«•— 1-
HBi
.101
•'—*"«,-.,
-------
AIR POLLUTION ASPECTS
OF
ALDEHYDES
Prepared for the
National Air Pollution Control Administration
Consumer Protection & Environmental Health Service
Department of Health, Education, and Welfare
(Contract No. PH-22-68-25)
Compiled by Quade H. Stahl, Ph.D,
Litton Systems, Inc.
Environmental Systems Division
7300 Pearl Street
Bethesda, Maryland 20014
September 1969
-------
FOREWORD
As the concern for air quality grows/ so does the con-
cern over the less ubiquitous but potentially harmful contami-
nants that are in our atmosphere. Thirty such pollutants have
been identified, and available information has been summarized
in a series of reports describing their sources, distribution,
effects, and control technology for their abatement.
A total of 27 reports have been prepared covering the
30 pollutants. These reports were developed under contract
for the National Air Pollution Control Administration (NAPCA) by
Litton Systems, Inc. The complete listing is as follows:
Aeroallergens (pollens)
Aldehydes (includes acrolein
and formaldehyde)
Ammonia
Arsenic and Its Compounds
Asbestos
Barium and Its Compounds
Beryllium and Its Compounds
Biological Aerosols
(microorganisms)
Boron and Its Compounds
Cadmium and Its Compounds
Chlorine Gas
Chromium and Its Compounds
(includes chromic acid)
Ethylene
Hydrochloric Acid
Hydrogen Sulfide
Iron and Its Compounds
Manganese and Its Compounds
Mercury and Its Compounds
Nickel and Its Compounds
Odorous Compounds
Organic Carcinogens
Pesticides
Phosphorus and Its Compounds
Radioactive Substances
Selenium and Its Compounds
Vanadium and Its Compounds
Zinc and Its Compounds
These reports represent current state-of-the-art
literature reviews supplemented by discussions with selected
knowledgeable individuals both within and outside the Federal
Government. They do not however presume to be a synthesis of
available information but rather a summary without an attempt
to interpret or reconcile conflicting data. The reports are
-------
necessarily limited in their discussion of health effects for
some pollutants to descriptions of occupational health expo-
sures and animal laboratory studies since only a few epidemio-
logic studies were available.
Initially these reports were generally intended as
internal documents within NAPCA to provide a basis for sound
decision-making on program guidance for future research
activities and to allow ranking of future activities relating
to the development of criteria and control technology docu-
ments. However, it is apparent that these reports may also
be of significant value to many others in air pollution control,
such as State or local air pollution control officials, as a
library of information on which to base informed decisions on
pollutants to be controlled in their geographic areas. Addi-
tionally, these reports may stimulate scientific investigators
to pursue research in needed areas. They also provide for the
interested citizen readily available information about a given
pollutant. Therefore, they are being given wide distribution
with the assumption that they will be used with full knowledge
of their value and limitations.
This series of reports was compiled and prepared by the
Litton personnel listed below:
Ralph J. Sullivan
Quade R. Stahl, Ph.D.
Norman L. Durocher
Yanis C. Athanassiadis
Sydney Miner
Harold Finkelstein, Ph.D.
Douglas A. Olsen, Ph0D.
James L. Haynes
-------
The NAPCA project officer for the contract was Ronald C.
Campbell, assisted by Dr. Emanuel Landau and Gerald Chapman.
Appreciation is expressed to the many individuals both
outside and within NAPCA who provided information and reviewed
draft copies of these reports. Appreciation is also expressed
to the NAPCA Office of Technical Information and Publications
for their support in providing a significant portion of the
technical literature.
-------
ABSTRACT
The principal effect of low concentrations of
aldehydes on humans and animals is primary irritation of the
mucous membranes of the eyes, upper respiratory tract, and skin,
Animal studies indicate that high concentrations can injure
the lungs and other organs of the body. Aldehydes, particu-
larly formaldehyde, may contribute to eye irritation and
unpleasant odors that are common annoyances in polluted
atmospheres. Aldehydes, either directly or indirectly, may
also cause injury to plants.
Aldehyde emissions result from incomplete combustion
of hydrocarbons and other organic materials. The major
emission source appears to be vehicle exhaust, but significant
amounts may be produced from incineration of wastes and burn-
ing of fuels (natural gas, fuel oil, and coal). In addition,
significant amounts of atmospheric aldehydes can result from
photochemical reactions between reactive hydrocarbons and
nitrogen oxides. Moreover, aldehydes can react photochemically
to produce other products, including ozone, peroxides, and
peroxyacetyl nitrate compounds. Local sources of aldehydes
may include manufacturing of chemicals and other industrial
processes that result in the pyrolysis of organic compounds in
air or oxygen.
-------
Reported emission data from various sources have
been compiled for aldehydes in general and for formaldehyde
and acrolein. Initial ambient air measurements of aliphatic
aldehydes by the National Air Sampling Network in 1967 indicate
that the average concentrations for several cities range from
3 to 79 ng/m3.
Control of aldehyde emissions is being studied along
with current hydrocarbon (organic) control programs.
However, the use of certain combustion control techniques, such
as catalytic afterburners, may cause an increase in the amount
of aldehydes emitted.
No information has been found on the economic costs
of aldehyde air pollution or on the costs of its abatement.
Numerous analytical methods for determining "aldehydes,"
formaldehyde, and acrolein have been reported. Satisfactory
colorimetrie methods are available.
Two aldehydes—formaldehyde and acrolein—are of
particular interest in the study of air pollution and have
been given special attention in this report.
-------
CONTENTS
FOREWORD
ABSTRACT
1. INTRODUCTION 1
2. EFFECTS 4
2.1 Effects on Humans 4
2.1.1 Physiological Effects 4
2.1.1.1 Formaldehyde 5
2.1.1.2 Acrolein 9
2.1.2 Annoyance Effects . H
2.1.2.1 Odor 11
2.1.2.2 Eye Irritation 12
2.2 Effects on Animals 14
2.2.1 Commercial and Domestic Animals ... 14
2.2.2 Experimental Animals .... .... 15
2.2.2.1 Formaldehyde 15
2.2.2.2 Acrolein 17
2.2.2.3 Synergistic Effects 19
^.j Effects on Plants 21
2.3.1 Formaldehyde 23
2.3.2 Acrolein 24
2.4 Effects on Materials 24
2.5 Environmental Air Standards 24
3. SOURCES 27
3.1 Natural Occurrence 27
3.2 Production Sources 29
3.2.1 Formaldehyde Manufacture 29
3.2.2 Acrolein Manufacture ... 31
3.3 Product Sources 33
3.3.1 Formaldehyde Products 34
3.3.2 Acrolein Products 37
3.4 Other Sources 38
3.4.1 Atmospheric Photochemical Reactions . 38
3.4.1.1 Photochemical Formation of
Aldehydes 39
3.4.1.2 Products from Photooxidation
of Aldehydes 40
j.4.2 Mobile Combustion Sources 41
3.4.2.1 Automobiles 42
3.4.2.2 Diesel Vehicles 43
3.4.2.3 Aircraft. ... 43
3.4.3 Stationary Combustion Sources .... 44
3.4.3.1 Combustion of Coal 44
-------
CONTENTS (Continued)
3.4.3.2 Fuel Oil Combustion 45
3.4.3.3 Natural Gas Combustion ... 45
3.4.3.4 Incinerator Emissions .... 46
3.4.3.5 Emissions from Petroleum
Refineries 47
3.4.4 Noncombustion Sources 47
3.4.4.1 Thermal Decomposition .... 48
3.4.4.2 Drying or Baking Ovens ... 48
3.5 Environmental Air Concentrations 50
4. ABATEMENT 53
5. ECONOMICS 54
«>. METHODS OP ANALYSIS 55
6.1 Sampling Methods 55
6.2 Qualitative Methods 56
6.3 Quantitative Methods 56
6.3.1 Aldehydes 56
6.3.2 Formaldehyde 60
6.3.3 Aero le in 61
7. SUMMARY AND CONCLUSIONS 63
REFERENCES
APPENDIX
-------
LIST OF TABLES
1. Reported Sensory Responses of Man to Formaldehyde
Vapors
2. Reported Sensory Responses of Man to Acrolein
Vapors •
3. Reported Correlation Between Aldehyde Concentration
and Odor Intensity in Diesel Exhaust 13
4. Survival Time of Mice Exposed to Formaldehyde and
Acrolein in Presence of Aerosols 20
5. Eight-Hour Day Threshold Limit Values, American
Conference of Governmental Industrial Hygienists,
1967 25
6. Ambient Air Quality Standards ..... 26
7. Summary of Emissions of Aldehydes, 1963 28
8. Concentrations of Aldehydes in Atmosphere at El Monte
and Huntington Park, Calif 52
y. Summary of Qualitative Colorimetric Determination
Methods 57
10. Properties, Toxicity, and Uses of Some Aldehydes . . 89
11. Toxicity of Aldehydes to Animals via Inhalation . .
12. Reported Aldehyde Emission Data
13. U.S. Production of Formaldehyde, 1958-68 107
14. Principal U.S. Manufacturers of Acrolein and Formal-
dehyde 108
15. Uses of Formaldehyde in the United States, 1964. . . 109
16. Yields of Aldehydes via Photochemical Oxidation of
Hydrocarbon-Nitrogen Oxide Mixtures .
17. Reported Aldehyde Emissions from Automobile Engines 111
18. Reported Aldehyde Emissions from Diesel Engines . . 114
19. Reported Aldehyde Emissions from Commercial
Aircraft 119
-------
LIST OF TABLES (Continued)
20. Reported Aldehyde Emissions from Combustion of Coal . 121
21. Reported Aldehyde Emissions from Combustion of Fuel
Oil 122
22. Reported Aldehyde Emissions from Natural Gas
Combustion 124
23. Reported Aldehyde Emissions from Incinerators . . . .125
24. Aldehyde Emissions from Oil Refineries 127
25. Reported Aldehyde Emissions from Various Sources . .128
26. Industrial Oven Effluents 131
27. Concentration of Aldehydes in the Air, 1967 132
28. Concentration of Aldehydes in the Air, 1958-67 . . . 134
29. Concentration of Aldehydes in the Air, 1951-57 . . .136
30. Concentration of Aldehydes in Metropolitan Areas
by Population, 1958 137
31. Comparison of Methods for the Determination of
Formaldehyde 138
-------
1. INTRODUCTION
Aldehydes* are products of incomplete combustion of
hydrocarbons and other organic materials. They are emitted
into the atmosphere by exhaust from motor vehicles* incin-
eration of wastes, and combustion of fuels (natural gas,
fuel oils* and coal). Furthermore* aldehydes are formed from
the photochemical reactions between nitrogen oxides and
certain hydrocarbons* which are also emitted from the sources
*Aldehydes are organic compounds having a terminal
carbonyl group. The general formula for aldehydes is R-CHO,
where R represents either the hydrogen in the formula for
formaldehyde or a hydrocarbon radical (such as CH3- for
acetaldehyde or CHg^CH- for acrolein). In the aliphatic
series the first two aldehydes, formaldehyde (Gj) and
acetaldehyde (Ca), are gases at room temperature, while
propionaldehyde (C3) through hendecanal (CX1), are liquids.
