sites are often
remote from usual sources of supplies and protective equipment.
Find a source of replacement supplies near the site or take extra
supplies. If there are supplies that will be expended in great
quantity at the site, try to find a company that stocks the items
that will be needed.
Routine replacement of compressed breathing
air should be arranged by finding a fire department or company
that can provide a reliable supply. If possible, get a sample of
the air that can be supplied and have it tested for quality.
b. Deciding on Levels of Protection
Deciding on levels of protection to be used at a
hazardous waste site is an important but difficult process based
on assessment of the known or suspected hazards at the site. For
the purpose of choosing protective equipment, the hazards can be
grouped in three categories: unknown or severe respiratory
hazards plus severe skin exposure hazards; severe respiratory
hazards without severe skin exposure hazards; and moderate
respiratory hazards; with skin exposure unlikely.
For convenient reference, special groupings of
protective equipment have been designated as different "levels ci
protection." EPA guidelines for evaluating hazards and selectir.7
protective equipment have been discussed in detail earlier
this manual, and are briefly described later in this unit.
21-3
-------
c. Defining Special Areas for Contamination Control
An important part of planning an investigation and
the protective equipment needed is defining special areas for
contamination control. This requires defining the boundaries of
the contaminated site and the location of the decontamination
area. For safety and convenience, only one level of protection
should be required in each special area. Unprotected personnel
should be excluded from these areas, by procedure, by marking the
areas or by erection of a fence.
2. Preparation
Preparation should include developing special operating
safety procedures, gathering necessary safety and protective
equipment, and training personnel in use of protective equipment.
Getting in and out of bulky protective equipment, using
it while collecting samples, and following emergency procedures
should be practiced in advance of actual work. Practice will
make it easier to carry out tasks in the limited time provided by
special breathing apparatus. Practicing will also make it easier
to work in special protective equipment with less stress.
If the planned sampling activities require field
personnel to carry out operations that are not familiar, the
operations should be rehearsed, particularly if they are
hazardous or critical.
a. Conducting a Preliminary Survey
Before an investigation begins at a hazardous
waste site, before collecting hazardous waste samples or working
at the site, a preliminary survey should be conducted to get the
detailed information needed for developing specific safety and
health plans and for completing preparations. As one part of the
survey, it is important to observe physical hazards, measure
atmospheric concentrations of contaminants and gather other
information which can be used for selecting the levels of
protection that will be required for subsequent sampling and
investigation.
b. Assessing Physical Hazards
A preliminary survey should include a thorough
inspection to assess physical hazards at the site and make
efforts to identify hazardous materials from container markings.
Look for and record problems such as rough
terrain, open waste ponds or lagoons, unstable piles, bulged or
leaking drums, confined spaces, dead vegetation, discolored soil,
or standing water.
21-4
-------
c. Monitoring the Atmoshpere
Part of the preliminary survey is monitoring the
atmosphere at the site for concentrations of the contaminants
known or likely to be present in the air at the site. If the
contaminants are not known, samples should be taken for
laboratory analysis.
Measure the concentrations of organic vapors,
including concentrations of combustible gases and vapors, and
measure any ionizing radiation. Wind speed and direction should
also be monitored.
Concentrations of organic vapors can be measured
by a combination of two field instruments, an organic vapor
analyzer and a photoionizer. The organic vapor analyzer is a
portable hydrocarbon analyzer with optional capabilities for gas
chromatography. It can be used for monitoring total
concentrations of hydrocarbons.
The response time of the organic vapor analyzer is
relatively long. It does not respond fast enough to detect
vapors at a rapid walking speed. Personnel using the analyzer
and not walking slowly, could walk into a high concentration of
vapors before the meter could respond.
The photoionizer has a wide detection range, but
it too has a relatively long response time, and it is highly
directional and must be held close to a source before detection
is possible. High humidity and wind can cause the photoionizer
to give false readings.
In the absence of other information, the total
vapor concentrations measured during the initial survey can be
used to decide the level of personal protection needed at a
hazardous waste site and in the decontamination area.
If the total vapor concentrations are unexpectedly
high in areas outside of that tentatively designated as the
contaminated area, the boundaries may need to be enlarged.
d. Measuring Wind Speed and Direction
Wind speed and direction should be measured during
the initial survey and during subsequent activities at a
hazardous waste site. The wind indicator should be visible from
all points in the contaminated area at which there may be leaks,
so that personnel on site can see which way to evacuate in case
there is a leak of vapor or gas. If there are buildings or large
piles of waste on the site, there may be microenvironments in
which the wind does not blow in the same direction as it does on
most of the site.
21-5
-------
C. LEVELS OF PROTECTION
Protecting personnel from contact with, or exposure to,
chemicals at a hazardous waste site depends to a large extent on
protective clothing and equipment. Crew members should select
and use the combination of equipment that will provide adequate
protection, without encumbering them any more than necessary.
Definitions of how much protective equipment is "necessary"
are likely to vary subjectively from "everything" by an overly
cautious person, to "very little" by someone who is not concerned
about either immediate or delayed consequences of exposure.
1. Personal Protective Equipment for Hazardous Waste Sites
The personal protective equipment recommended for work
at hazardous waste sites consists of several types of protective
equipment or clothing:
o Respiratory protection, either air supplying or
air purifying
o Protective clothing for body protection
o Gloves and boots for hand and foot protection
o Eye and face protection
o Head protection
o Communication equipment
The major difference in the level of protection
recommended for different degrees of hazard is in the selection
of respiratory protection and protective clothing.
a. frevel h.
The maximum level of protection available is
called level A, and it includes:
o SCBA that operates in the positive pressure-
demand mode
o Fully encapsulating suit with gloves and
boots attached
o Second set of gloves
o Second set of boots
o Two-way radio
21-6
-------
The conditions requiring Level A protection
include the following:
o Unknown concentrations of hazardous material
o Vapor concentrations Immediately Dangerous to
Life or Health (IDLH)
o Material that could affect skin or eyes
o Toxic amounts of material that could be
absorbed
o An oxygen deficiency
o Necessity to enter confined spaces or a
hazardous environment
b. Level B
The next lower level of protection is called Level
B, and it includes:
o SCBA operating in the positive pressure-
demand mode
o Hooded suit that is chemical resistant
o Gloves and boots
o Second set of gloves
o Second set of boots
o Two-way radio
The conditions requiring Level B protection
include:
Unknown concentrations with a skin risk that
is slight
Concentrations Immediately Dangerous to Life
or Health (IDLH).
Concentrations too high for an air purifying
respirator
21-7
-------
o Toxic amounts that could not be absorbed by
the skin
o Oxygen deficiency
o Confined spaces or hazardous environment
c. Level C
The minimum acceptable level of protection at a
hazardous waste site is Level C, and it includes:
o Air purifying respirator with a full-face
mask
o Escape mask
o Fire resistant coveralls
o Gloves (optional)
o Cover boots over shoes or boots
o Eye Protection if for any reason a full-face
mask is not used
Remember that the tern "level of Protection" describes
a combination of equipment and clothing that should provide
protection against a particular group of hazards. The levels of
protection provided should change if hazards change. It is
appropriate to increase the level of protection required in an
area if the hazards increase after a level of protection has been
chosen for work in that area.
2. Known Materials and Known Concentrations
Selection of appropriate protective equipment to
prevent contact with or inhalation of excessive amounts of toxic
chemicals is relatively easy if personnel know what chemicals
they will be exposed to and at what concentrations. Then it is
possible to pick a respirator which will protect against the
inhalation hazard and the clothing that will protect against skin
contact.
However, simply selecting protective equipment for a
known exposure concentration may lead to problems.
Concentrations can change. Containers can rupture or leak ar.j
release more material, the wind can shift or change velocity ar.i
the sun can increase the pressure within containers and increase
evaporation from exposed liquids. Using equipment with very
21-8
-------
little margin for safety or with protection against only a
limited range of materials could lead to trouble if
concentrations increase or if other materials should be released
into the immediate environment.
3. Unknown Materials or Unknown Concentrations
It is much more difficult to select an appropriate
level of protection if the potential exposures are to unknown
hazardous materials, or to unknown concentrations. To prepare
for these situations, EPA has developed some guidelines for
judging the hazards and selecting protective equipment.
At a waste site, the basic presumption is that there
can be exposure to hazardous materials and that protective
clothing and equipment must be used. (Any assumption otherwise
should be made only if there is strong evidence that there is no
hazard of adverse exposures to the respiratory system, skin or
eyes.)
If the potential exposure included both inhalation and
skin contact hazards, the basic protection required is SCBA and
fully encapsulating suits, which are designed to prevent
penetration even of vapors and gases. SCBA and fully-
encapsulating suits are part of Level A protection.
If the potential exposure hazard is limited to
inhalation hazards only, the basic protection required is self
contained breathing apparatus (SCBA), which is part of Level B
protection.
4. Special Hazardous Areas
Level A or B protection is required for entry into
special hazardous areas such as confined spaces, oxygen deficient
atmospheres, and concentrations of toxic materials that are
Immediately Dangerous to Life or Health.
If organic vapors of unknown identity are present in
total concentrations greater than 5 ppm, Level A or B protection
is required. Level B protection is required for concentrations
from 5 to 500 ppm, and Level A protection is required if the
total organic vapor concentration is over 500 ppm.
Experience with use of portable field equipment,
reported by the EPA Emergency Response Division, has shown that
vapor concentrations around 5 ppm result when the measurements
are taken close to a main source of contamination, and that the
concentration will not routinely approach or exceed 500 ppm
except inside a closed building or in a contaminant spill area.
21-9
-------
5. Protection for Preliminary Surveys
The minimum protection recommended for a preliminary
survey of a hazardous waste site is self-contained breathing
apparatus and Level B protection. This assumes that exposure of
areas of the skin unprotected by Level B protective clothing is
expected to be either unlikely or not hazardous. If materials
are present which are likely to be absorbed through the skin,
Level A protection is recommended.
The only conditions where limited protective clothing
(Level C) may be acceptable at a hazardous waste site are:
o Taking environmental samples or making
environmental measurements in the vicinity of the
site, but out of areas likely to be highly
contaminated.
o Making preliminary surveys where the hazards of
the waste are known and there is not likely to be
any significant contact because the material is
confined, ventilated by the wind, or does not
release hazardous concentrations under conditions
at the time of the survey.
6. Work Limitations in Protective Equipment
In assigning work and assessing its effects, keep in
mind the work limitations in protective equipment. Wearing any
protective clothing or equipment increases the weight carried,
the breathing effort and the heat load. The increased heat load
from working in an encapsulating suit is great enough to require
careful attention to prevent severe heat stress effects.
(Guidelines for assessing environmental and physiological factors
and managing heat stress are provided in the unit on heat and
cold stress.)
Using protective equipment may make it necessary to
reduce the maximum working period between breaks and the total
working time per day. The working time for which it is safe to
allow a person to wear protective equipment depends on the
physical work load and on the heat load. Under "normal"
conditions, it is recommended that personnel work in respirators
and protective suits for no more than about three hours in one
day. Under hot conditions, the on-site working time may be as
little as 20 minutes at one time, and as little as 2 hours in one
working day.
21 - 10
-------
D. CONTAMINATION CONTROL AREAS
One means of simplifying the choice of personal protective
equipment required at a hazardous waste site is to establish
clearly-marked contamination control areas in which contamination
levels will be considered uniform. If these areas are defined
and used correctly, only one level of protection will be required
in each area.
The first special area to be established is the contaminated
area. If the hazardous waste and exposure to the waste can be
kept within a fenced area, defined as the contaminated area,
protective equipment for that exposure hazard will not need to be
used inside of the fence.
Since walking, sampling and working in the contaminated area
of a hazardous waste site can contaminate shoes, sampling
equipment and other equipment, there should be a decontamination
area to reduce the spread of hazardous waste beyond the
boundaries of the controlled areas.
One of the important reasons for marking the boundaries of
the contaminated area and controlling entry and egress is to
prevent tracking and transfer of hazardous material into areas
that are cleaner.
The third special area that needs to be designated for work
at a hazardous waste site is the clean area, or the support area,
which can be kept uncontaminated for storage of supplies and for
communication and control activities.
1. Contaminated Area
There will be a problem of setting boundaries when the
site includes waste containers which, if opened, can release
hazardous vapors. If space is available, the contaminated area
can be made large enough to provide adequate distance for vapors
to dissipate. If space is limited, sampling activities will have
to be conducted in a way that will minimize evaporation.
Boundaries of the contaminated area may have to be
changed if more hazardous waste is uncovered at the site or if
operations begin to spread contamination beyond the boundaries.
Access to the contaminated area should be limited to
one or two points at which protective equipment will be put on
when entering and removed when leaving. Part of the access area
should be reserved for clean equipment and part for
decontamination.
21 - ll
-------
2. Decontamination Area
A decontamination area should be set up at the point of
entrance to and exit from the contaminated area, so that
everything coming out of the contaminated area can be cleaned to
prevent spread of contamination.
3. Support Area
Supplies, showers, generator and other equipment for
work at the waste site should be in a support area located were
it will remain uncontaminated and "clean." No protective
clothing should be needed in the clean area.
The support area should be located where it is
accessible to the decontamination area and where it can be
reached from a road. Generally, the support area should be
upwind and uphill from the contaminated area.
4. Control and Communication Area
In the clean support area there needs to be a location
that is identified and equipped for communication and for control
of activities at the hazardous waste site. (This location is
sometimes referred to as the Command Post.)
E. DECONTAMINATION
An important but difficult task at a waste site is
preventing or reducing the spread, of hazardous material, by
sampling and other activities at the site. Ideally, all
contamination that is picked up on samples, sampling apparatus,
protective equipment and other items used at the site is removed
at the site and left there.
Decontamination is difficult even if the contaminants are
known and effective cleaning materials are available. Protective
clothing, gloves, and boots can sometimes absorb and retain
contamination, making decontamination difficult, or impossible.
If this is a problem, disposable protective clothing or
protective coveralls are recommended.
While it would be ideal if all contamination could be
removed within the decontamination area at the waste site, it may
only be possible to remove major contamination or to reduce the
contamination to a level that is reasonably safe. Equipment can
be packaged for subsequent testing and decontamination.
Since it is virtually impossible to prevent transfer of
contaminants from protective clothing to the wearer, even though
careful techniques are used, one of the important ways of
protecting personnel is to decontaminate the protective clothing
21 - 12
-------
before it is removed. This difficult task requires protective
equipment for the personnel who assist, and it requires speed if
a person in a fully-encapsulating suit has little breathing air
left.
Unless the contamination is severe, the level of protection
required for helpers working in the Decontamination Area will
probably be Level C with air purifying respirators.
If the waste at a site is considered extremely toxic,
personnel should have an opportunity to wash and shower,
preferably at the site.
Decontamination generally consists of washing the
contaminated item, followed by rinsing or a series of rinsings.
The washing should be done with a cleaning material which will
most effectively remove the contamination. If the contaminant is
known, the cleaning solution should be one which will dissolve or
react with the contaminant to change its form, composition or
solubility (without destroying the protective material). If the
contaminant is unknown, the solution will probably have to be
detergent and water.
F. CONTAMINATED SOLUTIONS AND EQUIPMENT
The appropriate steps for handling contaminated solutions
and equipment are to collect them for proper disposal, store them
within the contaminated area, and decontaminate or package them
for later decontamination.
Decontaminating solutions should be collected for proper
disposal.
The solutions and supplies such as brushes and sponges can
be stored within the contaminated area (if it is fenced).
Protective equipment can be cleaned in the decontamination
area, and cleaning solutions can be collected and disposed of
properly.
It is generally appropriate to leave the decontaminating
solutions and supplies in the contaminated area at the waste site
since the quantity of hazardous waste at the site is not changed
significantly by doing so. If, however, the decontamination
solutions are solvents which when used become hazardous waste,
they must be disposed of as required by the Resource Conservation
and Recovery Act. (This should be planned for in advance so that
the waste can be packaged and disposed of safely ar,i
conveniently.)
21 - 13
-------
Equipment which cannot be decontaminated or which has been
contaminated with extremely toxic material may have to be
packaged at the site and decontaminated later under controlled
conditions.
6. COLLECTION OF SAMPLES
Generally, the most intermittent and immediate exposure to
hazardous chemicals comes during the process of sample
collection. Both the immediate dangers of fire, explosion,
injury or splash, and of contamination are highest at this
point. Personnel should carefully plan the collection activity
to minimize danger as well as contact. A carefully thought out
and practiced procedure will insure proper equipment and help
foresee difficulties and hazards.
Not. all sampling situations can be foreseen or discussed.
This Unit will concentrate on the most frequent and most
hazardous situations normally encountered by EPA personnel.
1. Drums
The 55-gallon drum has become synonymous with hazardous
waste disposal. It is the most frequently used container for
disposal. Because of the drum's frequent appearance at hazardous
waste dump sites and the number of problems associated with
sampling it, special precautions and techniques must be followed.
a. Safety
Safety considerations for these operations must be
considered. During puncturing and sampling, the operator must be
protected from accidents. The following safety equipment is a
minimum requirement: rubber boots, rubber gloves, safety
glasses, and a hard hat.
Equipment for puncturing has been designed to
remove the operators from the puncturing area to a distance of at
least 50 feet, where they may be protected by barriers. Material
handling equipment backhoes, fork lift trucks, tractors, etc.,
should be shielded to protect the operators from any spraying or
spillage of the chemical in the drum.
b. Equipment
All tools used for drum opening should be of non-
sparking construction, i.e., drum hand wrench, and air or
hydraulic operated tools. A trade-off was made on the drum
plungers described elsewhere in this Unit. Stainless steel was
chosen instead of bronze because it is more durable. However,
21 - 14
-------
stainless steel is more capable of generating a spark, and for
that reason, the minimum recommended distance for operators from
the plunger during operations is greater.
Air and hydraulic equipment should have hoses of
such a length as to remove the operators to a safe area.
All drum handling equipment — backhoes, fork
trucks, tractors, etc., — should have polycarbonate or
comparable shields to prevent operators from being injured by a
release. The drum handling equipment would be more efficient if
a utility type industrial tractor were used. These tractors can
be designed to be equipped with the following attachments:
backhoe, a drum handling attachment with the ability to invert a
drum, a front-end bucket, and an attachment for the front-end
bucket which would allow the use of forks for equipment loading
and unloading.
Operators shall wear prescribed safety equipment
when opening or sampling drums, as described in an earlier
section of this unit.
c. Layout
The drums at the site should be placed in a
marshaling area or arranged in a manner which will allow sampling
personnel to work at the task of sampling without moving the
drums. Rows, usually two drums deep with an aisle space between,
are adequate.
Drums that can be opened with hand tools should be
opened and sampled in place.
Those drums that cannot be opened with hand tools
must be opened with a puncturing device.
At no time should an operator work alone in an
area where sampling or puncturing is being performed.
Only the large bung will be removed for sampling.
Drums are to be arranged in a vertical position
for puncturing and sampling.
d. Definitions
(1) Structurally Sound Drum
A drum which can be handled with mechanized
equipment without rupturing or puncturing.
21 - 15
-------
(2) Structurally Unsound Drum
High risk drum which is capable of being
handled but with extreme caution, and is in one of the following
categories:
o A drum which has a bulged head which is
most likely due to internal gas
pressure.
o A drum which is bulged on the side or
bottom most likely due to freezing and
expansion of the contents.
o A drum which has been deformed due to
mishandling.
(3) Drum With No Structural Integrity
A drum that has corroded to the extent that
only portions of the drum remain or with the drum liner exposed.
(4) Harking
A system of marking the drum and the sample
collected from the drum for later reference.
(5) Identification Marking
A system of marking the drum which identifies
the contents of the drum, to assist in the task of consolidation.
(6) Small Drum Site
A disposal site with one to 300 drums that
does not warrant the use of a mechanized sampling system.
(7) Medium Drum Site
A disposal site of 300-700 drums that
warrants the use of mechanized equipment, but not so large as to
require a puncturing type of operation.
(8) Large Drum Site
A disposal of over 700 drums which will
require the use of production type of puncturing procedures.
21 - 16
-------
(9) Controlled Area
Designated area where drums can be sampled
and/or punctured while:
o limiting access to only personnel
involved with sampling or
o providing for the ability to recover the
contents of the drum should rupture, and
o providing adequate fire and safety
precautions for personnel as prescribed
by the site manager.
e. Puncturing Methods
All of the methods listed below are designed to
remove the operators from the equipment area for maximum safety.
(1) Remote Drum Conveyor Method
The remote drum conveyor method is
recommended for large drum sites (see Figure 1). It is not
recommended that drums be adjacent to each other during
puncturing in case fire or explosion should occur. A pan is
included with a drain to recover any liquid spilled from a
ruptured drum. The pan should be emptied after each spillage.
(2) Backhoe Method
The backhoe method is a modification of the
standard single drum grabber mechanism. A hydraulic cylinder
(see Figure 2) has been added with a frame to provide a plunger
to puncture the top of the drum. The backhoe would grab a drum,
relocate it over a spill containment pan and puncture the drum.
The pan would recover any spillage or the contents of a drum in
case of rupture. The pan should be emptied after each spillage.
(3) Portable Drum Opening Method
The portable drum opener can be attached to
the top lip of a drum if it has not corroded away, or it can be
banded around the drum as shown in Figure 3. This method should
be used only if the drums are structurally sound, or are in an
area where a spill due to rupture could be controlled easily and
recovered. If puncturing occurs in the field, all personnel must
be notified and cleared from the area before puncturing. The
hoses for the portable opener should be at least 50 feet long to
remove the personnel from the drum to be opened.. Other drums
should not be relied upon to shield personnel.
21 - 17
-------
55 GAL. DRUM
CONVEYOR
REMOTE ,
LOCATION
NEEOLE VALVE
3 WAY VALVE
APPROX. 50FL OF HOSE
AIR/HYORAULIC CYLINDER
SPLASH PLATE
ORAIN TO VACUUM TRUCK,
WASTE RECOVERY SYSTEM
OR TANK
— FIG. I —-
REPLACEABLE. 316 STAINLESS S
v STEEL CONICAL PLUNGER H
N. (3IN. DIA. X 4IN. LG.)
DOORS ( 2 SIDES)
SPILL CONTAINMENT PAN L
SUPPORT FRAME C75 GAL CAPACITY\
BELT CONVEYOR
FORK LIFT SLOTS
REMOTE DRUM PLUNGER ARRANGEMENT
AND CONTAINMENT BOOTH
-------
to
M
VO
BACKHOE
ARM (REE)
HYDRAULIC LINES
ADAPTER BRACKET'
DRAIN TO VACUUM TRUCK,
WASTE RECOVERY SYSTEM
or tank
HYDRAULIC CYL.
WITH 6 IN. STROKE
SPLASH PLATE
REPLACEABLE 316
STAINLESS STEEL
CONICAL PLUNGER
(3IN.DIA.X 4IN.LG.)
STANDARD SINGLE
DRUM GRABBER
55 GALLON DRUM
- SPILL CONTAINMENT
^ PAN (PORTABLE)
TTj-f —1 75 GAL CAPACITY
— FIG" 2 -
BACKHOE DRUM PLUNGER ARRANGEMENT
K)
-------
FIGURE 3
SOFT. MINIMUM
AIR/HYDRAULIC
CYLINDER WITH
6 IN. STROKE
ADJUSTABLI
SLIDE
4—!
i
REMOTf
LOCATION
DRUM LIP
CLAMP
CHAIN BAND
ATTACHMINT
(USI WHIN ORUM
LIP CLAMP WON'T
HOLD DUI TO
UP CORROSION)
REPLACEABLE 316
STAINLESS STEE
CONICAL PLUNGE?
(3 IN. DIA.X 4IN.LC
ADJUSTABLE
TENSIONER
CLAMP
PORTABLE
21 - 20
-------
f. Assessment of Each Drum
Each drum should be checked for bulges, buckling,
deformations, and corrosion. If a drum has been subjected to any
of the aforementioned abuses, the drum will be classified as a
high risk drum. Treatment of the high risk drums will be
assessed later. All other drums can be classified as
structurally sound drums.
g. Structurally Sound Drums
These drums present the least amount of risk of
rupture during mechanical handling. A responsible member of the
sampling party should determine whether the drums can be opened
or punctured and sampled in place. This decision will be based
on the extent of clean-up in case of rupture, the danger involved
in a rupture and other factors such as the size of site and drum
spacing. Whenever possible, it is safest to puncture or sample
in a controlled area.
