Page 18 — Health Hazard Evaluation Report No. 85-274

21.
22.

23.

24,

25.

26.

27.

28.
29.

30.

31.

Evans EH. Casualties following exposure to zinc chloride smoke.
Lancet, Vol 249, pgs 368-370. 1945,

Milliken JA, Wash D, Kadish ME. Acute interstitial pulmonary
fibrosis caused by a smoke bomb. Canadian Medical Association
Journal. 88:36-39. 1963.

Schenker MD, Speizer FE, Taylor JO. Acute upper respiratory
symptoms resulting from exposure to zinc chloride aerosol.
Environmental Research. 25:317-324. 1981.

Schmahl K. Clinical signs of ZnCly smoke intoxication.
Pneumonalogic Vol 150:161-169. 1974.

National Institute for Occupational Safety and Health. Criteria
for a recommended standard: occupational exposure ‘to carbon
tetrachloride. Cincinnati, Ohio: National Institute for

Occupational Safety and Health, 1976. (DHEW) publication no.
(NIOSH) 76-133).

National Institute for Occupational Safety and Health. Criteria
for a recommended standard: occupational exposure to
tetrachloroethylene (perchloroethylene). Cincinnati, Ohio:

National Institute for Occupational Safety and Health, 1977. (DHEW
publication no. (NIOSH) 77-121).

National Institute for Occupational Safety and Health. Current
intelligence bulletin 20--tetrachloroethylene (perchloroethylene).
Cincinnati, Ohio: National Institute for Occupational Safety and
Health, 1978. (DHHS (NIOSH) publication no. 78-112).

Zey JN, Richardson F. Health hazard evaluation no. 87-109.
National Institute for Occupational Safety and Health. NIOSH,
Cincinnati, Ohio: (Final Report in preparation).

National Fire Protection Association (NFPA). NFPA 1500, standard

on fire department occupational safety and health program. Quincy,
Mass.

National Institute for Occupational Safety and Health. NIOSH/OSHA
occupational health guidelines for chemical hazards. Cincinnati,
Ohio: National Institute for Occupational Safety and Health,
1981. (DHHS (NIOSH) publication no. 81-123).

Clayton G., Clayton F. Patty's industrial hygiene and toxicology,
Volume 2B, Toxicology, 3rd revised ed. New York, New York: John
Wiley and Sons, Inc. 1981.

eee 4


-~*

.

Superior

Su PELLOL — sianat company, inc. W. Grayatone Road

Inexpensive smoke that’s efficient, effective, easy to use!

Spotewood, New Jersey
phone area code 201 251-0800

The Superior method of generating smoke by chemical reaction provides smokey atmospheres for training
exercises involving the use of self-contained breathing apparatus. The smoke has excellent obscuring power and
pungent odor revealing inadequate protection. Superior Smoke items contain No explosive materials and are the
only devices of this nature accaptable in the mails. It has a T.O.P. (total obscuring power) of 2100. T.O.P. is the
scientific method of determining the relative ‘etficiency of smoke generated by a given unit of smoke composition.

exclusive features,

By companion, Superior Smoke has a T.O.P. ten times greater than crude oil. More smoke,
plus low prices make Superior Smoke products your best buy.

The Superior Smoke No. 3C generates a
big 40,000 cubic feet of whitish gray
smoke while burning from two to three
minutes. Our most popular item for fire-
men training.

Shipping weight 5 ibs. per dozen. 55 = m isaes " _ a
Size 1%" x 6”. Mailable. Shipping weight 5 Ibs. per dozen.

The Superior Smoke No. 5D (notillustrated) generates 100,000 cubic feet of light gray smoke in five minutes. Long
fuses on each end permit muitipte units to be tied together for continuous burning to maintain an enormous and
sustained volume of smoke. Mailable. Sold in minimum units of six.

Size 1%" x 14”. Shipping weight 5% Ibs. for six.

Superior Smoke Grenades are engineered for use
where an instantaneous and exceptionally large
volume of smoke is required. They are solidly con-
structed with a dependable built-in pull-wire ignitor
and warranted for three years.

Supcuet SMORE GRENADE
ainecions

Gree arene termi on inewing mind

3 ~Patt 90 ne expace tgmase wg,

Pull guaran omg shorety sn6 threw greusoe
womedtaraly.

Superior Smoke Grenade generates 115,000 cubic
feet of smoke during 2-3 minutes burning time, size
2” x 5", weight 14 oz., not mailabie.

Fi neal ea

Superior Protessional Smoke Grenade generates 130,000 cubic feet of smoke while burning 2-3 minutes, size
2%" x 5" 1 Ib.; can be comfortably hand held: not mailable.

Printed in U.S.A. - Effective 3/87
Form S-1



. |
SECTION V - HEALTH HAZARD DATA
* See Cover Letter

THRESHOLD LIMIT VALUE

EFFECTS OF OVEREXPOSURE aes 7
Smoke can cause irritation of the bronchial and nasal

passages.
EMERGENCY AND FIRST AID PROCEDURES

Once exposure has ceased, any irritation quickly
disappears. Treat for smoke inhalation.

ber

SECTION VI - REACTIVITY DATA
STABILITY UNSTABLE CONDITIONS TO AVOID
STABLE STABLE x

INCOMPATABILITY (AMatenals (0 avoid)

HAZANGOUS DECUMPUSITION PROGCTS

CONDITIONS TO AVOID
HAZARDOUS MAY OCCUR
POLYMERIZATION

WILL NOT OCCUR

SECTION Vil - SPILL OR LEAK PROCEDURES

STEPS TO BE TAKEN IN CASE MATERIAL 15 RELEASED OR SPILLED ~

rT Mi Toy . : . .
WASTE DISPOSAL METHOD Smoke leaves no visible residue or lingering odors. Unreacted

smoke material...Do not allow contact with oils or solvents...Possible reaction

causing combustion.

SECTION VII - SPECIAL PROTECTION INFORMATION

RESPIRATORY PROTECTION (Specify type)

= i breathing apparatus.
VENTILATION LOCAL ExnausT SPECIAL

MECHANICAL (General) | OTHER 7

PROTECTIVE GLOVES: . EVE PROTECTION

OTHER PROTECTIVE EQUIPMENT
*See Cover Letter

~re

zi SECTION IX - SPECIAL PRECAUTIONS

—f PRECAUTIONS TO BE TAKEN IN HANOLING AND STORING coat
Temperatures above 33°C, and humidity

above 65% may shorten shelf life of Superior Smoke items.

OTHER PRECAUTIONS

PAGE (2) Form OSHA-20
Gro 930.540 ” Rev. May 72

ot BB nn =

ee



Page 12 — Health Hazard Evaluation Report No, 85-274

Direct reading samples used to assess the percent O02 indicated
that it never dropped below 21% even in the heaviest smoke clouds.
The concentration of HCl ranged from 1 to greater than 20 Ppm (>28

mg/m3) measured by gas detector tubes, and was detected in all of
the smoke clouds.

As previously stated, the smoke generating devices were used to
produce clouds similar in density to clouds used for firefighters
training exercises at the Cincinnati fire training facility.
According to fire department Staff, heavy smoke is needed to
simulate building fires. They stated that all of the clouds
Produced during our tests could have met this need, but the smaller
devices produced clouds that were too light to be totally effective
from the standpoint of obscuring vision.

Telephone Survey

Of the 69 organizations contacted we were able to interview fire
training personnel at 62 sites. Personnel at 21 of the 62
locations contacted reported that they had used smoke bomb type
devices indoors in their fire training programs. Sixteen of the 21
reported using Superior Signal devices; four of the remaining five
described smoke bomb type devices that were probably manufactured
by Superior Signal, but this was not confirmed at the time the

Phone call was made. Information obtained from these telephone
interviews is summarized in Table 8.

The number of years that the smoke bomb type devices were used at
these 21 locations ranged from 1 to 20. Seven contacts reported
that they had used the devices for a least 10 years and seven said
they had used them in 1987. It was difficult to always get
accurate information on the size of the training area since hotel
rooms and rooms in abandoned houses were sometimes used. The size
of the training area for the 20 locations that reported dimensions
ranged from 900 cubic feet to 36000 cubic feet. The average was
about 6000 cubic feet. The majority (14 of 22) of the training
areas were under 5000 cubic feet. The facility used to conduct the
NIOSH testing measured 6000 cubic feet in the main training area
and therefore was representative of a typical sized training area.

All but one location was using far more (from three times (3X) to
over 100X) smoke than necessary when compared to the manufacturer's
1987 usage guideline. The rough estimate of how much in excess of
the 1987 usage guideline was computed by dividing the volume of
space recommended by the manufacturer's 1987 guideline for the
number and type device(s) used (recommended volume for each device

times the number of devices used) by the volume of space actually
available.

.



Manufacturer's Specifications
for Five Smoke Devices Tested

Table 2

moke Vevice Name Burn Time Volume of Smoke produced
per unit (ft?)*

0 Secona Smoke Candle 0.5 minute 4,000

minute candle 1 minute 8,000

moke Bomb 3C** 2-3 minutes 40,000

moke Grenage 2-3 minutes 115,000

hite Smoke Pot 5-6 500,000

From manufacturer's literature.

* Reportea by manufacturer to be their most popular item for firefighter

training.


SUPERIOR SIGNAL COMPANY, INC. : {
MATERIAL SAFETY DATA SHEET :

Address: FP. OQ. Box 96, Spotswood, NJ 98884
Phone (201) 251-0800

SECTION 1: PRODUCT IDENTIFICATIO

Chemical Family: Screening Smoke
Trade Name: Superior Smoke for fire fighters smoke drills

SSaesseeseseessssses=

SECTION 2: PRODUCT INGREDIENTS (SMOKE)

Neither TLV nor PEL applicable because product is intended for use in
short term training exercises.

TLV 3 PEL , 8-hour time weighted
Hydrated Zinc Chloride 1 mg/m 1 mg/m average
Water Condensate 7 3 - 3
Carbon Monoxide 55 mg/m 55 mg/m

All other ingredients are present in negligable amounts and/or non=
hazardous.

Superior Smoke products are available in various sizes that provide

sufficient materials to create obscuring smoke for different sized
areas.

