RESPIRATORY PROTECTION FOR NITROTOLUENE

Condition Minimum Respiratory Protection*
Required Above 5 ppm

Vapor or Particulate

Concentration

50 ppm or 280 mg/m or less Any supplied-air respirator.

Any self-contained breathing apparatus.

200 ppm or 1120 mg/m? or Any supplied-air respirator with a full facepiece, helmet, or hood.

fess
Any self-contained breathing apparatus with a full facepiece.
A Type C supplied-air respirator operated in pressure-demand or other positive
Pressure or continuous-flow mode.

Greater than 200 ppm or Self-contained breathing apparatus with a full facepiece operated in pressure-

1120 mg/m? or entry and demand or other positive pressure mode.

escape from unknown

concentrations
A combination respirator which includes a Type C supplied-air respirator with a
full facepiece operated in pressure-demand or other positive pressure or continu-
ous-flow mode and an auxiliary self-contained breathing apparatus operated in
pressure-demand or other positive pressure mode.

Fire Fighting Self-contained breathing apparatus with a full facepiece operated in pressure-
demand or other positive pressure mode.

Escape Any gas mask providing protection against organic vapors and particulates.

Any escape self-contained breathing apparatus.

*Only NIOSH-approved or MSHA-approved equipment should be used.


other suitable material or by dissolving in a flammable

Solvent (such as alcohol) and burning in a suitable
combustion chamber equipped with an appropriate
effluent gas cleaning device.

REFERENCES

* American Conference of Governmental Industrial
Hygienists: “Nitrotoluene,” Documentation of the
Threshold Limit Values for Substances in Workroom Air
(3rd ed., 2nd printing), Cincinnati, 1974.

¢ Baskin, A. D. (ed.): Handling Guide for Potentially
Hazardous Commodities, Railway Systems and Manage-
ment Association, Chicago, 1972.

¢ Christensen, H. E., and Luginbyhl, T. L. (eds.):
NIOSH Toxic Substances List, 1974 Edition, HEW
Publication No. 74-134, 1974.

4 Nitrotoluene

* Grant, W. M.: Toxicology of the Eye (2nd ed.), C. C.
Thomas, Springfield, Illinois, 1974.

* Hamilton, A., and Hardy, H.: Industrial Toxicology
rd ed.), Publishing Sciences Group, Acton, Massa-
chusetts, 1974.

© International Labour Office: Encyclopedia of Occupa-
tional Health and Safety, McGraw-Hill, New York,
1971.

© Linch, A. L.: “Biological Monitoring for Industrial
Exposure to Cyanogenic Aromatic Nitro and Amino
Compounds,” American Industrial Hygiene Association
Journal, 35:426-432, 1974.

© Mangelsdorff, A. F.: “Treatment of Methemoglobin-
emia,” A.M.A. Archives of Industrial Health, 14:148-153,
1956.

* Patty, F. A. (ed.): Toxicology, Vol. II of Industrial
Hygiene and Toxicology (2nd ed. rev.), Interscience,
New York, 1963.

© Sax, N. L: Dangerous Properties of Industrial Materials
rd ed.), Van Nostrand Reinhold, New York, 1968.
* Stauden, A. (exec. ed.): Kirk-Othmer Encyclopedia of
Chemical Technology (2nd ed.), Interscience, New York,
1972.

* Stecher, P. G. (ed.): The Merck Index (8th ed.),
Merck Co., Inc., Rahway, New Jersey, 1968.

September 1978





Occupational Health Guideline for
Nitrotoluene

INTRODUCTION

This guideline is intended as a source of information for
employees, employers, physicians, industrial hygienists,
and other occupational health professionals who may
have a need for such information. It does not attempt to
present all data; rather, it presents pertinent information
and data in summary form.

SUBSTANCE IDENTIFICATION

* Formula: Ortho: 2-NO:C,H,CHs; Meta: 3-
NO,C.H,CHs; Para: 4-NO,C.H.CHs

¢ Synonyms: Orthonitrotoluene; o-nitrotoluol; metani-
trotoluene; m-nitrotoluol; paranitrotoluene; p-nitroto-~
lwol

© Appearance and odor: Ortho: Yellow liquid or solid
with a weak aromatic odor; Meta: Yellow liquid or solid
with a weak aromatic odor; Para: Pale yellow solid with
a weak aromatic odor.