(1) Opening the Drum
The first step is to use the manual hand
wrench. Only the large bung should have to be removed. Caution
must be taken to avoid causing a spark which would detonate an
explosive gas mixture in the drum. Slowly loosen the bung to
allow any gas pressure to escape. Once the bung is removed, the
drum is ready to be sampled. If the bung cannot be removed, the
drum will have to be punctured.
(2) Sampling the Drum
See the section on Sampling Procedures.
(3) Puncturing and Sampling in the Field
The methods for puncturing the drum are
listed below based on site size.
(A) Small Drum Site
If the number of drums is small, the
method most cost effective would be the portable plunger method
(see Figure 3). This mechanism can be attached to the top drum
lip or banded around the drum body. Hoses of approximately 50
feet long enable the operator to stand clear of the drum during
puncturing. (All personnel should evacuate the area during this
operation due to the possibility of an explosion.) After
puncturing, the drum is ready to be sampled.
21 - 21
-------
(B) Medium Drum Site
When the number of drums is between 300-
700/ the backhoe method will be the most effective method. With
the backhoe method shown in Figure 2, the puncturing can be done
with the drum sitting in a pan to catch any liquid if the drum
ruptures. Care must be taken to insure that no personnel are dn
the area during puncturing. After puncturing, the drum can be
situated for the sampling team to complete the sampling
procedure.
(C) Large Drum Site
If the number of drums is large, a
mechanized conveyor method is recommended for puncturing drums
(see Figure 1). With the conveyor method, drums should not be
adjacent to each other while being punctured for safety reasons
in case of an explosion or fire.
h. Structurally Unsound Drums
These drums are high risk drums; that is, they
could rupture during mechanical handling. Therefore, extreme
caution and safety methods should be used when sampling these
drums. Due to the high risk nature, all of these drums should be
punctured and sampled in a controlled area. The controlled area
should be away from any other drums in case of an explosion or
fire, it should have limited access both for personnel and
traffic and it should have stringent fire and safety precautions.
Puncturing of high risk drums should be done in a catch pan for
safety and ease of clean-up in case of a drum rupture. The
methods of puncturing are the same as for the structurally sound
drums.
i. Drums With No Structural Integrity
These are drums which have little of the drum
shell left due to corrosion or punctures. These drums may have
liners which are easily ruptured. The use of a vacuum system to
remove a sample and the contents of the drum is the optimum
method of handling these drums. In preparation for this, if
there is any room around the drum, dig a "moat" to contain the
contents of the drum. If the drum ruptured during the attempt to
get a sample, the sample can be obtained from the moat, and the
remaining liquid can be pumped into a new drum.
21 - 22
-------
j. Sampling Procedures
(1) Wear necessary protective clothing and gear.
(2) Choose the plastic or glass COLIWASA for the
liquid waste to be sampled, and assemble the sampler as shown in
Figure 4.
(3) Make sure that the sampler is relatively
clean. Any solids should be removed and the sampler drained to
prevent reactions before further sampling is attempted.
(4) Check to make sure the sampler is functioning
properly. Adjust, if necessary, the locking mechanism to make
sure the neoprene rubber stopper provides a tight closure.
(5) Put the sampler in the open position by
placing the stopper rod handle in the T-position and pushing the
rod down until the handle sits against the sampler's locking
block.
(6) Slowly lower the sampler into the liquid
waste. Lower the sampler at a rate which permits the levels of
the liquid inside and outside the sampler tube to be about the
same. If the level of the liquid in the sampler tube is lower
than that outside the sampler, the sampling rate is too fast and
a nonrepresentative sample will be obtained.
21 - 23
-------
U. A ...*
N>
H
I
to
TAPERED
STOPPER
MS
T-HANDLE-
1
.6.35 CM (2^1
LOCKING
BLOCK
1.52 M (5-0*)
[-2.86 CM Ilg)
!.
M
r
17.8 CM (r»
I&2 CM (4*>
T
-STOPPER ROD, PVC
0.95 CM 0.0.
H
.5*.
PIPE, PVC, 4.13 CM (|g) LO.
4.26 CM (lg» aO.
STOPPER, NEOPRENE, *9 WITH
g S.S. OR PVC NUT AND
H WASHER
SAMPLING POSITION
CLOSE POSITION
FIG. A
COMPOSITE LIQUID WASTE SAMPLER (COLIWASA)
-------
(7) When the sampler stopper hits the bottom of
the waste container, push the sampler tube downward against the
stopper to close the sampler. Lock the sampler in the closed
position by turning the T-handle until it is upright and one end
tightly rests on the locking block. (It should be noted that
this sampler will not sample the bottom one to two inches of the
drummed material, nor will it sample solids.)
(8) Slowly withdraw the sampler from the waste
container with one hand while wiping the sampler tube with a
disposable cloth or rag with the other hand. Place the cloth
into an appropriate container.
(9) Carefully discharge the sample into a
suitable container by slowly opening the sampler. This is done
by slowly pulling the lower end of the T-handle away from the
locking block while the lower end of sampler is in the sample
container.
k. Sample Container
Be sure the sample container has a wide-mouth
large enough for the Coliwasa to fit into and the container size
is sufficient to hold the volume contained in the Coliwasa. Also
be sure the sample container material and its cap are compatible
with the collected waste. Polyvinyl Chloride sample bottles
should be used for acids and bases and other water soluble
materials. Glass, preferably with a safety plastic coat, should
be used for hydrocarbons and solvents. Bakelite tops with Teflon
seals should be used with glass bottles.
After the sample bottle has been securely closed,
invert the sample bottle a few times to check for leaks.
Regardless of whether visible leaks are detectable
or not, wipe the bottles with rags to remove any wastes on the
outside. The rags should be disposed of at the site, as are
other hazardous wastes. All sample bottles should be thoroughly
decontaminated in the proper area before being shipped off site.
1. Marking the Sample and Drum
After the sample has been taken, cap the sample
container, attach the label, and mark the drum with paint or
other indelible marking system. The marking system should
correspond to the proposed laboratory sample marking protocol.
Put a plastic cap over the drum, or reinstall the bung, to
prevent any liquid (rain, etc.) from entering. Do not mark the
cover as it may be blown off by wind.
21 - 25
-------
m. Sampler
Although the Coliwasa and its improved models
remain the most frequently used sampler £or liquids, the problem
of cleaning and decontamination have yet to find simple
solutions.
Court cases and Agency enforcement actions are
highly dependent on the integrity of the sample, hence the
sampling procedure and the cleanliness of the equipment used are
very important.
Furthermore, subsequent handlers of sampling
equipment seldom have protective gloves on during the initial
handling, storing, and transporting of equipment. Agency crew
members should take care to practice Coliwasa decontamination
procedures before entering a site. The following steps are
recommended between each sampling and before leaving the site:
(1) Select the type of body tube that is
compatible with the suspected material to be sampled. PVC tubes
are best for acids, bases, or other water based substances.
Glass is best for hydrocarbons such as solvents. The Coliwasa
tube is designed to be economical enough for disposal if cleaning
and decontamination prove to be difficult or impractical. Always
take extra tubes with the sampler.
(2) While raising the filled Coliwasa from the
barrel, wipe the excess from the outside with a disposable rag.
Hold a rag under the tube as it is lifted to the sample
container.
(3) Secure the sample bottle from tipping over.
Slowly release the Coliwasa T-handle to prevent the contents from
splashing.
(4) Using a long-handled brush, rags, and a
solvent, clean the tube, both inside and out.
(5) Using a separate brush and rags, wash with
soap and water, then rinse with clean water.
(6) Before sampling again, inspect the tube for
signs of deterioration due to chemical incompatibility.
(7) All wash materials must be decontaminated or
disposed of on site as a hazardous waste.
21 - 26
-------
2. Ponds and Lagoons
The threat from ponds and lagoons comes from both
chemical hazards and physical hazards such as drowning.
Representative sampling procedures usually require five or six
samples that include both the aqueous phase and the bottom sludge
material. During the sampling, it is common practice to lean or
reach as far away from the bank as possible, increasing the
danger of slipping or falling into the pond. The following
safety precautions should be observed:
o Wear protective gear including boots, gloves, and
splash goggles.
o Always sample with two people present.
o Wear a life preserver or a safety line held by an
assistant.
o Remember, a sample container when full,
particularly at the end of a long pole, will weigh
considerably more than when empty. Such an
unanticipated strain may cause the sample taken to
over balance and fall into the pond. If
possible, lift samples straight up, using the
power of the legs rather than the back or arms.
If the sampling is being done over the side of a boat,
the added weight of a full sampler may be sufficient to cause the
boat to tip or rock dangerously. Notify other passengers in the
boat when you are about to lift the full sampler. Such warnings
will allow passengers to prepare to counterbalance the affects of
the weighted sample being lifted.
Samplers should be emptied into sample containers in a
spill pan to catch spillage, drippings, or overflow. Such pans
facilitate cleanup and decontamination. Gear such as samplers
and sampler lines, should be stored in the pans, rather than the
bottom of the boat where decontamination and cleanup are
difficult.
3. Haste Piles
Hazardous materials stored in waste piles are
frequently of a small granular size, such as sand and dust. The
particles frequently are easily blown, as dust, when the
hazardous materials are disturbed or dropped into the tops of
open boots or shoes. Agency crews should wear, as a minimum,
protective gear including air purifying, particulate removing,
respirators; protective coveralls; boots that can be laced up and
taped inside of pant legs; gloves, and protective eye gear.
21 - 27
-------
Waste piles should be approached from up wind. Large
piles, or piles near or inside of buildings with open sides, are
prone to whirlpool or multi-direction gusts. Efforts should be
made to disturb the pile as little as possible, minimizing the
amount of dust.
While you are in the vicinity of pile, clothing, boots,
and other gear contaminated with the dust should be thoroughly
rinsed down to remove dust.
21 - 28
-------
STUDENT EXERCISES
For sampling at the following hazardous waste sites,
describe the type of protective gear and the rationale used for
the selection.
A. 1. Know Waste - Hydrogen Cyanide
2. Vapor Concentration - 3 ppm
3. Oxygen - 21%
4. Wind - 20 mph
5. Site - Open Field
6. Containers - Oruns
Rationale
Protective Gear
Level
B. 1. Untawn
2. vapor Concentration «• 25 ppn
3. Oxygen - 18.1%
0
4. Wind - 0
5. Sit* - Building
6. Containers - Drums
21 - 29
-------
Rationale
Protective Gear
Levi
C. 1. Known Mute - Itichloroethane
2. Vapor Concentration - 4 ppn
3. Oxygen - 211
4. Mind - 10-15 nffc
3. Site - Open
6. Containers - Tank
Rationale
Protective Gear
Level
21 - 30
-------
0. 1. Kncwn Haste - Chloroacetic Acid
2. Vapor Concentration - 0
3. Oxygen - 21.lt
4. Hind - 5-10 nph
5. Site - Open
6. Containers - Drums
Rationale
Protective Gear
Level
If all of the above were represented at the same site:
Rationale
Protective Gear
21 - 31
-------
Level
21 - 32
-------
UNIT 22
SHIPPING REGULATIONS FOR CHEMICALS AND SAMPLES
A. INTRODUCTION
Preventing spills, fires and explosions of hazards major
materials during transportation is a goal of the U.S. Department
of Transportation (DOT). In order to protect the environment,
the public, and transportation employees from such incidents,
the DOT has developed and adopted rigorous standards for
packaging and identifying hazardous materials that are shipped by
any mode of transportation.
The DOT standard must be followed if you ship hazardous
chemicals or samples by any means of transportation other than an
EPA vehicle. DOT standards must also be followed for any
chemical, sample or hazardous material you may take with you (or
check in your baggage) on a flight by scheduled or chartered
aircraft. Some materials (such as nitric acid) are considered so
hazardous that they are totally prohibited from being shipped or
carried on aircraft.
The DOT standards can serve as a useful guide for handling
field samples and the chemicals and solvents needed for field
activities. Familiarity with the principles of the regulations
can help you package and identify hazardous materials for your
protection even if they are not regulated by DOT.
There is another use that can be made of information in the
DOT standards. If personnel ever have to respond to a
transportation spill of hazardous materials, they can obtain
important information about the identity of the materials carried
in the vehicle from the DOT required shipping papers, placards
and identification numbers. New DOT regulations require cargo
tanks and tank trucks to be marked on all four sides with a four-
digit number identifying the specific material being carried, and
the DOT has published a list of the numbers and corresponding
hazardous materials.
This unit will outline the general requirements of DOT
regulations that may apply to Agency personnel: classification
of hazards, packaging, marking and labeling, shipping papers, and
loading and placarding vehicles. This unit will also describe
how EPA has interpreted the regulations for handling
environmental samples and hazardous waste samples.
22-1
-------
B. GENERAL REQUIREMENTS
DOT regulations specify that no person may offer a hazardous
material for transportation by any commercial carrier within the
United States unless that material meets a series of specific
safety requirements.
The regulations list materials which must not be shipped by
or carried on aircraft, and some that are so sensitive to
explosion that they cannot be shipped by any mode of
transportation.
Shipments of hazardous material must first be properly
classified for their hazards. The DOT regulations require that
"each person who offers a hazardous material for transportation
shall describe the hazardous material on the shipping paper," and
shall include details on the classification of the material.
Hazardous materials must be prepared and packaged safely for
shipment, and the packages and shipping containers must be marked
and labeled to show the hazards of the contents.
The- DOT regulations also include requirements for loading
vehicles and for marking vehicles with warning placards and
material identification numbers.
The DOT has established specific definitions of Hazardous
Materials, and has recently broadened its regulations to define
and regulate Hazardous Substances and Hazardous Waste. DOT
regulations for hazardous materials that are shipped in low
concentrations or small quantities are not as restrictive as the
regulations for commercial concentrations or quantities.
"Hazardous material" is defined as a substance or material
which has been determined to be capable of posing an unreasonable
risk to health, safety, and property when transported in and
which has been so designated by the Secretary of Transportation.
"Hazardous substance" is a category that has been added to
the DOT regulations in cooperation with the Environmental
Protection Agency. Substances which have long term health
effects in the environment, such as PCB's, have been added to the
DOT regulations. Such substances are identified in DOT tables
by an E, and their reportable quantities in case of spill have
be$n listed.
"Hazardous waste" is defined as any material subject to the
hazardous waste manifest requirements of EPA regulations, or any
that would be subject to those requirements if there were no
interim authorization to a state.
22-2
-------
"Passenger-carrying aircraft" is defined as an aircraft that
carries any person other than a crew member, company employee, an
authorized representative of the United States or a person
accompanying the shipment.
"Cargo-only aircraft" is defined as an aircraft that is used
to transport cargo and is not engaged in carrying passengers.
••Vessel" includes every description of watercraft used or
capable of being used as a means of transportation on the water.
"STC" or single-trip container is a container that may not
be refilled and reshipped after having been previously emptied,
except as provided in DOT regulations.
"NRC" or non-reusable container is a container whose reuse
is restricted in accordance with the provisions of DOT
regulations.
"Carrier" means any person, group or company engaged in the
transportation of passengers or property by civil aircraft, or by
land or water, as a common, contract or private carrier.
C. CLASSIFICATION OF HAZARDS
1. Background
Safe shipment of hazardous material depends on
packaging and handling which provide protection for the specific
hazards of the material. In order to provide appropriate
protection, it is necessary to identify the hazards.
Samples which must be transported for laboratory
analysis may, if a reasonable doubt exists as to the hazard class
and labeling requirements, be given a tentative classification
based upon the:
o definitions of hazards in the DOT regulations,
o highest ranked hazard classifications in which it
fits, and the
o shipper's knowledge of the material.
Although the DOT regulations list and define twenty
different hazard classifications, all of them fit within two
broad categories: fire and explosion hazards, and health
hazards.
22 - 3
-------
a. Fire and Explosion Hazards
Fire and explosive hazards include the following
classes of material:
o Explosives
o Radioactive materials that could be explosive
o Flammable gases, liquids, and solids
(including those that are spontaneously
combustible or water-reactive)
o Pyrophoric liquids
o Combustible liquids
o Oxidizers and organic peroxides
o Compressed gas cylinders
b. Health Hazards
Health hazards include the following classes of
material:
o Poisonous materials (gases, liquids, solids)
o Etiologic agents (disease microorganisms or
toxins)
o Radioactive materials
o Corrosive materials
o Irritating materials
The DOT regulations define each classification of
hazardous materials and provide convenient Tables listing the
classifications for many commonly used materials. However, the
regulations apply to all materials which meet any specific
definitions, whether or not they are listed in the Tables. In
preparing to ship a material which may be hazardous, first look
to see if it is listed in the Tables; if it is not, then
determine whether it is hazardous by any DOT definition.
In order to classify the major hazard, or hazards, of
materials which are not listed in the Tables, the DOT regulations
establish a priority order of hazards. The classification -:t
hazards is listed below in descending order of seriousness.
22-4
-------
The highest DOT hazard classification is explosive
material, material that is designed to function by explosion.
Since EPA should not be shipping any military ordnance,
the listing starts with radioactive material.
DOT classification of Hazards of Materials
1. Radioactive material
2. Poison A
3. Flammable gas
4. Non-flammable gas
5. Flammable liquid
6. Oxidizer
7. Flammable solid
8. Corrosive material that is liquid
9. Poison B
10. Corrosive material that is solid
11. Irritating materials
12. Combustible liquid in containers exceeding
110 gallons
DOT has additional classifications but they include
materials of types and quantities not likely to be shipped by
EPA, such as organic peroxides and etiologic agents.
2. Categories of Hazards
These twelve classes of hazards can be grouped into
five broad categories:
o Radioactive Material
o Poisonous and Corrosive Materials
o Flammable Gas and Non-flammable Gas
o Flammable Liquid, Flammable Solid, and Combustible
Liquid
o Oxidizer
22-5
-------
The remainder of this section discusses readioactive
material; poisonous, corrosive, and irritating materials; and
oxidizers. Flammable and combustible materials were covered
previously in this manual.
a. Radioactive Material
Agency personnel are not likely to be shipping any
radioactive material unless they encounter it in an unusual
environmental or hazardous waste site sample. Based on DOT
regulations, a sample would not be classified as Radioactive
Material if the estimated specific activity is not greater than
0.002 microcurie per gram of material, and if the radioactivity
is essentially uniformly distributed through the material.
If the estimated specific radioactivity is greater
than 0.002 microcurie per gram, or not distributed uniformly, the
sample should be classified as Radioactive Material and packaged
and labeled accordingly. If personnel expect to encounter
radioactivity in their field work, and take samples that will be
classified as radioactive material, they should plan to take to
the field the special equipment needed to identify the hazard and
the packaging required for the sample.
b. Poisonous and Corrosive Materials
Poisonous materials are divided into three groups,
according to their hazard in transportation. The mutually
exclusive groups, in descending order of hazard, are: Poison A,
Poison B, and Irritating material (known previously as Poison C).
(1) Poison A Materials
Materials classified as Poison A (or
extremely dangerous poisons) must be labeled as Poison Gas.
Poison A materials are defined as "poisonous gases or liquids of
such nature that a very small amount of the gas, or vapor of the
liquid, mixed with air, is dangerous to life."
Ten materials are listed in the text of the
DOT regulations and ten others are listed in the Tables. The ten
examples given in the text of the regulations include
bromoacetone, cyanogen, cyanogen chloride, hydrocyanic acid,
phosgene, and nitrogen tetroxidenitric oxide mixtures containing
up to 33.2 percent of nitric oxide by weight. Most of the ten
materials have uses in organic syntheses; several are reported
elsewhere as military poison gases. The ten other materials
classed in the Tables as Poison Gas include arsine, germane,
nitric oxide, phosphine and several insecticides, including two
liquids shipped in combination with compressed gas.
22-6
-------
(2) Poison B Materials
Materials classified as Poison B are liquids
or solids which "are known to be so toxic to nan as to afford a
hazard to health during transportation" or which are presumed to
be toxic to nan because of the toxic effects shown when tested on
laboratory aninals.
If you have to decide whether a hazardous
naterial nust be classified as a Poison B naterial, you can do so
by conparing the toxicity inforaation reported in the NIOSH
Registry of Toxic Effects of Chenical Substances with the DOT
criteria for Poison B material. (Test data and the DOT
definitions nay differ slightly.)
There are three tests which define a Poison B
naterial: oral toxicity, inhalation toxicity, and skin
absorption toxicity.
(A) Oral Toxicity
A naterial is classified as a poison B
naterial if in the oral toxicity tests, a single dose of 50
nilligrans or less per kilogran of body weight, administered
orally, causes death within 48 hours in half or nore than half of
a gram of 10 or more white laboratory rats weighing 200 to 300
grans.
(B) Inhalation Toxicity
A naterial is classified as a Poison B
naterial if a continuous exposure of one hour or less, at a
concentration of vapor, mist or dust of 2 milligrams or less per
liter, produces death within 48 hours in half or more than half
of a group of 10 or nore white laboratory rats weighing 200 to
300 grans.
(C) Skin Absorption Toxicity
A naterial is also classified as a
Poison B material if, in skin absorption toxicity tests, a dosage
of 200 nilligrams or less per kilogram of body weight,
administered by continuous contact with the bare skin for 24
hours or less, produces death within 48 hours in half or more
than half of a group of 10 or more rabbits.
There is an exception that if experience
shows that the physical characteristics of a material, or the
probable hazards to humans, will not cause serious sickness or
death, the material does not need to be classified as a Poison B
naterial, even if test data would otherwise require such a
classification.
22-7
-------
Examples of materials which are classified as
Poison B include: aldrin, mecuricchloride, methyl bromide,
sodium cyanide, and almost all pesticides.
(3) Irritating Material
The only materials classified as Irritating
Material are tear gas and four compounds described as being
usable as tear gas.
(4) Corrosive Material
A corrosive material is a liquid or solid
that causes visible destruction or alteration of human skin
tissue at the site of contact, or that has a severe corrosion
rate on steel. A material is considered to be corrosive if
specified tests on rabbit skin destroy, or irreversibly change
tissue at the site of contact after an exposure period of 4 hours
or less, or if the rate on steel exceeds 1/4-inch per year in a
specified test.
Examples of corrosive materials include
hydrochloric acid, nitric acid in a concentration of 40 percent
or less, sodium hydroxide, and sulfuric acid.
Nitric acid in a concentration of more than
40 percent is also classified as an oxidizer, and is required to
be labeled as both an oxidizer and corrosive.
c. QxidiUere
DOT defines "oxidizer" or "oxidizing material" as
one which yields oxygen readily to stimulate combustion of
organic materials.
Samples of materials classified as oxidizers by
DOT are chlorates, permanganates, nitrates, and inorganic
peroxides.
DOT classifies as "organic peroxide" any organic
compound containing a bivalent oxygen structure which is
considered a derivative of hydrogen peroxide. However, the
classification excludes such peroxides.
Samples of materials classified as organic
peroxides by DOT are acetyl peroxide solutions containing not
over 25% peroxide, benzoyl peroxide, lauryl peroxide, and methyl
ethyl ketone peroxide solution containing not over 9% active
oxygen. DOT prohibits shipment of acetyl peroxide solutions
containing over 25% active oxygen, and methyl ethyl ketone
peroxide solutions containing more than 9% active oxygen.
22 — 8
-------
D. PACKAGING OF HAZARDOUS MATERIALS
"Packaging" is defined as the assembly of one or more
containers and any other components necessary to assure
compliance with the minimum packaging requirements of DOT
regulations. Packaging, as defined by DOT, includes containers,
portable tanks, cargo tanks, and tank cars including tanks with
multiple compartments.
DOT specification for packaging to be used for shipping
hazardous materials, is required to be designed and constructed,
and to have contents limited, so that under normal
transportation conditions:
o There will be no significant release of the hazardous
materials to the environment;
o The effectiveness of the packaging will not be
substantially reduced? and
o There will be no mixture of gases or vapors, in the
package which could rupture the packaging.
The DOT regulations contain elaborate and detailed
specifications for hundreds of different types of containers,
ranging from bottles to tank cars to barges. Although many of
the specifications include details that Agency personnel do not
need to be familiar with, such as the quality of lumber,
thickness of steel, and container construction features, there
are some general requirements that may apply to shipment of field
samples.
Closures must be adequate to prevent inadvertent leakage of
the contents under normal conditions of transportation. Gasket
closures must be fitted with gaskets of efficient material which
will not deteriorate in contact with the contents of the
container.