Superior #2B - 8,000 cu. ft: 227 m
Superior #3C ~ 35,000 cu. ft.: 1,133 m,
Superior #5D - 100,000 cu. ft.: 2,832 m,
Superior Smoke Grenade - 115,000 cu. ft.: 3,256 my
Superior White Smoke Pot - 500,000 cu. ft.: 14,158 m

Sesesesscasss Saeesssesscscssseessess= Seessseesess=

SECTION 3: PHYSICAL DATA (SMOKE)

Boiling Point: N/A

Vapor Pressure: N/A

Vapor Density: N/A

Solubility in Water: (Zine Chloride) Soluble

PH: No Data

Appearance and Odor: Gray to white with an odor of

sameeresesss: SEE

SECTION FIRE 7 EXPLOSION HAZARD DATA
(SMOKE): Flash Point (method used): None
Autoignition: N/A
Flammable limits in air: N/A

(SOLID PRODUCT): Extinguishing Media: Use media suitable for
surrounding fire.

(SMOKE/SOLID PRODUCT): Special fire fighting protective equipment:
self-contained breathing apparatus and full protective clothing.

sD/1
1/20/87


Page 3 — Health Hazard Evaluation Report No. 85-274

IL. INTRODUCTION

Iii.

On March 28, 1985, the National Institute for Occupational Safety and
Health (NIOSH) received a request from the International Association of
Fire Fighters (IAFF) to assess the hazards of using zinc chloride
(2nCl2) producing, smoke generating devices manufactured by the
Superior Signal Company, Inc, Spotswood, New Jersey. The requestor
moted that although these devices had been advertised as "medically
proven to be non-toxic", health problems, including deaths, had been
reported during some training exercises in which they were used. The

only specific cloud component identified by the manufacturer was zinc
chloride.

Information forwarded by the requestor indicated that chlorinated
hydrocarbons and HCl were also potential smoke cloud components .1~-3

A Department of the Navy report of a fatality resulting from a training
exercise in which a Superior Signal Company 5D smoke bomb was used
indicated that a number of chlorinated hydrocarbons were also detected
in the smoke cloud (dichloroacetylene, vinylidene chloride, chloroform,
carbon tetrachloride, trichloroethylene, tetrachloroethylene,
hexachloroethylene). No estimates of either the airborne concentration

of these hydrocarbons or percentage of the total cloud they constituted
were given.

NIOSH investigators initially conducted a laboratory test of the
smallest device sold to assess the chemicals present in a dense smoke
cloud. Based on this information two field tests were conducted in a
fire training facility to sample smoke clouds produced by five (5)
separate devices manufactured by the Superior Signal Company, Inc.

Results, recommendations, and status reports were distributed via
letters or interim reports in November 1985, March and Jume 1986, and
April 1987. During the investigation, three meetings were held with

Superior Signal Company, Inc. representatives to discuss the NIOSH
investigation.

BACKGROUND

Superior Signal Company manufactures several different zinc chloride
smoke generating devices; they differ primarily in their size and
amount of smoke produced. Each device has a rated burn-time and
corresponding volume of smoke. Until about the early 1980s,
advertising literature stated that these devices were “medically proven
to be non-toxic". The smaller devices i.e. the 30 second smoke candle,
have been commonly used for ventilation studies. Larger devices have
more often been used to generate smoke for training exercises such as
fire fighting and airport disaster drills.


P.O. BOX 96 © SPOTSWOOD, N. J. 08884

SEND SHIPMENTS TO:
West GREYSTONE ROAD

SUPERIOR SMOKE FOR FIRE TRAINING Ore Brings, N. J. 08857

For over twenty-five years, Superior Smoke has been successfully used
to develop smokey atmospheres for firemen training exercises involving
the use of self-contained breathing apparatus. In these drills, an
adequate amount of smoke is utilized (1) to obscure vision and (2) to
be sufficiently irritating to reveal improper procedures or faulty
equipment. Under these simulated fire conditions, instructors have a
high degree of confidence in their ability to properly train fire fighters
te perform a necessary community service, while minimizing the inherent
risi.s of their occupation.

Pit abet

Smoke crills are developed and performed under the direction of fire i
training instructors. With proper procedures delivered through clear |
instructions, firemen would not have any exposure to training smoke; i
however, ircums lea

gccur. instructors anticipating these incidents have found these
exposures to smoke i

Minutes with either no physiological effects or minor short term effects.
suchas those associated with smoke inhalation,

Normally, the smoke has a particle size of 10°" to 107® centimeters in
diameter; however, thirty seconds after it has been generated, the
particle size statistical distribution does not conform to the normal
bell-siaped curve. This phenomenon is caused by the smoke being a
mist rather than solids suspended in air. Superior Smoke is not a true
smoke, but contains a large percentage of atmospheric moisture that
provides high visual obscurity at low concentrations. The mist formation
is seeded by zinc chloride and some other products of combustion such
as free carbon. The toxicity of the materials must be represented :
relative to the application and brief exposure. ij

3

All smokes can be irritating, and normally this telltale sensation
ancourages personnel to move from areas of heavy concentrations. We
recommend the use of self-contained breathing apparatus for dense !
concentrations cr nrolenged lighter concentrations. :

At times, the users may not participate in a responsible manner caused f
by incomplete operational instructions for self-contained breathing !
equipment or less than prudent personal decisions. Our experience in
distributing Superior Smoke for fire training exercises reveals that in
many instances, excessive volumes of smoke are developed to obscure
vision, simulating fire conditions. Low concentrations of smoke allowed

to blend in a homogeneous mixture with room air provides obscurity
without causing excessive concentretions.

Swe.

Other Smokes are not SUPERIOR


Page 19 - Health Hazard Evaluation Report No. 85-274

32. National Institute for Occupational Safety and Health. Criteria
for a recommended standard: occupational exposure to chloroform.
Cincinnati, Ohio: National Institute for Occupational Safety and
Health, 1975. (DHEW publication no. (NIOSH) 75-114).

33. National Institute for Occupational Safety and Health. Criteria
for a recommended standard: occupational exposure to
trichloroethylene. Cincinnati, Ohio: National Institute for

Occupational Safety and Health, 1973. (DHEW publication no.
(NIOSH) 73-11025).

x. 'HORSHIP C! Ss

s Project Conducted and
Report Prepared by: John N. Zey, M.S., C.I.H.
Industrial Hygienist
Industrial Hygiene Section

Fred Richardson, M.D.
Medical Officer
Medical Section

Field Evaluation Assistance: Gregory A Burr, C.I.H.
Industrial Hygienist
Industrial Hygiene Section

Technical Advisors: Cincinnati Fire Department,
Fire Training Staff

Laboratory Evaluation: Ardith A. Grote
a Mark Millson
Karen J. Williams
Michele Bolyard
Marilyn Hawkins
John Palassis
Chemists -
Division of Physical Sciences
and Engineering

hess?

Colleen Ericson
. August Paoli
Norman K. Christensen
Chemists,
. i UBTL, Inc.,
Salt Lake City, Utah



Table 5

Partial Listing of Reported Episodes During Smoke Training
When Smoke Bomb Type Devices Were Used

Author

vate & Location

Type of Device*
and/or Exposures

Event

Summary of Report
Health Effect

Evans

vohnson &
Stonenil1

Milliken, Waugh
& Kagish

Macavly & Mant

1943; Matta

1959; Texas
(3 separate
incidents)

Pre-1963
Untario,
Canada

Pre-1y04
England?

Smoke generator;
zinc chloride
smoke

Screening smoke-
zinc chloride

Smoke bomb;
zinc chloride

Military smoke
canister; zinc
chloride

Smoke generating devices caught fire
and filled tunnel with estimated
volume of 100,000 ft? of smoke.

Two of 10 deaths occurred as late

as the 14th day after the accident.
Six weeks after the accident, two
people were still adversely affected.

17-19 year 01d airmen were accidentally
overexposed to smoke during routine
survival training.

35-year-old fireman participated in
fire exercise. Smoke generator was
place at bottom of depression -
buildings were on three sides.
Patient tried to extinguish bomb.

A colleague withdrew almost
immediately.

19-year-old was exposed to smoke
during a civil defense training
exercise, exposure time estimated
to be 4 minutes.

TO-deaths; dyspnea, chest tightness;
episternal and epigastric pain, red &
tearing eyes, cough with copious
expectoration; blood stained sputum,
nausea & vomiting, cyanosis, headache,
high fever, Two autopsies showed red
oedematous Tunas & mucous membranes;
ulceration at the bifurcation of the
trachea. Liver, kidney & cerebral
congestion.

Burning throat, paroxysmal coughing,
nausea & retching during first 48 hours,
dyspnea, fever & malaise. Temperature
to 105°F, developement of tachypnea

and cyanosis. Xray showed infiltrate
in both lungs. Symptoms negative

after 2-4 month.

Both subjects reported nausea, sore
throat, and chest tightness. Primary
subject had a fever, Xray showed diffuse
infiltrates 30 hours after exposure.
Cyanosis, and confusion, died on the
18th day.

Immediate complaints were retrosternal
pain, abdominal cramps, anxiety,
cyanosis, and high fever. X-ray showed
jung edema, necrosis, hemorrhage and an
infarct of the upper left lung.


de oh ae

Table 1

Sampling and Analytical Techniques for Air Samples

Collected in Smoke Clouds Generated by Zinc Chloride Smoke Generating Devices

Cincinnati Fire Training Building

Cincinnati, Ohfo
HETA 85-274

December 12, 1985

Material Evaluated

Media

Analytical Techniques

Inorganic acid

Chlorinated Hydrocarbons
(f.e., carbon tetrachloride,
hexachlorobutadiene)

Total-cinc

ORBO-53 tubes

A. Charcoal Tubes
6. ORBO-42

Mixed Cellulose
Ester Membrane Filter

Flow Rate
(LPM)
0.5
0.2 and 0.5
0.2 and 0.5

2.5 and 3

Samples were analyzed for chloride
by fon chromatography according to
NIOSH Method 7903. The A and B
sections of the silica gel tubes
were each separately desorbed in
10 ml of eluent and heated in a
boiling water bath for 10 minutes.
The resulting solution was filtered
through a 0.45 micron filter, and
an aliquot of each solution was
analyzed via a Dionex jon
chromatograph utilizing a WISP 710B
auto sampler.

Two charcoal tubes that were
qualitative air samples were
desorbed with | ml of CS2 and
screened by gas chromatography

with a flame fonization detector.
One sample was analyzed using

gas chromatography/MS for chemical
compound identification of detected
peaks. Remaining tubes were
desorbed and analyzed as above.