The lower members of the aliphatic series show a rapid decrease
in water solubility, whereas caproaldehyde (C6) and higher
molecular weight aldehydes have practically no solubility.73
The odors of aldehydes vary considerably. The lower aliphatic
aldehydes (Ci to C7) have pungent, penetrating, unpleasant
odors, while the higher aldehydes (C8 to C14) have generally
pleasant odors and are used in making perfumes. The aldehydes
above C14 have no appreciable odor.?3 Aldehydes with double
bonds (unsaturated), such as acrolein and crotonaldehyde,
tend to have a more penetrating and unpleasant odor than their
corresponding members in the aliphatic series. The aromatic
aldehydes generally have pleasing odors and are used in the
perfume and food-flavoring industries.73 Physical properties
of aldehydes are given in Table 10 in the Appendix.
Aldehydes are very reactive compounds. They can
easily undergo either reduction or oxidation reactions, as
well as addition reactions (including self-polymerization)
with many types of compounds. Detailed descriptions of these
reactions can be found in most organic chemistry textbooks or
encyclopedias.
-------
mentioned above. Thus* the ambient air is continually being
polluted by aldehydes from emission sources and from atmos-
pheric photochemical reactions. Moreover, aldehydes them-
selves can undergo photochemical reactions yielding oxidants
(including ozone, peroxides, and peroxyacyl nitrate compounds)
and carbon monoxide among the major products.
At low concentrations the principal effect of alde-
hydes on both humans and animals is irritation of the eyes
and upper respiratory tract. This is particularly true for
the lower molecular weight aldehydes. The unsaturated alde-
hydes are several times more toxic than the saturated aldehydes.
In addition, aldehydes have been involved in plant
damage. In some cases, the damage appears to be a result
of oxidants produced by the photochemical reaction of
aldehydes.
In the air pollution field major interest has been
shown in two specific aldehydes—formaldehyde and acrolein.
This is partly due to their effects on humans and to the
fact that their concentrations are generally higher than
those of other aldehydes present in the atmosphere. In
addition, some reports indicate that formaldehyde and
possibly acrolein may contribute to the odor and the eye
irritation commonly experienced in polluted atmospheres.
Thus, in addition to discussions of aldehydes in general.
-------
special attention has been given to formaldehyde and
acrolein in this report.*
* Aldehyde concentration data in this report are
calculated as formaldehyde. When necessary, conversion of
reported concentration data to ug/m3 was made by using the
following factors: for aldehydes and formaldehyde, 1.200
= 1 ppm; for acrolein, 2,500 ug/m3 = 1 ppm.
-------
2. EFFECTS
Despite the wide use of aldehydes and the consequent
potential of aldehydes as air pollutants, comprehensive
studies are not available as to their effect on humans, ani-
mals, plants, and materials. Particularly lacking are long-
term studies with low concentrations of aldehydes. Much of
the available information on toxicity of aldehydes pertains
to the effects from single, acute exposures on animals.
^.1 Effects on Humans
2.1.1 Physiological Effects
The principal effect on humans of aldehyde vapors
appears to be primary irritation of the eyes, respiratory
tract, and skin.52'70 The unsaturated (olefinic) and the
halogenated aldehydes generally cause more noticeable
irritation, than do the saturated aldehydes. Aromatic and
heterocyclic aldehydes generally cause less irritation than
saturated aldehydes. Furthermore, the irritant effect
decreases with increasing molecular weight within a given
aldehyde series. The toxicity of aldehydes appears to
correspond with their irritant properties, although there are
many exceptions. The toxicity of aldehydes generally decreases
70 182
as the chain length increases. ' However, the addition
of a double bond greatly increases the toxicity of aldehydes.
The lower, water-soluble aldehydes act chiefly on the eyes
and upper respiratory tract, while the higher, less soluble
aldehydes tend to penetrate more deeply into the respiratory
I fiQ
tract and may affect the lungs. °
-------
All aldehydes possess anesthetic properties.70'168
However, an anesthetic effect, observed mainly in animal
experiments, is usually obscured by the more prominent
irritant action on the eyes and upper respiratory tract.
Moreover, the quantities of aldehydes that are generally
tolerable by inhalation are so rapidly metabolized that no
anesthetic symptoms are observable. The degree of anesthetic
activity decreases with an increase in molecular weight of
aliphatic aldehydes.184
Sensitization can occur by cutaneous contact with
liquid solutions of aldehydes, but direct sensitization to
the vapor of aldehydes is rare.
In general, definite cumulative organic damage to
tissues, other than that related to primary irritation or
sensitization, is not commonly found.70 The fact that
aldehydes are readily metabolized in the body^ probably
accounts for the lacX of a cumulative-type damage.
Table 10 in the Appendix lists some of the toxic
effects of aldehydes on humans. Additional information on
particular aldehydes can be found in the review by Fassett.70
2.1.1.1 Formaldehyde
The principal effect of formaldehyde vapors on humans
appears to be irritation of the mucous membranes of the eyes,
nose, and other portions of the upper respiratory tract.47'70
76,83,133,168 vapors may also cause skin irritation. Symptoms
that have been observed from nonfatal exposures to formaldehyde
-------
include lacrimation, sneezing, coughing, dyspnea, a feeling
of suffocation, rapid pulse, headache, weakness, fluctuations
in body temperature, and, in sensitive persons, a dermatitis.
Inhalation of high concentrations can cause laryngitis,
bronchitis, and bronchopneumonia. Reported responses of
man to formaldehyde are summarized in Table 1.
Several reports indicate that irritation of the eyes
and upper respiratory tract can first be detected at approxi-
mately j.,200 ng/m3 (1 ppm) or below.38'127'132'154 According
to Fassett,70 no discomfort is noted until 2,400 to 3,600
p,g/m3 (2 to 3 ppm), when a very mild tingling sensation may
be detected in the eyes, nose, and posterior pharynx. At
4,800 to 6,000 iag/m3 (4 to 5 ppm), the discomfort increases
rapidly, and mild lacrimation may appear in some people.
People generally cannot tolerate this concentration for more
than 10 to 30 minutes. Concentrations of 12,000 ng/m3 (10 ppm)
cause profuse lacrimation in all people and can be endured for
only a few minutes. In the concentration range of 12,000 to
24,000 jig/m3 (10 to 20 ppm), breathing becomes difficult,
coughing occurs, and irritation extends to the trachea. Upon
removal from this exposure, lacrimation subsides promptly,
but the nose and respiratory irritation may persist for an
hour or more. The concentration at which serious inflammation
of the bronchi and upper respiratory tract would occur is not
known, but it has been estimated that exposure to 60,000 to
-------
TABLE 1
REPORTED SENSORY RESPONSES OF MAN TO FORMALDEHYDE VAPORS
Concentration
( uq/m3 )
12
70
80
98
156-540
300-6,000
600
1,000
1,080-1,920
1,200
2,400-3,600
4,800-6,000
6,000
12,000
24,000
24,000
24,000
60,000-120,000
Exposure
Time Response
Eye irritation threshold
Odor threshold
Chronaximetric response
threshold
Cortical reflex
threshold
Irritant threshold
Irritant threshold
Odor threshold
Slight irritation
Irritant threshold
Odor threshold
8 hr Tolerable; mild irrita-
tion of eyes, nose, and
posterior pharynx
10-30 min Intolerable to most
people; mild lacrima-
tion; very unpleasant
Throat irritation
threshold
few min Profuse lacrimation
15-30 sec Lacrimation
30 sec Irritation of nose and
throat
1-2 min Sneezing
5-10 min May cause very serious
Ref .
172
127,128
127,128
127,128
38
154
195
127
132
70
70
70
210
70
33
33
33
70
damage
-------
8
120,000 ug/m3 (50 to 100 ppm) for 5 to 10 minutes might
cause serious damage. (See Section /.2.2.1 for a discus-
sion of the effects of high concentrations of formaldehyde
on experimental animals.)
Repeated exposures to formaldehyde vapors may result
in chronic irritation of the eyes, nose, and other portions
of the upper respiratory tract.47' 16® Inflammation of the
eyelids may also result from repeated exposures.
Dermatitis and skin sensitization from cutaneous
exposures to formaldehyde solutions and related derivatives
are well documented. According to Fassett, skin sensitiza-
tion from exposure to formaldehyde vapors is rare; furthermore,
no cases of authentic pulmonary sensitization have occurred.
However, persons who have already developed an eczematous
skin sensitization may have a skin reaction on exposure to
formaldehyde vapors.
Melekhina127'128 conducted studies to determine
sensory threshold responses to formaldehyde. The odor
threshold concentration for very sensitive people was 70
ug/m3. Reflex reactions threshold concentration for optical
chronaxy tests was 80 |jg/m3 , and for dark adaptation the
concentration was 98 ug/m3 . Concentrations up to 2,500 jag/m3
produced no detectable changes in the frequency and rhythm
of respiration.
-------
All fatal poisonings reported from formaldehyde have
resulted from ingestion.
2.1.1.2 Acrolein
Acrolein vapors are highly toxic to humans. The vapor
is extremely irritating to the eyes and respiratory tract.70'
80,143,168,185 symptoms that have been reported from inhalation
of acrolein include lacrimation, swelling of the eyelids,
shortness of breath, pharyngitis, laryngitis, bronchitis,
oppression in the chest, and somnolence.48'133,143 ,phe
reported responses of man to acrolein vapors are summarized
in Table 2.
Concentrations of acrolein as low as 625 |ig/m3 (0.25
ppm) can cause moderate irritation of the eyes and nose in 5
185 919
minutes. »•"«•" Slight nasal irritation occurs from a 1-
minute exposure to acrolein at 2,500 (jg/m3 (1 ppm). After
2 to 3 minutes at this concentration, eye irritation is quite
noticeable and after 4 to 5 minutes it becomes practically
intolerable. Sim and Pattle182 reported that lacrimation
occurred within 20 seconds at 1,880 [ag/m3 (0.805 ppm) and
within 5 seconds at 2,800 ng/m3 (1.22 ppm). Smith185
reported that moderate eye and nasal irritation is produced
from a 5-second exposure at 13,750 iag/m3 (5.5 ppm), while a
20-second exposure is painful. Exposures to 54,500 ug/m3
(21.8 ppm) are immediately intolerable to humans.185
Pulmonary edema may develop from exposures to high concentra-
tions of acrolein.48 Sax168 reports that inhalation
-------
10
TABLE 2
REPORTED SENSORY RESPONSES OF MAN TO ACROLEIN VAPORS
Concentration
(ua/mM
525
600
625
800
1,500
x,750
j.,880
2,500
2,500
2,500
2,500
2,800
4,500
4,500
13,750
13,750
13,750
54,500
375,000
Exposure
Time
5 min
20 sec
1 min
2-3 min
2-3 min
4-5 min
5 sec
1 min
3-4 min
5 sec
20 sec
60 sec
Immediate
10 min
Response
Odor threshold
Dark adaptation response threshold
Moderate irritation
Odor threshold
Respiratory rhythm and wave
amplitude response threshold
Chronaximetric response threshold
Lacrimation
Slight nasal irritation
Slight nasal irritation and
moderate eye irritation
Eye and nose irritation
Moderate nasal irritation;
practically intolerable eye
irritation
Lacrimation
Slight eye irritation
Profuse lacrimation; practically
intolerable
Slight odor; moderate eye and
nasal irritation
Painful eye and nasal
irritation
Marked lacrimation; vapor
practically intolerable
Intolerable
Lethal
Ref.