PERMISSIBLE EXPOSURE LIMIT (PEL)

The current OSHA standard for nitrotoluene is 5 parts
of nitrotoluene per million parts of air (ppm) averaged
over an eight-hour work shift. This may also be ex-
pressed as 30 milligrams of nitrotoluene per cubic meter
of air (mg/m*). The American Conference of Govern-
mental Industrial Hygienists has issued a Notice of
{ntended Changes of its recommended Threshold Limit
Value for nitrotoluene from 5 ppm to 2 ppm with a skin
notation.

HEALTH HAZARD INFORMATION

© Routes of exposure

Nitrotoluene can affect the body if it is inhaled, if it
comes in contact with the eyes or skin, or if it is
swallowed. It is readily absorbed through the skin.
© Effects of overexposure

Nitrotoluene may affect the ability of the blood to carry
oxygen. This may cause a bluish discoloration of the

skin, irritability, drowsiness, nausea, rapid pulse, head-
ache, weakness, shortness of breath, and unconscious-
Ness.

© Reporting signs and symptoms

A physician should be contacted if anyone develops any
signs or symptoms and suspects that they are caused by
exposure to nitrotoluene.

* Recommended medical surveillance

The following medical procedures should be made
available to each employee who is exposed to nitroto-
luene at potentially hazardous levels:

1. Initial Medical Examination:

—A complete history and physical examination: The
Purpose is to detect pre-existing conditions that might
Place the exposed employee at increased risk, and to
establish a baseline for future health monitoring. Exami-
nation of the blood, nervous system, gastrointestinal
system, and cardiovascular system should be stressed.
The skin should be examined for evidence of chronic
disorders.

—A complete blood count: Nitrotoluene has been
shown to cause methemoglobinemia. Persons with
blood disorders may be at increased risk from exposure.
A complete blood count should be performed, includ-
ing a red cell count, a white cell count, a differential
count of a stained smear, as well as hemoglobin and
hematocrit.

2. Periodic Medical Examination: The aforementioned
medical examinations should be repeated on an annual
basis. Methemoglobin determinations should be per-
formed if overexposure is suspected or signs and symp-
toms of toxicity occur.

© Summary of toxicology

Nitrotoluene, whether absorbed as vapor by inhalation
or as liquid through the skin, has a potential for produc-
ing methemoglobin and subsequent anoxia. Signs and
symptoms of overexposure are due to the loss of
oxygen-carrying capacity of the blood. The onset of
symptoms of methemogiobinemia is insidious and may
be delayed up to 4 hours; headache is commonly the

These recommendations reflect good industrial hygiene and medical surveillance practices and their implementation will
assist in achieving an effective occupational health program. However, they may not be sufficient to achieve compliance
with all requirements of OSHA regulations.

U.S. DEPARTMENT OF HEALTH AND HUMAN SERVICES
National Institute for Occupational Safety and Health

September 1978

U.S. DEPARTMENT OF LABOR
Occupational Safety and Health Administration


first symptom and may become quite intense as the
severity of methemoglobinemia progresses. Cyanosis
occurs when the methemoglobin concentration is 15%
or more. Cyanosis develops early in the course of
intoxication, first in the lips, the nose, and the ear lobes,
and is usually recognized by fellow workers. Until the
methemoglobin concentration approaches approximate-
ly 40%, the individual usually feels well, has no com-
plaints, and will insist that nothing is wrong. At methe-
moglobin concentrations of over 40%, there usually is
weakness and dizziness; at up to 70% concentration
there may be ataxia, dyspnea on mild exertion, tachy-
cardia, nausea, vomiting, and drowsiness.