Polyethylene used for containers must be compatible with the
material placed within the container, and must not be so
permeable that a hazardous condition could be caused during
transportation and handling.
In order to prevent rupture of containers of liquids due to
thermal expansion, the regulations specify that packagings must
not be completely filled. The regulations specify that
sufficient expansion space, or outage, must be provided within
the container so that it will not be liquid full at 55oC (130oF).
All containers must be tightly and securely closed, and
inside containers must be cushioned to prevent breakage or
leakage. Samples generally can be shipped in non-specification
22-9
-------
containers, if the quantities are limited to about one pint, and
if the containers are tightly closed and securely cushioned to
prevent breakage.
E. HAZARDOUS MATERIALS TABLES
See the Hazardous Materials Table in Section 172.101 (or
Appendix A, Table 2 at the end of this manual); this is the basic
reference for using the DOT shipping regulations.
Column 1 has four coded designations, the most significant
of which is the letter E which identifies materials which are
subject to the requirements pertaining to hazardous substances if
the concentration of the material 10%, or a lower concentration,
depending on the quantity.
Column 2 lists the proper shipping name of materials
designated as hazardous materials.
Column 3 contains a designation of the hazard class
corresponding to each proper shipping name. A material for which
the entry in this column is "Forbidden,w is prohibited from being
offered or accepted for transportation unless the materials are
diluted, stabilized, or otherwise modified to reduce the hazards
to an acceptable level.
Column 3A lists the identification numbers assigned to
hazardous materials.
Column 4 specifies the label required to be applied to each
package.
Column 5 references the applicable packaging section of the
DOT regulations. Exceptions are noted in Column 5A, and
reference to specific packaging requirements and certain
additional exceptions are noted in Column 5B.
Column 6A specifies the maximum net quantity permitted in
one package, for transportation by passenger-carrying aircraft,
and Column 6B specifies the maximum quantity permitted in one
package, for transportation by cargo only aircraft. Notice that
the quantity allowed in cargo-only aircraft is greater.
Look now at the specific information for acetone, the eighth
entry on the part of the page shown.
In Column 2 it can be seen that the proper shipping name for
acetone is acetone.
In Column 3 it can be seen that acetone is classified as a
flammable liquid. The identification number for acetone is
UN1090. The required label is Flammable Liquid. The packaging
22 - 10
-------
exceptions are listed, and it is seen that the maximum net
quantity of acetone allowed in one package in a passenger
carrying aircraft is one quart. If personnel had to ship a
large quantity of acetone to a field site, they would be
permitted to ship up to ten gallons in one container in an
aircraft that carried cargo only.
F. HARKING AND LABELING
Marking and labeling regulations require that each person
who offers, for transportation a hazardous material in a package
having a rated capacity of 110 gallons or less shall mark and
label the package to meet DOT requirements.
1. Marking
The required marking must include:
the proper shipping name of the material,
the identification number assigned to the
material,
the EPA-required markings if the material is a
hazardous waste, and
special markings if the package contains liquid
materials.
Proper Shipping Name
The "proper shipping name" for a hazardous
material is the name which has been assigned and listed in the
DOT regulations. The proper shipping name is usually the
technical name for the material, but there are some exceptions.
It is necessary to check the listing and use the name specified
there.
If the proper shipping name for a mixture or
solution that is a hazardous substance does not identify the
constituents making it a hazardous substance, the name or names
of such hazardous constituents must be entered with the proper
shipping name shown on each package.
b. Identification Number
The package is to include the four digit
identification number listed in the DOT Hazardous Materials
Tables, preceded by UN or NA as appropriate. (The numbers
preceded by UN are associated with descriptions considered
o
o
o
o
a.
22 - 11
-------
appropriate for both international and domestic shipments, and
those preceded by NA are associated with descriptions appropriate
for shipments within the United States and Canada.)
c. Marking for Hazardous Liquids
Liquid hazardous materials must be packed with
closures upward and the outside package must be legibly marked
"THIS SIDE UP" or "THIS END UP" to indicate the upward position
of the inside packaging. (There is a limited exemption from this
requirement for ground transportation of packages containing
Class 1C flammable liquids in containers of one quart or less.)
2. Labeling
Required labeling must include:
o the required hazard label or labels, and
o the Cargo Aircraft Only label, if required because
the shipment is not permitted aboard passenger-
carrying aircraft.
Each package must be clearly labeled with the required
diamond shaped hazard warning label. Labels generally must be
placed on the surface of the package near the proper shipping
name. (Labels may be placed on a securely attached tag, or
affixed by other suitable means to compressed gas cylinders, to
packages with very irregular surfaces that would prevent affixing
a label, and to packages which have dimensions less than those of
the required label and which contain no radioactive material.)
When labeling is required, labels must be displayed on
at least two sides or two ends of, each package containing
radioactive material, and each package having a volume of 64
cubic feet or more.
Warning labels are usually required for only one
hazard.
Although most hazardous material packages are required
to be labeled to signal only one class of hazard, there are some
materials with more than one hazard, which require labeling of
two classes of hazard.
For example, any material that is classed as Explosive
A, Poison A or Radioactive and that meets the definition of
another class as well, must be labeled as required „ for each
class. Any material classed as Poison B material that also meets
the definition of a Flammable Liquid must be labeled as both:
POISON B and FLAMMABLE LIQUID.
22 - 12
-------
Any material classed as Oxidizer or Flammable Solid
that also meets the definition of a Poison B material must be
labeled for both hazards.
o OXIDIZER and POISON
O FLAMMABLE SOLID and POISON
A material classed as a Flammable Solid, that also
meets the definition of a water reactive material, must have two
labels attached: FLAMMABLE LIQUID and DANGEROUS WHEN WET
Since July 1, 1983, there are five other combinations
of hazards that require packages to bear two different classes of
warning labels:
o CORROSIVE and POISON
o POISON and CORROSIVE
o FLAMMABLE LIQUID and CORROSIVE
o FLAMMABLE SOLID and CORROSIVE
o OXIDIZER and CORROSIVE
Here are four examples of some of the materials
currently required to have two labels:
o Fluorine, which is in the hazard class of
nonflammable gas, is required to be labeled with
POISON and OXIDIZER hazard labels.
o Germane is required to have the POISON GAS and the
FLAMMABLE GAS hazard labels.
o Nitric acid with a concentration over 40%, which
is classed as a corrosive liquid, has to be
labeled as an OXIDIZER and as a CORROSIVE.
o Fuming nitric acid has to be labeled as an
OXIDIZER and as a POISON.
22 - 13
-------
TABLE 22-1
Material
Class of Hazard
Required labels
Fluorine
Nonflammable Gas POISCN and OXIDIZER
Germane
Poison A
POISON GAS and FLAMOHLE
GAS
Nitric acid,
over 40%
Corrosive Liquid OXIDIZER and CORROSIVE
Nitric acid
fuming
Oxidizer
OXIDIZER and POISON
6. SHIPPING PAPERS
Each person who offers a hazardous material for
transportation must describe the hazardous material on the
shipping paper in an exact and specific manner.
The shipping paper must include:
o proper shipping name for the material,
o identification number for the material (2 letters and 4
digits), and
o hazard class (unless the hazard is included in the
shipping name).
If any solid or liquid material in a package meets the
definition of a poisonous material, notwithstanding the class to
which the material is assigned by DOT regulations, the word
"Poison" must be entered on the shipping paper in association
with the shipping description.
If the hazardous material is to be offered for
transportation by air, and the regulations prohibit
transportation aboard passenger carrying aircraft, the words
"Cargo Aircraft Only" (or Cargo-Only Aircraft) must be entered on
the shipping paper after the basic description of the material.
The shipping paper must show the total quantity of the
hazardous material being shipped. It also must include a
certification that the hazardous materials listed on the shipping
paper are properly classified, described, packaged, marked and
labeled, and in proper condition for transportation according to
DOT regulations. Finally, the shipping paper must include the
shipper's signature.
22 - 14
-------
H. PLACARDING OF VALOES
DOT regulations require shippers to provide, and carriers to
use, placards for vehicles transporting more than 1000 pounds of
hazardous material in one load. Placards are required on both
sides and both ends of vehicles and railcars carrying more than
1000 pounds of hazardous materials.
Placards on railroad cars can provide important information,
particularly if the car has been derailed.
Cargo tanks and tank cars are required to have the contents
identified with a four-digit hazard identification number. The
numbers may be placed within the placard, except for Poison Gas,
Radioactive Material, and Explosives. If the numbers are not
placed within the placard, they are to be 4 inches high on an
orange background located below the placard.
The DOT has published an Emergency Response Guidebook for
Hazardous Materials, which is available through the Government
Printing Office and book stores. The Guidebook lists the
materials alphabetically with their identification numbers, and
also lists all numbers in numerical order to provide a cross
reference to the shipping names of materials.
I. LOADING OF VEHICLES
DOT regulations for loading vehicles can be used as
guidelines for EPA field activities. Any container or package of
hazardous material placed in a vehicle should be secured against
movement within the vehicle in which it is being transported, and
should be braced or secured to prevent movement against other
containers of hazardous material.
Reasonable care should be taken to prevent undue rise in
temperature of containers and their contents during transit.
All reasonable precautions must be taken to prevent dropping
of containers, or batteries, containing corrosive liquids.
Storage batteries containing any electrolyte should be loaded so
they are protected against other material falling onto or against
them.
J. SHIPPING SAMPLES
DOT regulations were not intended to cover shipment of
samples collected by Agency personnel. However, the Agency has
deemed it prudent to comply with the regulations for shipment of
all samples which may be hazardous.
22 - 15
-------
The designation of samples as "Hazardous" is based on
judgement of the conditions where the sample is taken and the
possibility that the sample may be hazardous, in transportation,
or to personnel receiving the samples in the laboratory. If a
sample can be hazardous in transportation, as defined by the DOT
regulations, it must be packaged and identified according to the
regulations.
If the sample does not meet DOT definitions but may,
nonetheless, be hazardous to personnel handling and receiving it,
it should be packaged and identified to the same standards.
1. Environmental Samples
In general, "environmental samples" are those that are
not expected to be grossly contaminated with high levels of toxic
or hazardous materials. Examples of environmental samples are
those taken from streams, ponds, or wells and from the ambient
air.
Environmental samples that are preserved with hazardous
materials such as nitric acid or sulfuric acid will in most cases
have such dilute concentrations of the preservative that the
sample will not have to be handled as a hazardous sample.
Environmental samples should be packaged just as
securely as hazardous samples, mainly to protect the integrity of
the sample. However, no DOT labeling should be used, no DOT
shipping papers are required, and there are no restrictions on
the mode of transportation (unless dry ice is used for
preservation).
2. Hazardous Samples
a. Classification Overview
"Hazardous samples" are those that are taken where
high concentrations of hazardous materials are likely. For
example, soil or water at spill sites or hazardous waste sites,
samples from drums or tanks, leachates from hazardous waste
sites, and water sources that are likely to be highly
contaminated such as pits, ponds, lagoons and sampling wells.
Samples of hazardous materials must first be
classified into the DOT categories of hazards. Then the samples
must be packaged, and marked and labeled. Finally, the samples
must be shipped as specified in DOT regulations.
If the material in the sample is known, or can be
identified in the field, determination of the DOT hazard class
and required labeling can be done simply by reference to the DOT
22 - 16
-------
regulations. If, however, the specific hazards of a sample
cannot be determined with certainty in the field, informed
judgement must be used.
b. Classifying Unknown Suspected Hazardous Materials
There are several steps which should be taken to
judge the appropriate DOT class of a material that is suspected
of being hazardous. The following is a generalized procedure for
classification of hazards, including the simplified steps that
can be used by agreement between EPA and DOT.
This procedure should be used only when reliable
identification of the material cannot be made in the field. The
purposes of using this procedure are to meet DOT regulations as
well as to provide protection for field and laboratory personnel.
If a material fits within the definition for a particular class
of hazard, the sample should be classified accordingly and
subsequent handling, packaging, labeling and shipment should
comply with the corresponding DOT regulations for that class.
Here is a simple outline of the order of judgement
or determination necessary to classify the hazard of a sample:
o If the material is likely to be an Explosive,
it is classified as an Explosive.
o If it is not, is it a radioactive material?
If it is, classify it accordingly.
o If not, is the material likely to be a
compressed gas which may fall into the
category of a Poison Gas, a Flammable Gas, or
a Non-Flammable Gas?
o If a material does not fit into any of these
classes of hazard, a field sample can be
classified as a Flammable Liquid, by
agreement between EPA and DOT.
Use of the flammable liquid classification avoids
the need for field testing, which might be almost impossible in
some situations. The packaging that is required for a Flammable
Liquid will provide all of the protection required for any
material with a lesser hazard. Using the flammable liquid label
is acceptable for samples which have no greater hazard. However,
frequent use of the flammable liquid hazard label for materials
which are not flammable liquids may eventually create problems in
the laboratory if the label comes to be considered meaningless.
22 - 17
-------
c. Communication About Hazards of Samples
For protection of both field and laboratory
personnel, it is important for every person taking a sample to
potify others about the hazards of the sample. DOT labels do not
give enough information about combinations of hazards or unique
characteristics of field samples. Therefore, we recommend the
use of several channels of communication about unusual or
particularly hazardous samples: Precautionary information such
as a written note accompanying the sample or information written
on the outer container holding the sample, a phone call to the
laboratory which will receive the sample, or use of a hazard
signal system.
3. Samples and Hazardous Materials to be Shipped or Taken
on Aircraft
Samples and chemicals to be shipped or taken on
aircraft deserve special attention. DOT regulations prohibit
shipment of certain hazardous materials, and Federal law forbids
the carriage of hazardous materials aboard aircraft in your
luggage or on your person. Violations can result in severe
penalties, up to $25,000 and five years imprisonment.
Hazardous materials include explosives, compressed
gases, flammable liquids and solids, oxidizers, poisons,
corrosives and radioactive materials. There are exceptions for
small quantities of medicinal and toilet articles carried in your
luggage and certain smoking materials carried on your person. If
you need further information, contact your airline
representative.
Dry Ice, or solid carbon dioxide, has a limited hazard
classification if used to preserve samples shipped by aircraft.
Packaging must be marked with the designation ORM-A and
arrangements to ship dry ice must be made in advance with the
carrier.
Any chemicals or solvents that need to be transported
to or from a field site rapidly can be shipped by aircraft only
if you can comply fully with DOT regulations. Samples and
materials that cannot be shipped by any passenger carrying
aircraft can, in many cases, be shipped by cargo-only aircraft.
Although there are many companies that ship air freight
on cargo only aircraft, shipment may depend on available space,
and delivery time may not be predictable. If you select a
shipping company that specializes in rapid shipment and delivery
of small packages, be sure you know what limitations they have
for accepting hazardous materials.
22 - 18
-------
4. Recommendations
Taking solvents and analytical chemicals to the field,
and bringing samples back to the laboratory, entails the risk of
having a container break or leak during the trip. If this occurs
there can be loss of material, risk of injury to personnel, and
contamination of equipment and the environment.
Packaging hazardous materials to prevent spills or
leakage is as important for protection of Agency personnel as it
is for carrier employees. Harking and labeling packages and
containers of hazardous materials should be routine within EPA,
even for materials which may never be shipped by a carrier.
It is believed that it would be appropriate for every
EPA vehicle which carries hazardous materials or hazardous
samples to have a list of hazardous materials being carried in
the vehicle. In case of an accident, the list would provide
information on hazardous materials in the vehicle, just as
shipping papers are used for information on hazardous materials
involved in large transportation incidents.
22 - 19
-------
STUDENT EXERCISES
The following samples are to be shipped. Answer the
following questions concerning each.
1. What is the proper hazardous material label for 40% nitric
acid?
2. If a material is a flammable liquid as well as a poison B,
what is its proper hazard label?
3. If a substance is both a corrosive and a flammable liquid,
what is its proper label?
4. Environmental samples do not require what three things for
shipping?
5. If a substance is unknown, but is not believed to be
explosive, corrosive, or poisonous, %*iat is its OOT hazard class?
22 - 20
-------
APPENDICES TABLE OF CONTENTS
Appendix A Figure 1
Hazardous Materials From Non-specific Sources Pages, 3-7
Appendix A Figure 2
CERCLA List, Page 9-13
Appendix A Figure 3
Toxic Pollutants, Page 15
Appendix A Figure 4
Basis for Listing Hazardous Waste, Page 17
Appendix A Figure 5
Hazardous Constituents, Page 19-23
Appendix B
Guide to Compatibility of Chemicals, Page 25-38
Appendix C
Material Safety Data Sheet, Page 40-41
1
-------
APPENDIX A FIGURE 1
HAZARDOUS MATERIALS PROM NON-SPECIFIC SOURCES
2
-------
0 CFR Ch. I (7-1-88 Edition) | Environmental Protection Agency
Xil**^bDNCENTRATION OF COH-
^BlAHACTERISTIC OF EP
Continued
Contaminant
Maximum
concentra-
tion
(milligrams
per mat)
a d
wcury
lenium—
*er
drin (1.2.3,4,10,10-hexaclv
ofo-1,7-epoxy-
: ,4,4a,$,6,7,8,8s-octahydro-
i ,4-endo. endo-S,S-dimeth-
ino-naphthatenfi.
dans (1,2,3,4.5,6-hexa- chlor-
>cyclohexane, gamma isomer.
thoxycNor (1,1.1-Trichloro-
,2-bis tp-methoxy
r>enyl)ethane)..
aphene Technical
hlorinated camphene, 67-68
ercent chlorine).
O. (2,4-Oiehlorophenoxyace-
: acid).
5-TP Sitvex (2.4.5-Trichto-
phenoxyptopionic acid).
5.0
0.2
1.0
5.0
0.02
0.4
10.0
05
10.0
1.0
D—IUH of Haxardout
Wattes
ral.
iM
beeri~ex<
is a hazardous
In this subpart,
beerT&xcluded from thte
260.20 and-260.22.
imlnlstrator will indicate
isting the classes or types
ed in this Subpart by em-
or more of the following
0)
(Q
M
(E)
.te M
identifies the constitu-
sed the Administrator to
as an EP Toxic Waste
Waste (T) in 55 261.31
.zardous waste listed in
3 assigned an EPA Has-
Number which precedes
.he waste. This number
in complying with the
notification requirements of Section
3010 of the Act and certain record-
Keeping and reporting requirements
under Parts 262 through 265, 268, and
part 270 of this chapter.
(d) The following hazardous wastes
listed in § 261.31 or 5 261.32 are subject
§ 261.31
to the exclusion limits for acutely haz-
ardous wastes established in §261.5:
EPA Hazardous Wastes TTri fflffino
F021, F022, F023, F026, arf&F027. ^
[45 PR 33119, May 18, 1980, as\muiUl!U U
46 PR 14294, Apr. 1, 1983; 50 PR 2000, Jan.
14,1985; 51 FR 40636, Nov. 7,1986]
8 261.31 Hazardous wastes from non-specific sources.
The following solid wastes are listed hazardous wastes from non-specific
sources unless they are excluded under §§ 260.20 and 260.22 and listed in Appen-
dix IX.
Industry and EPA hazardous
waste No.
Generic:
F00I....
F002-
F003—
F004
F005...
F008..
F019-
F007..
F008-.
Fooe...
F010-
F01U
F012-
Hazardous waste
The following spent halogenated solvents used in degreasing: Tetrachloroethylene.
trichkxoethylene, methylene chloride, 1,1,1-trichloroethane. carbon tetrachloride,
end chlorinated fluorocartoons; all spent solvent mixtures/blends used In degreas-
ing containing, before use, a total of (en percent or more (by volume) of one or
more ol the above halogenated solvents or those solvents listed in F002. F004,
and F005; and slid bottoms from the recovery ol these spent solvents and spent
solvent mixtures.
The following spent halogenated solvents: TetracMoroethylene, methylene chloride,
trichloroethylene, 1,1,1-trichloroethane. chlorobenzene, 1,1,2-trichloro-1,2,2-trifluor-
oethane, ortho-dichlorobenzene. trichlorofluoromethane, and 1,1,2-trichloroethane;
all spent solvent mixtures/blends containing, before use, a total of ten percent or
more (by volume) of one or more of the above halogenated solvents or those
listed in F001, F004, or F005; and stiU bottoms from the recovery of these spent
solvents and spent solvent mixtures.
The following spent non-halogenaled solvents: Xylene, acetone, ethyl acetate, ethyl
benzene, ethyl ether, methyl isobutyl ketone, n-butyt alcohol, cydohexanone, and
methanol: ail spent solvent mixtures/blends containing, before use, only the above
spent non-halogenaled solvents; and al spent solvent mixtures/blends containing,
before use, one or more of the above non-haiogenated solvents, and, a total of
ten percent or more (by volume) of one or more of those solvents listed in F001,
F002, F004, and F0O5; and stn bottoms from the recovery of these spent solvents
and spent solvent mixtures.
The following spent non-lwlogenated solvents: Cresols and cresyfic add, and
nitrobenzene; all spent solvent mixtures/blends containing, before use. a total of
ten percent or more (by volume) ol one or mora of the above non-hatogenated
solvents or those solvents listed in F001, F002, and F005; and stiU bottoms from
the recovery ol these spent solvents and spent solvent mixtures.
The following spent non-hatogenated solvents: Toluene, methyl ethyl ketone, carbon
cfisulfide, isobutanot, pyridine, benzene, 2-ethoxyethanoL and 2«itropropane; all
spent solvent mixtures/blends containing, before use, a total of ten percent or
more (by volume) of one or more of the above norvhalogenated solvents or those
solvents feted in FOOt, F002, or F004; and still bottoms from the recovery of
these spent solvents and spent solvent mixtures.
Wastewater treatment sludges from electroplating operations except from the
following processes: (1) Sulfuric add anodizing of aluminum; (2) tin plating on
carbon steel; (3) line plating (segregated basis) on caibon steel; (4) aluminum or
zinc-aluminum plating on carbon steel; (5) deaning/stripping associated with tin,
zinc and aluminum plating on caibon steel; and (6) chemical etching and milling ol
aluminum.
Wastewater treatment sludges from the chemical conversion coaling of aluminum
Spent cyanide plating bath solutions from electroplating operations
Plating bath residues from the bottom of plating baths from electroplating operations
where cyanides are used in the process.
Spent stripping and cleaning bath solutions from electroplating operations where
cyanides are used in the process.
Quenching bath residues from oil baths from metal heal treating operations where
cyanides are used In the prooess.
Spent cyanide solutions from salt bath pot cleaning from metal heat treating
Quenching waste waler treatment sludges from metal heat treating operations where
cyanides are used in the process.
20-142 0-88 14
407
-------
§ 261.32
40 CFR Ch. I (7-1-88
Industry and EPA hazardous
waste No.
F024..
F020
F021
F022..
F023..
F026.
F027-
F028-
Hazardous watte
Wastes, Including but not limited to, distillation residues, heavy ends, tart, and
reactor dean-out waste* from the production of chlorinated aliphatic hydrocar-
bons, having carbon content horn one to five, utilizing tree radical catalyze*
processes. [This (sting does not include tight ends, spent litter* and filter aids,
spent dessicants, wastewater, wastewater treatment sludges, spent catalysts, m
wastes fisled in { 261.32.].
Wastes (except wastewater and spent ca/bon from hydrogen chloride purificeSon)
from the production or manufacturing use (as a reactant. chemical intermediate, or
component in a formulating process) of tit- or tetrachlorophenol, or of intern*,
diates used to produce their pesticide derivatives. (This listing does not include
wastes from the production ol Hexachlorophene from highly purified 2,4,5-
trichlorophenot.).
Wastes (except wastewater and spent carbon from hydrogen chloride purification)
from the production or manufacturing use (as a reactant, chemical intermediate, or
component in a formulating process) of pentachtoropheoot, or of Intermediate!
used to produce its derivatives.
Wastes (except wastewater and spent carbon from hydrogen chloride purification)
from the manufacturing use (as a reactant, chemical intermediate, or component h
a formulating process) of tetra-, penta-, or hexechlorobenzenes under alkaline
conditions.
Wastes (except wastewater and spent carbon from hydrogen chloride purification)
from the production of materials on equipment previously used for the production
or manufacturing use (as a reactant, chemical intermediate, or component In a
formulating process) of tri- and tetrachlorophenols. (This fisting does not include
wastes from equipment used only for ihe production or use of Hexachlorophene
from highly purified 2.4>trichlorephenoL).