Ill
141
185
141
141
141
182
185
185
80
185
182
185
185
185
185
185
185
143
-------
11
of acrolein may cause an asthmatic reaction.
No cases of chronic toxicity are known.48'70'185
However, repeated contact with the skin may produce chronic
irritation and a dermatitis. Acrolein is reported to be a
weak sensitizer.168
Plotnikova141 studied some of the sensory responses
of man to acrolein. The threshold concentration of acrolein
on the reflex action and optical chronaxy was determined to
be 1,750 ug/ra3, while i,500 ug/m3 was the threshold for
respiratory rhythm and wave amplitude. Threshold response
to dark adaptation was established at 600 ug/m3, which was
below the measured odor threshold of 800 ug/m3 .
There was one reported case of fatal poisoning from
acrolein inhalation of 375,000 ug/ra3 (150 ppm) for 10
minutes.143
2.1.2 Annoyance Effects
Several studies have been made to determine the
contribution of aldehydes to the odor and eye irritation
resulting from air pollution. Although present studies
indicate that these effects are not entirely the result of
atmospheric aldehydes, the aldehydes seem to contribute in
some degree to these effects.
2.1.2.1 Odor
The reported odor threshold values for formaldehyde
and acrolein appear to be in the range of 70 to 1,200
-------
12
(0.06 to 0.2 ppra) and 525 to 800 ug/m3 (0.2 to 0.3 ppm),
respectively (see Sections 2.1.1.1 and 2.1.1.2). Three
65 155 216
separate studies ' on odors in diesel exhaust (see
Table 3) indicate that the odor threshold for aldehydes
(measured by modified Schiff reagents) is in the range of
600 to 14,400 iig/m3 (0.5 to 12 ppm). Although these studies
show a correlation between odor intensity and aldehyde
concentration, the relationships differ somewhat. Linnell
and Scott ^ found that the concentration of formaldehyde
and acrolein in diesel exhaust, when diluted to the odor
threshold, was too low to be a major contributing factor to
the odor of diesel exhaust. In contrast, Fracchia et -1
measured the concentration of certain aldehydes in automobile
exhaust and concluded that the odor might be due to an
additive effect of all the concentrations of these aldehydes.
2.1.2.2 Eve Irritation
"Eye irritation is by far the most noticeable obnoxious
symptom of smog as far as the public is concerned," according
84
to Hamming and MacPhee .
In 1960, Renzetti and Bryan1 found a good correlation
between intensity of eye irritation and the concentration of
total aldehydes (measured by bisulfite method) and of formal-
dehyde in the Los Angeles smog. Renzetti and Schuck148 studied
the photooxidation of hydrocarbons and found that formaldehyde
and acrolein accounted for the majority of the eye irritation
-------
13
TABLE 3
REPORTED CORRELATION BETWEEN ALDEHYDE CONCENTRATION
AND ODOR INTENSITY IN DIESEL EXHAUST
Aldehyde Concentration
(ua/m3 )*
Odor
Unit
0
1
2
3
4
5
Odor Intensity
No odor
Very faint
Faint
Easily noticeable
Strong
Very strong
Reference
155
624
6,600
57,600
504,000
Reference
65
1,140
4,800
21,600
96,000
Reference
216
8,520
14,400
25,200
42,000
72,000
120,000
*Calculated as formaldehyde.
-------
14
produced by photochemical products. However, the concentra-
tion of these aldehydes needed to produce eye irritation in
these experiments was well in excess of measured atmospheric
concentrations. Several other compounds were thought to
explain eye irritation,172'193 but most have not proved to
be of major importance, with the exception of peroxyacyl
172
nitrate compounds. Recently, Schuck et al. found in
simulated atmosphere experiments that the linear correlation
between eye irritation intensity and formaldehyde concentra-
tion does not hold at concentrations below 360 ug/m3 (O.j
ppm). In fact, concentrations of 60 ng/m3 (0.05 ppm) and
600 ug/m3 (0.5 ppm) produce the same irritation intensity in
most of the people exposed. Furthermore, it was found that
the human eye can detect and respond to as little as 12 ug/m3
(0.01 ppm) formaldehyde. Thus, these authors predicted that
the concentration of formaldehyde and pexoxyacetyl nitrate
in polluted air can account for most of the detected eye
irritation.
Recent data of interest in relation to these
findings are the ambient air concentrations in the Los Angeles
area: for aliphatic aldehydes, 196.8 ug/m3: for formaldehyde,
163.2 u9/ro3 ? and for acrolein, 27 ug/m3.
2.2 Effects on Animals
2.2.x Commercial and Domestic Animals
Mo cases were found of injury or death of domestic or
commercial animals from environmental exposure to aldehydes.
-------
15
2.2.2 Experimental Animals
The effect of aldehyde vapors on animals is similar to
that found in humans (see discussion in Section 2.1). The
principal effect observed is primary irritation to the mucous
membranes of the eyes and the upper respiratory tract,particu-
larly the nose and throat. Exposure to high concentrations of
aldehydes may cause injury to the lungs as well.
Fassett70 has summarized the reported toxicity data
on exposures of animals to aldehydes; part of his summary
(toxicity from inhalation of aldehydes) is given in Table 11
in the Appendix.
2.2.2.1 Formaldehyde
Studies indicate that high concentrations of formalde-
hyde, besides causing prompt and severe irritation of the eyes
and respiratory tract, may cause injury to the lungs and
1 Q O
other organs. Thus, Skog, exposing rats (in groups of
eight) to high concentrations of formaldehyde (e.g., 960,000
ug/m3 or 800 ppm), found hemorrhages and pulmonary edema and
signs of hypercrinemia and perivascular edema in the liver
and kidneys. Salem and Cullumbine exposed groups of 50
mice, 20 guinea pigs, and 5 rabbits simultaneously to
formaldehyde (19,000 ug/m3) and other aldehydes for periods
up to 10 hours. Autopsy of the animals killed by the vapors
showed expanded edematous and hentorrhagic lungs, fluid in the
pleural and peritoneal cavities, consolidation, distended
alveoli, and ruptured alveolar septa. In addition. Murphy
-------
16
et al.136 found in a. group of eight male rats that the
alkaline phosphatase activity in the liver was increased
after the rats inhaled 4,200 iag/m3 (35 ppm) formaldehyde
for 18 hours.
The response of lung functions has been studied
~e ")(i f\*) 1 '5'5
with normal and tracheotomized animals. ' ' The
responses to formaldehyde inhalations were an increase in
flow resistance and in tidal volume and a decrease in the
respiratory rate. According to Amdur,^5 the responses of
tracheotomized animals were similar, but much greater, than
those observed with the normal animals. The author
attributed this result to the fact that the tracheal cannula
prevents removal of the formaldehyde by the nasal and upper
airway passages. In contrast, Davis et al.6^ recently
reported that in comparison with normal animals, tracheotomized
animals showed an increase in respiration rate accompanied by
a decrease in tidal volume. These findings were ascribed to
the fact that the receptors for the responses observed in the
normal animals are in the upper airway (i.e., larynx and
above), which was blocked in the tracheotomized animals.
Exposure of the larynx and the nasopharynx of the tracheotomized
animals elicited the responses shown by normal animals.
Investigators have demonstrated that formaldehyde can
cause cessation of ciliary activity.55'59'101 In one study,59
low doses of formaldehyde, such as 3,600 ug/m3 (3ppm) for
-------
17
50 seconds or 600 \ig/m3 (0.5 ppm) for 150 seconds, caused
cessation of ciliary beat in anesthetized, tracheotomized
rats.
79
In a Russian study, Gofmekler investigated the
effects of continuous exposure of pregnant rats to concen-
trations of formaldehyde of 12 and 1,000 ng/m3. Two groups
of 12 female rats were exposed, each group to one concentra-
tion. Another group of 12 pregnant rats was used for con-
trol. The two groups of test rats were also exposed to
formaldehyde vapors 10 to 15 days prior to impregnation.
Significant results were subsequently found. The mean
duration of pregnancy was prolonged by 14 to 15 percent from
exposure to both concentrations. A regular decrease in the
number of fetuses per female was found with the higher con-
centration of formaldehyde. Furthermore, the exposure to
formaldehyde appeared to cause an increase in the weight of
the thymus, heart, kidneys, and adrenals in the offspring.
This effect, the author concluded, was apparently a com-
pensatory reaction to unfavorable environmental conditions.
On the other hand, the lungs and liver, the organs which
are directly affected by formaldehyde, showed a decrease in
weight following the aldehyde exposure.
2.2.2.2 Acrolein
Acrolein, as most other unsaturated aldehydes, is
much more irritating and toxic than the aliphatic aldehydes.
-------
18
Thus, the lethal concentration (LDgo) of acrolein for rats
is approximately one-third that for formaldehyde and approxi-
mately 0.005 that for propionaldehyde, its aliphatic counter-
part.
The damage to the lungs and other organs described
156 183
for formaldehyde applies equally to acrolein. J'J Murphy
et al.136 reported an increase in alkaline phosphatase activity
in the liver from exposure to 3,250 ug/m3 (2.x ppm) acrolein
for 40 hours.
Murphy et al. exposed guinea pigs (group of 10) to
1,500 ug/m3 (0.6 ppm) acrolein to determine respiratory
responses. The results indicate that acrolein vapors increase
the flow resistance and tidal volume, while decreasing the
respiration rate. The magnitude of these effects increases
with high concentrations of acrolein. The effects were found
to be reversible upon return to clean air. Results from the
administration of certain drugs indicated that the acrolein-
induced increase in respiratory resistance is probably due to
bronchoconstriction mediated through reflex cholinergic
stimulation.
81
Gusev et al. continually exposed groups of 10 rats
each to 150, 510, and 1,520 ug/m3 of acrolein in air over a
period of several weeks. The rats exposed to the 1,520 ug/m3
concentration for 24 days showed a loss of weight, changes
in conditioned reflex activity, a decrease in cholinesterase
-------
19
activity of whole blood, a fall of ooproporphyrin excretion
in the urine, and an increase in the number of luminescent
leukocytes in the blood. Exposures to 150 ug/m3 acrolein
for 61 days caused only d rise in the number of luminescent
leukocytes in the blood.
Catilina et al.43 exposed rats to 500,000 ug/m3 (200
ppm) acrolein for 10 minutes once a week for 8 weeks. Lung
damage was still observable 6 months after the exposure
period ended.
2.2.2.3 Svnergistic Effects
Several investigators have found that the effects of
aldehydes on animals can be significantly increased in the
presence of an aerosol. LaBelle et al.1^ exposed mice to
constant concentrations of formaldehyde and acrolein (15,000
ug/m3) in the presence and absence of aerosols. Nine differ-
ent substances were used as aerosols, including solids and
liquids. The time for 50 percent survival of the mice
(minimum of 6 mice in 12 groups) was measured. The results
are shown in Table 4. Significant increases in death rates
were found for both formaldehyde and acrolein with some of the
aerosols. These investigators also noted that the active
aerosols increased the pulmonary edema caused by formaldehyde
and acrolein.