Two qualitative ORBO-42 samples were
analyzed according to NIOSH Method
2518. Samples were desorbed for 1
hour in a sonic bath with 1 ml of
hexane and screened by GC/FID as
above. Major peaks were the same
as a charcoal tube, remaining
ORBO-42 samples were not quantitated

Filters were analyzed for zinc using
atomic absorption spectroscopy.
Samples were ashed with nitric and
perchloric acids according to NIOSH
Method 7300 and diluted to 25 ml.
Analyses were completed using NIOSH
Method 7030.


U DEPARTMENT OF LABOR OMe ee eS 87
. Occupational Safety and Heaith Administration

; MATERIAL SAFETY DATA SHEET

Required under USDL Safety and Health Regulations for Ship Repairing,
ed Shipbuilding, and Shipbreaking (29 CEFR 1915, 1916, 1917)

SECTION!

MANUFACTURER'S NAME EMERGENCY TELEPHONE NO.

Superior Signal Company, Inc. (201) 251-0800

ADDRESS (Number, Street, ity, State, and ZIP Code) .
z NJ_08857 - p Box 96, Spotswood Ni oggay |
CHEMICAL NAME AND SYNONYMS

TRADE NAME AND SYNONYMS

i CHEMICAL FAMILY FORMU
i
SECTION Il - HAZARDOUS INGREDIENTS
= T T 1
. PAINTS, PRESERVATIVES, & SOLVENTS * nie ALLOYS AND METALLIC COATINGS % | Une
| PIGMENTS Not Applicable BASE METAL
| CATALYST ALLOYS
: VEHICLE METALLIC COATINGS
FILLER METAL

SOLVENTS PLUS COATING OR CORE FLUX

ADDITIVES OTHERS

OTHERS
i TLV

HAZARDOUS MIXTURES OF OTHER LIQUIDS. SOLIDS, OR GASES % | (units)

oa SECTION IH - PHYSICAL DATA

BOILING POINT (°F,)

SPECIFIC GRAVITY (H,0=1)

VAPOR PRESSURE (mm Hg.) BE COR ATILE
VAPOR DENSITY (aIR=1) EVAPORATION Rate

SOLUBILITY IN WaTER

APPEARANCE AND OOOR Superior Smoke - Color: Gray to White; Odor: Burning Paper

SECTION !V - FIRE AND EXPLOSION HAZARD DATA

FLASH POINT (Method used) |FLAMMaaLE LIMITS Ler vei
t
EXTINGUISHING MEDIA

SPECIAL FIRE FIGHTING PROCEDURES . * : :
Superior Smoke generating items do not contain any

rapid oxidizing materials,
UNUSUAL FIRE ANDO EXPLOSION HAZARDS

24.

PAGE (1) (Continued on reverse side) Form OSHA.20

Rev. May 72


Page 16 - Health Hazard Evaluation Report No. 85-274

* they notice any problem (such as a leak in the SCBA). Anyone
experiencing any breathing difficulties should receive a medical
evaluation and appropriate medical treatment as soon as possible.

5. While an SCBA, worn by a trained individual will eliminate the
inhalation hazard associated with the zinc chloride smoke
generating devices, it is recommended that thought be given to what
the real goals of fire training exercises are and what atmospheric
characteristics are required to fulfill those goals. For example,
is it necessary to generate a dense smoke to obscure vision, or can
the face shield of the SCBA be modified to obscure vision. Once
goals are delineated, a decision can be made as to whether the use
of the zinc chloride devices are indicated or whether alternative
methods should be evaluated. Whatever method is finally chosen
should be based on the risks and benefits associated with each.

IX. REFERENCES

1. Granols J. Firefighters disclose april mishap. Columbia
Missourian Newspaper. Columbia, Missouri. Page 1, June 3, 1981.

2. Graf D, Training Officer - Medina Volunteer Fire Department.
Letter to the National Fire Protection Association. Medina, North
Dakota. June 15, 1983.

3. Department of the Navy. Report of fatality following inhalation of
zinc chloride smoke. Department of the Navy, Commander Training
Command, U.S. Atlantic Fleet, Norfolk, Virginia. Letter of
April 28, 1981.

4, Centers for Disease Control. Morbidity and mortality weekly report
- NIOSH recommendations for occupational safety and health

standards. Vol 35, No. 1S. September, 1986. Centers for Disease
Control. Atlanta, Georgia.

5. Occupational Safety and Health Administration. OSHA safety and

health standards. 29 CFR 1910.1000. Occupational Safety and
Health Administration, revised 1983.

6. American Conference of Governmental Industrial Hygienists.
Threshold limit values and biological exposure indices with
intended changes for 1986-87. Cincinnati, Ohio: ACGIH, 1986.

7. American Conference of Governmental Industrial Hygienists.

Documentation of the threshold limit values. 5th ed. Cincinnati,
Ohio: ACGIH, 1986.

z
Hl
nd

=
a


Page 8 ~ Health Hazard Evaluation Report No. 85-274

cloud components are zinc chloride, hydrochloric acid, and a
mixture of chlorinated hydrocarbons.

The primary effects of acute exposure to aerosolized HCl are due to
its corrosive properties. Exposure to HCl has been shown to be
associated with pulmonary, laryngeal, oral, nasal and conjunctival
irritation; the magnitude of effect is in proportion to the
concentration.859 The irritant effect of the vapors on the
respiratory tract may produce bronchitis, pulmonary edema and
death. The OSHA standard and ACGIB-TLV for HCl is 7 mg/m? as a
ceiling value not to be exceeded. The concentrations of HCl
considered by NIOSH to be IDLH is 140 mg/m3,10

Zinc chloride, which reacts with water to produce HCl is an
irritant to eyes, mucous membranes, and skin. Inhalation may
precipitate a cough (with or without Sputum production), stridor, a
sensation of chest tightness, dyspnea, pulmonary edema, and
cyanosis, and, in case of very high exposure, death, 8-41 The

OSHA standard for zinc chloride is 1 mg/m3 (8 hour-TWA). The
ACGIH-TLV is 2 mg/m? as a short-term exposure level (STEL) for a
15-minute period. The concentration of zinc chloride considered by
NIOSH to be IDLH is 2000 mg/m3,10

It should be noted that since zine chloride and HCl both produce
respiratory effects, and, in the absence of scientific data to the
contrary, it is prudent to assume that exposure to smoke clouds
containing both would result in additive effects,

Chlorinated hydrocarbons, as represented by the substances detected
in this evaluation, may be responsible for numerous symptoms,
Table 4 presents the target organs affected and signs/symptoms of
overexposure. Several of those hydrocarbons detected are suspect
human carcinogens; however, the potential acute respiratory effects
from exposure to the zinc compounds and HCl are of more immediate
concern considering how these devices are used during fire training
exercises. The carcinogen issue is complex, especially when the
exposure is to a mixture of compounds. For a more detailed
discussion on exposure to carcinogens in general, the interested
reader is referred to several sources in the literature ,12-17

VI. RESULTS

A.

Literature Review

Reports received from the requestor and a literature review
revealed at least ten separate incidents of adverse health effects
among individuals exposed to the smoke produced by zinc chloride
smoke generating devices.1-3,18-24 these incidents are
summarized in table 5,

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om Cy Hes . .
Cy lt hy (pentec lene btedienc 2) &
CHECROBCN BE ne 1 >) .
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| YF DICHLERS ST YEON Cy Oh, q hetac hlaze butadiene 2
ce cong (> 4) 1
‘ H1500,% Terchicecatydene 2
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tie es suru supresene pereent ul Zine chiuriue tor all z1N¢ Compounds as identitied in an air sample.

Table 8 '

Telephone Survey
Evaluation of Fire Training Smoke Generation
HETA 85-274
December 1987 & January 1988

Number of
Years Device Last year Volume (ft3) Type of Number Comparison of Usage to
Source/State Used Used of Training Area Device* Used Manufacturers 1987 Criteria

Lecatur Fire vept./ :
Alabama 3 1986 960 3c 1-2 In excess (36X-72X)
Ketchikan Fire Lbept./
Alaska 10-12 1983 1250 5D 2-68 In excess (160X-480X)
State Fire Training Serv.
Alaska 1981 5180 3c 7b In excess (7X)
Anchorage Fire Vept./
Alaska 3 1981 12800 3C 1-2 In excess (3X-5X)
Flagstaft Fire Lept./
Arizona 1 1987 3200 3C 2-3¢ In excess (22X-33X)
vakdale fire Vept./
CAlitornia 7 1982 900 5D 2 In excess (222X)
boise Fire Vept./
Idaho 1u-15 1986 1440 3C** 2-3 In excess (49X-73X)
Garden City Fire Vept./ Vacant
Kansas ° 1976 Houses 3C** - -
Larson City/
Nevaaa 10-12 1981 1150 3¢ 1-2 In excess (30X-61X)

State Fire Stangards

ana Training/

New Hampshire 10 1978 1200 3c* q-2d In excess (29X-58X)



Sra

Page 5 — Health Hazard Evaluation Report No. 85-274

structure, The lower floor, which has one room that measured 30 ft
x 25 ft x 8 ft (6000 ft3), was used for this test. A stairway

and ceiling/floor grilles connect all three floors.
Battery-operated pumps with the appropriate sampling media attached
via flexible tubing, were suspended at breathing height (5 1/2 ft.)
from the ceiling of the first floor. For each of the two tests
conducted, 1-2 samples were collected for identification of HCl,
chlorinated hydrocarbons, metals, and zinc compounds. Two 3C smoke
bombs were ignited simultaneously for the first test, and one white
smoke pot was used in the second test. After 25 minutes, the doors
were opened and all pumps were turned off. The building was
allowed to clear before the next test was started.

The primary purpose of the December 1985 test was to determine air
concentrations of the various decomposition products from the two
devices forwarded by the requestor in an actual fire training
facility. Due to uncertainties as to the amount of smoke
generated, percentage of each component and analytical
requirements, the doors and windows were closed. Firefighters
present during the test indicated that doors and windows are
normally closed during fire training exercises. Area air samples
were obtained for total zinc, HCl, and chlorinated hydrocarbons,
including chloroform, carbon tetrachloride, trichloroethylene,
perchloroethylene, hexachloroethane, and hexachlorobutadiene.
Sampling and analytical methods are presented in Table 1.

April 1986 Test

The April 1986 test was conducted at the same facility as the
December test with several objectives in mind: (1) to determine if
the 3C smoke bomb and white smoke pot generated similar clouds in
two separate tests, (2) to test additional Superior Signal smoke
generating devices to determine if they produced similar clouds,
(3) to determine if the smoke clouds produced were similar in
density to those normally used by the Cincinnati Fire Department,
which normally burns household furnishings to generate smoke.