Wastes (except wastewater and spent carbon fro*. hydrogen chloride purification)
from the production of materials on equipment pre.iously used for the manufactur-
ing use (as a reactant, chemical intermediate, or component In a formulating
process) o(tetra-. penta-, or hexaehlorobenzene under alkaline conditions.
Discarded unused formulations containing tri-, tetra-, or pentachlorophenol or d*
carded unused formulations containing compounds derived from these cNorophsn-
ols. (TWs fisting does not Include formulations containing Hexachlorophene sythe-
slzed (ram prapurified 2,4.&-WcNorophenot as the sole component).
Residues resulting from the Incineration or thermal treatment of sot contaminated
with EPA Hazardous Waste Noe. F020, F021, F022, F023, F028, and F027. ..... ...
*0,T) should be used to specify mixtures containing IgnHable and toxic constituents.
[46 FR 4617, Jan. 16, 1981, as amended at 48 FR 27477, May 20, 1981; 49 FR 5312, Feb 10
1984; 49 FR 37070, Sept. 21, 1984; 50 FR 66S, Jan. 4, 1985; 50 FR 2000. Jan. 14, 1985; 50 FR
53319, Dec. 31,1985; 51 FR 2702, Jan. 21, 1986; 51 FR 6541, Feb. 25,1986)
6 261.32 Hazardous wastes from specific sources.
The following solid wastes are listed hazardous wastes from specific sources
unless they are excluded under $$ 260.20 and 260.22 and listed in Appendix EX.
Industry and EPA hazardous
waste No.
Hazardous waste
Hazard
code
Wood preservation; KOOt
Inorganic pigments;
K002
K003
KMU
KOOS
K00S . ..
KOOT
KOOS
Organic cfwimlcaltj
K00»„
K010
Kois zzzzzzzz
K014™
K01S
Bottom sedknent sludge from the treatment of wastewaters from wood preserving
processes that use creosote and/or pentachlorophenol.
Wastewater treatment sludge from the production of chrome yellow and orange
pigments.
Wastewater treatment sludge from the producfton of motybdate orange pigments
Wastewater treatment sludge from the production of zinc yellow pigments
Wastewater treatment sludge from the production of chrome green pigments
Wastewater treatment sludge from the production of chrome oxide green pigments
(anhydrous and hydrated).
Wastewater treatment sludge from the production of kon blue pigments
Oven residue from the production of chrome oxide green pigments
Oisfltatloo bottoms from the production of acetaldehyde from ethylene._
Oistfflatkm side cuts from the production ol acetaldehyde from ethylene
Bottom stream from the wastewater stripper in the production of acrytonitrie
Bottom stream from the acetoniHe column in the production of acrylonitrite
Bottoms from the acetorttrie purification column In the production of acrytoniWe
Still bottoms from the dsSlatlon of benzyl chloride...—
ro ,
CO
(T)
(0
m
m
m
(T) '
m
(T)
(an
(R.n
m
ro
408
-------
Environmental Protection Agency
§ 261.32
Industry and EPA hazardous
waste No.
Hazardous waste
Hazard
code
KOie.
KOI 7.
K016..
K019.
K020.
K021-
K022..
K023..
K024..
K093..
K094..
K025.
K026 -
K027-
K028..
K029
K095..
K096..
Heavy ends or distillation residues from the production of carbon tetrachloride
Heavy ends (still bottoms) from the purification column in the production o<
eplchlorohydrin.
Heavy ends from the fractionation column in ethyl chloride production
Heavy ends from the distillation ol ethylene dichloride In ethylene dichloride
production.
Heavy ends from the distillation of vinyl chloride In vinyl chloride monomer
production.
Aqueous spent antimony catalyst waste from fluoromethanes production
Distillation bottom tars from the production of phenol/acetone from cumene
Distillation Hght ends from the production of phthaRc anhydride from naphthalene..-
Distillation bottoms from the production of phthalc anhydride from naphthalene
Distillation light ends from the production of phthaDc anhydride from ortho-xylene
Distillation bottoms from the production of phthalic anhydride from orlho-xylene
Distillation bottoms from the production ot nitrobenzene by the nitration ol benzene..
Stripping still tails from the production of methy ethyl pyridines
Centrifuge end distillation residues from toluene dSsocyanate production..
K030
K083.
K103.
K104.
K085.
K105.
Spent catalyst from the hydrochlorinator reactor in the production of 1,1,1-trichlor
oethane.
Waste from the product steam stripper In the production of 1,1,1-trichloroethane
Distillation bottoms from the production of 1,1,1-trichloroethane
Heavy ends from the heavy ends column from the production ol 1,1,1-trichloroeth-
ane.
Column bottoms or heavy ends from the combined production of trichloroethylene
and percHoroethyiene.
Distillation bottoms from aniline production
Kill.
K112-
K113.
K11«.
K115-
K116.
K117
K118
K138
Inorganic chemicals;
K071
K073.
K106
Pesticides;
K03t
K032
Process residues from aniline extraction from the production of aniline
Combined wastewater streams generated from nitrobenzene/aniline production
Distillation or fractionation column bottoms from the production ot chlorobenzene*
Separated aqueous stream from the reactor product washing step In the production
of chlorobenzenes.
Product wsshwaters from the production of dinitrotoluene via nitration of toluene
Reaction by-product water from the drying column in the production of totuenedta-
mine vie hydrogenation of <£nitrotOluene.
Condensed Squid light ends from the purification of toluenediamine in the production
of toluenediamine via hydrogenation of dinitrotoluene.
Vidnals from the purification of toluenediamine in the production of toluenedia/ntne
via hydrogenation of dinitrotoluene.
Heavy ends from the purification ol toluenediamine h the production of toluenedia-
mine via hydrogenation of (SnRroioluene.
Organic condensate from the solvent recovery column In fte production of toluene
dSsocyanate via phosgenatkm of totuenedtamjne.
Wastewater from the reactor vent gas scrubber in the production of ethylene
dibromide via bromination of ethene.
Spent adsorbent solids from purification of ethylene dibromide in the production of
ethylene dibromide via brominalion of ethene.
Still bottoms from the purification of ethylene dibromide in the production of ethylene
dibromide via bromination ot ethene.
Brine purification muds from the mercury cell process in chlorine production, where
separately prepurified brine Js not used.
Chlorinated hydrocarbon waste from the purification step of the diaphragm eel
process using graphite anodes in chlorine production.
Wastewater treatment sludge from the mercury cell process in chlorine production
K033
K034 —
K097._
By-product salts generated in the production of MS MA and cacodyfc add..
Wastewater treatment sludge from the production of chlordane..
K035
K038
K037
K038
K039
K040 ;
Wastewater and scrub water from the chlorination of cydopentadiene in the
production of chlordana.
Filter solids from the filtration of hexacMorocydopentadtene in the production of
chlordane.
Vacuum stripper
-------
§261.33
40 CFR Ch. I (7-1-88 Edition)
Industry and EPA hazardous
waste No.
K042
K043
K099 —
K123
K124.
K12S.
K120
S
Explosives:
K044
K045.
KMC.
K047.
Petroleum refining;
K048
K049.
K090.
KOSt.
K052.
Iron and steel:
K061
K062.
Secondary )ead:
K069 r. i
K100.
Veterinary .pharmaceuticals:
K084
K10I
K102
Ink formulation: K086
Coking:
K060.
K067.
Hazardous waste
Heavy ends or distillation residues from the dfe&Hation of tetrachkxobenzene in the
production ol 2,4,5-T.
2,6-Oichkxophenol waste Irom the production ol 2,4-0
Untreated wastewater from the production of 2,4-0
Process wastewater (including supemates, filtrates, and washwaters) from the
production ol ethylenebisdithiocarbamic add and its salt
Reactor vent scrubber water from the production ol ethylenebisdithiocarbamic acid
and its salts.
Filtration, evaporation, and centrifugation solids from the production of ethylenebis-
dHhiocarbamic add and its salts.
Baghouse dust and floor sweepings in milling and packaging operations from the
production or formulation ol elhylenebistfthiocarbamic add and its salts.
Wastewater treatment sludges from the manufacturing and processing of explosives..
Spent carbon from the freatment of wastewater containing explosives..
Wastewater treatment sludges from the manufacturing, formulation and loading ol
lead-based Initialing compounds.
Pink/red water from TNT operations
Dissolved air flotation (DAF) float from the petroleum refining industry
Slop ol emuWon solids from the petroleum refining industry
Heat exchanger bundle cleaning sludge tram the petroleum reining industry...
API separator sludge from the petroleum refining industry
Tank bottoms (leaded) from the petroleum refining industry
Emission control dust/sludge from the primary production ol steel in electric
furnaces.
Spent pickle liquor generated by steel finishing operations of facilities within the iron
and steel industiy (SIC Codes 331 and 332).
Emission control dust/sludge from seoondaiy lead smelting "
Waste leaching aoMon from add leaching of emission control dust/sludge from
Wastewater treatment sludges generated during the production of veterinary pharma-
ceuticals from arsenic or organo^rseric compounds.
Distillation tar resMies from the distillation of aniline-based compounds in the
production of veterinary pharmaceuticals from arsenic or organo-arsenic com-
pounds.
Residue from the use of activated carbon for decolorization in the production ol
veterinary pharmaceuticals from arsenic or organo-arsenic compounds.
Solvent washes and sludges, caustic washes and sludges, or water washes and
sludges from cleaning tubs and equipment used in the formulation of ink from
pigments, driers, soaps, and stabilizers containing chromium and lead.
Ammonia stta Rme sludge from coking operations....
Decanter tank tar sludge from coking operations-
Hazard
code
0)
m
cn
C)
(T)
(T)
or (f) of this
section.
Environmental Protection Aget
(b) Any off-specification con.
chemical product or manuf:
chemical intermediate which, i
specifications, would have the
name listed In paragraph (e) •
this section.
(c) Any residue remaining 1;
tainer or in an inner liner t
from a container that has h
commercial chemical product
ufacturlng chemical inter
having the generic name li
paragraph
-------
Ch. I (7-1-88 Edition)
:ene in the
washwaters) from the
enebisdithiocerbemic acid
*oduction ol ethytenebis-
jing operations from the
i and its salts.
irocessing of explosives..
xplosives _
mulalioo and loading of
i industry
efning industry.
41 ol steel in electric
facilities within the iron
ntrol dust/sludge from
i '
i of veterinary' pharma-
-------
§261.33
40 CFR Ch. I (7-1-88 Edition)
Environmental Protection Age
Chemical
abstracts No.
PI 19
7803-55-6
P099
506-61-8
P010
7778-39-4
P012
1327-53-3
P011
1303-26-2
P011
1303-28-2
P012
1327-53-3
POM
692-42-2
P036
896-28-6
P0S4
151-56-4
P067
75-55-8
P013
542-62-1
P024
106-47-6
P077
100-01-6
P028
100-44-7
P042
51-43-4
P046
•122-09-6
P014
106-98-5
P001
¦61-81-2
O
P028
100-44-7
P01S
7440-41-7
P017
596-31-2
P018
357-57-3
P04S
39186-18-4
P021
592-01-6
P021
592-01-8
P022
75-16-0
P095
' -*75-44-5
P023
107-20-0
P024
106-47-6
P026
5344-82-1
P027
542-76-7
P029
544-92-3
P029
544-92-3
P030
T.T....H,
P031
460-19-5
P033
506-77-4
P033
506-77-4
P034
131-89-5
P0I6
542-86-1
P038
696-28-6
P037
60-57-1
P038
692-42-2
P041
311-45-5
P040
297-97-2
P043
55-91-4
P004
309-00-2
P060
465-73-6
P037
80-67-1
post
•72-20-8
P044
60-61-S
P048
122-09-8
P047
•534-52-1
P048
51-28-5
P020
68-65-7
P085
152-16-9
phi
107-49-3
POM
296-04-4
P049
541-53-7
P050
115-29-7
P068
145-73-3
post
72-20-6
post
72-20-8
Substance
Ammonium vanadate
Argentate(1-). bis(cyano-C)-. potassium
Arsenic acid HiAsOi
Arsenic oxide AstO>
Arsenic oxide ASiO»
Arsenic pentoxide
Arsenic trioxide
Arsine, diethyl-
Arsonous dichloride, phenyt-
Aziridine
AziriiSne, 2-methyt-
Barium cyanide
Benzenamine, 4-chloro-
Benzenamine. 4-nitro-
Benzene, (cNoromethyl)-
l^-BenzenedW, 4-(1-hydroxy-2-(methytamino)eltiyt)-, (R)-
Benzeneethanamine. alpha.aipha-din)ethy4-
BenzenethM
2H-1-Benzopyran-2-one, 4-hydroxy-3-(3-oxo-1-phenylbutyl)-. & salts, when present at concentrations
greater than 0.3%
Benzyl chloride
Beryffium
Bromoacetone
Bntdno
2-Butanone, 3,3-dbnethyl-1 -(methytthioK
0-tmethylamino)cefbonyl] oxkne
Caldum cyanide .
Calcium cyanide Ca{CN)i
Cartoon (Ssutfide
Carbonic dichloride
Chloroecetaldehyde
p-CNoroaniline
1-eii».?MlphB.flbeta.6bota.6aaipha;7beta. 7aaJpha>-
2,73,6-Oimethanonaphth (2,3-bladrene, 3,4.5.8,9,9-hexsdiloro-1 a,2,2a,3.6,6a,7,7a-octahydro-.
(1aalpha,2beta,2abeta,3alpha.6alpha.6abeta.7beta. 7aalphah & metabolites
Oimethoata
alpha.alpha-0(memylphenefrytamlne
4,6-Otnitro-o-cresol, ft salts
2,4-Oinitrophenol
Oinoseb
Diphosphoramide, octamethyt-
Oiphoaphoric add. tetraethyl ester
OisuHoton
Dithiobiuret
Endosuttan
EndothaH
Endrin
Endrin, ft metabolite*
412
Haz-
ardous
Chemical
waste
abstracts Na
No.
P042
51-43-4
Epinephrine
P031
460-19-5
Ethanedinitrile
P066
16752-77-5
Ethanimidothioic acid,
N-(((methytamino)c;
P101
107-12-0
Ethyl cyanide
P054
151-56-4
EthyteneMne
P097
52-85-7
Famphur
P056
7782-41-4
Fluorine
P057
640-19-7
Fluoroacetamide
P058
62-74-6
Fluoroacebc acid, sot
P06S
628-86-4
Fulminic acid, mercur
P059
76-44-8
Heptachlor
P062
757-58-4
Hexaethyl tetraphospr
P116
79-19-6
HydrazinecarbothioarT
P068
60-34-4
Hydrazine, methyl-
P063
74-90-8
Hydrocyanic add
P063
74-90-6
Hydrogen cyanide
P096
7803-51-2
Hydrogen phosphide
P060
465-73-6
Isodrin
P007
2763-96-4
3(2H)-lsoxazolone. 5
P092
62-36-4
Mercury. (acetato-O);
P065
628-86-4
Mercury fulminate (R
P062
62-75-9
Methanamine, N-me!
P064
624-83-9
Methane, isocyanato
P016
542-68-1
Methane, oxrtjjalchk
P112
509-14-8
Methane, te|^^^ 1
P118
75-70-7
Methanettw^H
P050
115-29-7
6,9-Methan^^ *
he xachloro-1,5,5a/
P059
76-44-6
4,7-Methano-IH-inde
3a.4,7.7a-letrahydr
P066
16752-77-5
Methomyl
P068
60-34-4
Methyl hydrazine
P064
624-83-9
Methyl isocyanate
P069
75-86-5
2-Methydactonitrile
P071
298-00-0
Methyl parathion
P072
86-66-4
alpha-Naphthytthiour
P073
13463-39-3
Nickel carbonyl
P073
13463-39-3
Nickel caibonyt Ni(C
P074
557-19-7
Nickel cyanide
P074
557-19-7
Nickel cynaide Ni(Cf
P075
'54-11-5
Nicotine, 6 salts
P076
10102-43-9
Nitric oxide
P077
100-01-6
p-Nitroaniline
P078
10102-44-0
Nitrogen cfiowde
P076
10102-43-9
Nitrogen oxide NO
P078
10102-44-0
Nitrogen oxide NOi
P081
55-63-0
Nitroglycerine (H)
P082
62-75-9
N-Nitrosodimethylar
POM
4549-40-0
N-Nitrosomethylyiny
P085
152-16-9
Octamethylpyropho:
P087
20816-12-0
Osmium oxide OsO
P087
20816-12-0
Osmium telroxide
P088
145-73-3
7-OxabicyctoC 2.2.1)
P089
56-38-2
Parathion
P034
131-89-5
Phenol, 2-cydohex>
P048
51-28-5
Phenol. 2.4-dinitro-
P047
>534-52-1
Phenol, 2 methyl-4.
P020
88-85-7
Phenol, 2 (1 methyl
P009
131-74-8
Phenol. 2.4,6-trinilrc
P092
62-38-4
Ptienyt0iC ¦
S : ,rriio)me>
-------
Environmental Protection Agency
§ 261.33
Haz-
ardous
waste
No.
Chemical
abstracts No.
Substance
P042
51-43-4
Epinephrine
P031
460-19-5
Ethanedinitrile
poee
16752-77-5
Ethanimidolhioic add,
N-t[(methylamino)eait>onylJoxy]-. methyl ester
P101
107-12-0
Ethyl cyanide
POM
151-56-4
Ethytoneimine
POO 7
52-65-7
Famphur
pose
7762-41-4
Fluorine.
P057
640-19-7
Fluoroacetamide
P058
62-74-8
Fluoroaoetic acid, sodium salt
P065
628-86-4
Futminic acid, mercury(2 +) salt (R,T)
P059
76-44-8
Heptachlor
P062
757-58-4
Hexaethyl letraphosphate
PUS
70-19-8
HydraziriecaftoothiOBmide
P068
60-34-4
Hydrazine, methyl-
P063
74-90-6
Hydrocyanic acid
P063
74-90-8
Hydrogen cyanide
P098
7803-51-2
Hydrogen phosphide
P060
465-73-6
Isodrin
P007
2783-98-4
3(2HHso*azotone, 5-(aminomethyQ-
P092
62-38-4
Mercury, (acetato-OJphenyi-
P065
628-86-4
Mercury fulminate (R.T)
P082
62-75-9
Methanamine, N-methyt-N-nitroso-
P064
624-63-9
Methane, isocyanato-
P018
542-68-1
Methane, oxybistchkxo-
Pt12
509-14-8
Methane, tetranitro- (R)
P116
75-70-7
Melhanethiol, trichloro-
P050
115-29-7
6.9-Methano-2>4,3-benzo
-------
§261.33
Ha*
ardous
waste
No.
P044
P043
P089
P040
P097
P071
PflO
P098
P096
PD99
P070
P101
P027
P069
P061
P017
P102
P003
POOS
P067
P102
pooe
P075
PI 14
P103
P104
P104
PI05
P106
P106
P107
P107
P106
P0I8
P10S
PI IS
P109
PtIO
PI11
P112
P062
P113
pita
P114
P115
P109
P04S
P049
POM
P11S
POM
P072
P093
P123
PI 18
PI 19
P120
P120
POM
POOl
P121
P121
P122
40 CFR Ch. I (7-1-88 Edition) I Environmental Protection Agenc
Chemical
abstracts No.
Substance
60-51-5
55-91-4
56-38-2
297-97-2
82-85-7
298-00-0
78-40-2
151-50-8
151-50-8
506-81-8
116-06-3
107-12-0
542-78-7
75-86-5
55-63-0
598-31-2
107-19-7
'107-02-8
107-18-6
75-55-8
107-19-7
504-24-5
¦ 54-11-5
12039-52-0
830-10-4
508-64-9
, 508-64-9
26628-22-8
143-33-9
143-33-9
1314-98-1
1314-96-1
1 57-24-9
3S7-S7-3
«57-24-9
7446-18-6
3689-24-5
78-00-2
107-48-3
509-14-8
757-58-4
1314-32-5
1314-32-5
12099-52-0
7446-18-6
3689-24-5
39196-18-4
541-53-7
108-98-5
79-19-6
5344-82-1
OO OO'^
103-85-5
8001-35-2
7S-7&-7
7803-55-8
1314-62-1
1314-62-1
4549-40-0
• 61-81-2
557-21-1
557-21-1
1914-84-7
Phosphorodithioic acid, O.O-dimethyl S-t2-(methy1amino)-2-oxoeUtyO eslar
PhosphorofluorMc add. bi»<1-methyle(riyf) ester
PhosphorotNoic acid. 0.0-Qnylloxinie
PropeneriMe
PropanenH/te, 3-chkxo
Propanenitrfle, ?-ftydroxy-2-methyt-
1,2,3-Propanetiiol, trinitrate (R)
2-Propanone. 1-txomo-
Propargyl alcohol
2-Propenal
2-Aop»t-«l
1^-Propytenimine
2-Propyn-1-ol
4'PyMnanina
PyrtSne, 3-, & salts
Setertous add, dthaUum(1 +) salt
Sotonouroa
S8ver cyanide
Silver cyanide Ag(CN)
Sodkjm azide
Sodium cyanide
Sodium cyanide Na(CN)
Strontium sulfide
Strontium sulfide SrS
StrychnicSn-10-one. & sate
Strychnidin-10-ofW, 2,3-dknethoxy-
Strychnine, & salts
Sulfuric acid,
U353
106-49-0
Benzenamine, 4-meth>
U158
101-14-4
Benzenamine, 4.4'-me
U222
636-21-5
Benzenamine. 2-meth.
U181
99-55-8
Benzenamine, 2-meth:
U019
71-43-2
Benzene (l,T)
U038
510-15-6
Benzeneacetic add. 4
U030
101-55-3
Benzene, l-bromo-4-t
U03S
305-03-3
Benzenebutanoic ado
U037
108-90-7
Benzene, chioro-
U221
25376-45-8
Benzenetfamine. ei-tr
U028
117-81-7
1,2-Benzenedfc£rboox>
U068
84-66-2
l^-Benzenedcarboxy
U102
131-11-3
1,2-Benzene
U107
117-84-0
1.2-Benzene
-------
Environmental Protection Agency
(f) The commercial chemical prod-
ucts, manfacturlng chemical interme-
diates, or off-specification commercial
chemical products referred to in para-
graphs (a) through (d) of this section,
are identified as toxic wastes (T),
unless otherwise designated and are
subject to the small quantity genera-
tor exclusion defined in § 261.5 (a) and
(g).
Haz-
ardous
Chemical
Substance
waste
abstracts No.
No.
U001
75-07-0
ACetaldehyde (1)
U034
75-67-6
Acetaldehyde, trichlofo-
U167
62-44-2
Acetamide. N-(4-ethoxypheny<)-
U005
53-96-3
Acetamide. N-9H-fluoran-2-yi-
U240
•94-75-7
Acetic add. (2.4-dichlorophenoxy)-, salts & esters
U112
141-76-6
Acetic add ethyl ester (1)
U144
301-04-2
Acetic acid, lead(2+) salt
U214
S63-«8-e
Acetic acid, thal!ium(1 +) salt
see
93-76-5
Acetic acid, (2,4.5-trichtorophenoxy)-
F027
U002
67-64-1
Acetone 0)
U003
75-05-6
Acetonitrie (I.T)
U004
96-66-2
Acetophenone
U005
53-96-3
2-Acetytaminofluorene
U006
75-36-5
Acetyl chloride (C.R.T)
U007
79-06-1
Acryiamide
U008
79-10-7
Acrylic add (1)
U009
107-13-1
Acryfonitrfle
U011
61-62-5
Amttroto
U012
62-53-3
Aniline (I.T)
U138
75-60-5
ArsMc acid, dimethyl-
1)014
492-80-6
Auramine
U015
115-02-6
Aza serine
U010
50-07-7
AzMno(2f',3':3.4]pyTtooxylic acid, bis(2-ethylhexy0 ester
U069
84-74-2
1,2-Borizenedicarboxyfic acid, dibutyl ester
U088
84-66-2
1,2-Benzenedicarboxylic add, dethyl ester
U102
131-11-3
1,2-Benzenedicarboxyiic acid, dimethyl ester
U107
117-84-0
1,2-Benzeneoxylic add, dioctyl ester
U070
95-50-1
Benzene. 1.2-dichloro-
U071
541-73-1
Benzene. 1,3-dichloro-
U072
106-46-7
Benzene. 1.4-dichloro-
U060
72-54-8
Benzene, 1,1'-<2^-dichloroethytidene)bis(4
-------
§ 261.33 40 CFR Ch. I (7-1-88 Edition)
Haz-
ardous
waste
No.
