Toxicity for the primary gases found in fires
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...by Dr. Vytenis Babrauskas, Fire
Science and Technology Inc.
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Background
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| I headed up the fire toxicity research of the National Institute
of Standards and Technology (NIST, formerly National Bureau of Standards) from
1985 until this program was completed in 1991. One of the most common questions
which I was asked in that capacity was: "What are the important gases one
should study/measure/analyze in fires?" The simplest answer remains:
"Carbon monoxide." Speaking very roughly, this one gas accounts for about
1/2 of the fire toxicity problem. Further details can be found in: Babrauskas,
V., The Generation of CO in Benchscale Fire Tests and the Prediction for
Realscale Fires, Fire and Materials 19, 205-213 (1995).
In some cases, the simple answer does not suffice. Chemists,
regulatory officials, etc. want to know which additional gases may contribute a
non-negligible amount to fire toxicity. No unique answer is possible, since the
circumstances of each fire are different. Certainly, different materials produce
different combustion products; for example, a polymer with no chlorine atoms
would not produce hydrogen chloride among its products. Having said this, valid
reasons could be seen for wanting a "shopping list" of gaseous agents. Thus, I
created such a shopping list. This was published in the first edition of NIST's
fire model HAZARD I. While such a list will always be subject to debate, the
advantage of the NIST one was that it had to undergo the very rigorous review to
which NIST publications are subjected. Thus, instead of being just one
scientist's opinion, it had the consensus of the fire toxicity research and the
fire modeling groups and the informed consent of higher management.
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Compilation of toxicity data
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| The table below presents the results for toxicity as the
toxic potency variable LC50, and is an inverse scale. That is,
smaller numbers denote greater toxicity. For substances of undetermined
composition (e.g., burning plastics), the units used are normally g
m-3. The meaning of this variable is the amount of mass which needs
to be dispersed into a volume of 1 m3 in order to cause a 50%
probability of lethality. For substances where the composition is known (e.g.
pure gases), the LC50 is usually expressed in units of ppmv. The
definition here is that 1 ppmv of a gas means the there is one part of gas per 1
million parts of air. The "v" denotes that we mean parts by volume and not parts
by weight.
In some cases, human data are available from industrial
accidents and such. In most cases, it is necessary to use animals as surrogates.
These must be selected so that the biological system which is affected by a
particular toxin is one which functions relatively similarly in man. For
example, hydrogen chloride inhalation data from mice have generally been
considered to be a poorer prediction of human fatality than data from rats, due
to respiratory system differences. In all cases, of course, the numbers are only
estimates and can never be actually confirmed on humans.
The time of exposure is also important for determining the
effects from toxic gases. In general, a higher concentration allows only a
shorter time, for the same biologic effect to be reached. If the concentration
is exactly hyperbolic, that is, (concentration)x(time)=constant, then this gas
is said to follow Haber's Law. Almost any gas shows deviations from this
simple relationship, but for rough estimating purposes it can be used if better
data are unavailable. For fire toxicity data, the exposure period normally used
is 30 minutes.
Users often ask "Why do you compile data for lethality instead
of data for incapacitation?" This is a legitimate question, since usually we
would like to know for how long a person will be all right in fire, not just
when the morgue has to be called. The reason why such a compilation was not
developed by NIST is a practical one. It is usually possible to obtain reliable
measurements of animal lethalities. By contrast, the concept of incapacitation
does not even have a workable definition. The conditions of incapacitation
depend greatly on the task which is to be done. Incapacitation can also be
affected by alcohol intoxication, and by various medical conditions; these have
not been adequately studied in combination to derive usable guidance. The NIST
recommendation to users was derive a hypothetical incapacitation level
(EC50) by reducing the LC50 values by a suitable margin,
say 2- to 4-fold.
As a small sidelight, while the values of EC50 will
be expected normally to be several-fold lower than the corresponding
LC50 values, occasionally the opposite is seen. During the early
1980s when the so-called USF toxicity test was being evaluated, many strongly
lethal gas mixtures were documented to have unexpected large EC50's
(the test used mice and measured EC50 levels only). These turned out
not to be measurement errors, but systematic problem formulation errors. The
animals which showed the surprisingly high EC50 values were, in fact,
the "walking dead." They were able to perform the tasks required of them in the
EC50 testing procedure while they were already mortally
injured.