To satisfy the first and second objectives, five different smoke
generating devices, all manufactured by Superior Signal Company,
Inc., were evaluated separately inside the Cincinnati Fire
Department's fire training facility. The devices tested were the
30-second candle, 1 minute candle, 3C smoke bomb, smoke grenade,
and white smoke pot (Table 2). Each type of device was tested on
both April 8 and 9, 1986. For each test, 1-2 samples were
collected for identification of HCl, zinc compounds, metals, and
chlorinated hydrocarbons. During each test, the oxygen (02)


Page 4 - Health Hazard Evaluation Report No. 85-274

Iv.

The Material Safety Data Sheet (MSDS) dated May, 1972, from the
manufacturer (forwarded to NIOSH in June, 1985) stated that smoke
generated by these devices could irritate bronchial and nasal passages,
that once exposure ceased any irritation would disappear quickly and
that affected individuals should be treated for smoke inhalation. The
MSDS stated that for other than "casual" exposure, a self-contained
breathing apparatus (SCBA) should be used. There was no information on
smoke cloud components on the MSDS, but a cover letter stated that the
smoke contained zinc chloride, combustion products and high moisture.

The letter also stated that these devices had been used for over 25

years to develop smokey atmospheres for training firefighters in the
use of SCBAs.

The five devices NIOSH purchased through a commercial supplier were
shipped without MSDS's or supplemental information. Labels on the
smoke generating devices contained warnings that all smoke, including.
smoke produced by these devices, could irritate breathing passages if
respiratory protection was not used. The label on the largest device
tested (white smoke pot) also stated that the device should not be used
in confined spaces without an SCBA because the generated smoke could

displace oxygen. None of the labels contained information on the smoke
cloud components.

METHODS

A. ite: e Se

A comprehensive literature search was conducted to determine the
number and types of episodes that have occurred where adverse

health effects have been associated with ZnCl2 smoke generating
devices.

B. Laboratory Test
To qualitatively determine the probable components of the smoke
cloud produced by the zinc chloride smoke generating devices, two
30-second smoke candles (the smallest device sold by Superior
Signal Company, Inc.), were ignited inside a cardboard box and the

resulting cloud was sampled for gases, vapors, metals, and
inorganic acids.

c. F. Tes

December 1985 Test

Based on the laboratory tests, additional testing was done at the
Cincinnati Fire Department fire training facility on December 12,
1985. The fire training facility is a three-story brick

3.
od


Page 17 - Health Hazard Evaluation Report No. 85-274

8. Proctor, NH, Hughes, JP, Chemical Hazards of the Workplace, 1978,
J.B. Lippincott.

9. Parmeggiani, L (et al, eds), Encyclopedia of Occupational Health
and Safety, 1983, ILO.

10. National Institute for Occupational Safety and Health. NIOSH/OSHA
pocket guide to chemical hazards. Cincinnati, Ohio: National

Institute for Occupational Safety and Health, 1981 (DHHS (NIOSH)
publication no. 78-210).

ll. Last, J (et al, eds), Public Health and Preventive Medicine, 12th
edition, 1986, Appleton-Century-Crofts.

12. Pitot HC. Environmental modifiers in carcinogenesis. IARC

Publication no. 39, Host Factors in Human Carcinogenesis. pgs
165-76, 1983.

13. Harris CC. Concluding remarks: role of carcinogens,
cocarcinogens, and host factors in cancer risk. Human
carcinogenesis. Academic Press, 1983.

14. Pastorino U, Berrino F, Gervasio A, Pesenti V, Riboli E,
Crosignani. Proportion of lung cancers due to occupational
exposure. Int. J. Cancer, 33:231-237 (1984).

15. Arcos JC. An overview - part II, cancer: chemical factors in the
environment. American laboratory. 29-42, July 1978.

16. Fairchild EJ. Guidelines for a NIOSH policy an occupational
carcinogenesis. Annals NY Acad Sci, 271:200-207, 1976.

17. National Institute for Occupational Safety and Health. NIOSH
comments on OSHA identification classification and regulations of
potential occupational carcinogens, advanced notice of proposed
rulemaking (ANPR). April 5, 1982.

18. Johnson F, Stonehill R. Chemical pneumonitis from inhalation of
zinc chloride. Diseases of the Chest, 40:619-624, 1961.

19. Knaan G, Mulho M, Tirosh M, Lichtig H, Pugnner Y. Pulmonary

involvement following exposures to zine chloride smoke. Harefuah
79(11):489-92. 1970.

20. Macauley M. Smoke bomb poisoning. J Royal Army Medical Corp. Vol
110:27-32. 1964.

Btey oe


a

Page 7 - Health Hazard Evaluation Report No. 85-274

Vv. CRITERIA

A.

Environmental Criteria

As a guide to the evaluation of the hazards posed by workplace
exposures, NIOSH field staff usually employ environmental
evaluation criteria for assessment of a number of chemical and
physical agents. Some of these criteria are intended to suggest
levels of exposure to which most workers may be exposed up to 10
hours per day, 40 hours per week for a working lifetime without
experiencing adverse health effects. Since fire training exercises
are of short duration these long-term exposure are not as
relevant. They are presented in this report as points of
reference. Short-term criteria, [15 minute short-term exposure
criteria, ceiling level criteria and concentrations that are
considered to be immediately dangerous to life or health (IDLH)),
are more relevant for evaluating the acute health effects of
exposures to these smoke clouds.

When exposure occurs to a mixture of substances it is usual
practice to consider the effects of those that elicit similar
responses to be additive. That is, if one is exposed to 5
milligrams per cubic meter of air (mg/m3) of chemical A and 5
mg/m? of chemical B, and both are respiratory irritants, then
from the standpoint of potential health effects, the exposure in a
general sense is often thought of as an exposure to 10 mg/m? of a
respiratory irritant. There can also be a synergistic effect.
That is, the overall effect is greater than each singular effect
or, in some cases, an additive effect.

The primary sources of environmental evaluation criteria for the
workplace are: 1) NIOSH Criteria Documents and recommendations, 2)
the American Conference of Governmental Industrial Hygienists’
(ACGIH) Threshold Limit Values (TLVs), and 3) the U.S. Department
of Labor (OSHA) occupational health standards.4-/ Often, the
NIOSH recommendations and ACGIH TLVs are lower than the
corresponding OSHA standards. Both NIOSH recommendations and ACGIH
TLVs usually are based on more recent information than are the OSHA
standards. The OSHA standards also may be required to take into
account the feasibility of controlling exposures in various
industries where the agents are used; the NIOSH-recommended
exposure limits, by contrast, are based primarily on concerns
relating to the prevention of occupational disease.

Toxicity of Chemicals Measured in the Smoke Clouds

Inhalation is the only significant route of exposure to the smoke
constituents relevant to this hazard evaluation. The primary smoke


Table 3

Sampling and Analytical Techniques for Air Samples
Collected in Smoke Clouds Generated by Zinc Chloride Smoke Generating Devices

Cincinnati Fire Training Building

Cincinnati, Ohio
HETA 85-274

April 8-9, 1986

Analytical Techniques

haterial Evaluated Media Flow Rate
(LPM)
Hydrochloric Acid ORBU-53 tubes 0.5
‘
Chlorinated Hydrocarbons Charcoal Tubes 0.2 and 0.5
li.e., Carbon tetrachloride,
hexachlorobutadiene)
Metals Mixed Cellulose 1,5 and 2
Ester Membrane Filter
Mixed cellulose 2

Zinc Compound

laentitication Ester Filter

Samples were analyzed for hydrochloric acid by
fon chromatography according to NIOSH Method
7903. The A and B sections and A section plugs
of the silica gel tubes were each separately
desorbed in 10 ml of eluent and heated in a
bofling water bath for 10 minutes. The
resulting solution was filtered through a 0.45
micron filter, and an aliquot of each solution
was analyzed via a Dionex ion chromatograph
utilizing a WISP 710B auto sampler.

Ten charcoal tubes were evaluated qualitatively.
Each sample was desorbed with 1 mi of CS2 and
screened by gas chromatography with a flame
ionization detector. Since all chromatograms
were similar, only two of the ten-samples were
further analyzed using gas chromatography/mass
spectrometry (GC/MS)for identification of
detected peaks. Based on the GC/MS results the
remaining tubes were desorbed and with 1 mi

CS2 and quantitated for five chlorinated
compounds.

Samples were ashed with concentrated nitric and
perchloric acids. The residues were dissolved
ina dilute solution of the same acids and the
resulting sample solutions were analyzed for
trace metal content using (inductively coupled
plasma-Atomic Emission Spectroscopy GCP-AES).

Analysis via Transmission Electron microscopy
via Zumwalde-Dement procedure outlined in NIOSH
publication no. 77-204. Twenty randomly
selected grid openings were examined on each
sample preparation at 18,000x magnification,
Elemental analysis was performed on at least 50
of the various components of each sample
preparation.


This Health Hazard Evaluation (HHE) report and any recommendations made herein are for the specific facility evaluated and may not be
universally applicable. Any recommendations made are not to be considered as final statements of NIOSH policy or of any agency or individual
dditional HHE reports are available at http://www.cdc.gov/niosh/hhe/

involve

Es

Public Health Service

Convers for Oleeae Control & National institute for Occupational Setety and Health

U.S. DEPARTMENT OF HEALTH AND HUMAN SERVICES @

Health Hazard
Evaluation
HETA 85-274-1879

Report EVALUATION OF ZINC CHLORIDE

SMOKE GENERATING DEVICES
INTERNATIONAL ASSOCIATION OF
FIRE FIGHTERS

WASHINGTON, D.C.


Page 10 — Health Hazard Evaluation Report No. 85-274

c.

yu: ve Ss. t.
December 1985 test

Table 6 presents the results of sampling conducted at the
Cincinnati fire training facility in December 1985 of smoke from
both the 3C smoke bomb and the white smoke pot. Materials detected
in quantifiable concentrations during one or both tests were HC1,
zinc, chloroform, carbon tetrachloride, trichloroethylene,
perchloroethylene, hexachloroethane, and hexachlorobutadiene.