OA Oft
Amdur ' investigated the response of guinea pigs
to inhalation of formaldehyde in the presence and absence of
-------
TABLE 4
SURVIVAL TIME OF MICE EXPOSED TO FORMALDEHYDE AND
ACROLEIN IN PRESENCE OF AEROSOLS105
Formaldehyde
Aerosol
Concentration
Aerosol (Size, LI) (ua /liter)
None
Triethylene glycol (1.8)
Ethylene glycol (2.0)
Mineral oil (2.1)
Glycerin (2.0)
Sodium chloride (2.6)
Dicalite (3.3)
Celitec (2.9)
Attapulgus clay (3.3)
Santocel CFe (2.7)
2210
2920
1420
1280
2320
420
360
960
310
STsoa
(min) Significance0
147
71 ++
168 0
72 ++
114 ++
114 +
118 +
102 ++
157 0
145 0
Aerosol
Concentration
(uq/liter)
380
500
240
220
390
70
60
160
50
Aero lain
ST5oa
(min}. Significance*1
87
73
106
69
94
71
91
99
78
65
0
0
+
0
+
0
0
0
+
jTime for 50 percent survival of mice.
"0 = no significance, + = significant, ++ = highly significant.
Cpiatomaceous earth.
Highly absorptive clay.
Commercial silica gel.
to
o
-------
21
sodium chloride aerosols (approximately 0.04 n* in diameter).
The concentration of formaldehyde varied from approximately
84 to 56,400 ug/m3 (0.07 to 47 ppm), with and without the
presence of 10,000 |jig/m3 of sodium chloride aerosol.
Statistically significant increases in "respiratory work" as
a result of the aerosol were found when the formaldehyde
concentration was 360 ng/m3 (0.3 ppm) or above. Moreover,
compared with the pure vapor, the formaldehyde-aerosol
mixture delayed the recovery after discontinuation of the
exposure. Further experiments indicated that as the amount
of aerosol was increased from 0 to 3,000 |jg/m3 , 10,000 pg/m3 ,
and 30,000 jig/m3 . an increase in flow resistance was also
observed. The authors concluded that sodium chloride aerosol/
which is itself inert, can cause the response to formaldehyde
to be potentiated (the higher the concentration of aerosol,
the greater the effect), and also prolong the response,
compared with the response to the pure vapor.
2.3 Effects on Plants
There is very little information available on the
effects of atmospheric aldehydes on plants. Moreover* most
of the data has been derived from studies of product mixtures
obtained from the irradiation of aldehydes, hydrocarbons, or
hydrocarbon-nitrogen oxide mixtures. While these resulting
- micron.
-------
22
mixtures contain some aldehydes, they also contain other
compounds, some unidentified, which may be phytotoxicants.
Thus, in these studies, the role of aldehydes in plant damage
may well be obscured by the presence of other compounds.
Brennan et al.39 reported in 1964 that the damage to
foliage of Snowstorm petunias grown in a greenhouse was
related to the high aldehyde content of the ambient air.
Leaf damage occurred when the aldehyde content exceeded 240
ug/ta3 (0.2 ppm) for 2 hours or 360 ug/m3 (0.3 ppm) for 1
hour. Injury, which appeared within a day or two after the expo-
sure, was characterized by symptoms of necrotic banding
of the upper leaf surface and glazing of the lower leaf
surface. Although the damage was similar to that found with
photochemically produced pollutants or "oxidant" type phyto-
toxicants in the atmosphere,* the level of "oxidants" in the
atmosphere was below normal on the days that the aldehyde
content was sufficient to cause plant damage.
However, these data do not prove that aldehydes
directly attacked the plant tissue. Other explanations might
be that there is a synergistic effect with a high concentration
*A similar type of plant damage was shown by Taylor
et al.^OO from polluted ambient air in California and from
irradiated mixtures of nitrogen dioxide and hexene. Stephens
et al.3-93 induced similar damage to petunias with irradiated
mixtures of (a) automobile exhaust, (b) olefins and nitrogen
oxide, (c) olefin and ozone, and (d) aldehydes.
-------
23
of aldehydes or that aldehydes react photochemically to yield
phytotoxicant products that may be undetected by the methods
of analysis used. Indeed, several studies have shown that
irradiation of certain aldehydes will cause formation of
phytotoxicant compounds other than the original aldehydes. °'
23,88,193,199 Stephens et al. 193 found that irradiated alde-
hydes yielded phytotoxicants that caused oxidant-type damage
to petunias and bean plants. Hindawi and Altshuller®8
irradiated propionaldehyde and nitrogen oxide mixtures and
concluded that irradiation of propionaldehyde in air will
definitely cause appreciable plant damage to tobacco wrapper,
pinto bean leaves at various stages of development, and
petunias. In contrast, irradiated formaldehyde-nitrogen
oxide mixtures caused no observable plant damage.2-*'88
Recent studies indicate that irradiation of most aldehyde-
nitrogen oxide mixtures produces PAN*-type products, among
other compounds. (See further discussion under Atmospheric
Photochemical Reactions, Section 3.4.1).
2.3.1 Formaldehyde
Haagen-Smit et al.**2 found no evidence of damage to
alfalfa after 2 hours' exposure to 2,400 ng/m3 (2 ppm) of
formaldehyde, but did find atypical alfalfa damage after 5
hours at 8,400 jag/m3 (7 ppm) of formaldehyde. Hindawi and
*PAN: peroxyacetyl nitrates.
-------
24
Altshuller88 found no damage to pinto beans, tobacco wrapper,
and petunias from exposure to mixtures of formaldehyde-
nitrogen oxide that had been irradiated for 4 hours.
2.3.2 Acrolein
Data indicate that acrolein may be a phytotoxicant.
Haagen-Smit et al.8^ reported oxidant-type damage to alfalfa
grown in a greenhouse and exposed to 250 ug/m3 (0.1 ppm) of
acrolein for Q hours. Similar damage, along with atypical
leaf damage, was observed with spinach, endive, and beets
exposed to acrolein vapor concentrations of 3,000 ug/m3 (1.2
ppm) for 4.5 hours or 1,500 ug/m3 (0.6 ppm) for 3 hours.
Darley et al.61 found oxidant-type damage to 14-day-old pinto
bean plants exposed to approximately 5,000 ug/m3 (2 ppm) of
acrolein for four successive 35-minute periods. However,
Hindawi and Altshuller88 observed that 2,500 \jg/m3 (1 ppm) of
acrolein, produced from the irradiation of 1,3-butadiene-
nitrogen oxide mixture, caused no damage to petunia, pinto
bean, or tobacco wrapper.
2.4 Effects on Materials
There are no data available to indicate the effect of
atmospheric concentration of aldehydes on materials.
2.5 Environmental Air Standards
The American Conference of Governmental Industrial
Hygienists has adopted 8-hour threshold limit values for
occupational exposure to several aldehydes (see Table 5).204
-------
25
TABLE 5
EIGHT-HOUR DAY THRESHOLD LIMIT VALUES, AMERICAN
CONFERENCE OF GOVERNMENTAL INDUSTRIAL
HYGIENISTS, 1967204
Aldehyde
Acetaldehyde
Aero le in
Chloroacetaldehyde
Crotonaldehyde
Fo rmaldehyde
Furfural (sfcin)b
ppm
200
0.1
la
2
5
5
uq/m3
360,000
250
3,000a
t>,000
0,000
20,000
aThis is a "ceiling" value, which should not
be exceeded at any time.
"Cutaneous exposure can significantly contri-
bute to harmful effects.
In 1968, the American Industrial Hygiene Association52
recommended ambient air quality values for certain aldehydes
to prevent sensory irritation of any form, as follows:
Formaldehyde 120 ug/m3 0.1 ppm
Aerolein 25 ug/m3 0.01 ppm
Total aldehydes 240 |ag/m3 0.2 ppm
(as formaldehyde)
West Germany and Russia have established ambient air
quality standards for acetaldehyde, acrolein, formaldehyde,
and furfural.197 These standards are summarized in Table 6.
-------
TABLE 6
AMBIENT AIR QUALITY STANDARDS197
.
Aldehyde
i
Acetaldehyde
Acrolein
Formaldehyde
Furfural
Country
West Germany
Russia
West Germany
Russia
West Germany
Russia
Czechoslovakia
West Germany
Russia
Basic
uQ/m3
4,000
10
100
36
14.4
18
80
50
Standard
Averaging
Time
30 min
30 min
24 hr
30 min
24 hr
24 hr
30 min
24 hr
Permissible Standard3
uq/ma
12,000
10
25
300
84
42
60
250
50
Averaging
Time
30 min
20 min
30 min
20 min
30 min
20 min
30 min
30 min
20 min
aNot more than once every 4 hours,
to
-------
27
3. 3. SOURCES
Aldehydes that pollute the atmosphere result from
two main sources: (1) incomplete combustion of organic com-
pounds and (2) atmospheric photochemical reactions involving
mainly hydrocarbons and nitrogen oxides. Thus, the highest
concentrations of atmospheric aldehydes are expected to be
in the populated areas where combustion of fuels and motor-
vehicle exhaust emit significant amounts of aldehydes and
compounds that form aldehydes through photooxidation.
Emission data reported for certain towns, cities,
and counties of the United States are summarized in Table 12
in the Appendix. The highest reported value for a city is
1,139 tons of aldehydes per year for the city of St. Louis.
Emission of aldehydes from various sources as reported by
certain cities and counties is shown in Table 7. These data
indicate that emission of aldehydes to the atmosphere is
primarily due to automobile exhaust, followed by burning of
wastes and combustion of fuel.
3.1 Natural Occurrence
Natural sources of aldehydes do not appear to be
important contributors to air pollution. Acetaldehyde is
found in apples and as a by-product of alcoholic fermentation
processes.73 Other lower aliphatic aldehydes are not found
in significant quantities in natural products. Olefin and
aromatic aldehydes are present in some of the essential oils
-------
TABLE 7. SUMMARY OF EMISSIONS OF ALDEHYDES, 1963
(tons/year)
97
Source
Road vehicles (gasoline)
(diesel)
Railroads and vessels
Fuel use (residential)
(industrial)
Fossil fuel steam electric plants
Other fuel use
Municipal incineration
Residential incineration
Industrial and commercial
incineration
Open burning (dumps)
(on -site)
Aircraft (jet piston, turboprop)
Total
•
•u •
35
IM
o -
.§
£S
I9
14
10
°
b
26
89
.
c£
O
GO -
C) 4J
« o
^O ^J
SA^A
b
9
11
10
b
6
110
16
206
H
H
•H
fl *
U&
j|
146
3
75
36
20
1
2
7
371
150
811
H
H
H
§%
>i
•rl C
•o g
£8
134
2
23
34
135
8
3
2
53
140
534
H
H
H
«
8S
£8
b°
12
2
1:
«
t
30
9
63
Total
1,508
60
196
358
207
16
28
39
25
86
546
580
28
3,695
Percent
40.8
1.6
5.3
9.7
5.6
0.4
0.8
1.0
0.7
2.3
15.3
15.7
0»8
100.0
aExcluding city of St. Louis
"Less than 0.5 tons/year.