U0t7
0223
0239
U201
U127
0056
U220
UtOS
utoe
U09S
0169
U183
U18S
U020
U020
0207
U061
U247
0023
U234
0021
0202
U203
U141
uoeo
0064
U248
0022
U197
U023
uoes
U021
0073
uoai
U095
0225
U030
U128
U172
U031
U159
U160
U053
1)074
U143
U031
0136
0032
0238
U178
0097
U114
U062
U21S
0033
U156
U033
U211
0034
0035
U036
UOM
0037
0038
0038
Chemical
abstracts No.
98-67-3
26471-62-5
1330-20-7
108-46-3
118-74-1
110-82-7
108-88-3
121-14-2
606-20-2
98-82-8
98-95-3
608-93-5
62-68-8
96-09-9
98-09-6
95-64-3
50-2&-3
72-43-5
98-07-7
99-35-4
92-87-5
, ¦ 81-07-2
94-59-7
120-58-1
94-58-6
189-55-9
•61-81-2
60-92-6
106-51-4
98-07-7
1464-53-5
¦" 92-87-5
91-94-1
119-90-4
119-93-7
75-25-2
101-55-3
87-68-3
924-16-3
71-36-3
78-93-3
1338-23-4
4170-30-3
764-41-0
303-34-4
71-46-3
75-60-5
13765-19-0
61-79-6
615-53-2
79-44-7
' 111-54-6
2303-16-4
6533-73-9
353-60-4
79-22-1
953-50-4
56-23-5
76-67-6
30S-03-3
67-74-9
494-00-1
106-90-7
510-15-6
S9-60-7
Substance
Benzene, (dichlofomethyl)-
Benzene, 1,3-sothiazol-3(2H)-one, 1,1-dioxide, & salts
1.3-Benzodioxole, 5-(2-propenyt>-
1,3-Benzodioxole, 5-{1-propenyf>-
1,3-8e«zoethoxy-
tt,1'-eiphenyl)-4,4"-dtamir», 3,3"-dimethyt-
Bromofomi
4-Bramophenyl phenyl ether
1,3-Butadiene, 1,1,2.3,4.4-hexacMon>-
1-8utanamlne, N-butyt-N-nitroeo-
1-Butanol (0
2-Butanone (l.T)
2-Butanone, peroxide (R.1)
2-Butenal
2-Butene, 1,4-cScNoro- (l.T)
2-Bulenotc add, 2-methyt-, 7-[[2,3-<8hydroxy-
2-(1-methoxyethyl)-3-methyt-t-oxobutoxy]methyt]-
2,3,5,7a-tetrahydro-1 H-pyrroRzin-1 -yt ester,
(1S-(1alpha(23.7(2$*,3n*),7aa)pha)]-
n-Butyl alcohol (Q
CacodyVc add
Calcium chromate
Cartoamic add, ethyl ester
Carbamic add, methyMtroso-, ethyl ester
Carbemic chloride, tfmethyt-
CaibamodHhiolc add 1,2-*thanedi
0074
764-41-0
'1,4-Oichloro-2-buter
U075
75-71-8
Dichlorodifluorometr
U078
75-35-4
1,1-Oichkxoethyfen.
0079
156-60-5
1,2-DicMofoeUiyler.
0025
111-44-4
Oichloroethyt ether
U027
108-60-1
Oichloroisopropyt e:
0024
111-91-1
DicNoromelhoxy el>
0081
120-63-2
2,4-Oichlorophenol
0082
87-65-0
2,6-Oichloraphenof
0084
542-75-6
1.3-Oichlotoptopene
0085
1464-53-5
1^3,4-Oiepmybuta-
0108
123-91-1
1,4-Diethyleneoxicfe
0028
117-61-7
Oiethythexyl phthalc
U086
1615-60-1
NK-Oietftythydrazir
0087
3286-58-2
O,O-0iethyl S-meth
U088
84-66-2
Diethyl phthalate
0089
56-53-1
Diethylstilbesterol
0090
94-58-6
Oihydtosafrole
0091
119-90-4
S.S'-Oimethoxybenz
0092
124-40-3
Oimethytamine (1)
U093
60-11-7
p-Oimethytaminoazi
0094
57-97-8
7,12-0imelhy
-------
Ch. I (7-1-88 Edition)
when present at concentration*
Environmental Prelection Agency
§ 261.33
Haz-
ardous
waste
No.
Chemical
abstracts No.
Substance
U042
110-75-8
2-CMoroethyl vinyl ether
U044
67-66-3
Chloroform
U046
107-30-2
CNorometlr/t methyl ether
U047
91-58-7
beta-CNoronaphthalene
VJ048
85-57-8
o-Chlorophenol
U049
3165-83-3
4-Chloroo-toiuidine, hydrochloride
U032
13765-19-0
Chromic add HiCrO,, calcium salt
U050
218-01-9
Chrysene
U0S1
Creosote
U052
1319-77-3
Cresoi (Cresyte add)
U0S3
4170-30-3
Crotonaldehyde
U055
98-82-6
Cumene (1)
U246
506-68-3
Cyanogen bromide eta)-
U057
108-94-1
Cyclohexanone (1)
U130
77-47-4
1,3-Cydopentadiene. 1,2,3.4,5.5-hexachloro-
U0S8
50-18-0
Cydophosphamlde
U240
»94-75-7
2.4-D. salts & ester*
U0S9
20830-81-3
Daunomycin
U060
72-54-8
DOO
U061
50-29-3
DOT
U062
2303-1&-4
DiaJiate
U063
53-70-3
Diberata.h3anthr#cflne
U064
189-55-9
Dibenzo(a,i)pyrene
U060
96-12-8
1,2-Dibromo-3-chloropropane
U069
84-74-2
Dibutyf phthalate
U070
95-50-1
oOicNoroberuene
0071
541-73-1
m-OicWoroberaene
U072
106-46-7
p-Dichlorobenzene
U073
91-94-1
3,3'-OicNorobenzidine
U074
764-41-0
1,4-Dichloro-24>i>tene (l,T)
U07S
75-71-8
OkttorodHluorornethane
U078
75-35-4
1,1 -Oichloroethytene
U079
156-40-5
1 ,2-Dichloroe1hytene
U025
111-44-4
DicNoroethyt ether
U027
108-80-1
Dichloroisopropyl ether
U024
111-91-1
Oichloromethoxy ethane
U061
120-63-2
2,4-OlcNorophenol
U0B2
87-65-0
2.6-OicMarophenot
U064
542-75-6
1,3-Dichlofopropene
U0B5
1464-53-5
1,23,4-Oiepoxybutane (l.T)
U108
123-91-1
1.4-DielhyleneoxMe
U028
117-81-7
Diethythexyl phthalate
U086
1615-60-1
N.N'-Oiethythydrazine
U087
3268-58-2
O.O-Oiethyl S-methyt dithiophosphate
U088
84-66-2
Oiethyt phthalate
U069
56-53-1
Diethytetibesterol
U090
94-58-6
Oihydrosahole
U091
119-90-4
3^'-Dfmethoxyt>enzkSne
U092
124-40-3
Dimethylamine 0)
U093
60-11-7
p-Oimethytaminoazobenzene .
U094
57-97-6
7,12-Oimethylbenz[alanthrBcene
U095
119-93-7
3,3'-Oimethy1benzidine
U096
80-15-9
a)pha,alpha-OimethylbenzyfhydroperoKide (R).
U097
79-44-7
Oimethylcarbamoyl chloride
U098
57-14-7
1.1-Oimethythyrfrazine
U099
540-73-8
1 ,2-Oimettiythydrazine
U101
105-67-9
2,4-Oimethylphenol
U102
131-11-3
Dimethyl phthalate
U103
77-78-1
Dimethyl sulfate
U105
121-14-2
2.4-0initK>toluene
U106
606-20-2
2,6-Dinitrotoluene
U107
117-84-0
Owvoctyt phthalate
Ut08
123-91-1
1,4-Oioxane
U109
122-68-7
1,2-Oiphenyfhydrazine
U110
142-84-7
Dipropytarrine (I)
U111
621-04-7
Onrvpropylnltrosamlne
417
-------
§ 261.33
40 CFR Ch. 1 (7-1-88 Edition)
Haz-
ardous
waste
Chemical
abstracia No.
Substance
No.
U041
106-69-6
Epichlorohydrin
U001
75-07-0
Ethanal (0
U174
55-10-5
Ethanamine, N-ethyt-N-nitreso-
U1S5
91-80-5
1,2-Ethanedtamirw, N,N-din»elhyl-N^2-pyridinyl-N'-(2-thienylmethyl)-
U067
106-93-4
Ethane, 1.2-dtbromo-
0076
75-34-3
E thane, 1,1-dicNoro-
0077
107-06-2
E thane, 1,2-dichloro-
U131
67-72-1
E thane, hexachloro-
0024
111-91-1
Ethane, 1,1'-lmethylenebis(oxy))bisl2-chloro-
U1I7
60-29-7
Ethane, 1.r-oxyt*s-(l)
UOSS
111-44-4
Ethane, 1.r-oxybis(2-chloro-
0184
76-01-7
Ethane, pentachloro-
u2oe
630-20-6
Ethane, 1,1,1,2-tetrachioro-
U209
79-34-5
E thane, 1,1,2,2-tetrachlon>-
U2ie
62-55-5
EthanethioanMe
0226
71-55-6
Ethane, 1,1,1-trichloro-
U227
79-00-5
Ethane, 1,1.2-trichioro-
U359
110-60-5
Ethanol, 2-ethoxy-
0173
,, 1116-54-7
Ethand, 2.2*-(nitrosoimino)bi*-
U004
98-66-2
Ethanone. 1-phenyl-
U043
75-01-4
Ethene, chtoro-
U042
110-75-6
Ethene, (2-chloroethoxy)-
U078
75-35-4
Ethene, 1,1-dtehloro-
U079
156-60-5
Ethene, 1,2-cScNofO-, (E>-
U210
127-18-4
Ethene, tetracNoro-
U228
79-01-4
Etheoe, trtchloro-
0112
141-78-6
Ethyl acetate (1)
0113
140-68-5
Ethyl acrytate (1)
0238
61-79-6
Ethyl carbamate (urethane)
U117
60-29-7
Ethyl ether (1)
U114
>111-54-6
EUiylenebisdithiocarbamic acid, salts 6 esters
U067
106-93-4
Ethylene dibromide
U077
107-06-2
Ethylene dtehloride
0359
110-60-5
Ethylene glycol monoethyl ether
0115
75-21-6
Ethylene oxide (I.T)
U116
96-45-7
Ethyfenethiourea
U076
75-34-3
Ethylidene dichloride
una
97-63-2
Ethyl methacrylale
U119
62-50-0
Ethyl methanesulfonate
U120
206-44-0
Fluoranthena
U122
50-00-0
Formaldehyde
0123
64-18-6
Formic acid (C,T)
U124
110-00-9
Furan (1)
U125
96-01-1
2-FurancaitoxaMehyde (I)
U147
106-31-6
2,5-Furandtone
0213
109-99-9
Furan, tetrahydro-(l)
U125
96-01-1
Furfural (1)
U124
110-00-9
Furfuran (Q
U206
16863-66-4
Glucopyranose, 2-deoxy-2-(3-osoureido)-. D-
U206
18883-66-4
D-GHjcose, 2-deoxy-2-(((rnethytnfeosoamino)-
caibonyllaminol-
U126
765-34-4
Glycidylaldehyde
U163
70-25-7
Guanidine, N-methyl-N'-nitro-N-nitroso-
U127
116-74-1
Hexachlorobenzene
U128
87-68-3
Hexachtorobutadtene
U130
77-47-4
Hexachlorecydopentadtooe
U131
67-72-1
HexacMoraethane
U132
70-30-4
Hexachlorophene
0243
1888-71-7
Hexachloropropene
U133
302-01-2
Hydrazine (R.1)
0086
1615-60-1
Hydrazine, 1,2-diethyl-
uoes
S7-14-7
Hydrazine, 1,1-dmeihyl-
0099
540-73-6
Hydrazine, 1.2-
U162
80-62-6
Methyl methacrylat
U161
108-10-1
4-Methyl-2-pentanc
0184
56-04-2
Methylthiourabl
0010
50-07-7
Mitomycin C
0059
20630-81-3
5,12-Naphthacenee
7.8.0.10-letrahyd
0167
134-32-7
1 -Naphthalenamine
0168 ,
91-59-6
2-Naphthalenamine
0026
494-03-1
Naphthalenamine,
0165
91-20-3
Naphthalene
0047
91-58-7
Naphthalene, 2-ch:
0168
130-15-4
1,4 NspMhalenedic
0236
72-57-1
27-NBpMhale'—«f
0166
130-15-4
1.4 N*;-'
0167
134-32-7
aipft.) - ni"
0168
91-59-6
bota fJs.'.'Jiytamip
0217
10102-45-1
N.tpc thalliun
-------
Environmental Protection Agency
§ 261.33
Haz-
ardous
waste
No.
Chemical
abstracts No.
SubJtance
U137
193-39-5
Inderal 1,2,3-cd)pyrene
U139
9004-66-4
Iron dextran
U190
65-44-9
1,3lso6«ojoh*et*fione
U140
76-63-1
Isobutyl alcohol (I.T)
0X1
120-56-1
Isosalrote
U142
143-50-0
Kepone
U143
303-34-4
lestocarpine
U144
301-04-2
Lead acetate
U148
1335-32-6
Lead, biscytri-
U14S
7446-27-7
Lead phosphate
U140
1335-32-6
Lead aubacetate
U129
56-69-9
Lindane
0163
70-25-7
MNNQ
0147
108-31-6
Maleic anhydride
0148
123-33-1
Maleic hydrazide
U149
109-77-3
Malononitrile
0150
146-62-3
Melphalan
U151
7439-97-6
Mercury
0152
126-96-7
Methacrytonrtrile (1, T)
0092
124-40-3
Methanamine. N-methyt- (1)
0029
74-63-9
Methane, bromo-
0045
74-67-3
Methane, chloro- (1, T)
U046
107-30-2
Methane, chloromethoxy-
U068
74-95-3
Methane, dibcomo-
uoeo
75-09-2
Methane, dicMOfO-
U075
75-71-6
Methane, dichlorodifluoro-
U138
74-66-4
Methane, iodo-
U119
62-50-0
Melhanesulfonic acid, ethyl ester
U211
56-23-5
Methane, telrachloro-
U153
74-93-1
Me thane thiol (1, T)
0225
75-25-2
Methane, tribfomo-
U044
67-66-3
Methane, trichloro-
U121
75-69-4
Methane, trichlorofluoro-
U036
57-74-9
4,7-Methano-1H-indene, 1,2,4,5.6,7,8,6-octachloro-2,3,3a,4,7,7a-hexahydro-
U1S4
67-56-1
Methanol (1)
U1SS
91-60-5
Methapyritene
U142
143-50-0
1.3,4-Metheno-2H-cyclobutaCcd]pentalei»-2-one, 1.1a.3.3a.4,5.5.5a.Sb.6-decaehlorooctahydro-
U247
72-43-5
Methoxychlor
Ut54
67-56-1
Methyl alcohol (1)
U029
74-63-9
Methyl bromide
U186
504-60-9
1-Methylbutadiene (1)
U045
74-67-3
Methyl chloride 0.7)
U1S6
79-22-1
Methyl chlorocarbonate (I.T)
U226
71-55-6
Methyl chloroform
U157
56-49-5
3-Methylcholanthrene
U1S8
101-14-4
4,4'-Methytenebis(2-chloroaniline)
U068
74-95-3
Methylene bromide
uoeo
75-09-2
Methylene chloride
U159
78-93-3
Methyl ethyl ketone (MEK) (I.T)
U160
1338-23-4
Methyl ethyl ketone peroxide (R.T)
0138
74-86-4
Methyl iodide
U161
108-10-1
Methyl isobutyl ketone (1)
0162
60-62-6
Methyl methacrytate (I.T).
utet
108-10-1
4-Meihyt-2-pentanone (1)
U164
56-04-2
Methytthiouraci'
U010
50-07-7
Mitomycin C
U0S9
20830-61-3
5.12-Naphthacenedione, 6-acetyl-10-f(3-amino-2,3,6-lrideaxy)-alpha-L-(ym>tiexopyranosyl)oicy)-
7,8,9,10-tetrahydro-6,8,1 1-trihydroxy-l-rnethoxy-, (8S-Cis)-
U167
134-32-7
1 -Naphthalenamine
U168
91-59-6
2-Naphthalenamine
0026
494-03-1
Naphthalenamine, N,N'-bis(2-cNwoethyl)-
utes
91-20-3
Naphthalene
U047
91-56-7
Naphthalene, 2-chloro-
0166
130-15-4
1,4-Naphthalenedione
U230
72-57-1
2,7-Naphthalenedisutfonic acid, 3.3'-[(3,3"-
-------
§261.33
40 CFR Ch. I (7-1-88 Edition)
Chemical
abstracts Na
U169
96-95-3
uiro
100-02-7
U171
79-46-9
U172
924-16-3
U173
1116-54-7
U174
$5-18-5
U176
759-73-9
U177
664-93-5
U178
615-53-2
U179
100-75-4
U180
•30-55-2
U181
99-55-6
UI93
1120-71-4
U058
50-18-0
U11S
75-21-8
UI26
765-34-4
U041
106-69-6
U182
123-63-7
U183 ,
606-93-5
U184
76-01-7
U1B5
82-66-6
See
87-86-5
F027
U161
108-10-1
utee
504-60-9
UI87
62-44-2
UI88
106-95-2
U048
95-57-6
U039
59-50-7
uoei *
120-63-2
U082
87-65-0
U089
56-53-1
U101
105-67-9
U052
1319-77-3
U132
70-30-4
U170
100-02-7
See
87-66-5
F027
See
58-90-2
F027
See
95-95-4
F027
See
86-06-2
F027
U150
148-62-3
UI4S
7446-27-7
U087
3288-56-2
U18S
1314-60-3
U190
85-44-8
U191
109-06-6
U179
100-75-4
U192
23950-56-5
U194
107-10-8
U11I
621-64-7
U1I0
142-84-7
U066
96-12-6
U083
76-67-5
U149
109-77-3
U171
79-46-9
U027
106-60-1
U193
1120-71-4
See
93-72-1
F027
U23S
126-72-7
U140
78-63-1
U002
67-64-1
U007
79-06-1
U084
542-75-6
U243
1688-71-7
Substance
Nitrobenzene (I.T)
p-Nitrophenol
2-Nitropropane (I.T)
N-Nitroso
U180
930-55-2
Pyrrolidine, 1-nitre
U200
50-55-5
Reserpine
U201
108-46-3
Resordnol
U202
' 81-07-2
Saccharin, S sal'
U203
94-59-7
Safroie
U204
7783-00-8
Selenious acid
U204
7783-00-6
Selenium dioxide
U205
7486-56-4
Selenium sulfide
U205
7486-56-4
Selenium sulfide
U015
115-02-6
L-Serine, diazoac
See
93-72-1
Sdvex (a^fc^
F027
•
U206
16883-68-4
Streptoz^^
U103
77-76-1
Sulfuric acid, dim
U189
1314-60-3
Suffur phosphide
See
93-76-5
2,4,5-T
F027
U207
95-94-3
1,2,4.5-Tetrachtof
U208
630-20-6
1,1,1,2-Tet/achlor
U209
79-34-5
1,1,2.2-TelracWOf
U210
127-18-4
Tetrachlofoethyle
See
58-90-2
2,3.4.6-Tetfachto«
F027
U213
109-99-9
Tetrahydrofuran {
U214
563-68-8
ThatKum(l) acetat
U215
6533-73-9
ThalHum(l) carta
U218
7791-12-0
ThaRHjm(l) chloric
U216
7791-12-0
Thallium chloride
U217
10102-45-1
ThaffiumO) nitrate
U218
62-55-5
Thtoacetamida
U153
74-93-1
TNometfta'X)! (J,7
U244
137-26-6
Thiop^ c»yiKart)
U219
62-56-6
Thiourea
U244
137-26-8
Thuar*
U220
108-68-3
U221
25376-45-6
• ne
U223
26471-62-5
T'.*»e».-« •-•--.73
U328
95-53-«
& "
U353
106-49-0
p * • < k- «
U222
636-21-S
0 * . \ • nkc
U011
61-62-5
U227
79-00-5
• • . . - - *tt
U228
79-01-8
• ¦ « . -
U121
75-69-4
' * V-
See
95-95-4
.4 <*¦
F027
See
86-06
•
F027
U234
99-35 «
.
U182
123-63 '
- ?
U235
126-72
U236
72-5'
U237
68-7«,
U176
759-7?
s
U177
684-91
• '
0043
75-0'
•
420
-------
Environmental Protection Agency
§261.33
Haz-
ardous
waste
No.
Chemical
abstracts No.
Substance
U009
107-13-t
2-Propenenitrfle
U152
128-98-7
2-Propenenitrile, 2-methyl- (|,T)
uooe
79-10-7
2-Propenotc acid (1)
U113
140-88-5
2-Propenoic acid, ethyl ester (l)
U118
67-63-2
2 Propenotc acid, 2-methyl-, ethyl ester
U162
60-62-6
2-Propenoic acid. 2-methyl-, methyl ester (I.T)
U194
107-10-8
n-Propytamine (I.T)
U063
78-87-6
Propylene dichloride
U148
123-33-1
3,6-Pyridazinedione, 1^-dihydre-
U196
110-88-1
Pyridine
U191
109-08-8
Pyridine, 2-methyt-
U237
66-75-1
2,4-OH,3H) PyrimWnedione. 5-tbis(2-
chioroethyOamlnoJ-
U164
56-04-2
4(1H)-Pyrimidinone, 2,3-dihydro-6-methyl-2-thioico-
uteo
830-55-2
PyrroMlne, 1-nilroso-
U200
50-55-5
Reserpine
U201
108-46-3
Resorcinol
U202
• 81-07-2
Saccharin, & sslta
U203
84-58-7
Salroie
U204
7783-00-8
Selentoua acid
U204
7783-00-8
Selenium dioxide
U205
7488-56-4
Selenium sulfide
U205
7488-56-4
Selenium sulfide SeSi (R,T)
U015
115-02-6
L-Serine, tiazoacetate (ester)
See
93-72-1
Sitvex (2,4,5-TP)
F027
U206
18883-68-4
Streptozotodn
U103
77-78-1
SuHuric acid, rSmethyl ester
U189
1314-80-3
Sulfur phosphide (R)
See
93-76-5
2,4,5-T
FQ27
U207
95-94-3
1,2,4,5-TetracMorobenzene
U208
630-20-6
1,1,1,2-TetracNoroethaiM
U209
79-34-5
1,1,2,2-Tetrachloroethane
U210
127-18-4
Tetrachloroethylene
See
58-90-2
2,3,4,6-Tetrachlorophenol
F027
U213
109-99-9
Tetrahydroluran (1)
U214
563-68-8
Thallkimfl) acetate
U21S
6533-73-9
ThaHum(l) carbonate
U2ie
7781-12-0
ThalRumfl) chloride
U216
7791-12-0
Thallium chloride Ttd
U217
10102-45-1
ThalBum(l) nitrate
U218
62-55-5
Thioacetamide
U153
74-93-1
Thiomethanol (I.T)
U244
137-26-8
Thioperoxydicarbonic diamide ((HiN)C(S))iS>, tetramethyV-
U219
62-56-6
Thiourea
U244
137-26-8
Thiram
U220
108-88-3
Toluene
U221
25376-45-8
Toluenediamine
U223
26471-62-5
Toluene diisocyanate (R.T)
U328
95-53-4
o-Toluidine
U353
106-49-0
p-Toluidine
U222
636-21-5
o-Toluidine hydrochloride
U011
61-82-5
1H-1.2.4-Triazol-3-emine
U227
79-00-5
1,1 ^-Trichloroethane
U228
79-01-6
TricNoroethytene
U121
75-69-4
TricWoromonoHuoromelhane
Sea
95-95-4
2,4,5-TricMorophenol
F027
See
88-06-2
2,4,6-Trichlorophenol
F027
U234
99-35-4
1,3,$-Trinitrobenzene (R,T)
U182
123-63-7
1,3.5-Trioxane, 2.4,6-trimethyt-
U235
126-72-7
Tris(2,3-
-------
Part 261, App. I
40 CFR Ch. I (7-1-88 Edition)
Haz-
ardous
waste
No.