HCl was present at concentrations of 7.3 to 10.0 mg/m3 in the 3¢
smoke bomb cloud and at 177 to 338 mg/m? in the white smoke pot
cloud. The current exposure criterion for both OSHA and ACGIH is 7
mg/m3 as a ceiling value not to be exceeded.5,6 NIOSH's
recommended IDLH level is 140 mg/m3,10

The airborne concentrations of total zinc ranged from 5.1 to 7.1
mg/m3 in the cloud from the 3C smoke bomb and 8.6 to 17 mg/m3

in the cloud from the white smoke pot. Assuming these values
represent zinc chloride (the principle component reported by the
manufacturer), the corresponding zinc chloride concentrations are
11 and 15 mg/m3 in the cloud from the 3C smoke bomb and 18 and 35
mg/m3 in the cloud from the white smoke pot. The ACGIH
short-term exposure criterion is 2 mg/m3 for a 15-minute
exposure.6

Hexachlorobutadiene was not detected in the 3C smoke bomb cloud but
was present at 1.72 and 2.78 mg/m3 in the white smoke pot cloud.
The only current exposure criterion is the ACGIH TLV, which is 0.24
mg/m? as an 8-hour TWA.© ACGIH considers this material to be

an industrial substance suspect of carcinogenic potential for
man.6,7

Octachlorocyclohexadiene and hexachlorobenzene were also detected
in area samples used to quantitate the cloud components. The
collection media used was not adequate to quantitate these
substances; each was present in trace quantities.

April 1986 Test

Table 7 presents the results of air sampling in the smoke clouds
produced by the five smoke devices tested. HCl was measured in
each cloud at concentrations ranging from 2 to 17 mg/m3 for the
smallest device (30 second candle), and from 12 to 224 mg/m3 for
the largest device (white smoke pot). The additional test
conducted in a smaller room on the second level of the fire
training facility resulted in HCl concentrations of 24 to 421

+ 2S


Page 9 - Health Hazard Evaluation Report No. 85~274

The reports reveal that:

1.

All but one of the incidents involved the use of zinc chloride
smoke generating devices in some type of fire training exercise
or disaster drill. The remaining incident resulted from
accidental burning of approximately 80 smoke generating
devices. Some articles specified the smoke device as a
Superior Signal product, but in most cases the device
manufacturer was not identified.

Some of the incidents resulted from the unintentional
inhalation of zinc chloride smoke as a result of problems with
respiratory protection devices and/or buddy breathing exercises.

In some of the incidents, participants stated that the smoke
generating devices were chosen because advertisements indicated

the devices were non-toxic or irritation was assumed to be the
principle hazard.

The health effects that were reported are generally consistent
and included: breathing problems, chest pains, hot and cold
flashes, headache, fever, fatigue, sore throat, nausea, cough
and death. Where autopsies or X-rays were conducted, pulmonary
and cardiac abnormalities were reported (Table 5).

Reported problems date back to 1943 and involved from one to 70
individuals. Deaths were reported in at least three separate
incidents. In one of these, an employee's face mask came
apart, but he stayed in the smoke for fear of "messing up"
filming of a training exercise.

In some of the reports, statements were made that the smoke

generating devices had been used previously with no known
problems.

In one report, measured air concentrations of zinc chloride,

were in excess of 4000 mg/m3, A concentration of 2000
mg/m} has been listed by NIOSH as IDLH.

Qualitative Air Sampling Results

The results of the laboratory test with the 30-second smoke candles
indicated that the principal smoke cloud components were zinc
compounds (i.e., zinc chloride, zinc oxide, zinc metal, etc.) and

HCl.

Over 50 chlorinated hydrocarbons, including several suspected

human carcinogens such as carbon tetrachloride, chloroform, and
perchloroethylene (Figure 1) were also identified.


MATERIAL SAFETY DATA SHEET (continued)

Seeeesssssees:

SECTION 7: CISPOSAL METHOD

(SMOKE): Ventilate area: Use iocal exnaust to keep exposure to a
minimum. The length of exposure could be reduced further by opening
doors and windows. Push/pull ventilation will speed smoke evacuation.

(SOLID PRODUCT): Disposal Method: Dispose in chemical Gisposal area
in a manner that complies with local, state and federal reaulations.

soa:

The information herein is given in good faith, but no
warranty, expressed or implied, is made.

SD/1
1/20/87

w



: Table 8 (continued) '

Number of
Years Device Last year Volume (ft3) Type of Number Comparison of Usage to
source/State Used Used of Training Area Device* Used Manufacturers 1987 Criteria
Charlottesville
Municipal Fire Vept./ .
Virginia 1 1987 11500 3C 8-104 In excess (24X-30X)

NUTES:

“rere cac es

*

ak

= Wanted lots of smoke, used rooms in abandoned single family residences.

Also used grenade and white smoke pot in larger area of the building.
Start with z-3 then add devices to reduce visibility to zero. When read of potential problem got product literature.

Also used yellow grenade in same sized room. Wanted to completely obsure vision.
Usea in difterent training facilities, also used abandoned houses. Room size listed is an average.

Very heavy smoke.

Used smal] mobile home most often, also used abandoned houses.

Used a lot of different facilities (i.e. motel rooms, house, commercial building), also used 5D smokg bomb.

Basement training area (2400 ft?) was tighter - had less leakage, than their training tower (9000 ft’), thus used
tewer devices, even though basement training area was larger than training tower.

Used hallway of abandoned school. Used 8-10 bombs at once, then add bombs as needed to heavy smoke, total of 12 dozen

bombs used over 8 1/2 hour period.

= Some contacts identified the manufacturer as Superior Signal Co. but did not know the device ID no., their description

was sufficient to indicate which device (usually the 3C smoke bomb) they had used.
= Contact could not identify smoke bomb manufacturer but the description suggested that the device they had used was a

Superior Signal Co. smoke bomb, the device described sounded like a 3C smoke bomb.

a

"

"

w


Table 8 (continued) '

Number of .
Years Device Last year Volume (ft3) Type of Number Comparison of Usage to
Source/State Used Used of Training Area Device* Used Manufacturers 1987 Criteria

Training Institute/
New York 3 1986 6400 5D 1-2e In excess (16X-32X)
Jamestown Fire Dept./
New York 2 1985 12500 3 3 In excess (8X)
Utica Fire vept./
New York 1 1983 9000 3C** i In excess (4X)

Bend Fire Vept./

Oregon 1987 3000 5D 1 In excess (33X)

Corvalis/ 4 1987 3800 5D 1 In excess (26X)

Oregon 12800 5D 1 In excess (8X)

Penaleton Fire Vept./

Uregon 10-12 1983 9000 3c** 1 In excess (4X)

Aberdeen Rural Fire Vept./ ’

South Vakota 3 1987 1120 3c if In excess (31X)

Fernly Vol. Fire bept./

South Dakota 1987 3920 3c 2g In excess (18X)

Pierre Fire Dept./

South Dakota 15-20 1985 1200-2400 3¢ 4-5h In excess (58X-146X)

Ft. Worth Fire Vept./ 6-7 1987 2400 3C 5-61 In excess (72X-88X)
9000 3c 2-3) In excess (9X-12X)

Texas

od Lo ie a



Page 6 ~ Health Hazard Evaluation Report No. 85-274

content was determined using an Edmont Oxygen Meter, model 60-625.
Additionally, Draeger* gas detector tubes were used to evaluate
the 02 and HCl content of the clouds. Sampling and analytical
methods are presented in Table 3.

To evaluate the third objective (smoke cloud density),.an official
from the Cincinnati Fire Department's fire training staff served as
a technical advisor during the tests. This individual-was asked to
set up the facility as he would for their training exercises,
observe the density of each cloud, and state whether or not he
believed it to be similar to the clouds produced during their
training exercises. Discussions with the technical advisor prior
to air sampling indicated for training purposes that heavy clouds
were needed to obscure visibility in the training building, thus
simulating smoke conditions in an actual building fire.

With doors and windows closed, as during training, four to six
units of the three smaller devices and one each of the two larger
devices were used. On the second day, the number of 3C smoke bombs
and grenades was increased because the technical advisor felt that
the smoke clouds generated on the first day were not dense enough.
On the first day, the smaller devices were ignited outside and
tossed into the fire training facility, per directions on product
labels. On the second day, for each test, all devices were placed
inside the fire training building and ignited simultaneously. On
the second day of testing a white smoke pot was also tested on the
second floor to determine air concentrations of HCl and chlorinated
hydrocarbon generated in a smaller area.

leph Si

In December 1987 and January 1988, fire training personnel at 62
different fire training organizations across the United States were
contacted by telephone to obtain information related to the use of
smoke bomb type devices. A United States Atlas and city telephone
“information” service was used to obtain the phone numbers of fire
departments. Those organizations which we knew had experienced
problems with the smoke bombs, that had been written about in the
literature; or who NIOSH had already spoken with about fire
training were omitted from this telephone survey.

Once the fire training organization was contacted, a training
offical was questioned to determine if the organization had used
smoke bomb type devices. Those indicating that they had used these
devices were further questioned as to the number and type of

devices used, how long they have been using them, and the manner in
which they used the devices.



Page 20 ~ Health Hazard Evaluation Report No. 85-274

Originating Office: Hazard Evaluations and Technical
Assistance Branch

Division of Surveillance, Hazard

Evaluations, and Field Studies

Report Typed by: Linda Morris
Clerk-Typist
Industrial Hygiene Section

D IBUTI. A

Copies of this report are currently available upon request from NIOSH,
Division of Standards Development and Technology Transfer, Publications
Dissemination Section, 4676 Columbia Parkway, Cincinnati, Ohio 45226.
After 90 days, the report will be available through the National
Technical Information Service (NTIS), 5285 Port Royal, Springfield,

Virginia 22161. Information regarding its availability through NTIS
can be obtained from NIOSH Publications Office at the Cincinnati
address. Copies of this report have been sent to:

1. International Association of Fire Fighters (IAFF)
2. Cincinnati Fire Department

3. Superior Signal Company, Inc.

4. OSHA, Region V

5. National Fire Protection Association (NFPA)

For the purpose of informing affected employees, copies of this report
should be distributed through appropriate channels to fire training
personnel.


The Superior White Smoke Pot is the ultimate in smoke gener-
ators for fire or disaster training. Activated by a sure fire pull
wire ignitor, it generates over 500,000 cubic feet of dense white
smoke, sufficient to simulate a city block sized disaster area, WHITE
during a five to six minute burning time. The ignitor and smoke SMOKE POT
generating materials are enclosed in a sturdy sealed metal con-

tainer, with an easily removed U-Press-it closure, protecting them
from atmospheric changes, the principal cause of ignition fail-
ures and unsatisfactory performance. Warranted for three years.
6%" x 4”, shipping weight 4 Ibs. Not mailable.