GO
-------
29
in fruits and plants. These include citronellal, in rose
oil; citralf in oil of lemongrass; bensaldehyde, in oil of
bitter almonds; cinnamaldehyde, in oil of cinnamon; anisalde-
hyde, in anise; and vanillin, in the vanilla bean.
j.2 Production Sources
Aldehydes are commercially manufactured by various
processes, depending on the particular aldehyde. In general,
they are prepared via oxidation reactions of hydrocarbons,
hydroformylation of alkenes, dehydrogenation of alcohols,
and addition reactions between aldehydes and other compounds.
The commercial manufacture of formaldehyde and aerolein
is discussed in the following sections. Formaldehyde is a
very important chemical and is produced in the largest quan-
tities by far of all the aldehydes.
3.2.1 Formaldehyde Manufacture
Formaldehyde production in the United States has
generally shown a steady growth since manufacture was first
begun.210'211 The United States production figures for
formaldehyde for 1958 through 1968 (see Table 13 , Appendix)
illustrate this general growth to over 4 billion pounds in
1968. The data also indicate that most of the formaldehyde
is consumed by the manufacturer. A list of the major manu-
facturers of aldehydes in the United States is given in
Table 14 in the Appendix.
-------
30
Industrial plants producing formaldehyde may be
local sources of atmospheric pollution. Levaggi and
Peldstein113 found that approximately 3,000,000 ng/mj
(2,580 ppm) of formaldehyde and 290,000 lag/m*1 (162 ppm) of
acetaldehyde were in the effluent from a formaldehyde plant.
Most formaldehyde is manufactured from oxidation of
methanol. H However, a small amount (14 percent of total
production in the United States in 1960) is produced by the
partial oxidation of gaseous hydrocarbons.
The methanol process involves passing a methanol
vapor air mixture over a catalyst. Some manufacturers use
a silver or copper catalyst at 450° to 650°C, while others
use an iron-molybdenum oxide catalyst at 300° to 400°C. With
the metallic catalyst, the alcohol-air mixture is rich in
methanol and yields a methanol solution of formaldehyde.
With the oxide as catalyst, an alcohol-lean mixture is used
which produces a substantially methanol-free solution.
Generally, two main reactions can occur—dehydrogenation
and oxidation, which are represented by Equations 1 and 2,
respectively:
cat.
CH3OH . > HCHO + Ha (Equation 1)
cat.
CH3OH + JjOa > HCHO + HaO (Equation 2)
-------
31
In the metal-catalyzed process, the main reaction is
dehydrogenation (Equation 1), with little if any formalde-
hyde formed via oxidation. The oxide-catalyzed process, in
contrast, proceeds mainly via the oxidation reaction. Product
vapors are passed from the converter to a series of contra-
current water scrubbers to cool the gases and dissolve the
formaldehyde. Excess methanol is removed by fractional
distillation.
In the hydrocarbon oxidation process, the reaction
can occur with or without a catalyst in the presence of air
or oxygen. The main disadvantage of this process is the
formation of numerous oxidation products, including other
aldehydes, alcohols, and organic acids. Thus, the recovery
of the important products requires specific and complicated
separation procedures. In fact, this process is used
primarily for manufacture of other products, with formalde-
hyde recovered as a by-product.
3.2.2 Acrolein Manufacture
Aerolein is produced by two manufacturers in the
United States (see Table 14 in the Appendix). Data on the
production and sales of acrolein are not available. The
commercial methods of preparation are discussed below. No
data were found on the emission of acrolein or other alde-
hydes from these processes.
-------
32
Aerolein is generally commercially produced either
by the direct oxidation of propylene or by the cross-
so 185
condensation of acetaldehyde with formaldehyde. '
In the oxidation of propylene the hydrocarbon vapor
is passed over a catalyst at 300° to 350°C in the presence
of air or oxygen. The catalysts are generally metallic
oxides such as cuprous oxide, oxide mixtures of bismuth
and molybdenum, oxide mixtures of cobalt and molybdenum,
oxides of antimony plus other metals/ and various other
combinations. The general reaction is given in Equation 3.
cat.
(Equation 3)
The principal by-products are water and carbon dioxide from
the undesired complete oxidation of the propylene. Excess
propylene is used to avoid complete combustion. Other
products that are formed in minor amounts include formalde-
hyde, acetaldehyde, propionaldehyde, and acetone. The
formed acrolein passes along with the other by-product gases
through a cooler and then through an aqueous scrubber.
Fractional distillation is used to separate the acrolein
from the water and other water-soluble products.
The second method, cross-condensation of acetaldehyde
with formaldehyde, is also a vapor phase reaction in which
the two reactants are passed over a catalyst at 300° to 350°C,
-------
33
The catalysts used are generally associated with promotion
of dehydration reactions and include lithium phosphate on
activated alumina and sodium silicate on silica gel. The
reaction is represented in Equation 4.
cat.
+ CHaCHO > CHa=CH-CHD + HjjO (Equation 4)
Acetaldehyde is most frequently used in excess since formal-
dehyde is the more difficult component to recover of the
two unreacted components. The by-products of the reaction
include crotonaldehyde, methanol, propionaldehyde, carbon
dioxide, carbon monoxide, hydrogen, and tar. The tar remains
on the catalyst and thus decreases the efficiency of the
conversion. The catalyst is reactivated with air and steam
at 400°C. The effluent gas containing acrolein leaves the
converter, passes through a cooler, and subsequently through
a water scrubber to remove the nonoondensables. The acrolein
is separated from the aqueous mixture by fractional distilla-
tion.
3.3 Product Sources
Aldehydes have a wide variety of uses in numerous
industries, such as the chemical, rubber, tanning, paper,
perfume, and food industries. The major use is as an inter-
mediate in the synthesis of organic compounds, including
alcohols, carboxylic acids, dyes, and medicinals. Uses of
-------
34
formaldehyde and aerolein are discussed in further detail in
the following sections.
3.3.x Formaldehyde Products
Formaldehyde is commercially marketed chiefly in the
form of an aqueous solution containing 36 to 50 percent by
weight of formaldehyde. Dilution is necessary since pure
formaldehyde will polymerize readily on standing. Formalde-
hyde is also sold in other forms, including paraformaldehyde
(polymeric hydrate), trioxane (a cyclic polymer), hexameth-
ylenetetramine, and various alcoholic solutions.
Its chemical and physical properties, as well as its
low price, have made formaldehyde a widely used chemical.
Formaldehyde has immense utility as illustrated by its use
as a resinifying agent, synthetic agent, hardening agent,
stiffening agent, tanning agent, disinfectant, bactericide,
and preservative.2 "f2 The consumption of formaldehyde by
uses is shown in Table 15 in the Appendix. Synthetic resins
account for over half of the consumption.
Formaldehyde has numerous applications in a variety
of fields; these include:210'211
Resins. In addition to the resins listed in Table 15
in the Appendix, formaldehyde is used to make resins from
aniline, aromatic hydrocarbons, ketones, urethane, and other
compounds. These resins find widespread applications in the
electrical, automotive, building, chemical*and petroleum
industries.
-------
35
Agricultural Uses. The urea-formaldehyde concen-
trates are used for preparing slow-releasing nitrogen
fertilizers and for preventing plant diseases by destruction
or control of microorganisms.
Analysis. Small quantities of formaldehyde are used
in the qualitative and quantitative analysis of chemical
compounds.
Catalysts. Formaldehyde and its derivatives are used
as catalysts and in the preparation of catalysts for the
manufacture of hydrocarbons, alcohols, and resins.
Concrete. Plaster, and Related Products. Formalde-
hyde is employed as one of the addition agents to make con-
crete, plaster, and related products impermeable to liquids
and grease.
Cosmetics. It is useful as an antiperspirant and as
an antiseptic in dentifrices, mouthwashes, and germicidal
and detergent soaps.
Deodorants. It is used as an air deodorant in public
places and the home and for deodorizing numerous products.
Disinfectants and Fumigants. Formaldehyde can destroy
bacteria, fungi, molds, and yeasts and is therefore used in
disinfectant applications.
Dyes and Dvehouse Chemicals. It is employed in the
synthesis of dyes, stripping agents, and various specialty
chemicals of the dye industry.
-------
36
Embalming Fluids and Preservatives. It is an ingre-
dient in embalming fluids and in preservatives for waxes,
polishes, adhesives, fats, oils, starches, ferns, flowers,
textiles, anatomical specimens, etc.
Explosives. Formaldehyde is used in synthesis of
explosives such as pentaerythritol tetranitrate.
Fireproofina Material. It is an ingredient in
manufacturing several fireproofing compositions applied to
fabrics.
Fuels. Numerous solid fuels contain formaldehyde
polymers.
Hydrocarbon Products. Formaldehyde is used in oil-
well operations, in refining of hydrocarbons, and for
stabilization in gasoline fuels.
Insecticides. Certain insecticidal solutions for
killing flies, mosquitoes, moths, and other insects contain
formaldehyde.
Leather. Formaldehyde is used as tanning agent of
white washable leather, hides, and hairs; also used as a
preservative and disinfectant of leather products.
Medicinals. It is used in synthesis of numerous
medicinal preparations, including vitamins and vaccines, and
as a detoxifying agent.
Metals. Formaldehyde and its derivatives are used
as pickling addition agents, for control of corrosion
-------
37
of metals by hydrogen sulfide, in preparation of mirrors, in
electroplating, and as metal sequestering agents.
Paper. Formaldehyde is used for improving the wet-
strength, water-resistance, shrink-resistance, and grease-
resistance of paper, coated papers, and paper products.
Photographic Materials. It is used to harden and
insolubilize film and in reducing silver salts.
Proteins. It is employed in production of protein
fibers.
Rubber. It is used in vulcanization and modifica-
tion of natural and synthetic rubber, and in the synthesis
of rubber accelerators and antioxidants.
Solvents and Plasticizers. Formaldehyde is used in
synthesis of polyhydroxy compounds, formals, and other
methylene derivatives for solvents and plasticizers.
Starch. It is used to modify properties of starches.
Surface-Active Agents. It is employed in synthesis
of several surface-active compounds.
Textiles. It is used to make natural and synthetic
fibers crease-resistant, crush-proof, flame-resistant, shrink-
proof, etc.
Wood. Formaldehyde is an ingredient in wood preserv-
atives .
3.3.2 Acrolein Products
Acrolein is consumed in large quantities in the
-------
38
manufacture of several derivatives* including 1,2,6-hexane-
triol, hydroxy adipaldehyde, and glutaraldehyde.80 One of
the largest single uses of acrolein is in the synthesis of
methionine, an amino acid used to fortify chicken and dog
foods. Acrolein is also an ingredient in synthetic resins.
3.4 Other Sources
Significant amounts of atmospheric aldehydes,
particularly formaldehyde, are a result of photooxidation
of unsaturated hydrocarbon pollutants. In addition, some
important contributing sources of aldehyde air pollution
are the burning or heating of organic compounds. These
sources include mobile combustion (automobiles, diesel
vehicles, and aircraft), stationary combustion (units that
burn coal, oil, natural gas, or waste materials), and non-
combustion sources (e.g., chemical oxidation processes, and
drying and baking in ovens).