CHEMICAL AND PHYSICAL PROPERTIES

© Physical data

1. Molecular weight: 137.1

2. Boiling point (760 mm Hg): Ortho: 222 C (432 F);
Meta: 232 C (450 F); Para: 238 C (460 F)

3. Specific gravity (water = 1): Ortho: 1.16; Meta:
1.16; Para: 1.3

4. Vapor density (air = 1 at boiling point of nitroto-
luene): 4.7

5. Melting point: Ortho: —4 C (25 F); Meta: 16 C (61
F); Para: 52 C (126 F)

6. Vapor pressure at 20 C (68 F): Ortho and Meta:
0.15 mm Hg; Para: 0.12 mm Hg

7. Solubility in water, g/100 g water at 20 C (68 F):
Ortho: 0.06; Meta: 0.05; Para: 0.004

8. Evaporation rate (butyl acetate = 1): Not applica-
ble
© Reactivity

1. Conditions contributing to instability: Heat

2. Incompatibilities: Contact with strong oxidizers or
sulfuric acid may cause fires and explosions.

3. Hazardous decomposition products: Toxic gases
and vapors (such as oxides of nitrogen and carbon
monoxide) may be released in a fire involving nitroto-
luene.

4. Special precautions: Nitrotoluene will attack some
forms of plastics, rubber, and coatings.
¢ Flammability

1. Flash point: Ortho: 106 C (223 F) (closed cup);
Meta: 101 C (214 F); Para: 106 C (223 F)

2. Autoignition temperature: Data not available

3. Flammable limits in air, % by volume: Lower:
Ortho: 2.2 (calculated); Meta and para: 1.6 (calculated)

4. Extinguishant: Carbon dioxide, dry chemical,
foam
© Warning properties

1. Odor Threshold: Information is not available.

2. Eye Irritation Level: Nitrotoluene is not known to
be an eye irritant.

3. Evaluation of Warning Properties: This substance
is treated as a material with poor warning properties.

MONITORING AND MEASUREMENT
PROCEDURES

2 Nitrotoluene

° General

Measurements to determine employee exposure are best
taken so that the average eight-hour exposure is based
on a single eight-hour sample or on two four-hour
samples. Several short-time interval samples (up to 30
minutes) may also be used to determine the average
exposure level. Air samples should be taken in the
employee's breathing zone (air that would most nearly
represent that inhaled by the employee).

* Method

Sampling and analyses may be performed by collection
of vapors using a silica gel adsorption tube with subse-
quent desorption using methanol and gas chromatogra-
phic analysis. Also, detector tubes certified by NIOSH
under 42 CFR Part 84 or other direct-reading devices
calibrated to measure nitrotoluene may be used. An
analytical method for nitrotoluene is in the NIOSH
Manual of Analytical Methods, 2nd Ed., Vol. 3, 1977,
available from the Government Printing Office, Wash-
ington, D.C. 20402 (GPO No. 017-033-00261-4).

RESPIRATORS

* Good industrial hygiene practices recommend that
engineering controls be used to reduce environmental
concentrations to the permissible exposure level. How-
ever, there are some exceptions where respirators may
be used to control exposure. Respirators may be used
when engineering and work practice controls are not
technically feasible, when such controls are in the
process of being installed, or when they fail and need to
be supplemented. Respirators may also be used for
operations which require entry into tanks or closed
vessels, and in emergency situations. If the use of
respirators is necessary, the only respirators permitted
are those that have been approved by the Mine Safety
and Health Administration (formerly Mining Enforce-
ment and Safety Administration) or by the National
Institute for Occupational Safety and Health.

© In addition to respirator selection, a complete respira-
tory protection program should be instituted which
includes regular training, maintenance, inspection,
cleaning, and evaluation.

PERSONAL PROTECTIVE EQUIPMENT

¢ Employees should be provided with and required to
use impervious clothing, gloves, face shields (eight-inch
minimum), and other appropriate protective clothing
necessary to prevent repeated or prolonged skin contact
with solid or liquid nitrotoluene.

© Non-impervious clothing which becomes contami-
nated with nitrotoluene should be removed promptly
and not reworn until the nitrotoluene is removed from
the clothing.

September 1978



* Employees should be provided with and required to
use dust- and splash-proof safety goggles where solid or
liquid nitrotoluene may contact the eyes.