White Smoke Pot: Handle carefully. Avoid exposure to smoke
without respiratory protection. Do not use in confined areas
without self contained breathing mask, as dense smoke may
displace oxygen in atmosphere.

Superior Smoke items generate a gray or white smoke depending upon density and lighting conditions.
It simulates actual fire smoke in appearance and smell without lingering odors or residue to damage
clothing and walls. Because of these features, any reasonable size room or building can be used for smoke
drills. With a T.O.P. of 2100, Superior Smoke provides maximum obscurity with minimum concentration.
It is sufficiently irritating to allow trainees to detect defective mask or improper utilization of same. Fires
can be prevented by using Superior Smoke to locate breaks in chimneys and leaks in heating units.

MASK DRILLS: Fire departments, civil defense and rescue units should hold regular drills to maintain the
efficiency of smooth operating procedures while wearing masks under difficult and frequently dangerous
conditions. Trainees should be instructed thoroughly in the operation of equipment and practice until they
can don the equipment, check gauges and adjust valves without hesitation. This gives assurance and may
prevent panic or mistakes, with dire circumstances later. The room to be used for drills should contain
furniture, rearranged from time to time to prevent familiarity with the layout. Retrieving a can or some
easily identifiable object will teach men to feel their way through smoke. Some instructors require train-
ees to carry sand bags or saw wood to become accustomed to the breathing restrictions encountered
while wearing a mask. Frequently trainees are required to remove masks, blow out the smoke and re-
place to familiarize them with the procedure in event a mask is accidentally torn off in smoke. The glow
frorn a highway flare or the flame and heat from a barricaded fire gives valuable practice in sizing up
a fire and its location through the smoke by a faint glow or tell-tale wave of heat. Regular drills

teech men to handle themselves and their equipment with a minimum of effort and panic enabling

them to concentrate on their assigned jobs of sizing up and fighting fires or making rescues.

FIRE DRILLS: Employees should be instructed on procedure in event of fire. They should know the loca-
tion of exits, fire extinguishers and fire hoses. Group leaders should be given special assignments and
be prepared to supervise speedy evacuation of the building and to close doors to prevent the spread
of fire. Training in rudiments of fire fighting are helpful in controlling the fire until firemen arrive. Af-
ter one or two practice drills, an unannounced drill with Superior smoke simulating a fire, will quickly
dispel any lax tendencies towards fire drills and drive home the necessity of preparedness. Lives are
needlessly lost every year through lack of adequate fire drills.

Recommendations and product information are believed to be accurate, but the furnishing of it does not con-
stitute the making of a product or process warranty of Seller.

Superior warrants that this product conforms to the Product Description contained in this literature.
Superior makes no other warranty, whether expressed or implied, including warranties of merchantabili
or of fitness for a particular purpose or application. No statements or recommendations contained herein are
fo be construed as inducements to infringe any relevant patent, now or hereafter in existence. Superior neither
assumes nor authorizes any representatives or other person to assume for it any obligation of liability other
than such as is expressly set forth herein. Under no circumstances shall Superior be liable for incidental, con-

sequential or other damages from any alleged negligence, breach of warranty, strict liability or any other
theory, arising out of the use or handling of this product.

CAUTION: Handle with care. All smoke, including Superior can irritate breathing passages without res
piratory protection.



“ged ps

_Appendix B
TELEPHONE (201) 251-0800

P.O. BOX 96 © SPOTSWOOD, N. J. 08884 SENO SHIPMENTS To:

West GReystone Road
Ovo BrioGE. N. J. O88S7

SUPERIOR SMOKE FOR FIRE TRAINING

To develop smokey atmospheres, an adequate amount of smoke is
utilized (1) to obscure vision and (2) to be sufficiently irritating
to reveal improper procedures or faulty equipment. Under these
simulated fire conditions, instructors have a high degree of
confidence in their ability to Properly train fire fighters to

perform a necessary community service, while minimizing the inherent
risks of their occupation.

Smoke drills are developed and performed under the direction of fire
training instructors. With proper procedures delivered through clear
instructions, firemen would not have any exposure to training smoke;
however, circumstances such as leaky masks, equipment failure,
incomplete instructions and personnel performance inadequacies do
occur. Instructors anticipating these incidents have found these
exposures to smoke generally range from thirty seconds to several
minutes with either no Physiological effects or minor short tern
effects such as those associated with smoke inhalation.

At times, the users may not Participate in a responsible manner
caused by incomplete operational instructions for self-contained
breathing equipment or less than prudent personal decisions. Our
experience in distributing Superior Smoke for fire training exercises
reveals that in many instances, excessive volumes of smoke are
developed to obscure vision, simulating fire conditions.

Low concentrations of smoke allowed to blend in a homogeneous
mixture with room air provides obscurity without causing excessive
concentrations, Allow the smoke generator to finish generating smoke
before entering smokey atmosphere, Superior smoke products produce
smoke during stated periods of time; however, the smoke cloud can
remain in suspension for 15-30 minutes when not ventilated.

Other Smokes are not SUPERIOR


US havy

Columbia, Mo.
newspaper

Schenker,
Speizer,
Taylor

Fire department

3/4/81
Un Board Ship,

April 1981
Columbia,
Le

198l

6/13/83
Medina, NU

Superior Signal
5D smoke bomb

Superior Signal
Company Smoke Bomb

Military smoke
canister; zinc
chloride smoke

Superior Signal
Company smoke bomb

Table 5 (continued)

22-year-old male during fire-
fighting exercise on ship had

had respirator facepiece come apart.
Stayed in smoke for 5 minutes for
of “messing up" exercise.

Device chosen because it was
advertisement as non-toxic.

Welded galvanized pipe during
previous days.

During buddy breathing exercise

a fire fighter was overcome.
Participants noted that device

were marketed as “medically

proven safe and non-toxic".

Had reportedly used bombs for years.

82 “victims” and 28 medical personal
personal were exposed to smoke during
an airport disaster drill.

Fire chief developed problem with
smoke pac during training exercise
ina garage. Bombs warned of
irritation, Buddy breathing exercise
chief inhaled a “breath” of smoke.

Cough, sore throat, shortness of breath
Over next 4 days

complained of cough and was

lethargic. Died on 5th day. Autopsy
showed bilateral severe necrotizing
pneumonitis and dilatation of right
atrium and ventricle.

Respiratory and intestinal inflammation
Swollen lymph nodes, chills, headache,
nausea, fatigue, and sore throat.

Immediate cough, hoarse, sore throat.
Later symptoms were nausea,
fatigue and headache

Difficult breathing, chest pains,
hot and and cold flashes, and
nervousness. At hospital emerqency
room. Temperature = 101°,
Ooxygen administered.

Recovery within 24 hours

*Smoke device/exposure are described in the article, or abstract for the reported episode.



The amount of amoke generated during these exercises was typical of
that used in the past to achieve effective vision obscuration, but was
far in excess of that currently recommended by the manufacturer.
(Prior to 1987 the manufacturer's literature did not specify how many
devices were recommended for a given volume of space.)

Results of a telephone survey we conducted in December, 1987 and
January, 1988 with fire training personnel at 62 locations throughout
the United States revealed that all but one of the fire training
organizations that used these devices were using far in excess of that
specified in 1987 manufacturer's recommendations.

_ se eS

Dense clouds generated by ZnCl2 smoke generating devices should be
considered hazardous. NIOSH sampling documented exposures to HCl which
exceed OSHA and ACGIH ceiling levels and the NIOSH IDLH level. While a
properly operating self-contained breathing apparatus worn by a
well-trained individual offers adequate protection against the smoke,
even short-term exposure without respiratory protection to the
components of the dense smoke cloud presents a health hazard.
Recommendations for precautionary measures to be taken by firefighters

to minimize potential inhalation health hazards are presented in
Section VIII.

Keywords: SIC 2899 (Miscellaneous chemical preparations) and 9224 (Fire
Fighters) smoke bomb, smoke generating devices, zinc chloride,
hydrochloric acid, chlorinated hydrocarbons


wees

Page 13 - Health Hazard Evaluation Report No. 85-274

VIt.

For example, if two 3C smoke bombs were used in a 1000 cubic foot
Space, an estimate of the degree of excess usage can be computed as
follows: (2 X 35,000 cubic feet) divided by 1000 cubic feet =
70,000 divided by 1000, or 70 times (70X). The result of this
computation for each usage situation appears in the last column of

Table 8. This computation for the NIOSH tests ranged from 8X to
83K.

Eleven of the 21 contacts who had used the smoke bomb devices
reported that they did not have the manufacturer's literature and
several others said they were not sure if they had the literature.

DISCUSSION AND CONCLUSIONS

Information from a literature review indicates that there have been
significant adverse health effects, including death, from exposure to a
dense smoke cloud produced by zinc chloride smoke generating devices.
Those individuals affected were either not wearing respiratory
protection (SCBA), or had problems with the SCBA.

The zinc chloride smoke generating devices manufactured by Superior
Signal, Inc. have been commonly used during fire training exercises.
These devices were used by about 30% of the 62 fire training personnel
contacted by telephone. It appears that the primary goal in using
these devices is to produce an atmosphere that simulates those
conditions which may be experienced in an actual fire and that one
important consideration is that vision be effectively obscured.
Manufacturers’ literature (see Appendix A) which was available at the
time of these surveys (1985 and 1986), did not specify how many or
which types of smoke generating devices should be used in a given size
training area. Updated information (see Appendix B), which was
available in 1987, did include information on which devices to use for
different sized areas and, by the 1987 criteria, the number of devices
used in the NIOSH tests was far in excess of what the manufacturer is
now recommending. However, information obtained from several fire
training sources suggested that the conditions which were evaluated
during this study were representative of the way in which these devices
have commonly been used. The telephone interview conducted in December
1987 and January 1988 with fire training personnel at 62 separate
locations across the United States also indicated that it has been
common practice to generate more smoke than recommended in the
manufacturer's 1987 literature. The next most commonly reported method
of generating fire training atmospheres was the actual burning of a
wide variety of combustible materials (furniture, mattresses, straw,
etc.). Other smoke generating techniques (artifical smoke called
Roscoe and Pepper Fogger) and blackening the face piece to obscure
vision were also mentioned.