3.4.1 Atmospheric Photochemical Reactions
Atmospheric photochemical reactions may be major
contributors to aldehyde air pollution in some areas. The
importance of this source does, of course, depend upon such
factors as concentration of atmospheric reactants and amount
of sunlight. Furthermore, the presence of atmospheric
aldehydes may also contribute to production of other photo-
chemical pollutants by (1) photochemical reactions of the
aldehydes to form new products, and (2) interaction of an
-------
39
aldehyde or its photochemical products with other atmos-
pheric pollutants to yield additional products. Thus, the
photochemical aspects of air pollution are quite complicated
and not yet thoroughly understood. Reviews on the subject
have been prepared by Stern,195 Altshuller and Bufalini,
Wayne,213 and Leighton.110
3.4.J..J. Photochemical Formation of Aldehydes
Aldehydes are major products in the photooxidation
of reactive hydrocarbons. This includes such systems as
olefin-nitrogen oxides,12'23'169,170,181,191,192,193,205
aromatic-nitrogen oxides,23'103'169'192 olefin-ozone,11'13'175
olef in -molecular oxygen, 7,157,158 an
-------
40
air sample taken in Los Angeles, Calif., between 7 and 8 a.m.
contained approximately 120 ug/m3 (0.1 ppm) of formaldehyde.
Upon irradiating this sample in sunlight for several hours,
the formaldehyde increased over threefold to 420 ug/m3 (0.35
ppm). The final concentration of "aldehydes" (calculated as
formaldehyde) was approximately 600 ug/m3 (0.5 ppm). In a
similar experiment, Sigsby et al.180 found that irradiation
of diluted automobile exhaust (which contained approximately
120 iig/m3 (0.1 ppm) of aldehydes) caused the aldehyde level
to increase by a factor of five. Formaldehyde accounted
for approximately 60 percent of the total aldehydes in the
irradiated mixture.
3.4.1.2 Products from Photooxidation of Aldehydes
The concentration of aldehydes in photochemical
reactions appears to be important in determining the products.
Thus, while peroxyacids and diacetyl peroxides are the major
products from photooxidation of high concentrations of
aldehydes,42,123,124,125 these products have not been produced
from photooxidation of atmospheric concentrations of aldehydes,
In general, the products of photooxidation at low
partial pressures of aldehydes in the presence of nitrogen
oxides are carbon monoxide, lower aldehydes, nitrates, and
oxidants.8'10'14'15'18'145'146 The oxidants produced include
ozone and allcyl hydroperoxide (hydrogen peroxide in the case
of formaldehyde). In addition, peroxyacyl nitrate compounds
-------
41
are found in small amounts. Hence, the products in
some cases are reactive species that contribute to eye
irritation and plant damage.
Furthermore f the photochemical products from alde-
hydes can react with olefins and aromatic hydrocarbons.19
Although the rates of these reactions are less than the
photochemical olefin-nitrogen oxide reactions* the rates are
significant When considering photochemical atmospheric
reactions.
The reactivity of aldehydes appears to be slightly
greater than that of ethylene, similar to the reactivity of
substituted aromatic hydrocarbons/ but less than that of
olefins and diolefins.8'23
j.4.2 Mobile Combustion Sources
A major source of aldehyde pollution may be the
emissions from motor vehicles. Conlee et al. determined
the contribution of motor vehicle emissions to air pollution
by comparing the concentration of pollutants at the entrance
and exit of the Sumner Tunnel, a one-way, 1.1-mile-long tunnel
in Boston, Mass. Their results indicate that approximately
83 percent of the atmospheric aldehydes in that area were
due to motor vehicles. Furthermore, motor vehicles emit
reactive hydrocarbons that can undergo photochemical oxida-
tion to produce additional amounts of aldehydes (see discus-
sion in Section 3.4.1).
-------
42
3.4*2.1
The automobile is probably a major source of aldehyde
air pollution. Estimations of aldehyde emission rates vary
considerably, from 3.4 to 18.7 lb/1,000 gal of gasoline.45'50'
93,119,217 The reported emission data are summarized in Table
17 in the Appendix. Prom these data, it appears that the
concentration of aldehydes emitted varies during the different
engine modes in the following order: deceleration » acceler-
ation > cruise > idle. Other important factors in the amount
of aldehydes emitted are type of gasoline and type of engine.
The condition of the engine may also be a very important factor.19'
Sigsby et al.180 reported that aldehydes are present
in diluted automobile exhaust to the extent of approximately
120 (Jig/m3 (0.1 ppm) at atmospheric levels. Other studies on
the irradiation of automobile exhaust indicate that approxi-
mately 10 to 20 percent of the atmospheric aldehydes may be
due to the exhaust.10'109
Formaldehyde is the major aldehyde in automobile
exhaust, accounting for 50 to 70 percent of the total alde-
hydes. 77,95,96 Acrolein accounts for approximately 3 to 10
percent (on mole basis) of the total aldehydes. ^2» 77
Several other aldehydes have been identified in auto-
mobile exhaust; these include acetaldehyde,31'68'77 propionalde-
hyde.6'31'68 n-butyraldehyde , 68 iso-butyraldehyde,6'68 tri-
methylacetaldehyde,6 iso-valeraldehyde,77 crotonaldehyde,6'31' 77
and benzaldehyde.32' 77
-------
43
3.4.2.2 Diesel Vehicles
Reported aldehyde emissions from diesel engines are
given in Table 18 in the Appendix. The estimated emission
rates are given as 10 to 16 lb/1,000 gal of fuel.45'93 This
is similar to that reported for automobiles (see Section
3.4.2.1). From these data it appears that the aldehyde emis-
sions are usually lower at part loads and higher at no load
or full load. Reckner et al.3*46 determined the amount of
formaldehyde* aerolein, and aldehydes in emissions from diesel
engines. These data indicate that formaldehyde generally
constitutes 50 to 70 percent of the total aldehydes, and
acrolein 5 to 10 percent of them.
3.4.2.3 Aircraft
Studies reporting aldehyde emissions from aircraft
are summarized in Table 19 in the Appendix. The emission
rate ranges from 0.2 to 2 pounds of aldehydes per hour for
a four-engine jet aircraft; the total emissions per flight
(including arrival and departure) range from 0.3 to over 4
pounds of aldehydes.78,117,122,197 The ^^GiB*! aldehyde
present in the jet-engine emissions was formaldehyde, generally
accounting for greater than 60 percent of the total aldehydes.117
It was estimated that 0.1 tons of aldehydes from aircraft were
emitted per day in Los Angeles County in 1960. This figure
was predicted to increase sixfold by 1965.78
-------
44
3.4.3 Stationary Combustion Sources
Stationary combustion sources contribute to aldehyde
air pollution. Although they are considered to be minor
sources of aldehydes compared with automobile emissions and
atmospheric photochemical reactions, these stationary com-
bustion sources may contribute significantly if the equip-
ment is not operating correctly or the control methods are
inadequate. 9 Only the principal sources for which emission
data were available are discussed in the following sections.
3.4.3.1 Combustion of Coal
Aldehydes and formaldehyde have been found in small
amounts from sources that burn coal.56'122'140'187 Wbhlers
and Bell218 estimated the amount of aldehydes produced from
the combustion of bituminous coal at 2 Ib/ton of coal.
Emission of aldehydes from anthracite coal was assumed to be
1 Ib/ton of coal, based on the more complete combustion from
higher flame temperatures. More recent data give the value
at less than 0.01 Ib/ton of coal.122'140
Formaldehyde emissions from different types of coal-
burning power plants range from 0.06 to 0.25 ppm before the
ash collector and 0.07 to 0.12 ppm after the ash collector.56'187
Data of emissions from combustion of coal are
summarized in Table 20 in the Appendix.
-------
45
3.4.3.2 Fuel Oil Combustion
Emission rates of aldehydes from sources using fuel
oil range from nearly 0 to 14.8 Ib/gal of oil, according to
Hovey, Risman, and Cunnan.93 The average for distillate oil
(density of 7 Ib/gal) was given as 2 pounds of aldehydes per
1,000 gallons of oil, while emission from residual oil (density
of 8 Ib/gal), which is used by the large consumers, was
estimated at half that amount. Chass and George summarized
the results from various industrial and commercial oil-fired
equipment. The data ranged from 3 to 52 ppm aldehydes in
stack effluent or 0.02 to 1.8 pounds of aldehydes per hour.
These results and others are summarized in Table 21 in the
Appendix. The aldehyde emission rates vary with the type,
size, and condition of the equipment. In fact, it is common
to judge the operating condition of oil-fired equipment by the
odor produced by aldehydes in the effluent gas.
3.4.3.3 Natural Gas Combustion
A summary of reported aldehyde emission data from
the burning of natural gas in various home appliances and
industrial equipment is shown in Table 22 in the Appendix.
The aldehyde emissions vary from 2 to 49 ppm, depending on
the source. Hovey, Risman, and Cunnan93 reported a range of
0 to 60 pounds of aldehydes per million cubic feet of gas
consumed, with an average of 10 lb/106 ft3 of gas. They gave
the average for propane and butane as 26 and 34 lb/106 ft3
-------
46
of gas, respectively. Weisburd,214 on the other hand,
reported aldehyde emissions from power plants as approximately
1 lb/106 ft3 (0.02 lb/l,000 Ib of gas) and for industrial
use as 2 lb/106 ft3 (0.1 lb/1,000 Ib of gas). Vandaveer and
Segeler208 found formaldehyde and acetaldehyde in the emissions
from burning natural, coXe-oven, or butane gas. The aldehyde
emissions may be much greater when no afterburners are used
or when the correct air-to-fuel ratio is not maintained.
3.4.3.4 Incinerator Emissions
Table 23 in the Appendix summarizes the data on alde-
hyde emissions from different types of incinerators. Reported
aldehyde emissions from multistage municipal incinerators
average about 1.x Ib/ton of refuse (49 ppm).93'122'197 How-
ever, emissions from small domestic incinerators vary from
0.x to nearly 16 Ib/ton of refuse (1 to 67 ppm).93'197 Back-
yard incinerators have been reported to have emissions as
high as 29 Ib/ton (760 ppm).197 Formaldehyde and acrolein
are probably the principal aldehydes in the emissions.98
Stenburg et al. reported that formaldehyde content in the
emissions increases with (1) a decrease in gas temperature,
(2) an increase in excess air, and (3) a decrease in refuse
feed rate.
Alpiser7 reported that aldehyde emission from a
small-batch automobile incinerator (primary chamber holds
one automobile) was 3 ppm with an afterburner or 16 ppm
without an afterburner.
-------
47
As a comparison, open-dump burning has been estimated
at 3.0 to 4.0 pounds of aldehydes per ton of refuse,93'122
or 6,000 pounds per day per million people.64 Aldehyde
emissions from open burning of paper and garden trimmings
were estimated at 2.1 and 5.7 Ib/ton of material, respectively.93
3.4.3.5 Emissions from Petroleum Refineries
Petroleum refineries are local sources of aldehyde
emissions. A Los Angeles survey29 indicated that catalytic
cracking units emit 19 pounds of aldehydes per 1,000 barrels
of feed (3 to 130 ppm) in the fluid unit and 12 lb/1,000 bl
of feed in the thermofor units. Smaller amounts of aldehyde
emissions also originate from the refineries' boilers,
processor heaters, and compressor engines. Total aldehyde
emissions from oil refineries for the Los Angeles area amount
to approximately 2.4 tons/day. A summary of the emission
factors is given in Table 24 in the Appendix.