SANITATION

* Skin that becomes contaminated with nitrotoluene
should be promptly washed or showered with soap or
mild detergent and water to remove any nitrotoluene.
¢ Eating and smoking should not be permitted in areas
where solid nitrotoluene is handled, processed, or
stored.

© Employees who handle solid or liquid nitrotoluene
should wash their hands thoroughly with soap or mild
detergent and water before eating or smoking.

COMMON OPERATIONS AND CONTROLS

The following list includes some common operations in
which exposure to nitrotoluene may occur and control
methods which may be effective in each case:

Operation Controls
Use in the manufacture Process enclosure;
of toluidines for the local exhaust
production of dyes, ventilation; general
intermediates for dilution ventilation;
vulcanization personal protective
accelerators, gasoline equipment
inhibitors, and flotation
agents; use as an
analytical reagent
Use in the manufacture Process enclosure;
of dinitrotoluenes for local exhaust
production of ventilation; general
explosives; manufacture dilution ventilation;
of nitrotoluene-sutfonic personal protective
acids for production of equipment
azo and stilbene dyes
Use in organic Process enclosure;
synthesis for focal exhaust
intermediates of dyes, ventilation; general

sun screening agents,
and fuchsin— a red dye
used in textile and
feather industries

EMERGENCY FIRST AID PROCEDURES

In the event of an emergency, institute first aid proce-
dures and send for first aid or medical assistance.
© Eye Exposure

If solid or liquid nitrotoluene get into the eyes, wash
eyes immediately with large amounts of water, lifting
the lower and upper lids occasionally. Get medical
attention immediately. Contact lenses should not be
worn when working with this chemical.

© Skin Exposure

dilution ventilation;
personal protective
equipment

September 1978

If solid or liquid nitrotoluene gets on the skin, promptly
wash the contaminated skin using soap or mild deter-
gent and water. If solid or liquid nitrotoluene penetrates
through the clothing, remove the clothing immediately
and wash the skin using soap or mild detergent and
water. Get medical attention immediately

° Breathing

If a person breathes in large amounts of nitrotoluene,
move the exposed person to fresh air at once. if
breathing has stopped, perform artificial respiration.
Keep the affected person warm and at rest. Get medical
attention as soon as possible.

© Swallowing

When solid or liquid nitrotoluene has been swallowed
and the person is conscious, give the person large
quantities of water immediately. After the water has
been swallowed, try to get the person to vomit by
having him touch the back of his throat with his finger.
Do not make an unconscious person vomit. Get medical
attention immediately.

© Rescue

Move the affected person from the hazardous exposure.
If the exposed person has been overcome, notify some-
one else and put into effect the established emergency
rescue procedures. Do not become a casualty. Under-
stand the facility’s emergency rescue procedures and
know the locations of rescue equipment before the need
arises.

SPILL, LEAK, AND DISPOSAL
PROCEDURES

¢ Persons not wearing protective equipment and cloth-
ing should be restricted from areas of spills or leaks until
cleanup has been completed.

* Ifnitrotoluene is spilled or leaked, the following steps
should be taken:

1. Ventilate area of spill or leak.

2. For small quantities of liquid nitrotoluene, absorb on.
paper towels. For small quantities of solid nitrotoluene,
sweep onto paper or other suitable material. Remove to
a safe place (such as a fume hood) and burn the paper.
Large quantities of liquid nitrotoluene can be collected
and atomized in a suitable combustion chamber
equipped with an appropriate effluent gas cleaning
device. Large quantities of solid nitrotoluene can be
reclaimed; however, if this is not practical, dissolve in a
flammable solvent (such as alcohol) and atomize in a
suitable combustion chamber equipped with an appro-
priate effluent gas cleaning device.

© Waste disposal methods:

Nitrotoluene may be disposed of:

1. For liquid nitrotoluene, by absorbing it in vermicu-
lite, dry sand, earth or a similar material and disposing
in a secured sanitary landfill.

2. By atomizing liquid nitrotoluene in a suitable com-
bustion chamber equipped with an appropriate effluent
gas cleaning device.

3. By making packages of solid nitrotoluene in paper or

Nitrotoluene 3