Page 15 - Health Hazard Evaluation Report No. 85-274

In December 1986, NIOSH was informed of another episode which occurred
in October 1986. During a high rope rescue training exercise in which
a Superior Signal Company 5D smoke bomb was used to create smoke, 5 of
6 participants experienced adverse health effects. NIOSH is currently
investigating this episode. 28 Those experiencing adverse health
effects were interviewed by a NIOSH physician. These people were
either not wearing an SCBA or had a problem with the SCBA. Reported
symptoms and the number of people who reported each symptom included:
sore throat (3), difficulty breathing (2), joint (upper and lower

extremities) stiffness, pain (2), chills and fever (2), headache q1)
and generalized fatigue (1).

The National Fire Protection Association (NFPA) publishes consensus
standards for fire fighters. The NFPA recently published a standard on
fire training (NFPA 1500). The standard states that smoke generating
devices that produce hazardous atmospheres should not be used.29

Updated product information was received from Superior Signal Company
in early 1987. It contained instructions that "“{ndividuals should be
urged not to accept exposures that cause minor irritation, but to leave
the area". Smoke cloud components identified were hydrated zine
chloride, water condensate and carbon monoxide. There was no mention
of HCl or chlorinated hydrocarbons. However, usage guidelines were
provided and comments relating to buddy breathing, taking respirators

off to “experience the environment" and usage during office type fire
drills were omitted.

VIII. RECOMMENDATIONS

These recommendations are directed at the users of zinc chloride smoke
generating devices. Other recommendations have been sent to Superior

Signal Company concerning labeling, dissemination of usage guidelines
and MSDS information.

1. Dense smoke clouds produced by all of the zinc chloride smoke
generating devices NIOSH has tested should be considered

hazardous. No smoke generating device should be considered safe or
non-toxic.

2. Before smoke generating devices are used, technical data sheets and
MSDS information should be obtained and reviewed.

3. Practices like "buddy breathing" should not be conducted in "zinc
chloride” smoke clouds.

4, Wo one should enter a zinc chloride smoke cloud without a properly
fitted and operating SCBA. Additionally, everyone involved in the
training should be made aware of the potential hazards. Anyone who
enters a cloud should be instructed to leave the area immediately i


eS

SET

HETA 85-274-1879 NIOSH INVESTIGATORS:
MARCH 1988 John N. Zey, MS, CIH
EVALUATION OF ZINC CHLORIDE Fred Richardson, M.D.

SMOKE GENERATING DEVICES

INTERNATIONAL ASSOCIATION OF
FIRE FIGHTERS

WASHINGTON, D.C.

I.

SUMMARY

In March 1985 the National Institute for Occupational Safety and Health
(NIOSH) received a request from the International Association of Fire
Fighters (IAFF) to evaluate the hazard of smoke clouds produced by zinc
chloride (ZnC1z) smoke generating devices. The requestor noted that
the devices, advertised as "medically proven to be non-toxic", had been
implicated in a number of training exercises during which participants
experienced adverse health effects, including breathing difficulties,
chest pains, joint pains, chills, fever, and death.

A NIOSH literature search indicated that adverse health effects had, in
fact, been reported in at least ten episodes; however, those affected
were either not wearing a respirator or the respirator had
malfunctioned. Literature obtained from the manufacturer in June 1985
reported that the smoke clouds contained ZnCl2, combustion products,
and high moisture. Previous investigations had reported finding
hydrochloric acid (HCl) and numerous chlorinated hydrocarbons in the
smoke clouds. Qualitative tests by NIOSH, as a preliminary effort in
this investigation, identified zinc compounds, HCl and over 50
chlorinated hydrocarbons in the smoke cloud. Based on these
qualitative data, five separate smoke generating devices were
quantitatively evaluated using area sampling techniques during
simulated fire training exercises at the Cincinnati Fire Department's
fire training facility in December 1985 and April 1986.

Airborne HCl concentrations ranged from 2 to 420 mg/m3. 2nClo
concentrations ranged from 11 to 498 ng/m3 - The HCl concentrations
documented exceed the OSHA and ACGIH ceilirig level criteria of 7
mg/m3 and the NIOSH IDLH (immediately dangerous to life or health)
concentration of 140 mg/m3, The @nGl2 concentrations measured
exceed the ACGIH short-term exposure limit of 2 mg/m3.

Numerous chlorinated hydrocarbons, several of which are suspect human
carcinogens were also detected. One of ghese, perchloroethylene, was
present in concentrations of 20-540 mg/m>. Among those chlorinated
hydrocarbons detected were carbon tetrachloride, hexachlorobutadiene,
hexachloroethane, and chloroform. It should be noted that, from the
standpoint of fire training exercises, the acute health risks
associated with exposure to the zinc compounds and HCl are of more
immediate concern than the carcinogenic risks from the chlorinated
hydrocarbons. A properly used SCBA would protect against all of these
exposures.


_Superior® ®

NO RESIDUE — : NO EXPLOSIVES
SUPELEOT sora. comeany, we.

W. Greystone Read Spotewoed, + New Jersey
phone area code 201 251-0800

The revolutionary Superior method of generating smoke by chemical reaction makes previous methods of

burning materials to create smoke particles as inefficient and obsolete as the horse drawn fire engine. It

leaves no residue to stain the interior of buildings or clothing. Superior Smoke items contain no explosive

materials and are the only devices of this nature acceptable in the mails. It has a T.O.P. (total obscuring

power) of 2100. T.O. P. is the scientific method of determining the quantity of smoke generated by a given

unit of smoke composition. By comparison crude oil has a T.O. P. of 200. More smoke, exclusive safety fea-
‘ Superior §

The Superior Smoke Bomb No. 3C
generates a big 40,000 cubic feet of
whitish gray smoke while burning from
two to three minutes. Our most popular
item for firemen training. :
Shipping weight 5 Ibs. per dozen. a
Size 1%" x 6”. Mailable. Shipping weight

The Superior Smoke Bomb No. 5D (not illustrated) generates 100,000 cubic feet of light gray smoke in five
minutes. Long fuses on each end permit mulitple smoke bombs to be tied together for continuous burning
to maintain an enormous and sustained volume of smoke. Mailable. Sold in minimum units of six.

Size 1%" x 14". Shipping weight 5% Ibs. for six.

Superior Smcke Grenades are engineered for use
where an instantaneous and exceptionally large
volume of smoke is required. They are solidly con-
structed with a dependable built-in pullwire ignitor
and warranted for three years.

2—Putl tab 00 expose agnor ning,

J—Fell agnnior ng tharply and threw grenese
setmodtatsly

Superior Smoke Grenade generates 115,000 cubic
feet of smoke during 2-3 minutes burning time, size
2” x 5", weight 14 oz., not mailable.

Superior Professional Smoke Grenade generates 130,000 cubic feet of smoke while burning 2-3 minutes,
size 22" x 5” 1 |b.; can be comfortably hand held; not mailable.

Printed in U.S.A. — Effective 12/79
Form $1

ie
ee



Health Effects of the Primary Smoke Cloud Components Detected

Cincinnati Fire Training Building
Cincinnati, Ohio

HETA 85-274

Chemical

TOLH

Health Effects

Target Organs

Reference

Tetrachloroe thy lene
(CC1,=¢C1z)

Hexachloroethane

(uc 5-CU15) ‘

Hexachlorobutadiene
(UU Z=LCT-CCF=CC1 2)

dinc Chloriae Fune
(anelz)

Hyarochloric Acid
(het)

Carbon letrachloride
(CCl)

Chlorotorm
(CHET 3)

Vricnloroe thy lene
(CHC1=CC1z)

500 ppm

30U ppm

Z00U mg/m

10U ppm
(140 mg/m)

300 ppm

1000. ppm

1000 ppm

irritation of eyes, nose, and

throat; nausea, flushing of face

and neck, vertigo, dizziness,

incoordination, headache, erythemia,

liver tumors in animals

eye irritation, liver tumors tn animals

eye and nose irritation, kidney tumors

in animals

irritation of nose and throat,

conjunctivitis cough, copious sputum,
chest pain, pneumonia, pulmonary

fibrosis, fever, cyanosis, tachypnea,

burning skin

inflammation and ulceration of nose,

throat, cough, burning throat,
choking, burning eyes and skin,
dermatitis

central nervous system

depression, nausea, vomiting, liver and
kidney damage, skin irritation, liver

cancer

dizziness, dullness, nausea, headache,

fatigue, hepatomegaly, eye and skin
irritation, liver or kidney tumors

headache, vertigo, visual

disturbances, tremors, somnolence,
nausea, vomiting, irritation of eyes,
dermatitis, liver tumors in animals

liver, kidneys, eyes, upper
respiratory, central nervous
system

eyes
kidneys

respiratory system, lungs,
skin, eyes

respiratory system, lungs,
skin, eyes

central nervous system, eyes
lungs, liver, kidneys, skin

liver, kidneys, heart, eyes
skin

respiratory system, heart,
liver, kidney, central
nervous system, skin

4,7,10,26,27,30

4,7,10,30

7,31

7,10,30

7,10,30

4,7,10,25,30,31

4,7,10,30,31,32

4,7,10,30,31,33

IWLK = Concentration of subject chemical reported to be immedia
inaividual exposed without adequate protective equipment.

- = No IDLH value.

uy dangerous to life and/or health of


PREFACE

The Hazard Evaluations and Technical Assistance Branch of NIOSH conducts field
investigations of possible health hazards in the workplace. These
investigations are conducted under the authority of Section 20(a)(6) of the
Occupational Safety and Health Act of 1970, 29 U.S.C. 669(a)(6) which
authorizes the Secretary of Health and Human Services, following a written
request from any employer or authorized representative of employees, to
determine whether any substance normally found in the place of employment has
potentially toxic effects in such concentrations as used or found.

The Hazard Evaluations and Technical Assistance Branch also provides, upon
request, medical, nursing, and industrial nygiene technical and consultative
assistance (TA) to Federal, state, and local agencies; labor; industry and
other groups or individuals to control occupational health hazards and to
prevent related trauma and disease.

Mention of company names or products does not constitute endorsement by the
National Institute for Occupational Safety and Health.