3.4.4 Noncombustion Sources
When organic compounds are heated in the presence of
air or an oxygen source, aldehydes and other oxygenated hydro-
carbons may be produced. This is particularly true of the
more reactive organic compounds such as olefins and aromatic
compounds. Sources of this type of emission include
industries manufacturing oxygenated organic compounds (e.g.,
aldehydes, alcohols, carboxylic acids) and processes in which
solvents are removed by use of drying or baking ovens. Very
-------
48
little information is available on the aldehyde emissions
from these sources. Some emission data from these sources
can be found in Tables 25 and 26 in the Appendix.
3.4.4.1 Thermal Decomposition
In addition to the industrial sources of aldehydes
via thermal decomposition of organic compounds mentioned
above, the following examples illustrate other sources that
may yield aldehydes in this manner. Babies placed in
incubators following surgery were found to have respiratory
problems caused by formaldehyde that had been formed by
thermal decomposition of exhaled ether when it came in con-
tact with the heating elements of the incubators.1^9 Occu-
pational and community exposure to acrolein may result from
the thermal decomposition of glycerine from fats and oils. *
Henson87 suggested that acrolein is the important cause of
the irritant effects from exposure to vapors from the cooking
of fatty food over intense heat.
3.4.4.2 Drying or Baking Ovens
Processes in which organic solvents are heated may
be local aldehyde emission sources which contribute to the
overall aldehyde air pollution. A major process of this type
is the coating of materials. The coating substance (dissolved
in an organic solvent) is applied to the material, which is
subsequently dried or baked in an oven to remove the solvent.
Examples of operations using such procedures are automobile
-------
49
painting* coating of paper with resins or adhesives, and
application of protective coatings to metals. Brunelle,
Dickinson, and Hamming41 determined the aldehyde, formalde-
hyde, and acrolein content of the effluent gases from
several of these processes (see Table 26, Appendix). The
solvents used included alkanes, aromatics, alcohols, and
ketones. In each case, measurable amounts of aldehydes were
produced with some values over 120,000 jag/m3 (100 ppm)
aldehydes (as formaldehyde). Maximum values for formaldehyde
and acrolein were 62,400 tig/m3 (52 ppm) and 25,000 ng/m3 (10
ppm), respectively. The aldehyde concentration appeared to
be higher in the samples taken after passing through the after-
burner than in the samples taken at the oven before the after-
burner. Similarly, data reported by Daniel son60 showed that
the use of afterburners with paint-baking ovens may increase
the aldehyde concentration up to tenfold, although almost
complete removal of aldehydes is possible in some cases.
Wallach^lZ analyzed the effluents from the baking of
lithograph coatings in which mixtures of aliphatic and
aromatic solvents were used. Total aldehydes ranged from
14,000 to 224,000 ug/m3 (12 to 186 ppm) before passing through
afterburners. Samples taken after the effluent passed through
a high-temperature burner showed both an increase and «
decrease in aldehyde concentration with no apparent pattern or
reason. Samples taken after catalytic combustion treatment
-------
50
showed that aldehyde concentration increased up to 250 percent
after treatment.
3.5 Environmental Air Concentrations
In 1967, the National Air Sampling Network began the
monitoring of aldehydes.126 The data for 1967, the latest
available, are presented in Table 27 (Appendix). The averages ranged
from 3 to 79 ug/ra3 of aldehyde (calculated as formaldehyde)?
the maximum values ranged from 5 to 161 iig/m3 .
Other areas reported aldehyde air concentrations
before establishment of the National Air Sampling Network
program. The data reported from 1951 to 1967 are given in
Tables 28 and 29 in the Appendix. Until the early 1960's,
the analysis method used was the sodium bisulfite method,
which is not specific for aldehydes and is sensitive to some
ketone as well (see discussion in Section 6.3.1).
Table 30 in the Appendix gives the aldehyde concentration
in the air of different metropolitan areas (by population) in 1958
as reported by Wohlers and Bell and cited by Stern.194
Cholak49 reported that the aldehyde (calculated as
formaldehyde) concentrations for the ambient air in several
cities sampled in 1946 to 1951 ranged from 0 to 324 jjig/m3
(0 to 0.27 ppm), with the averages ranging from 48 to 216
ng/roa (0.04 to 0.18 ppm).
It is generally reported that of the aldehydes
present in the atmosphere, 50 percent is accounted for as
-------
51
formaldehyde and 5 percent as acrolein.17'109'147'167
Recent measurements have been made in El Monte and Hun ting ton
Park, Calif., for aliphatic aldehydes, formaldehyde, and
acrolein.174 The data* shown in Table o, are for two high-
oxidant days.
-------
52
TABLE 8
CONCENTRATIONS OF ALDEHYDES IN ATMD SPHERE AT
EL MONTE AND HUNTIN6TON PARK, CALIF.174
Date
1968
10/22
10/23
Time
P.S.T.
0738
0850
0956
1130
1235
1338
1442
0745
0850
1000
1130
1235
1340
1445
Aliphatic
Aldehydes
EL MONTE, CA1
81.6
108.0
88.8
66.0
144.0
177.6
100.8
114.0
92.4
58.8
49.2
51.6
HUNT ING TON PARK,
10/22
10/23
0555
0658
0815
0921
1115
1240
0545
0647
0904
1010
1208
1330
51.6
70.8
96.0
166.8
196.8
105.6
46.8
207.6
146.4
Formal-
dehyde
30.0
42.0
39.6
58.8
106.8
108.0
48.0
57.6
37.2
22.8
33.6
CALIF.
27.6
31.2
68.4
120.0
163.2
97.2
32.4
28.8
91.2
116.4
109.2
60.0
Acrolein
5.0
7.5
7.5
10.0
20.0
20.0
10.0
7.5
10.0
2.5
5.0
12.5
15.0
7.5
7.5
12.5
15.0
27.5
17.5
10.0
7.5
20.0
25.0
20.0
15.0
-------
53
ABATEMENT
Aldehydes are only some of the oxygenated hydro-
carbons that are present in vehicle exhausts, incinerator
effluents, and industrial emissions. Other compounds
classified as oxygenated hydrocarbons are alcohols, ethers,
ketones, carboxylic acids, and organic esters. Control
methods for these oxygenated compounds, as well as for
aldehydes, are considered under the hydrocarbon control
programs. Control methods being currently studied include
more effective combustion methods and the use of direct-
flame and catalytic afterburners.
Although these methods generally decrease the
amount of hydrocarbon emissions, they may actually produce
greater amounts of aldehydes and other oxygenated hydro-
carbons. Evidence for this can be seen from some of the data
on aldehyde emissions from various sources given in Table 25
in the Appendix. In some cases, the amount of aldehydes
increases tenfold by the use of afterburners in drying-
oven processes.
-------
54
ECONOMICS
No information has been found on the economic costs
of aldehyde air pollution or on the costs of its abatement.
Data on the production and consumption of formalde-
hyde and acrolein are presented in Section 3.
-------
55
6. METHODS OF ANALYSIS
There are numerous methods of analysis for aldehydes—
too many to be covered thoroughly in this report. Only
those methods that have been used for or appear applicable to
determining formaldehyde, aerolein, or the "aliphatic"
aldehydes in air samples or emission source samples will be
discussed. Other methods of analysis for aldehydes can be
found in the reviews of Altshuller,9 Sawicki,159 Altshuller
et al.M22 Parr,69 and Reynolds and Irwin.151
6.1 Sampling Methods
Generally, common sampling methods employ bubblers
or impingers containing a reactive reagent. In some cases
the reactive reagent may result in a color product that may
be used in the analysis procedure. Examples of the
commonly used reagents are 3-methyl-2-benzothiazolone hydra-
zone (MBTH),16'17'131'177 sodium bisulfite,63'68'78 and «,
mixture of sodium bisulfite and sodium tetrachloromercurate-
(II)106'221 for "aldehydes"; chromotropic acid17'22'114'177
for formaldehyde; and 4-hexylresorcinol17'177 for acrolein.
These reagents are preferred because they have high collection
efficiencies (generally two bubblers in series yield 95
percent or better collection efficiencies) and produce
fairly stable nonvolatile products, thus avoiding excess loss
of aldehydes via evaporation or formation of undesirable
by-products.
-------
56
In some cases, water is used as the collection
medium,67,77,118 reportedl> with high efficiency.
6.2 Qualitative Methods
The presence of aldehydes can be determined by
infrared spectroscopy. The carbon-hydrogen stretch vibra-
tion of the aldehydic group adsorbs as a doublet in the j.5
to 3.7 p region. Furthermore, the carbonyl of an aldehydic
group has an adsorption band in the 5.7 to 6.0 u region,
which, unlike the carbonyl bands of ketones and carboxylic
acids, disappears when <* chloroform solution is treated with
phosphorus pentachloride.161
Many oolorimetric methods applicable to formaldehyde,
acrolein, and "aldehydes" have been used for spot tests
or detector tube methods. Some of the more common methods
are summarized in Table *•
6.3 Quantitative Methods
fc.3.1 Aldehydes
Recently one method has been used extensively to
determine total water-soluble "aliphatic" aldehydes in
atmospheric sampling.17'34' 35,90,91 since 1967 j^g method
has been used by the National Air Sampling Network of the
National Air Pollution Control Administration126 according to
the procedure described by Morgan et a^..131 This method
was first proposed by Sawicki et. al..167 and refined by
Hauser and Cummins.86'177 The latter method uses 3-methyl-
2-benrothiazolone hydrarone (MBTH), with sulfuric acid added
-------
TABLE 9
SUMMARY OP QUALITATIVE COLORIMETRIC DETERMINATION METHODS
Reagent
Indole
Puchsin (Schiff method)
4-Phenylazo-phenyl-
hydrazine sulfonic acid
2-Hydraz ino-benzothiazole
+ p-nitrobenzenediazonium
fluob orate
2-Hydraz ino-benzothiazole
(HBT)
3-Methyl-2-benzothiazolone
hydrazone (MBTH)
(J-acid) 6-amino-l-
naphthol-3-sulfonic acid
Color
Orange to red
Violet to blue
Red to blue
Blue to green
Blue
Blue
Blue
Limits of Identification in Microa
Aldehydes
~0.05-1
~1-30
0.2-0.4
0.2-200
0.01-3.0
0.1-80
0.01-11
Formaldehyde
0.2
1
0.25
0.2
0.01
0.1
0.03
Acrolein
0.2
0.3
rams
Ref.
28
71
71
71,
163
162
167
164
in
-------
58
to avoid the dilution necessary in the earlier procedures.
The sensitivity is approximately 2.4 ng/m3 (2 ppb), measured
as formaldehyde. Aldehydes react with the MBTH to form a
very stable product, which, upon oxidation with ferric
chloride, produces a blue cationic dye that is measured
at 628 mu. Compounds which interfere with the analysis
include aromatic amines, imino heterocyclics, carbazoles, azo
dyes/ stilbenes, Schiff bases, dinitrohydrazone (DNP) aldehyde
derivatives, and compounds containing the p-hydroxy styryl
group.177 Since most of these compounds are not gaseous or
water soluble, they will not generally interfere in analysis
of atmospheric samples. Formaldehyde reacts in this proce-
dure about 25 percent greater than the other aliphatic
aldehydes and about 300 percent greater than branched-chained
and unsaturated aldehydes. Altshuller and Leng16 have
suggested that a correction factor of 1.25 be used to take
into account the various aldehyde responses to the method.