By inspecting the list, one can readily see that CO is not
greatly toxic and that there are many more gases found in fires which are
notably more toxic. The reason why CO is considered the primary agent is simply
due to its copious generation by all fires. The importance of any toxic gas
species to a particular fire must reflect both its toxicity and its actual
concentration in that particular fire. This is the fractional effective
dose concept and algorithms are available for using it. Such data cannot be
tabulated in a handbook fashion, however, since the concentrations are
completely specific to the fire in question.
It may be noted from the references that most of the data are
from the 1980s and earlier. This can largely be explained by the fact that major
fire toxicity research groups at NIST, the Southwest Research Institute,
Hungtingdon, and other institutes were closed or dispersed around the start of
the 1990s. This was largely due to 'a job well-done,' but budgetary
considerations were also an issue.
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Miscellaneous caveats
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| The data assembled here refer only to acute exposures. Thus, they are
pertinent to civilians encountering an unwanted fire. A fire fighter, by
contrast, may be exposed to fire gases on a recurring basis. A number of
research studies have been conducted in this area, but they have not yielded any
similar table to this one for chronic exposure effects.
Burn and thermal exposure injuries have been extensively studied, but there
is little data on combinations of thermal and toxic gas injuries. Some
arithmetic scaling laws have been proposed, but there is no satisfactory
validation of them. At the moment, the situation is viewed non-interactive. In
fire modeling, it is common to compute thermal and toxic exposures and to
declare as governing the first one where limit values are reached.
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Table of primary fire gas toxicities
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| Formula |
Gas |
Assumed LC50 for man (ppmv) 5 min |
Assumed LC50 for man (ppmv) 30 min |
Reference data (species, minutes) h=man; r=rat; m=mouse; p=primate; EC=conc. for effect; LC0=conc. at which first lethal effects are observed |
|
CO2 |
carbon dioxide |
>150,000 |
>150,000 |
[1] LC(r,30) =470,000 |
|
C2H4O |
acetaldehyde |
-- |
20,000 |
[2] LC(m,240)=1500 LC0(r,240)=4000 LC(ham,240)=17,000
[3] LC(r,30)=20,000 LC(r,240)=16,000 |
|
C2H4O2 |
acetic acid |
-- |
11,000 |
[2] LC(m,60)=5620 |
|
NH3 |
ammonia |
20,000 |
9,000 |
[4] EC(m,5)=20,000 EC(m,30)=4400
[5] EC(r,5)=10,000 EC(r,30)=4000 |
|
HCl |
hydrogen chloride |
16,000 |
3,700 |
[6] r,p
[7] LC(r,5)=40,989 |
|
CO |
carbon monoxide |
-- |
3,000 |
[1] LC(r,30)=4600
[8] LC(h,30) 3000 |
|
HBr |
hydrogen bromide |
-- |
3,000 |
[2] LC(m,60)=814 LC(r,60)=2858 |
|
NO |
nitric oxide |
10,000 |
2,500 |
[3] 1/5 as toxic as NO2 LC(h,1) 15,000 |
|
COS |
carbonyl sulfide |
-- |
2,000 |
[2] LC0(var.,3590)=10001400 |
|
H2S |
hydrogen sulfide |
-- |
2,000 |
[2] LC(m,60)=673 LC0(h,30)=600 LC0(mam,5)=800
[8] LC(h,30) 2000 |
|
HF |
hydrogen fluoride |
10,000 |
2,000 |
[2] LC(gpg,15)=4327 LC(p,60)=1774 LC0(h,30)=50 LC(m,60)=456
LC(r,60)=1276
[7] LC(r,5)=18,200
[8] LC(gpg,2)=300 LC(m,5)=6247 LC(r,5)=18,200 |
|
C3H4N |
acrylonitrile |
-- |
2,000 |
[2] LC(gpg,240)=576 LC(r,240)=500 |
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COF2 |
carbonyl fluoride |
|
750 |
[3] LC(r,60)=360 |
|
NO2 |
nitrogen dioxide |
5000 |
500 |
[4] EC(m,5)=2500 EC(m,30)=700
[5] EC(r,5)=5000 EC(r,30)=300
[7] LC(m,5)=831 LC(r,5)=1880 |
|
C3H5O |
acrolein |
750 |
300 |
[2] LC(m,360)=66 LC0(p,10)=153
[9] LC(p,5) 505 to 1025 |
|
CH2O |
formaldehyde |
-- |
250 |
[2] LC0(r,240)=250
[8] LC(r,30)=250 LC(r,240)=830(??)