Chemical
abstracts No.
Substance
U248
•81-S1-2
Warfarin, & salts, when present at concentrations of 0.3% or less
U239
1330-20-7
Xylene (1)
U200
50-55-5
Yohimben-16-caiboxyfic add. 11.17-<*roethoxy-18-f (3.4,5-trimethoxyberaoyf)oxyl-, methyl ester.
(3beta. 16beta,17alpha.18beta.20alpha)>
U249
1314-«4-7
Zinc phosphide Zn>Pi, when present at concentrations o! 10% or less
1 CAS Number given for parent compound only.
(Approved by the Office of Management and Budget under control number 2050-0047)
£45 FR 78529. 78541. Nov. 25, 1980, as amended at 46 FR 27477, May 20. 1981; 49 FR 19923,
May 10. 1984; 50 FR 2000, Jan. 14. 1985; 50 FR 28744, July 15, 1985; 50 FR 42942, Oct. 23.
1985; 51 FR 6541. Feb. 25.1986; 51 FR 10175. Mar. 24, 1986; 51 FR 28298, Aug. 6.1986; 52 FR
21306, June 5.1987; 52 FR 26012. July 10,1987; 53 FR 13383,13384, Apr. 22.19881
Appendix I—Representative Sampling
Methods
Appendix II—EP Toxicity Test
Procedures
The methods and equipment used for
sampling waste materials will vary with the
form and consistency of the waste materials
to be sampled. Samples collected using the
sampling protocols listed below, for sam-
pling waste with properties similar to the in-
dicated materials, will be considered by the
Agency to be representative of the waste.
Extremely viscous liquid—ASTM Standard
D140-70 Crushed or powdered material—
ASTM Standard D346-75 Soil or rock-like
material—ASTM Standard D420-69 Soil-
like material—ASTM Standard D1452-65
Fly Ash-like material—ASTM Standard
D2234-76 [ASTM Standards are available
from ASTM. 1916 Race St.. Philadelphia,
PA 191031
Containerized liquid wastes—"COLIWASA"
described in "Test Methods for the Eval-
uation of Solid Waste, Physical/Chemical
Methods." k U.S. Environmental Protec-
tion Agency, Office of Solid Waste, Wash-
ington, D.C. 20460. [Copies may be ob-
tained from Solid Waste Information. U.S.
Environmental Protection Agency, 26 W.
St. Clair St., Cincinnati. Ohio 45268]
Liquid waste in pits, ponds, lagoons, and
similar reservoirs.—"Pond Sampler" de-
scribed in "Test Methods for the Evalua-
tion of Solid Waste, Physical/Chemical
Methods." *
This manual also contains additional in-
formation on application of these protocols.
A. extraction Procedure
traction continued for mi nd<
hours, during which t>.
-------
APPENDIX A FIGURE 2
CEftCLA LIST
8
-------
CCRCIA Lut
Steam: Cmmcal WAant—Conftued Srcanc Cmmicm. WMHt—Canfttuod JnancMMCitWuTU—CoMmtd
Note Tbe |«n««ta| IbUnc fulftll* the i»-
lilnMM al SmiIm MMiltl Mm Cimpn-
IwmIn CMlmuMMil Rupotu*. Conp«n-
Hirrf end UaMlllr Act ICERCLAI. thai all
-baMtdou* iuMuicu," u defined In thai
JUL ihtU ba Ibtatf a* haiardoua malarlala
under the Hmiilom Mtliriala Tteiuporta-
UM Act. Thai dafioUlo* Include* tub-
iUKM ItoMd under Secllop llllbMlMAI o(
lha fidutl Walar Pollution Casual Act
irWPCAi Ttoote malarial* ham already
been Uaiad aa haaardoua ntbaUnca* to Uta
Hiurtwa Matorlala TaMa d Ihle aactloa.
and that lUUOf la oat rapaatad hara. Th*
dallnlilaa al "hanntoua aubataAca* to
CSRCLA alw tncludai iuMiku datlgnal-
id undar Secllen Hlltl •< lha FWPCA.
Section 10SI at lha Solid Waaia (Mapoaal
Act. and Section IIS al lha Clean Air Act.
Tha (ollowlna listing cenatai* al material*
4»l(natad under Ihota aiultoiUlM. Matert-
all indicated to lha lUtlni by an eaterlik 1*1
m alM lilted to lha Haiardoui Malarial*
' TaMa aa haiardoua mliitntn. Wlih rcapect
im atber naurlali to lha lollovlng tUUnc.
Ihoaa that arc not (arMdden materlala ar
fall •llhto a hexard claie ara not aublact to
lb* requirement* al Ihle Subchapter.
It thould bo noted that Sactton jMibl el
CPICLA praoldea that common and coo-
tract carrier* mar ba held liable undar that
Act lor lha raleaeo al a "haaardoua eub>
dance" aa defined to that Act. altar tha al-
fedi«a data al lha llMln* ol that lubitanc*
** a haiardoua material uodar tha Haaard*
eu* Malarial* Trantpottatlon Act.
inane CMmm Wmtii
IM
liMMW
UBM
t«M~
W>* ¦ ¦ i
(ISM
MNIM MK|I mm H
ut«<
'KM KM DMMI
w»«~
MMUMMMMMft
1001
Mtrnmm
WN
UOM
U09»
I Miyinnainiin
*U«l|lCNBMN|C.an
MNl
UJ04 . -
Afir>*C
*A*
'4{l>IQMlM
VI* • •
*****
i
00»l
mil .
'torn 0 l|
-------
S»«C*ICCmvmcju. v»a«w»—Coninu«4 iHOwCWwamiMifH CanMnmd incwcCkmcm. MUItm—ConHnyd Smotic Q«mcal Wa«H«—ConHnuad
-------
Smckic Cmmcm. Condnuad
SncwCMwMINitlll-GtNkMt
Snae Cmmcm. Wutii-CoMnu«4
Smcvic Chcmcai Wmms—ConttHMd
-------
-------
APPENDIX A FIGURE 3
TOXIC POLLUTANTS
14
-------
TABLE I.—SECTION 307—TOXIC POLLUTANTS
Aeenaphthene
Acrolein
Acrylonitrile
Aldrin/Dieldrin
Antimony and compounds*
Arsenic and compounds
Asbestos
Benzene
Benzidine
Beryllium and compounds
Cadmium and compounds
Carbon tetrachloride
Chlordane (technical mixture and metabolites)
Chlorinated benzenes (other than dichlorobenzenes)
Chlorinated ethanes (including I J-dichloroethane.
I.I.Mriehloroelhane. and hexachloroethane)
Chloroalkyl ethers (ehloromethyl. chloroethyl. and
mixed ethers)
Chlorinated naphthalene
Chlorinated phenols (other than those listed elsewhere;
includes trichlorophenols and chlorinated cresols)
Chloroform
2-chlorophenol
Chromium and compounds
Copper and compounds
Cyanides
DDT and metabolites
Dichlorobenzenes (1J-. 1J-. and I.dichlorobenzenes)
Dichlorobenzidine
Dichloroethylenes (1,1- and IJ-dichloroethylene)
2.4-dichlorophenol
Dichloropropane and dichloropropene
2.4-dimethylphenol
Dinitrotoluene
Diphenylhydrazine
Endosulfan and metabolites
Endrin and metabolites
Ethylbenzene
Fluorsnihene
Haloethers (other than those listed elsewhere: includes
chlorophenylphenyl ethers, bromophenylphenyl ether.
bis(dischloroisopropyl) ether, bis-(chloroethoxy)
methane and polychlorinated diphenyl ethers)
Halomeihanes (other than those listed elsewhere: in-
cludes methylene chlorid methylchloride. methyl-
bromide, bromoform. diehlorobromomeihane. tri-
chloronuoromethane. dichlorodinuoromethane)
Heptachlor and metabolites
Hexachlorobutadiene
Hexachlorocyelohexane (all isomers)
Hexachlorocyclopentadiene
Isophorone
Lead and compounds
Mercury and compounds
Naphthalene
Nickd and compounds
Nitrobenzene
Nitrophenols (Including 2.4-dinitrophenol) dinitro-
craol)
Nitrosamines
Pentachloro phenol
Phenol
Phthalate esters
Polychlorinated biphenyls (PCSs)
PoNnucleir aromatic hydrocarbons (including benzjn-
thracenes. benzoptrcncs. benio.luors.ithcrc. chry.
tenes. dibenzanthracenes. and indenopyrenes)
Selenium and compounds
Silver and compounds
2.J.7.8- Tetrachlorodibenzo-p-dioxin (TCDD)
Tetrachloroethylene
Thallium and-compound*
Toluene
Toxaphene
Trichloroethylene
Vinyl chloride
Zinc and compounds
* Tlx ictik "comwwMll'* lAall iacMi ortamc kwimk com.
15
-------
APPENDIX A FIGURE 4
BASIS FOR LISTING HAZARDOUS HASTE
16
-------
Appendix IV—[Reserved for
Radioactive Waste Test Methods]
Appendix V—[Reserved tor Infec-
tious Waste Treatment Specifica-
tions]
Appendix VI—[Reserved for
Etiologic Agents]
Appendix VII—Basis for Listing
Hazardous Waste
EPA
EPA
NO.
F001_
FOB.
F003..
HIM.
Hat.
«w_
*wa_
*0W_
*011..
mzraui unwuMns w wncn mo
Na
F02Q-
F021.™
F022-
F023.._
F024
imoMmoiywnii mmymi uww wiw*
omyMTOh ili«i*incnRniiran^ mvimi vm*
cNerid*. cwcinated fluorocaftoora.
Tatrachloroaiftyiana, inittiylwi cNoMib tricNor*
oaftytana. 1.1.1-WcWoroatfiana. 1,1J2-irtcMar-
oaOiaiM, eNorabanxana, l.i.2-trteNeio-l£2-
WchWuorowtmw. ortho-dtahtantoaniaiia. trich-
lerofluorotimnw.
NA
CraaoM and craayiic acid, nitrebanzana.
Tohjana, matfiyt eihyt katona, cibon
¦•obimnofc pyittna. 2-athoxyattanol
2-ritroprepana.
Cadmium, tacovaiant chromium, niekat, cysnkto
(comptewd).
Cywda (satis).
OwMa (sate).
Of*** (catti).
Oysnida (sans).
CyWds (sate).
ft*""* (rcvwptanad).
ctvomum, cyanida (comptaxad).
Haardous iwiilluam for wticft kstsd
T«tr»- and pawfcWorodtbawo-p^wana; tma
and pantscNorodfrftanzofurans; w» and
lairacHoraqfranois and thar cWcrephanoicy da-
nvallv* adds, aatara. atfiara, amnia and othar
Pant* and twcWoredaianiu-^dtoins: pants-
and haxacNdradbaraofurana; pantaeMoro-
nk^Mll aaul S|a|
pnonoi ino ra owvsww*
Tetra-, pana-, and
T«tr»-, and pantacWormJbwuo-^dioiana;
chtorophenott and Iwr cMoropftanaxy danva-
vGnnnmin^ i^wvoiomnii mnriufl*ltftTi*Ty'tPTrTw''***T*t*. hMOfw
toraeydohaKsna. banzai w. cMortiawwa. dWv
torabaraanaa, 1.2.4-ttcNorebareana, tafraehlor-
pindflhtofobmnnii htxscMofOfewv
hm, totumi^ nipMhilini>
-------
APPENDIX A PIGORE 5
HAZARDOUS CONSTITUENTS
18
-------
HAZAXSOOS COKSTITVOm
Aeetonltrll* (Ethanenitrlle)
Aeetpphenone (Ktltanone. t-phenyl)
l-talpna-Ac«Mnrib*nzyi)-4*
hydroxycoumarln and Mlt* (Warfarin)
3-Acttylamlnonuorene (Acetasilde. N-<9H-
fluaren-l-rlM
Acetyl eWorld* (Ethanoyl chloride)
l-Acetyl-3-thloum (Acetamldt. N-iamin-
othtoiomethylM
Acrolein (3-Prepenal)
Acrylamlde ll'Pnpmoldil
AerylonitrUe < 3-Propenenltrlle)
A/latoxliu
Aldrln U.l3.4.10.10-Re*aehloro-
1.4.4a.J.I.*a.lb-hexahydro-endo.exo-
l.tJ.t-Dlaethano naphthalene)
Ally I alcohol (3-Propan-l-ol)
Aluminum phoiphide
4-Amlnoblphenrl (tl.l'-BlphenyU-4-e»lne)
$. Amlno-Ua. J.I.Sa.lb-hexahydro.4.
(hydroxymethylvta-methoiy-9-methyl-
cubiatu uttrtnocr.r^.tlpmolet 1.3-
a!lrdole-4.7-dlone. (atari (Mitomycin CJ
(Axtrtnotrr-J.^IPTmloC l.3-ailndoie-4.T-
dtene. »-amino-»-(<oxy)methyM-MaJ.l.ta.lfe-
hex*hydr»lametho(y-S-metliy*i .
S-(AJiiinomeUiyl>-3-lsoxaioloi (J(JHM»o*e-
wIom. KamlnomethrlM 4-A/nlnopyrt-
dlM ifrnMtmmlM)
Amftrol* {IR-Ut-TniHlJ-MlMl
Aniline (haHMnlM)
AMlmow and compounda. N.Oi'
Araralte (Sulfuroua add. > oxide)
AfMiUe Uloxlde (Arsenic <111) oxide)
Auramine iBenaenemine. 4.4'-
carbonlmidoylbMNJt-DUneUiyK mono'
hydrochloride)
Axaserlne
Benxolbmuoranthene (M-BencofltsorMUi-
IM)
BenxoCJiriuo ran then* d.»-Ben»ofluor»nlh-
«nel
ItnoUlpmM (3.4-BetwoeTTene)
p-Benzoqutnone (1.4-Cyrfohexadlenedlone)
Bemouichlortde (Bemene. trichloromethyl-
i
Benerl chloride (Bmm (ctildrometiir IM
Beryllium and urn pound*. K.O-&*
BiK3-chloreethexymiethaiie (ZthajM. 1.1**
ImethrleneblMOxyilbUtt-chlor^l)
B1a(3 ether (ZUune. 1.1--
oxybU(3->
Cadmium and compounda. K-04.'
Caiclum chromate
Chlorinatedb«nunca. K.OA'
Chlortnaud «hiM. N.OA'
ChloHnaUd nuorocarbona. K.O
Oilorlnalcd naphlhaltn*. K.Oi.'
CtilorfMUd phenol. N.OA*
Ctilorpae*tald«hrd« (AettaldPhydt. chlpr»>i
CMorpalkyl tthtn. M.OJS.'
p-ChloroanUInt (8*nxtnamln«. «
ChlorPbrncan* iStmtM. chloro-)
Chlorebonxllaw (B*nz*nracttlc add. 4-
chlpr»-alpha^4Ui!ourea (Thiourea. (3-
ehloroohenyl)-)
3-OMorooroplonttrlle (Propanenitnl*. 3-
chlor»)
Chromium and eompounda. N.O.S.*
Chryeene
CiwanpMahyde (3-Butenall
Cyanlddt 'soluble talu and eomplexeai.
M.OA*
Cyanoftn lEihanedtnltrlle)
Cymaectn bromide (Bromine eyanide)
Cywioten chloride (Chlorine cyantdei
Cyeaain (beta-O-Glucopyranotide. imetnyi-
ONH-aaoxy imethyl-1
3i
Cyclop hotpnamide CK'I.J.l-Oxazxpnoi-
phoruie. (bws-chloroetltrl )ammo i tetra-
hydro-. 3-oxidei
19
-------
iipha-Hy*o-h(*opyrmno( yl way )-T J.f.lO*
tair»hydrp-4.l.n-t*lhydro«y*l-inatho*y.)
ODD (DlehterodlphanyldlehloroaUianai
(CUi«n«. l.l-dkhlor®.2J-bta
(XtAHM. U.Mrtehloro-2.2-bla(p-ehJoro-
phairtM
OlaiUU (S-(2J-dlehloroailyl)
diisoprspylthlocsrftamatai
Df baralaji laaldlna (lAi.»-D
CHbamlaJJaerldlna (l-X.7.t-D)b«merldln«>
OibimtiJiliaUirMM (IJJ,K)lbmuUi-
TH-OlbanastejJcartasaia i3,UI-Olbaaev
baaola)
OtbMM(Ml9rrMW (1 J.OOft«HP]THW>
DibanaotaJOpyraaa (LUt>OlbM»m*>
OibMHiaJlorrmt (UUMwnwntf
l J-Drt wo IQUorapcop—
M-dfchioroO
~DltlllOW*—» HlMMIt IWkWOlM
dlehJoo. N.OA*)
IT-Dtehloi uXiuMliw (tU*-MMNnylM.4'«
dUalac U--diehl«rO')
l>Ptemof»l butana 4fcb»
CieMMiodinuar— tluai (Mathaaa. die*
lorodUIuor»l
Ll-OieflJoroMJiuM (BhrlMm dtehlprtdai
U-DleltlOfMtlUfM
loro.. K.O&1
U-DIcWotwum iFiwntot dtcftlorld*)
Dtehloroprepanol H.OJ.* (PiuuaiiuL dletl-
low.. N.OJi'1
Dtchloroproeana. H.O&.* (Piuiiana. diefc-
lei». N.OA'I
UOIdilMamM ll-flipiM LS-dkb*
loi»)
OMdna ydra tadoKTp
1.4:a.<.01mattianonapmhalana>
l-£l«-01aeegyButaaa (U-llnMM)
0Mi7tanM (Anuia. dlatftyM
NJf-DMIijrtlirdmtM
dlatiiyti
OMr 'I Phosphor*
nltroohanyt atari
DWthyl phthalau lU-hmiMMartMrlh
•eid. dlathyt atm
O.O-Oixhr* O-3-pjrradnyi phoapftoroth-
lorn la iPftoaohorothMc add. 0.04Miirl
O-pyraatayl aatar
(HiMiml li>
DtathylatUbaatafot <4.4-suiban«dtol.
ajpha.alpha-dlathyi. MMdMydrafan phoa-
phata. <£>•>
Dihydraaafrola (Banana. U-mtUirltno-
dioxy-4-propyi-i
2.t-DUiydrexy-aJpha-(matftyUjnJnoRnathyl
bamyi alcohol (1.2-BanzanadJoi. 4-{l-hy-
drexy-2--2-oioatliyM
2J'-D(matho*jrba«ldtaa (CU-Btphanyll-
4.4'dUatna. M'4lmailMiM
P-OtoBthylamlnaa*ehin*«na (Baraaiumlna.
NJ»-4imathyl-4-( phraytasoM
T.12-Dimathylbanc(a]anlhncafta (1.2-Ban-
nnUintam. UJ-dlaatftyto
M*-OtmaUiylbanadliia (tU-BlphanylM.*-
<"*¦»'¦¦* M'-dlaathyl-)
Olmathyleartamayt ehiortda (Carbamoyl
ehloflda. dlmathyl-)
Li-Dtmathyttiydradna (Hydrata*. 1.1-dl-
matlirM
L2-D(aatityU«ydrulna (Hydradaa. L2-41-
maUiyt-)
UOlMttfVUMiliylililatitMaagM. 0>
t (math y I am Inn) cvaanytlodm CTJiio>
(MM)
aipha^Iphk-Dtaaihylphanattaytaaiisa fCuv-
anamlna. Li-dlraatfiyt-Z-phanyi-)
K-OtaMhylplMaal (Phmol 2.4-dlnathyl-)
Oteathyt pbUialau (l.J-
BanianaUleartwayUe add dlnathrl atari
ObMthyi niUau (SulXorle add. dimathri
anarl
OUUtnMoMN. N.OA' (Banaana. dUti»,
K-Oi'l
4.*-Plnitw a ey—l and alia (Phanoi. L4-
illnliru I niaUirt-. and aim
14-Otaltrophanol (Phanoi. l4-dUUtra>i
2.4-Otnitrotolaaaa (Baniana. I-m«thyl-L4-
dimtro>>
a.f'Otauawotaam (Batoana. l-
dlaniM
Dl-n-oc«yl phUialau (1.2-
BanrmadJeartaayilo addb dtoctyl aatar)
ki-OI«nM 11.4-Olathylana oiidai
Dtphanytamina (Banxanaaioa. tf-phanyl-)
Ul-Otphanylhydmim (Hydndnt. 1.2-di-
phanyl-)
D> i»prBpylnltraaaintna (W-Kltraw dl-n-crp.
pylaimnai
ObulfotM cO.O-dtathyl S-I2-
(athyltlileiaUiyll phaashoradlthloau)
t4>OitMoM«m iThtalmModiewMfiie dla>
CndoaaltM <*-Wertomana. U-dlmathanot.
1.4J.<.T.7-ha«aehtor». cydk tuldtai
B«Mn and mauMIUi (l.2J.4.10.1»-has-
aehlor»«.T-«ooay.L4.4aJ.(.'7J.la.
oeuhydr»
dimethanonaehtiiaietie. uid maObolMaat
CUtyt cartanaM (Urathan) tCartamle add.
athyl aatar)
Ethyl eyanlda (preeaneniUlle)
BhrlaniBUdlthlottrwwlc add. nlta and
Mean (U-CthanadlylMaeartaoMdUWeie
20
CUiylaiMUBiM (iUUWUiM
Ethylana oatda (Oatnna)
KUiylanatiUoan* < 2- InudaasUdtnaOihma I
CUtyi matliaerrUM (2-Prapanole add. 2-
matbyl>. (thyt (atari
CUtyl mathanasuUaruua (MathaoaauMpnie
add. athyt aatarl
FluorMtliaM (BanaoOJclfluoranai
Pluortna
-------
3-Pluoroacetamlde (Acetamlde. 3fluoro-)
nuoroaeetle acid. tedium salt (Acetic add.
fluoro-. sodium tail)
romaldehyde (Methylene oxide)
Formic add (Methanoic tdd)
Glyddylaldehyd* (l-Propanol-2.J-epoxy>
Balomethane. N.O J.*
Reptschlor (4.TMethano.|Hlndeno.
l.t.J.e/T.I.I-heptaehloro-Ja. 4.1.1a-
tetrahydro-i
Beptachlor epoxide (alpha. beta, and
luoi Isomer*) (4.T-Methano-lH-lnd«ne.
L4.S.«.T.a.».heptaehloro-3.J-*poxy-3s.4.T.7.
tetrahydro-. alpha, beta, and tamma iso-
mers)
Bexachlorabemen* (Benxene, hexsehloro-)
Bexachlorobutadlefl* ll.J-8utadl*n*.
1.1.2J.4.4-hexachloro->
Hexaehloroeyelohtxane (all laomen) (tin-
dam and isomers)
Bexachiorocyclopentadlen* (lJ-Cyelopen-
tadlene. UJ.4.S.3-hexachloro->
Bexachloroethan* (Ethan*. l.l.l.J.SJ-hex-
aetilsro-)
L2J.4.10.10-Rexacnlor»-t.4.4a.S.«.
dlmethanonaphUialme)
Rtxachlorophene itr-MtlkrltMbUl.Lti
erlchloraphcflolll
Rexachlorapropm* (1-Propen*.
hcxacMoro.)
Rinnhrl tetnphosphat* (Tetraphoa-
pttorte add. hexaethyl MMr>
Rydrastne (Dlamln*)
Bydrocyanle add (Hrdroftn cyanide)
Hydrofluoric add (Hydrocm fluoride)
Bydroten wUld* (Sulfur hydride)
Hydrsxydlmethylanln* oxldo (Cacodylle
add)
tndeno(l.3.3-cd)oyrene (UMU-
phenylenopyren*)
ledomtthan* (Methyl Iodide)
Iron dextran (finle dextran)
tsocyanlc add. methyl ester (Methyl is*
cyanat*)
Iso butyl alcohol (1-Propanol. I-methylo
Isosafrol* (Benxene. U-methylenedloxy-4-
allyl<)
Kepone (Dec*chloroect*hydro>l.3.4-Meth-
ano-2H-crdobuta(ed]pentalen-2-one >
Uuiecaipln* (3-Butenole add. 2-methyl-. 7-
((tMhydniy-h I -m*tltoxy«thy I >>3.
methyl-l-oxobuloxy)methylM.3.9.7a>
tetranydr^lK-pyrrelUln-l-yl taurl
Lead and compound*. N.OA'
Lead acetate (Acetic add. lead salt)
Lead phosphate (Phosphoric add. lead wit)
Ltad nibMiuH (Lead. bla(acetat»
O KetraAydroxytrt- I
Malde anhydrld* <2.S- Purandlone)
MaJttc hydradde (U-Dlhydro-J.O-pyrldtsln-
edlone)
MaJononltiile (Fropanedlnltrflo)
Melphalan (Alan Ins. l-(p-bl*(2-
ciiloroethyl)ainlnolDh*fiyl-. L->
Mercury tulmlnaf* irulmlnie add. mercury
mLV
Mrmrr and ljl-ipu jiidju X.OS.'