Appendix A

ote 4, [~, REPLY MESSAGE “)
tg GREET 800-243-5250 \_ dav cg to Fit Grayare Window Envelope # EW10P - REORDER ITEM # F269
FROM
rc Mr. John Zey | gs
10 NIOSH uperior SIGNAL COMPANY, INC.
: Mail Stop R-11 : P. 0. BOX 96
4676 Columbia Parkway SPOTSWOOD, NEW JERSEY 08884
Cincinnati, OH 45226 (201) 251-0800
/suBsECT:___Request for Material Safety Data Sheet ____. DATE: June Uh, 1985
vou }

In response to your recent inquiry, we have enclosed literature, cover letter
and material safety data sheet.

1 would welcome the opportunity to be of
further service.

SUPERIOR SIGNAL COMPANY, INC.

bm ZB aka 277 Cape?
Enclosures .
PLEASE REPLY TO ————e — SIGNED Barbara Marques, Secretary
REPLY
on)
\ pare: SIGNED /
tem # F269 = Wheeler Group Inc. 1979

THIS COPY FOR PERSON ADDRESSED


MATERIAL SAFETY DATA SHEET (continued)

Unusual fire and explosion hazards: » ne Known

SEGHSS Mais omesessesesceseece

Sesiissssesesssseecesss

SECTION 5: REACTIVITY DATA

Stability: Stable under normal conditions.

Hazardous decomposition Products: See Section 2

Hazardous polymerization: None Known

SRereeinsssssssessesessse

SECTION 6: HEALTH HAZARD ASSESSMENT (SMOKE)

General: Superior Smoke can be used without hazard if applied as
directed, Smoke drills with full dress including self-contained
breathing apparatus are rigorous tests of respiratory protection
equipment and confirm operational competence. Lack of irritation is
proof of adequate Protection. If protection is not adequate, some
irritation may occur. Two major components in the initial undiluted
smoke are zinc chloride and water condensate. The main effects of
the smoke are irritation of the throat, an awareness of an odd odor,
and the appearance of smoke, These effects act as a warning and are

desirable to prevent voluntary overexposure. Individuals should be
urged not to accept exposures that cause minor irritation, but to
deave the area,

Ingestion: Not a significant route of exposure.

Eye Contact: Accute exposure is not likely to induce eye irritation.

Skin Absorption: Not a significant route of exposure,

Inhalation: Acute exposure can cause irritation of the respiratory
tract and mucous membranes, Irritation is a warning Property of
smoke materials; in itself irritation is not usually regarded as a
toxic effect unless it is sufficient to cause inflammation and then
inflammation, not irritation, is the toxic effect.

Effects of Overexposure: Irritation of the respiratory passages;
cough; nausea. Gross overexposure to dense smoke concentrations for
periods of ten minutes or more could result in throat irritation and
mucous membrane congestion requiring medical treatment. Coughs,
chills, fever and pulmonary edema can result from overwhelming
exposure. Increasingly sever overexposure is likely to result in
increasingly sever irritation and inflammation to all mucous
Membranes contacted by the smoke with most severe effects usually
appearing in the respiratory tract,

Emergency and First Aid Procedures: Remove victim to fresh air. Tf
breathing is difficult, get medical attention.

SD/1
1/20/87


Results of Environmental Sampling in Smoke Clouds trom tive Separate smuke Lenerating vevices

Cincinnati Fire Training Facility
Cincinnati, Ohio

HETA 85-274

April 8-9, 1986

Range of Concentrations for Chemicals Measured in Smoke Cloud (mg/m3)

Smoke No. of

bevice bevices Perchioro~ hexachToro-- hexachToro- T of

Tested Used Date HC1 ethylene* CC14* butadiene* — ethane* Zn ZnCl g** ZnC1g***

Po

su Sec candle 6 (4/8 2-17 ND ND 5-10 16-19 34-40 -05-.07
“ 6 aly 2-5 ND ND (5-11) 22-23 46-48 60-70 uD

1 min candle o 4/8 3-16 ND ND (4,9-5) 19-23 40-48 ND
“ o 4/9 4-10 ND ND (5-5.7) 29-37 61-75 50 ND

SL smoke bomb 4 4/8 10 67-80 ND ND 16-20 47-59 99-124 -16-.21
. o 419 27-36 80-96 ND ND 15-18 57-68 120-143 80-90 122-,25

brenades L 4/8 14-45 48-88 ND ND (5-10) 26-30 55-63 -03-,04

Grenades 2 4/9 38-110 145-163 (4.8-5) ND 16-24 63.7-64 = 133-134 60-70 209-21

White smoke pot 1 alo 102-224 470-535 29-43 (4,9-5) 29-38 155-237 326-498 =28-.54
. 1 4/9 12-60 347-538 27-29 (4,9-5) 16-39 7-39 99-124 90-95 772-113
“ 1 4/9 24-421 = 282-596 22-31 (ND-5) (5)-16

ACGIH = 7-C 1340-STEL 125~-STEL 224-T 100-T None 2-STEL 2-STEL 0.15-T

MUSH = None MWEL 12.6-C None LEL None None NONE <0.10-T

USHA = 7-C 2010-C 150-C None 10-T None 1-T 1-T 0.50-T

Sample times were 25 minutes unless otherwise indicated in table by air concentration being underlined.
() indicate that the chemical was present in the air sample at a level above the laboratory limit of detection, but helow

for these samples.

the laboratory limit of quantitation, the numbers listed are estimates.

HUT Hydrochloric acid
Utlg = Larpon tetrachloride

*

an = Zinc

inCly = Zinc chloride

r = Leagd

ND == None detected

SILL = Short-term exposure limit

c = Ceiling value not to be exceeded
MNEL = Minimize workplace exposure level
LFL = Lowest feasible level

a
zinc chlorige.

Time-weighted Average, & hours for ALGIH and OSHA, 8 or 10 hours for NIOSH

Chemical considered to be a carcinogen by NIUSH, and/or OSHA and/or ACGIH
Values for zinc chloride are calculated by multiplying the total zinc measured by a factor of 2.1.

This assumes a1? zinc measured is

wax = These values represent percent of zinc chloride for all zinc compounds as identified in an air sample.

Sample times are less than 25 minutes



Se

ee ae

Page 11 - Health Hazard Evaluation Report No. 85-274

mg/m for the white smoke pot. Results from sixteen of 21
samples collected during two days of testing exceeded the current
OSHA and ACGIH ceiling value of 7 mg/m3 for HCl. Results from
samples in the smoke clouds generated by the white smoke pot
exceeded the ceiling value by up to 60 times, depending on which
room was used for the test. NIOSH's recommended IDLH level is 140
mg/m.

Perchloroethylene was present in all the smoke clouds.
Concentrations ranged from 20 mg/m3 for the smaller devices to
596 mg/m3 for the white smoke pot. The air concentrations never
exceeded ACGIH or OSHA short-term or TWA criteria. Since NIOSH
considers perchloroethylene to be a suspect human carcinogen, NIOSH
recommends that workplace exposures be controlled to the lowest
feasible level. Carbon tetrachloride, hexachlorobutadiene, and
hexachloroethane were also detected in some of the clouds. All
three of these materials are considered to be suspect human
carcinogens by either NIOSH, OSHA, or ACGIH.4-7»25-27 the
presence of suspect human carcinogens in the smoke clouds should
not be ignored, but the potential acute health effects from
exposure to the zinc compounds and the HC] are of more immediate
concern considering how these devices are used.

Air concentrations of zinc ranged from 16 to 237 mg/m3. Once
again, the highest concentration was measured in clouds produced by
the white smoke pot. Calculated zinc chloride (ZnCl2)
concentrations from the total zinc measured, assuming all the zinc
measured was ZnClo (which is consistent with information supplied
by the company), ranged from 34 to 498 mg/m?, The ACGIH STEL
(short term exposure limit) is 2 mg/m3. Thus, the 2nCl2
concentrations exceeded the STEL by as much as 249 times.
Additional sampling to identify which zinc compounds were present
in the clouds indicated that the percent of zinc chloride ranged
from 50% in the l-minute candle to 90-95% for the white smoke pot.
Most of the remaining zinc was present as, zinc oxide.

The NIOSH REL for zinc oxide is 15 mg/m3 as a 15-minute ceiling
value [10 hour TWA is 5 mg/m3] and the ACGIH STEL for zinc oxide
is 10 ng/m3. Therefore even if 50% of the zinc is present as
zinc oxide, the short-term exposure criteria for both the chloride
and the oxide are exceeded. Lead was also measured in most of the
clouds, at concentrations up to 0.54 mg/m3, The OSHA standard

for lead is 0.05 mg/m3, as an 8 hour TWA. There is no short-term
criteria for lead.


Page 14 ~ Health Hazard Evaluation Report No. 85-274

The field tests were designed to identify and measure the concentration
of the components of the zinc chloride smoke cloud produced during
simulated fire training exercises, documented that hazardous
atmospheres were produced, and that IDLH atmospheres could be generated
depending on the type and number of devices used and the volume of the
training facility. The most important components of the smoke cloud
are the zinc compounds (primarily zinc chloride but possibly some zinc
oxide) and HCl because of the severe respiratory effects which they may
cause in a dense cloud exposure situation. A variety of chlorinated
hydrocarbons, including several that are suspect human carcinogens,
were also identified in the dense smoke clouds. However, while this
finding cannot be ignored, the potential respiratory effects from
exposure to the zinc compounds and the HCl are of more immediate
concern considering how these devices are used during fire training.

Manufacturer's literature, at the time the field data was collected,
did not specify what type, or how many, zinc chloride smoke generating
devices should be used in a given size area, One of the most important
criteria, from the standpoint of the fire training officials, was that
vision be effectively obscured. Updated manufacturer's information,
available in 1987, does include this information, and, by the 1987
usage criteria, far more smoke was generated than recommended.
Additionally, the smoke generating devices are often obtained without

the material safety data (MSDS) and other supplemental manufacturers'
information

A well trained individual wearing a properly operating SCBA will be
adequately protected while in the atmospheres generated by the devices
evaluated as part of this study; however, even a short-term unprotected

exposure to the components of a dense smoke cloud could result in
serious health effects.

This study did not evaluate alternative smoke generating methods. The
atmosphere produced by another common method of generating fire
training atmospheres, actual burning of combustible materials, although

not studied by NIOSH, should also be considered hazardous and warrants
the use of an SCBA. °

Advertisements suggesting that these smoke generating devices are safe
were mentioned in some articles. According to the manufacturer, this
was based on a toxicity evaluation conducted by a physician in the
1950s. That assessment was based on the assumption that zinc chloride
was the only significant smoke cloud component and there was no
sampling of actual ZnClz concentrations and no mention of HCl and
other substances.

ee

“ahaa AE nce