[3] LC(cat,480)=700 LC(m,120)=700 |
|
SO2 |
sulfur dioxide |
500 |
-- |
[2] rodents poor; LC0(m,300)=6000
[8] LC(var.,5) 600 to 800 |
|
HCN |
hydrogen cyanide |
280 |
135 |
[10] LC(r,5)=570 LC(r,30)=110
[7] LC(r,5)=503 LC(m,5)=323
[8] LC(h,30)=135 LC(h,5) 280 |
|
C9H6O2N2 |
toluene diisocyanate |
-- |
100 |
[2] LC(gpg,240)=13 LC(rbt,180)=1500 LC(r,360)=600 LC(m,240)=10
[8] LC(m,r,rbt,gpg,240)=9.7 to 13.9 |
|
COCl2 |
phosgene |
50 |
90 |
[2] rec. 50 ppm short exp.
[11] LC(h,30) 90 |
|
C4F8 |
perfluoroisobutylene |
28 |
6 |
[2] LC(r,10)=17 LC(r,5)=28
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References
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| [1] Levin, B. C., Paabo, M., Gurman, J. L., Harris, S. E., and Braun, E.,
Toxicological Interactions Between Carbon Monoxide and Carbon Dioxide,
Toxicology 47, 135-164 (1987).
[2] Sax, N.I., Dangerous Properties of Industrial Materials, Van
Nostrand Reinhold, New York (1984).
[3] American Conference of Governmental Industrial Hygienists, Inc.,
Documentation of the Threshold Limit Values, ACGIH, Cincinnati
(1980).
[4] Sakurai, T., Toxic Gas Test by the Several Pure and the Mixture Gas, in
the Third Expert Meeting of the Canada-Japan-United States Trilateral
Cooperative Study on Fire Gas Toxicity, Ottawa (1984). Published as NBS report
NBSIR 88-3753 (1988).
[5] Nishimaru, Y., Study on Evaluation of Toxicity of Gas Using Pure Gas, pp.
613-628 in Proc. of the 7th Panel Meeting of the U.J.N.R. Panel on
Fire Research and Safety (NBSIR 85-3118), N. H. Jason and K. Davis, eds., [U.S.]
Nat. Bur. Stand. (1985).
[6] Hartzell, G. E., et al., Intoxication of Rats by Carbon
Monoxide in the Presence of an Irritant, J. Fire Sciences
3, 263-279 (1985).
[7] Higgins, E.A., Fiorica, V., Thomas, A.A., and Davis, H.V., Acute Toxicity
of Brief Exposure to HF, HC , NO2, and HCN with and without CO,
Fire Technology 8, 120-130 (1972).
[8] Kimmerle, G., Aspects and Methodology for the Evaluation of Toxicological
Parameters during Fire Exposure, JFF/Combustion Toxicology
1, 4-51 (1974).
[9] Kaplan, H. L., et al., Combustion Gases in Postcrash Aircraft Fires
(DOT/FAA/CT-84/16), Federal Aviation Administration, Atlantic City (1984).
[10] Levin, B. C., et al., Effects of Exposure to Single or
Multiple Combinations of the Predominant Toxic Gases and Low Oxygen Atmospheres
Produced in Fires, Fundamental and Applied Toxicology 9, 236-250
(1987).
[11] Clayton, G.D., and Clayton, F.E., eds., Patty's Industrial Hygiene
and Toxicology, vols. 2a-2c, Wiley-Interscience, New York
(1982).
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This article © Copyright 1996, 1997 by Vytenis Babrauskas.
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