Methacrylonltrll* (2-Propenenitrlle. 7-
methyl*)
M*than«thlol (TMomethanol)
M*thapyiD*m (Pyridine. 2-((2- '
dlmeUiylamino>ethyl)-3-thenylamln»->
Mttholmyl (AceUmidie add. N«
((methylcarbamorl)oxylthJo-. ' methyl
«*ur
Methoxychlor (Ethan*. l.l.l-trlehloro-2J--
Mstp-methosyphcnylM
2-Methytaxindlne(1.2-PTooyl«ntmlfi«> -
3-M«thylcholantnr«n*
(BencUlaeeanthrylene. 1.2-dlhydro-l-
methyl.)
Methyl chlorocarbonat* (Carbonochlortdle
acid. methyl ester)
4.4'-Methylcnebls(3-chloroanillA*) (Bencen-
amlne. 4.4'-methylenebl»<3-cnioro->
Methyl ethyl ketone (MSX) (3-Butanonei
Methyl hydraslne (Kydraxlne. methyl-)
3-MethyUactonitrtle (Propancnltnle. 2 hy-
droxy-2-methyl-)
Methyl methaerylat* (2 Propetiole add. 2-
methyl-, methyl eater)
Methyl methanesultenata (Methanesulfonlc
add. methyl etter)
3-Methyl-3-(niethylthlo>proploneldehrde-».
(methylearbonyl) oxlme (Propanal. 3-
m«thyl-34methylthloK O-
KmethyUmlnoKarbonytloxtm*)
N-Methyl-N'-Mtro-N-nltrosotuanldln*
(Ouanidlne. N-nltroto-N-methyl-N'-nitro-i
Methyl paiathlon (O.O-dlmethyl 0-(4-nltro-
phenyl) phetphorothloat*)
McthytUUouradl (4-lU-Pyrlmldlnone. 2.1-
dlhydr»-«-mettiyl-2-thloxo>>
Mustard iu (Sulfide. b(s(3-)
Naphthalan*
1.4-Naphthoqulnon* (1.4-Naphthalene-
dlon*>
l-Napnthyiamlne (alpha-Naphthylamlne)
INsphtftylunlne (beta-Napnthylamine)
l-Naphthyl-l-thlourea I Thiourea, 1-naphth-
alenyl-i
Mtckcl and compounds. N.O J.*
Nickel earbonyl (Nickel tetraearbonyl)
Nickel cyanide (Nickel (III cyanide)
Nicotine and taiu (Pyridine. (S)-)-(l-
methyl-S-pyrrolMlnylK and aalui
Kltrte oxide (Nltra«en (II) oxide)
p-Nltroanillne (Bemenamin*. 4-nltr»i
Nltrebendne (Be nunc, nltro-i
Nltrocen dloilde (Nltrocen (IV) oxide)
Nltrocm muilard and hydrochloride salt
(EUianamlne. >)
4-Kltraqulnollne-l-oxld* (Qulnollne. 4-nitro.
I-oxide-)
Nltrosamlne. K.OA1
N-Nltrotodl-n-butylamlne (l-Butanamine.
N-butyl-N-nltroeo-i
N-Nltroeodletlunoiamln* (Xthanot 2.T-
(nitrosolmlnoibla.)
N-Nitrosodiethyiamin* (Cthanamme. N-
ethyl-N-nitra*o>)
N-Nltraodtmethylamln* (Dlmethylnitrosa-
inlnei
N-Nltraeo-N-ethylurea (Carbamid*. N-ethyl-
Nnlt™o-t
N-Nltraomethylethylamino (Cthanamine.
N-methyl-N-nitro»)
N-Nltmo^-methylurea (Carttaimd*. N-
'CiOrx
scld. metAylnitroeo-. ethyl estert
N-Nltraomethylrinylamin* (Ethenamine.
N-methyl-N-nltros^)
N-Nltrosomorpholln* (Morpholln*. N-nt-
traoo-)
N-Nltro*onornlcotln*(Nomlcotin*. N-
nitroeo-)
N-Nltrosopip*rtdlM (Pyridine, hexaltydro-.
N-nttrg»)
Nltreaopyrroildlne (Pyrrol*, utrahydr*.. S-
mtfa*o>)
N-Nltroaaeareodn* (Sarcosui*. N-nitroso-i
-------
I-Wttro*-toluldlne (Senenaalne. J-methyl-
OetameUiylpyrophoephoramlde (Dlpnoe-
Btiormmld*. octamethyl-l
Otraiiun tetroxlde (Oniua tTtUi oxide)
t-0*abtcyelo{JJ.Uheptane-«-dlearto«yUe
scid (OidoUttl)
Paraldehyde (l.JJ-TMoaane. 2.4.5-trt-
methyl*)
Pvathlon (PhoepMrothloie add. O.O-
diethyl O^MNlnphmrii tater
Ptntacnierobenaeno (Btravm. pcntachloro-
Pentaehloroethane (SUuna. pentadilor*)
PmtachloroaltrsOenMtM (PCNB) (Benaane.
pentachloronltr*)
Peniadilorophenol (Phenol pen tech lore-)
PheMCettt (AceUmtdO. »-(«^UMXr-
phenylV)
Phenol (Immm hydro**-)
Phonylanortlamlno (miunwllimlnti
Phenyimercucy miuu (Mercury.
N-Phenylthtoarea miowH. phnyt-i
rhewtM (Carton/I chloride)
Pttoepltlne (Bydrocen phoephlde)
Phaephorodlthlote add. O.O-dlethyl »
((ethylthloimethyU eater (Phortut
riMKlMMIlMl add. O.O-dlmethri O-tp-
((dlmetiiylamlaoieuUonyMplianytl eater
(Paaphurl
PhUulle add cetera, W.O.S.* (Boom. U*
tertenlh add. —tin. H.04.1
PhUialM anhydride (U-
IfcaHmiilhi artrt nihiilrlrtal
J-FleoUne (Pyridine. l-methyM
Potyefalortnatcd Nphenyl N.OA*
PMaaataa cyanide
rntamiiwi dim cruUi miiuuwU #
tTM». pPHHllll)
Pronamlde (»Dtchla*»IMU-dbiotfcyM>
propywylihawaiiiiila)
U-Prewe aultooe (U-OxaihteUna. !*¦
dioxide)
»Propy lamiae (l-Piupenamlne)
Propylthiouracil
(OndacaiaothylanodlamlnQ Kjr-MdS>
ehluiutwiuylK dlhydroehlortde)
«Pi u pm in dconoii
Rmrplno (TohiabaivH-eartoKylie
lU?-dlnethoay»tfr<(3.«>
nMthw?t«wilMrK methyl eater)
Rceordnol (U-Winumillnll
Sacehartn and nlta i L3-B iriiPlanHilawlliv-
one 1 J-diosMe. and aaltai
SKIOMMmm. U-nWimdloiH-
aiiyM
Selentoue add (Selenium dtostte)
Selenium aad empau* N.O A*
SMdIim sulfide (Sulfur trtonldc)
Sdenourea (Carhaiiiimirtnoolonn
SUv«r aad fowipnuiute R-Ql'
SUvor cyanide
Sodium eyiaMl
SttwmoMcW (D-qinBOPTTinma. l-deosy.
t-(3-methyl*»>nUraooaretdoM
SUooUum inifMt
Strychnine aad aalta (Strrrhnldln-lO am.
and aalta)
UXtfrTeuachtorobonnao (Benaena.
i ijHiffirtUofO't
U.TJ-TwidilaiadttiMi p illualn (TCSOI
(Dlbenio p dloaln. UT.Mncliloi»t
Tetraehioroetbana. N.OJ.* (Cthane. M>
neiiloi». KOA')
l.l.U>Tetmhlorethaiie (EUtane. ULU-t*
ineMtfM
l.lJ.JTtuaehlortUiane (CUiane. 1.UJ-U-
traenior*)
TetraelUoroethano (Cthene. LLJJUtnch-
lor^l
Tetnchloranethane (Carton tetrachloride)
IJ.t.f.-TttrachloropAeftoi (Phenol. - L3.4.C.
tttrachloroo
Teu»cthyldlUilaoyrophoeohate (D(thlopyr<
ophoephorle add. tetraethyl-ester)
Tetraetftyt lead (Plumtone. tetmethyM
Tetracuiylpyropheephate (Pyrophoaphorte
add*, tetraethyl eateri
Tetranitrancthane (Methane. tetnnttrM
Thallium and compounda. N.O-S.'
Tfcallle oslde (Thallium (XIII oslde)
Thallium (J) acetate (Acetic add. thallium
(IlaalU
Thallium <11 earhonata (Cartonle add. dllft-
allium (I) Mltl
Thallium (I) chloride
Thallium (I) nltnue (Nitric add. thallium
(IlaalU
Thallium aelenlU
Thallium (1) aullato (Sulfur* add. thallium
(I)aalU
Thieaeetaaeide tlthaeetiUeamldef
(Hrdrnnwrartwrhlnemlilal
ThJourt* (Cirtuldi tliio*)
Thluram (BMdtmethytthlocafbamoyt) dl-
nlflrtei
Toluene (Besaeaa. methyl-)
Tolueaedlamiaa (PUalnotelueno)
»-Toluldlne hydradileftde (Benaanamln*. I-
methrt>. hrdroehlortde)
Tdrleae itllanriaiiau (Beraane. U-dllao-
eraaatametlvt-l
Toaaphene (Camphena. octachlora>>
Tuiwiamwuiliane (Bretaoforai)
i (Seraena. U.Mr«eb>
LLl-ThelUofeetiMee (Methyl cklcnlmi
LlJ*TMetJoroetlune (CUune. l.Utrteh-
Ioro>)
Tiiettlofoethene (TneUoroetliytene>
TttdtieeemethaeeUUel (MetlianeOUot
orieiUor9»)
TttehloraaMMRuareaMthaae (MeUuuM.
tfldUorofluer^i
llJ-Tnehloropheaol (PhenoL tiimteh-
14.»Tlh lUiwimliaiiul (Phenot lUMefe>
lOTHehlorephenaayacetle add
(MO) add. LlS-trtciiloroenenoxy-)
».4^THehle«ut>heMuayp«oo(eaie aetd (14.S-
m (SO*osi (Praetonote add.
trtehlorepheaoxyvt
TMchlofopreeeeeu W.OA* (Propane, titeh-
lor». K.OA')
m-TWdUainiinmaiia (Progano. MJ-trtcto-
lor»
O.O.O-Trtethyt phoephorothloato iPk»
pdoreUiloie add. O.O.O^detbyl eater*
nw»T> Halt* uhinmiie (Benatne. tJJ-trtnt>
K»t
Trtnl aarldlnyl» phoaphlne nildde (Maa>
phlne nitride. tdail*adildlny|.i
TMtHllii wiwimi uu»l> phoapliau U Pro-
bumL iMIbnofr. flhonfiuii
Tl| nan Woe (tT-Naphthalenedlaullen*
add. lT4(U*-dlmethyli I.l'-Mpnenyli>
i.r-dlyliWdapoHblaU amtno-*-hrdro»y..
tetneodlum aalt)
Uracil muaurd (Undl VCMaiS.
eftlaroetlirDamlnol-i
Vanartlc add. ammonium alt (ammonhim
ranadawi
Vanadium pentosMo (Vanadium iVt oaldei
VTnyl chloride (CUwne. chlot^i
Zlnecranldo
anophaopiUdo
C4d PR n4TT. May ». IMU M P* »TOC
Juno 3.1 Mil
22
-------
APPENDIX B
GUIDE TO COMPATIBILITY OP CHEMICALS
24
-------
GUIDE TO COMPATIBILITY OP CHEMICALS
The Guide is based in part upon information provided to the Coast Guard by
(he National Academy of Sciences - U.S. Coast Cuard Advisory Committee on
Hazardous Materials and represents the latest information available to the Coast
Cuard on chemical compatibility.
The accidental mixing of one chemical cargo with another can in some cases
be expected to result in a vigorous and hazardous chemical reaction. The genera-
tion of toxic gases, the heating, overflow, and rupture of cargo tanks, and .fire and
explosion are possible consequences of such reactions.
The purpose of the Compatibility Chart is to show chemical combinations
believed to be dangerously reactive in the case of accidental mixing. It should be
recognized, however, that the Chart provides a broad grouping of chemicals with
an extensive variety of possible binary combinations. Although one group, gener-
ally speaking, can be considered dangerously reactive with another group where
an "X" appears on the Chart, there may exist between the groups some combina-
tions which would not dangerously react. The Chart should therefore not be used
as an infallible guide. It is offered as an aid in the safe loading of bulk chemical
cargoes, with the recommendation that proper safeguards be taken to avoid
accidental mixing of binary mixtures for which an "X" appears on the Chart.
Proper safeguards would include consideration of such factors as avoidance of the
use of common cargo and vent lines and carriage in adjacent tanks having a
common bulkhead.
The following procedure explains how the Cuide should be used in determin-
ing compatibility information:
(1) Determine the reactivity group of a particular product by referring
to the alphabetical list in Table 7.1.
(2) Enter the Chart with the reactivity group. Proceed across the page.
An "X" indicates a reactivity group that forms an unsafe combina-
tion with the product in question.
For example, crotonaldehyde is listed in Table 7.1 as belonging in Croup 19
(Aldehydes). The Chart shows that chemicals in this group should be segregated
from sulfuric and nitric acids, caustics, ammonia, and all types of amines (aliphatic,
alkanol, and aromatic). According to note A. crotonaldehyde is also incompatible
with non-oxidizing mineral acids.
25
-------
It is recognized there are wide variations in the reaction rates of individual
chemicals within the broad groupings shown reactive by the Compatibility Chart.
Some individual materials in one group will react violently with some of the
materials in another group and cause great hazard; others will react slowly, or not
at all Accordingly, a useful addition to the Guide would be the Identification of
specific binary combinations which are found not to be dangerously reactive, even
though in "X'r appears on the chart for those two chemicals. A few such
combinations ire listed in Table 7J; other safe combinations will be listed in
subsequent revisions.
26
-------
COMPATIBILITY CHART
nco GAOWS
it
r
U
i!
0
¥ S
I O
M >
U X
Si
35
3*
j
a
«#
4
v r
o
e r
c 3
I •>
4 e
. MOfeOllQlltMO MINIUlAeiOl
. luiruuc 4cio
tmu>c 4Cio
. QWCAWC AglOt
. CAUIKJ
, AMMOdlA
. AllFMATlC AXtMfl
, n<«*OVAMINC|
. A»Q— A TIC AMWft
. AMIOCI
. o«c*«ic Awxtemoii
.ItOCTAMtll
l« #I«V ACItAfl
urci
MtuUO iwtu
. AimcM osioci
. cKHvoaONrOfti*
.«IT0*C»
. MO(MTOCI
. AlCOMOtLCVrceU
.fHNOUCMtOlf
. e^AQiACTAn loiunon
. ourtMt
. HHAftmt
, ABOMAtK WT0<0<»I»0W|
. Miicuuwiom HTowecAwtow wnimn
. C1MM
. vmvi MAiiOCf
. m*IQ6|m*M0 AVOAOOMO"*
. MtfAliU
i. c*mo« otmv»ioi
». im/ouICULA»»
-------
NOTES TO COMPATIBILITY CHART:
REACTIVITY DIFFERENCES (DEVIATIONS) WITHIN CHEMICAL GROUPS
A Acrolein (19), Crotonaldehyde (19},and 2-Ethyi-3-propy1
acrolein (19) are not compatible with Croup 1, Non-Oxi-
dising Mineral Aeida.
8 Xaophorona (18), and Mealtyl Oxide (18) arc not compatible
with Croup 8, Alkanolaainee.
C Aerylie AcId (*) it net eoapatibla with Croup 9, Aroaatle
Aainea.
0 Allyl Aleohol (15) la not eoapatibla with Croup 12, Iao-
eyanatea.
K Furfuryl Aleohol (20) la not coapatifile with Croup 1,
Ron-oxidising Mineral Acida.
T Furfural Alcohol (20) ia not eoapatibla with Croup 4,
Organle Acida.
C Dichloroethyl ether (36) ia not eoapatibla with Croup 2,
Sulfuric Aeid.
B Trichloroethylene (36) ia not eoapatibla with Croup 5,
Cauatiea.
X Ethylenediaaine (7) ia not eoapatibla with Ethylene 01-
chloride (36).
28
-------
ALPHABETICAL LISTING OF COMPOUNDS
Hame
Acetaldehydfc
Acetic Acid
Acetic Anhydride
Acetone
Acetonitrile
Acrolein (inhibited)
Acrylic Acid (Inhibited)
Aerylonitrile
(inhibited)
Adiponitrile
Allyl Alcohol
Allyl Chloride
Aainoethylethanolanine
Ammonia, Anhydrous
Ammonium Hydroxide
(28Z or less)
Acimonium Nitrate, Urea,
Meter Solutions
(containing Ammonia)
Ammonium Nitrate, Urea,
Water Solutions (not
containing Ammonia)
Amyl Acetate
Amyl Alcohol
Amyl Tallate
Aniline
Asphalt
Asphalt Blending Stocks:
Roofers Flux
Straight Run Residue
Benzene
Benzene, Toluene
Xylene (crude)
Butadiene (Inhibited)
Butane
Butyl Acrylate
(inhibited)
Butyl Acetate
Butyl Alcohol
Butylamine
Croup
Croup
No.
Name
No.
19
Butyl Benzyl Phthalate
34
4
Butylene
30
11
1,3-Butylene Glycol -
20
18
Butylene Oxide
16
37
Butyl Ether
4 1
19
Butyl Hethaerylate
4
(inhibited)
14
Butyreldehyde
19 .
15
Butyric Aeid
4
37
IS
15
Camphor Oil (light)
18
8
Caprolaetam Solution
22
6
Carbolic Oil
21
Carbon DisuLfide
38
6
Carbon Tetrachloride
36
Caustie Potash Solution
5
Caustie Sods Solution
5
6
Chlorine
*
Chlorobenzene
36
Chloroform
36
43
Chlorosulfonie Acid
*
34
Corn Syrup
43
20
Creosote, Coal Tar
2 1
34
Cresols
21
9
Crcsylate Spent Caustic
33
Solution
5
Crotonaldehyde
19
33
Cuaene
32
33
Cyclosllphatle Resins
31
Cyclohexane
31
Cyelohexano1
20
32
Cyelohexanone
18
Cyclohexylamine
7
32
Cynene
32
30
31
Decaldehyde
19
14
Deeane
31
34
Oecene
30
20
Oecyl Alcohol
20
7
Decyl Acrylate
(inhibited)
14
29
-------
ALPHABETICAL LISTING OF COMPOUNDS (Continued)
Deeylbenzene 32
Dextrose Solution 43
Dlacetone Alcohol 20
Dlbutylaaine 7
Dibutyl Phthalate 34
Diehlorobensene 36
Diehlorodifluoroaethane 36
1,1-Diehloroethane 36
Dichloroethyl Ether 41
Diehloroaethane 36
1.1-Dichloropropane 36
1.2-Diehloropropane 36
1.3-Dlehloropropene 15
Dieyelopentadiene 30
Diethanolaaine 8
Dltth;liala« 7
Diethylbencene 32
Diethylene Cljeel 40
Diethylene Glycol Mono-
butyl Ether 40
Diethylene Clyeol Mono-
butyl Ether Acetate 34
Diethylene Glycol Mono-
•thyl Ether 40
Diethylene Clyeol Mono-
aethyl Ether 40
Dlethylenetrlaalne 7
Dlethylethanolaaine 8
Diheptyl Phthalata 34
Diisobutylene 30
Oilsobutyl Carblnol 20
Dilsobutyl Ketone 18
Dilsode-eyl Phthalata 34
Dlisopropanolaaine ' 8
Diisopropylaaine 7
Dlaethylaalne 7
Diaethylethanolaaine 8
Diaeehylforaaalde 10
Dinonyl Phthalata 34
.Dioetyl Phthalata " 34
1,4-Oloxana 41
Diphenyl-Oiphenyl Oxide 33
Diphenylaethane Dilso-
eyanata 12
Dl-n-propylaaine 7
Dlpropylana Clyeol 40
Distillate*:
Straight Run
33
Plashed Feed Stocks
33
Dtundeeyl Phthalata
34
Dodeeane
31
Dodecanol
20
Dodeeene
30
Dodaeylbanzena
32
Epiehlorohydrin
17
Ethane
31
Ethanolaaine
8
Ethoxylated Alcohols
Cu-Cij
40
Ethoxy Triglycol
40
Ethyl Acetate
34
Ethyl Aleohol
20
Ethyl ^crylata
(Inhibited)
14
Ethylaaine
7
Ethyl Bentene
32
Ethyl Sutanol
20
Ethyl Chloride
36
Ethylene
30
Ethylene Chlorohydrln
20
Ethylene Cyanohydrin
20
Ethyiancdlamina
7
Ethylene Dibroaide
36
Ethylene Oichloride
36
Ethylene Clyeol
20
Ethylene Clyeol Mono-
butyl Ether
40
Ethylene Clyeol Mono-
butyl Ether Aeetate
34
Ethylene Clyeol Mono-
ethyl Ether
40
Ethylene Clyeol Mono-
ethyl Ether Acetate
34
Ethylene Clyeol Mono-
aethyl Ether
40
Ethylene Oxide
«
Ethyl Ether
4 t
Ethylhexaldehyde
2-Ethyl ftexanol
20
2-Ethylhexyl Aerylate
(inhibited)
14
30
-------
ALPHABETICAL LISTING OF COMPOUNDS (Continued)
Ethyl Hexy 1 Talla.t e
Ethyl Hethscrylate
(inhibited)
2-Ethyl-3-Propyl
Acrolein
Formaldehyde Solution
(37-SOX)
Formic Acid
Furfural
Furfuryl Alcohol
34
14
19
19
4
19
20
Jet Fuels:
JP-1 (Kerosene) 33
JP-3 33
JP-4 33
JP-5 (Kerosene, Heavy) 33
Kerosene
33
Latex, Liquid Synthetic 43
Css Oil:
Cracked
Caroline Blending Stocks:
Alkylates
Refornatea
Casollnes:
Casinghead (natural)
Automotive (containing
over 4.23 grans lead
per gallon)
Aviation (containing
not over 4.86 grams
lead per gallon)
Polymer
Straight Run
Clutaraldehyde Solution
Clycerlne
Clycol Dlacetate
Clyoxal Solution
Heptane
Hexamethyleneimine
He xane
Hexanol
Hcxene
Hexylene Clyeel
Hydrochloric Acid
Hydrofluoric Acid
Isophorone
Isoprene (inhibited)
33 Hesityl Oxide
Hethane
33 Hethyl Acetate
33 Hethyl Acetylene, Pro-
padlene Mixture
33 (Stabilized)
Methyl Acrylate
(inhibited)
33 Methyl Alcohol
Methyl Amyl Acetate
Hethyl Amyl Alcohol
33 Methyl Bromide
33 3-Hethyl Butyraldehyde
33 Hethyl Chloride
19 Methyl Ethyl Ketone
20 2-Methyl-5-Ethyl
34 Pyridine
19 Methyl Formal (Dimethyl
Formal)
Methyl Isobutyl Ketone
31 Methyl Isobutyl Carbinol
7 Hethyl Hethacrylate
31 (inhibited)
20 (alpha-) Methyl Styrene
30 (inhibited)
20 Hineral Spirits
1 Monochlorod Ifluoro-
1 methane
Morphollne
Motor Fuel Antiknock Co»-
18 pounds Containing Lead
30 Alky Is
18
31
34
30
14
20
34
20
36
19
36
18
4 I
18
20
14
30
33
36
7
31
-------
ALPHABETICAL LISTING OP COMPOUNDS (Continued)
Naphthai
Coal Tar
33
Lard
34
Solvent
33
Olive
34
Stoddard Solvent
33
Pais
34
Varnish Marker*' and
Peanut
34
Painter*' (7SZ)
33
Safflower
34
Naphthalene (aolten)
32
Soya Bean
34
Nitric Aeld (70% or
Tueua-'
34
lets)
3
Vegetable
34
Nitric Acid (93X)
*
Miscellaneous Oils,
Rittobensere
A3
including:
1- or 2-Nitropropane
43
Absorption
33
Nitrotoluene
A3
Aroaatlc
33
Kenan*
31
Coal Tar
33
Nonene
30
Hearteut Distillate
33
Nonyl Alcohol
20
Linseed
33
Nonyl Phenol
21
Lubricating
33
Nonyl Phenol.
Mineral
33
(ethoxylated)
AO
Mineral Seal
33
Moto(
33
Neatafoot
33
Oetan*
31
Penetrating
33
Octene
30
Range
33
Oceyl Aleohol
20
Resin
33
Octyl Aldehyde
19
Resinous Petroleua
33
Octyl Epoxytallate
3A
Rosin
33
Oil*:
Sp«ra
33
Clarified
33
Spindle
33
Coal Oil
33
Spray
33
Crude Oil
33
Tall
34
Oieael Oil
33
Tanner'a
33
Fuel Oil*:
Turbine
33
33
Oleua
*
do. 1-0
33
No. 2
33
No. 2-0
33
Pentadeeanol
22
No. 4
33
Pentane
31
No. 3
33
Pentene
30
No. 6
33
Pentyl Aldehyde
19
Residual
33
Perehloroethylene
36
Road
33
Petrolatua
33
Tranafomer
33
Petroleua Naphtha
33
Edible Oil*, including:
Phenol
21
Caator
3A
Pentaehloroethane
36
Coconut
3A
Phosphorle Acid
1
Cotton Seed
34
Phosphorus
*
Fish
34
Phthalic Anhydride
(aolten) *
11
32
-------
Alphabetical listing of compounds (Continued)
Polybutene
30
Tetradecanol
70
Polyethylene Clycols
40
Tet radecene
30
Polyme thy'l.ene Polyphenyl
-
Tetradecylbenzene
32
isocyanate
12
Tetraethylene Clycol
40
Polypropylene
30
Tetraethylenepentamlne
7
Polypropylene Clycol
Tetrahydrofuran
4 1
Methyl Ether
40
Tetrahydronaphthalene
32
Polypropylene Clycols
40
Tetrasodiuro Salt of
Propane
31
EDTA Solution
43
Propanolamine
8
Toluene
32
Propionaldehyde
19
Toluene Diisocyanate
12
Propionic Acid
4
1,2,4-Trichlorobenzene
36
Propionic Anhydride
11
Trichloroethylene
36
Propyl Acetate
34
Tridecanol
20
Propyl Alcohol
20
Tridecene
30
Propylamine
7
Tr idecylbenzene
32
Propylene
30
Trlethanolamlne
8
Propylene Butylene
Tr iethylamine
7
Polymer
30
Triethyl Benzene
32
Propylene Clycol
20
Triethylene Clycol
40
Propylene Oxide
16
Triethylenetetramine
7
Propylene Tetramer
30
Tripropylene Clycol
40
Propyl Ether
41
Turpen tine
30
Pyridine
9
Undeeanol
20
Sodium Hydrosulfide
Undecene
30
Solution (45* or less)
5
Undecylbenzene
32
Sorbitol
20
Styrene (inhibited)
30
Sulfolane
39
Valeraldehyde
19
Sulfur (molten)
- *
Vinyl Acetate
Sulfuric Acid
2
(inhibited)
13
Sulfuric Acid, Spent
2
Vinyl Chloride
(inhibited)
33
Vinylidene Chloride
Tallov
34
(inhibited)
35
Tallow Fatty^Alcohol
20
Vinyl Toluene
1,1,2,2-Tetrachloro-
(Inhibited)
30
ethane
36
Xylene
32
* Because of very high reactivity or unusual conditions of
carriage, this product is not included in the Compatibility
Chart. If compatibility information is needed for a ship-
ment, contact Commandant (C-MHH-1/83), U.S. Coast Cuard,
400 Seventh Street, S.W., Washington, D. C. 20590.
33
-------
REACTIVITY GROUPS
I* Mon-Oxidlxing Mineral Aclda
Hydrochloric Acid
Hydrofluoric Acid
Phosphoric Acid
2. Sulfuric Acids
Spent Sulfuric Acid
Sulfuric Acid (98Z or less)
3. Hitric Acid
Ritrie Acid (70Z or less)
4. Organic Add*
Acetie Acid
Butyrie Acid
Formic Acid
Propionic Aeid
Acrylic Acid (inhibited)
5. Caustics
Caustic Potash Solution
Caustic Sods Solution
Cresylate Spent Caustic Solution
Sodiua Hydrosulfide Solution
(43X or less)
6. Aamonla
Aanonia, Anhydrous
Aaoonium Hydroxide (28Z or less)
Aanoniua Nitrate, Urea, Water
Solutions (containing Ammonia)
7. Aliphatic Amines
Butylamina
Cyclohexylanlne
Dibutylamine
Dlethylamlne
Methylene triamine
Dlisopropylamlne
Dinethylanlne
Dl-n-propylamine
Ethylamine
Cthylened iamine
Hexamethylenelmine
He thylanlne
Korphollne
Propylanlne
Tetraethylenepentaalne
Triethylamlne
Triethylenetetramine
8. Alkanolanlnes
Aminoethylethano1amine
Olethanolamlne
Diethylethanolamine
Diiaopropanolamine
Olaethylethanolamlne
Ethanblamine
Propanolamine
Trie thanolamine
9. Aromatic Amines
Aniline
Pyridine
2-Methyl-S-Ethylpyridlne
10. Amides
DlaethyIforoamlde
34
-------
REACTIVITY GROUPS (Continual
11. Organic Anhydrides
Acetic Anhydride
Phthallc Anhydride
Propionic Anhydride
12. I»ecy»n«tM
Dlphenylmethane Dllsoeyanate
Polyphenyl Polymethylene-
isocyanate
Toluene Dllsoeyanate
13. Vinyl Acetate
Vinyl Aeetate (inhibited)
14. Acrvlatea
Butyl Acrylate (inhibited)
Butyl Methacrylate (Inhibited)
Decyl Acrylate (Inhibited)
Ethyl Acrylate (inhibited)
2-Ethylhexyl Acrylate (inhibited)
Ethyl Methacrylate (inhibited)
Methyl Acrylate (inhibited)
Methyl Methacrylate (inhibited)
15. Substituted Allyls
Acrylonltrlle (Inhibited)
Allyl Alcohol
Allyl Chloride
1,3-Dlphloropropene
16. Alkylene Oxides
Propylene Oxide
Butylene Oxide
17. Eplchlorohydrln
Epichlorohydrin
18. Ketone*
Acetone
Camphor Oil
Cyclohexanone
Dlisobutyl Ketone
Isophorone
Mesityl Oxide
Methyl Ethyl Ketone
Methyl Isobutyl Ketone
19. Aldehydes
Acetaldehyde
Acrolein (inhibited)
Butyraldehyde
Decaldehyde
E thylhexaldehyde
Formaldehyde
Clutaraldehyde Solution
Clyoxal Solution
Methylbutyraldehyde
Octyl Aldehyde
Pentyl Aldehyde
Proplonaldehyde
Valeraldehyde
20. Alcohols. Glycols
Amyl Alcohol
Butyl Alcohol
1,3-Butylene Glycol
Cyclohexanol
Decyl Alcohol
Diacetone Alcohol
Dlisobutyl Carblnol
Dodecanol
Ethanol
Ethoxylated Alcohols
35
-------
REACTIVITY CROUPS (Contfnuadl
Ethyl Alcohol
Ethylbutanol
Ethylene Chlorohydrin
Ethylene Cyanohydria
Ethylene Glycol
2-Ethyl Rexanol
Furfuryl. Alcohol
Clycerin
Hexanol
Rexylene Glycol
Methanol
Methyl Alcohol
Methylanyl Alcohol
Methylisobutyl Carbinol
Oetyl Alcohol
Honyl Alcohol
Pentedecenol
Propyl Alcohol
Propylene Clycol
Sorbitol
Tallow Fatty Alcohol
Tetradecanol
Tridecanol
Undeeanol
21. Phenble and Cresola
Carbolic Oil
Creosote, Coal Tar
Cresola
Ronyl Phenol
Phenol
22. Caprolactaa Solution
Caprolactaa Solution
23 - 29. Unaaiigned
30. Oleflna
Butadiene (Inhibited)
Butena
Butylena
Decena
Dlcyclopentadiene
Dlisobutylene
Oodeeene
Ethylene
flexene
Iaopfene (inhibited)
Methyl Acetylene, Propadlene
Mixture (stabilised)
(alpha-) Methyl Styrene
(inhibited)
Nonene
Octene
Pentena
Polybutena
Polypropylene
Propylene
Propylene Butylene Polymer
Propylene Tetramer
Styrene (inhibited)
Vinyl Toluene (inhibited)
Tetradecena
Trideeene
Turpentine
Ondecene
31. Parafflna
Butane
Cycloaliphatic Resins
Cyelohexane
Decane
Oodeeene
Ethane
Heptane
Hexana
Methane
Nonana
Octane
Pentane
Propane
36
-------
REACTIVITY GROUPS (Continued)
32. Aromatic Hydrocarbons
Benzene
Benzene, Toluene, Xylene (crude)
Cumene
Cymene
Decylbenzene
Dlethylbenzene
Dodecylbenzene
Eehylbenzene
Naphthalene
Tecradecylbenzene
Tetrahydronaphthalene
Toluene
Trldecylbenzene
Triethylbenzene
Undecylbenzene
Xylene
33. Misc. Hydrocarbon Mixture*
Asphalt
Asphalt Blending Stocks
Diphenyl - Dlphenyl Oxide
Distillates
Cas Oil, Cracked
Gasoline Blending Stocks
Casolines
let Fuels
Kerosene
Mineral Spirits
Naphtha
Oils, Crude
Oils, Diesel
Oils, Coal
Oils, Fuel (No. 1 thru No. 6)
Oils, Residual
Oils, Road
Oils, transformer
Petrolatum
Petroleum Naphtha
34. Esters ,
Amyl Aceeate
Amyl Tallaee
Butyl Aceeate
Butyl Benzyl Phchalate
Castor Oil
Coconut Oil
Cottonseed Oil
Dibutyl Phthalate
Dlethylene Glycol Monobutyl
Ether Ace.tate
Dlheptyl Phthalate
Dllsodecyl Phthalate
Dinonyl Phehalate
DioeCyl Phthalate
Dlundecyl Phthalate
Ethyl Acetate
Ethylene Glycol Monobutyl
Ether Acetate
Ethylene Glyeol Monoethyl
Ether Acetate
Ithylhexyl Tallaee
Fish Oil
Glycol Dlaceeate
Lard
Methyl Acetate
Methyl Amyl Acetate
Octyl Epoxy Tallate
Olive Oil
Palm Oil
Peanut Oil
Propyl Aceeate
Safflover Oil
Soybean Oil
Tallow
Tucum Oil
Vegetable Oil
35. Vinyl Halldes
Vinyl Chloride (inhibited)
Vinylidene Chloride (inhibited)
36. Halogenated Hydrocarbons
Carbon Tetrachloride
Chlorobenzene
37
-------
REACTIVITY GROUPS ICondnutd)
Chloroform
Dichlorobenteae
1,1-Dichloroethane
Dichloroethyl Ether
Dichloromethane
1.1-Dichloropropane
1.2-Dichloropropane
Ethyl Chloride
Ethylene Dibronida
Ethylene Dichlorlde
Methyl Bromide
Methyl Chloride
Pentachloroethane
Perehloroethylene
1,1,2,2-Tetrachloroethane
1,2,4-Triehloroberiaene
Trichloroethylene
37. HItrIlea
Aeetonltrlle
Adlponltrlle
38. Carbon Disulfide
39. Sulfolana
Ethylene Clyeol Monomethyl
Ether
Nonylphenol, Ethoxylated
Polyethylene Glycols
Polypropylene Clyeola
Polypropylene Glycol Methyl
Ether
Soybean Oil*, Epoxidized
Tetraethylene Glycol
Trlethylene Glycol
Trlpropylene Glycol
41. Ethers
Butyl Ether
1,4-Dioxane
Ethyl Ether
Methyl Formal (Dimethyl
Formal) .
Propyl Ether
Tetrahydrofuran
42. Nitrocompounds
(¦one-) Nitrobenzene
1- or 2-Nitropropane
Nitrotoluene
40. Glycol Ethers
Diethylend Clyeol
Diethylene Clyeol Monobueyl
Ether
Diethylene Glycol Monoethyl
Ether
Diethylene Glycol Monomethyl
Ether
Dlpropylene Clyeol
Ethoxy Triglycol
Ethylene Glycol Monobutyl
Ether
Ethylene Glycol Monethyl
Ether
43. Miscellaneous Water Solutions
Aanoniuai Nitrate, Drea, Meter
Solutions (not containing
Anaonia)
Corn Syrup
Dextrose Solution
Latex Solutions
Tetrasodiua Salt of EDTA
Solution
38
-------
APPENDIX C
MATERIAL SAFETY DATA SHEET
39
-------
AOl, App. VII
40 CFR Ch. I (7-1-91 EdHfa,)
Chloromattiane; Pichloromothane: Trichlorwnettv
am; Carbon tmchlonde. CNoroatttylene; 1.1-
1^-OicNoro«mar«: tim-lj-
1,1-Oichloroethylene; 1.1,1-
Trichloroethane; 1,1.2-TricNoroetftane; TitcMor-
oathylone; 1.1.1 .2-Tetrachloroethane; 1,1.^2-
» » -*-'-¦¦¦ tfc ¦ ¦ « Jaan Boa.
TlVICniUIUVUwit, IVOKnwIvlBTNnVi rv«>*
tachloroethane; Haxachtoroathane; Ally) chlo-
ride (3-CNoropropane); DleNoropropana; Dteh-
torap>opana. 2-Chloro-l ,3-butadiana; Honetv
t9ro-l£-toutadirna; Hawichlorecyclopemadiane;
Bvratatia; CMoroLanraria; OicHornbanzena;
1,2,4-TrieNoretoanaana; Tetrachlorobenzene;
PentacNorobenzana; Hej^chto/obanione; Totu-
•m; Napranaiana.
Mi*, panta-, end hmchloredibmofurartt.
Tmi*, panta% And htncMofOdbM^dodnii
M, paffia-. and haMacWorodfraruoligano; tri-,
tatra-, and pantacftiwophanofr and thair chloro-
andothari
Tatra-, panta-, and ha—chlorodtoanio^»dtarina;
tatra-. panta-, and hwcacMorod^aiuolurana; trt-.
tatra-, and pamacNwuphanota and that cWoro-
Hanvalant dvofrtum, taad
Hanvalant ctvoraun, laad.
Hmmtam fitwpmuRt
Hoxavaiam cNoniin, laad.
Hanvalant chfOfrtunu
Cyanida (oomplaxad), haavdant ctvoinuii.
Haxavalant diomiuni
wiiuuionn, lonTBBaiyoii maviyiana iiMUi
masiyi wnhHi paiapij^Vi Nnnc aoB>
^ ¦- ' -- » -«- « I J -
wnwoni^ iwvnananyoa, 6nwaii
iTwnyi mww, parananyoa, vonnc am, ormjr*
AoylonMla,
KOi 5..
Koie..
K017.™
K018._
K018.....
Banz(a)anthraoene. baraoMpyrana. dfeanz(aji)-
anttvaoana, indano(l^3-od)pynma, pantactilor-
araanc. dvanun, tatra-, pente%
hapttchlorodibonio-tMfcoidna.
Denial anthracene, baraoQOfluoranthona,
baraocd)pyrane.
banz(a)anthraoane, (feau^aiuviiuini. aoarv
K020
K021..
K022..
K023..
KQ24.
K02S-
K026..
K027..
K028..
K029„
K030..
K031-.
K032-
K033-.
K034..
K035..
K036-
K037..
K038-
K039..
K040..
K041..
K042..
K043..
K044..
K04S-
K046-
K047..
K048..
K04S..
KD90..
K0S1..
K0S2..
Koeo..
K081-
Hazardoua oonatttuanta (or which (mo
Banzyl chloride, chiorobenzene, toluana. ba^
trichloride.
Hexachtorobenzane, hexachlorobutadiene, cater
taifacwonda. hexachloroethane. parclitoua»v
lana.
EpictHorohydrtn. chlorocfhora Cbutchtoromwyi
ether and Ma (2-enJoroathyt) ethera], tncto»
1,2-dichloroethane, Irtchloroathylena. hexacNa*.
butadiana. hawcachlorobanzana.
Ethylene dichtofxH. l.l,!-tnchtaroetf>ane, 1,1,2.
trtchloreothane. tatracNoroathanaa (1.1Z2-I».
traeMoroalhana and 1,1.1^1-ianchloroathm),
tricMoroattiytana. tatraehlowalhylana, cwbsn
cMoiotenn. vinyl cMorida. vnyi
Ethylana diehlortda. 1.1.1 -trichlotoathane. 1.U-
McMoraathana, tavaeMoroalhanas (1.1^2-t*-
trachioroathana and 1.1.1^-tatrachtoroatharw).
trieWoioainytane. laliachloioalhylana. caiton
chtarotoim. vinyl cMorida, vnyt'
i. ctnoretonn.
Phanoli .tan (potycycbc aromatic hydrooaibflnt)
tTwaiB annjwiQat 1 i^^apwiOQUBiQna*
ii^« it;—>a— h»¦ ¦ ¦ ¦ ¦ ¦ a a <*—* —*
Man-canRrooanrana, fc4wi0wMuana.
rarwoanyoa, pponaii 2^KiNna>
Toluana dtoocyanata. loluana-2,4-tfamina.
i»i «i*viQnioiw^WB«a, wHjp onionoa.
i»i,i*aiB»BOiOaa*ana»
cMortda, vinylidana ehtorida. eMorotomt
HaxacNorobanzana, haxachtorobutadMna. hax»-
cworoathana, l.l.li-tatrachloroathana. 1.1A2-
Aiaanie.
HwacWofocyclopanladiana.
HaKacWoroeyrtopantatllana.
Craoaota, etvyaana, napnmaiana, fluoranthana
banzo(b) fluoranthana. banzo(a)pyrana.
indano(lA3HBd) pyrana, banzo
-------
Environmental Protection Agoncy
Pt. 261, App. VIII
Haxavalent chromium, lead.
Load, cadmium.
Oo.
Oo.
Hexavalant chromium, taad, cadmium.
Marcury.
Chloroform. cartoon loiracNorido. haxacholroa#v
ana. trtchtoroathane. tatrachloroetftytene. dictv
loroethylana. 1,1,2^-tetrachloroethane.
Anion*, apherrytamme, nitrobenzene, pftanytona-
Phtha#e anhydride.
1,1,2-Wchioroethane, 1,1.
i,i,2£-tetracNoroaifian*.
1.2-dicNeroethan*, 1,1,1-1
CMordww, heptacMor.
Araente.
Oanzene. dichlorobenionea. McMorotoanwnaa, te>
trachtorobenzenea, pemacMcrobenxene, ha*-
achlorobenzane. benzyl chloride.
Lead, heavalertt chromium.
Phanoi, naphthalene.
Cyanide (complexes).
Chromium.
Oa
i. 1.1.2-
2,4-
-------
J.IBakei
BEE32Q
MATERIAL SAFETY DATA SHEET
J. T. Baker Chemical Co.. 222 Red School Lane. Phllllpsburg, N.J. 08865
1 SECTION 1. IDENTIFICATION OF PRODUCT
CHEMICAL NAME
Acatie Add, Gladal
FORMULA
CHjCOOH
SYNONYM OR CROSS REFERENCE
Mcthana aarboaylh add; Ethanote Acid
CAS NO:
EPA NO:
r SECTION II . HAZARDOUS INGREDIENTS
MATERIAL
NATURE OF HAZARO
SECTION III
I
PHYSICAL DATA I
BOILING POINT
MELTING POINT . , f 9Tf
VAPOR PRESSURE #airc. „JmBI
SPECIFIC GRAVITY 1Qg
VAPOR DENSITY (Alfl«1) ^
PERCENT VOLATILE BY VOLUME (%)
WATER SOLUSIUTY Tj.j|r|
EVAPORATION RATE
( ¦ 1)
appearance
Qwr, aolorlatt liquid with mom pwpH odor of Tlnafar.
SECTION IV .IFIRE AND EXPLOSION HAZARD DATA
FLASH POINT (method uted)
10TF. (at
FLAMMABLE UMITS
• 2ir
Lower
84%
Upper
16%
FIRE EXTINGUISHING
MEOIA
Watar ipny, dry chamial or carbon diorida.
SPECIAL FIRE-FIGHTING PROCEDURES
UNUSUAL FIRE ANO EXPLOSION HAZARD
Giva* off llamwwMe wear aboaa its (firfi point.
THRESHOLD UMIT VALUE
SECTION V . HEALTH HAZARD
10ppm addition: 3310mf/Vf
HEALTH HAZARDS
Caotaa taaara bum*. POISON May ba fitai If iwallowad. Harmful if intiaiad.
FIRST AIO PROCEDURES
6-19
Call a phytic! an. If iwadowad, do not giva •mariei. Giva tap watar, mflk or mMk of magnaiia. Giva whitat of
baatan with watar. If inhalad. ramova to frath air. In eaia of contact, bnmadiataty flMk ayai or thin with planty of
watar for at laait 13 minutai whHa ramoving contaminatad dodiing and thoot. Wadi do thing bafora rt-uia.
-------
SECTION vr. REACTIVITY DATA
STA8IUTY
stable
Can raact vigorouily with oxidizing malarial.
INCOMPATABILITY (malarial! (O avoid)
Cvbonataa; Hydroxidaa; many osidaa and pho^hatai, ate.
HAZAROQUS DECOMPOSITION PRODUCTS
hazardous
MAY OCCUR
CONDITIONS TO AVOID
POLYMERIZATION
WNX NOT OCCUR
X
SECTION VII . SPILL AND DISPOSAL PROCEnnncc -
SPILLS
fimnti iff wuuaa of funlrinn fn»ar rrnitarnhrtmf mrfacaa with to da aih or tedium bicarbonata. Mia and add
f tii>ii|i ii|l iliin |i and woah rtautral (rnaka IHmur tart) wait* down drain with axcati watar.
DISPOSAL
tiaaBwanl plant it local •mrlronmanttl rtgulationi parmlt.
SECTION VIII ; PROTECTION INFORMATION
RESPIRATORY PtaJitsLUUU liWMWy
Saffaontainad braathinf apparatus
1
VBCTttATICM
LOCAL
X
SPECIAL
MECHANICAL (gonorat)
X
OTHER
PROTECTIVE GLOVES ^ ^ ^ ^
EYE PROTECTION
Faea thiald
OTHER PnOTECnVE equipment
Approvad working dothat
stqaaqHTm
section nr. handlinc^andstorageprecalitionc.
UNVa
Koomm
warRJLirfr«w.
Ham. Kaa^in tightly etoaad contafatar, at a tampantura abwao T7"C.
to warm araa. Loowndowra eautiourty.
SECTION X. MISCELLANEOUS INFORMATION
tte no* v* liquid om
ft**
torn
ifofrL
r feayafc as «Mw. on dodiin*. Avoid bmtMn« vapor. Wath thoroagbty attar nanoimg.
ftOaiaii
Ilt miar—mat SaMvOai*SiM«« na* aiaartvneva*data a>taa*t«d i» •aooua tK^-eii
it >aawai naui ii"i ~t t twtaomty o> ma MftrmatioR *«im aaoowwoi »»ttty nncaunoxs "
•"T r,r, mcMoiw tofewaeMawaTsaieir OataSf-wtt hm* to im» «a weNHeai Mtantiane* mown a««iao'» »»
na* Htoraaoo"aiWin»io«a«Hae» n»»ca»eawr icm» i*a» in»fiwa« ia ina w« t»u«4.
-------