Most other colorimetric procedures that have been
described in the literature show even larger response to
formaldehyde in comparison with other aldehydes, and there-
fore, should not be used for quantitative determination of
aldehydes.9 Such methods include chromotropic acid, J-acid,
phenyl J-acid, Schiff's reagent, and phenylhydrazine reagent
(Schryver's method).
A continuous monitor method for "aldehydes,"221
based on the method of Lyles .et al.. ,118 is a modified Schiff
procedure using rosaniline and dichlorosulfulomercurate.
-------
59
The sensitivity is reported as 12 ijg/m3 (0.01 ppm), with a
collection efficiency of greater than 90 percent. Nitrogen
dioxide can cause interference in concentrations of U.D ppm
or more and its response to formaldehyde is greater than to
other aldehydes.
Infrared spectroscopy has been used to determine
aldehydes in irradiation chamber studies. ' The carbon-
hydrogen stretch vibration in the range of 3.5 to 3.7 u
was used.
The bisulfite method has been widely used for
147 149
analysis of "aldehydes" in atmospheric samples, '
automobile exhaust, ^7
-------
60
6.3.2 Formaldehyde
The colorimetric method of determining formaldehyde
with chromo tropic acid (l,8-dihydroxynaphthalene-3,6-disul-
fonic acid) has had widespread use. Several variations have
been described in the literature.21' 22,40,147,215
method proposed by Altshuller et al. ' appears to be
simple, rapid, and suitable for the analysis of effluents
and air samples. The sensitivity of this method is approxi-
mately 12 jag/in3 (0.01 ppm).16 Nitrogen dioxide, most
aldehydes and ketones, and straight-chain alcohols do not
interfere significantly.21'215 Aromatic hydrocarbons and
olefins can cause serious interference, but the use of
aqueous sodium bisulfite as the collection medium can reduce
this interference. Furthermore, compounds that are easily
converted via hydrolysis or oxidation to formaldehyde in
strong, warm sulfuric acid may also interfere. Compounds
of this type, which include sugars, formaldehyde polymers,
glyoxal, piperonal, and related compounds, have been dis-
cussed by Sawicki.159 The chromo tropic acid method has been
used in the analysis of air samples,17'21 incinerator
effluents,189'190 automobile exhaust,22 and diesel ex-
haust.36'114'115'146
Many other colorimetric methods have been used or
appear applicable to analysis of air samples. Sawicki
et al..164*166 found that 6-amino-l-naphthol-3-sulfonic acid
-------
61
(J-acid) and 6-anilino-l-naphthol-3-sulfonic acid (phenyl
J-acid) have greater sensitivity than the chromotropic acid.
However, these methods have not been used in analysis of
effluents or air samples. A comparison of these methods and
other spectrometric methods for determining formaldehyde
has been made by Sawicki et. aJU The results are shown in
Table 31 in the Appendix.
A continuous method for determining formaldehyde with
a sensitivity of 12 ug/m3 (0.01 ppm) has been reported.118'221
The method is a modified Schiff method using para-rosaniline
in sodium tetrachloromercurate(II) and sodium bisulfite. This
method has been used for analysis of air samples. Only two
aldehydes, acetaldehyde and propionaldehyde, gave positive
reactions.118
Polarographic methods33,54 mav aiso be applicable to
analysis of air samples, but at present they need further
study.
b.3.3 Aerolein
A highly sensitive spectrophotometric method for
acrolein has been developed by Cohen and Altshuller,^1 who
based their method on a reagent first proposed by Rosenthaler
and Vegezzi.153 Acrolein reacts with 4-hexylresorcinol in
an ethanol-trichloroacetic acid solution to yield a blue-
colored product with an absorption maximum at 605 ma. The
sensitivity is approximately 12.5 ug/m3 (0.005 ppm). The
method appears selective; no significant interferences were
-------
62
found from sulfur dioxide, nitrogen dioxide, ozone, aromatic
compounds, ketones, olefins, and other unsaturated alde-
hydes. ' Slight interferences are found with some
dienes and with malonaldehyde, which appears to form a
similar blue product. This method has been used in analysis
of automobile exhaust,22'51 diesel exhaust,36'114'146 and
atmospheric samples.17'147
Because colorimetric methods using tryptophan '
and phloroglucinol142'207 lack sufficient sensitivity and
have appreciable interferences, they are not useful for
analysis of air samples.51 A J-acid method can be used to
determine acrolein with a sensitivity of 0.01 ug, but
serious interference results with equal or higher amounts
of formaldehyde.166
Polarographic,54 gas chromatographic,68*94*134 and
paper chromatographic methods have been used in the analysis
of acrolein from vehicle exhaust and air samples. However,
these methods have not been generally applied because of the
complexity of the techniques.
-------
63
7. SUMMARY AND CONCLUSIONS
The most characteristic and important effect of
aldehydes—particularly of low molecular weight aldehydes—
for both humans and animals is primary irritation of the
eyes, upper respiratory tract, and skin. The observed
symptoms in humans from inhalation of low concentrations of
aldehydes include lacrimation, coughing, sneezing, headache,
weakness, dyspnea, laryngitis, pharyngitis, bronchitis, and
dermatitis. In most cases, the general and parenteral
toxicities of these aldehydes appear to be related mainly to
these irritant effects. The unsaturated aldehydes are several
times more toxic than the corresponding aliphatic aldehydes.
Also, the toxicity generally decreases with increasing
molecular weight within the unsaturated and aliphatic alde-
hyde series. Sensitization has occurred from contact with
formaldehyde solutions and other aldehydes, but sensitiza-
tion of the pulmonary tract rarely is produced by inhalation
of aldehydes. The anesthetic properties of aldehydes are
generally overshadowed by the stronger irritant effects.
Furthermore, concentrations that can be tolerated via in-
halation can usually be metabolized so rapidly that systemic
symptoms do not occur.
Formaldehyde concentrations as low as 600 ug/m3 have
been shown to cause cessation of the ciliary beat in rats.
Animal experiments have shown that aldehydes can affect the
-------
64
responses of the respiratory system, causing such effects as
an increase in flow resistance and in tidal volume and a
decrease in the respiratory rate. Exposure of rats to 150
Hg/m3 of acrolein for 2 months caused a rise in the number
of luminescent leukocytes in the blood. Exposure of animals
to high concentrations of aldehydes has been shown by several
investigators to produce edema and hemorrhages of the lungs
and fluid in the pleural and peritoneal cavities. In a
Russian study, formaldehyde was found to prolong the mean
duration of pregnancy in rats and decrease the number of
offspring. In addition* the weight of the lungs and liver
of the offspring was less than that of the controls' off-
spring, but other organs exhibited an increase in weight.
Animal experiments also indicate possible synergistic
effects between aldehydes and aerosols. Thus, acrolein and
formaldehyde in the presence of certain inert aerosols
appeared to be more toxic to mice than the pure compounds.
Experiments with guinea pigs showed that formaldehyde with
sodium chloride aerosols produced significant increases in
the "respiratory work" compared with the effect of the pure
vapor.
In addition to the toxic effects* aldehydes may
contribute to the annoyances of odor and eye irritation
caused by polluted air. Aldehyde concentrations have been
shown to correlate with the intensity of odor of diesel
exhaust and the intensity of eye irritation during natural
-------
65
and chemically produced smogs. Data indicate that as little
as 12 ug/m3 of formaldehyde can cause human eye response.
Aldehyde air pollution may result in oxidant-type
damage to plants, although atmospheric photochemically pro-
duced products from the aldehydes may actually cause the
damage rather than direct attacX by aldehydes.
There are no data available to indicate the effect
of aldehyde air pollution on materials.
Vehicle exhaust, particularly from automobiles,
appears to be the major emission source of aldehydes. How-
ever, significant amounts may also be produced from other
combustion sources such as open burning and incineration of
solid waste materials, and the burning of fuels (gas, fuel
oil, coal). Another source of aldehyde emission is the
thermal decomposition of hydrocarbons by pyrolysis in the
presence of air or oxygen. Sources of these emissions
include chemical manufacturing plants and industries that
use drying or baking ovens to remove organic solvents in
such processes as automobile painting and the manufacture
of coated paper and metals.
Air sampling data indicate that plants manufacturing
formaldehyde may be local sources of aldehyde pollution;
over 4 billion pounds of formaldehyde were manufactured in
the United States in 1968. However, the major amount of
aldehyde pollution in some areas of the United States is
-------
66
from the photochemical reaction between nitrogen oxides and
hydrocarbons. Hydrocarbons that yield formaldehyde are
olefins, and to a lesser degree, other aldehydes and aromatic
hydrocarbons. Diolefins produce most of the atmospheric
acrolein. Some data indicate that in certain areas over
two-thirds of the atmospheric aldehydes may have resulted
from photochemical reactions. Of course, the sources that
emit aldehyde pollutants are generally the same as those
emitting hydrocarbons and nitrogen oxides.
In addition, aldehydes themselves may undergo
photochemical reactions. They may produce, at low partial
pressures in the presence of nitrogen oxides, other products
such as carbon monoxide, lower aldehydes, nitrates, and
oxidants. The oxidants produced include ozone, peroxyacyl
nitrates, and alkyl hydroperoxides (hydrogen peroxide in the
case of formaldehyde). No peroxyacids or diacetyl peroxides
are found at low partial pressures of aldehydes.
In 1967 the National Air Sampling Network began to
report data for aliphatic aldehydes. The data for 1967 for
several cities show that the average concentrations of
aldehydes ranged from 3 to 79 ug/m3 and that the maximum
values ranged from 5 to 161 ng/m3. A Los Angeles area
report indicates that the maximum values for two "smog"
days in 1968 were 208 ug/m3 for aliphatic aldehydes, 163
ug/m3 for formaldehyde, and 27 ug/m3 for acrolein. Generally,
-------
67
formaldehyde accounts for 50 percent or more of the total
aldehydes* While acrolein accounts for about 5 percent.
Control of aldehyde emissions is being studied along
with current hydrocarbon (organic) control programs.
However, the use of certain combustion control techniques
such as catalytic afterburners, may cause an increase in the
amount of aldehydes emitted.
No information has been found on the economic costs
of aldehyde air pollution or on the costs of its abatement.
Colorimetric determination methods/ satisfactory for
analysis of air samples/ have been reported for aliphatic
aldehydes (sensitivity approximately 2.4 ug/m3 or 2 ppb),
formaldehyde (sensitivity approximately 12 ug/m3 or 10 ppb),
and acrolein (sensitivity approximately 12.5 ug/m3 or 5 ppb).
A continuous method for determining "aldehydes" based on a
modified Schiff method with a sensitivity of 12 ug/ra3 (0.01
ppm) has been reported.
Based on the material presented in this report/
further studies are suggested in the following areas:
(1) Identification of all the aldehydes present in
the atmosphere and their approximate concentration ranges.
Determination of the concentration/ geographical distribu-
tion/ and time distribution of the aldehydes that appear
to have important effects.
-------
68
(2) Expansion of research concerning the effects on
humans, animals, and plants of long-term exposure to low
concentrations of each of the aldehydes present in the
atmosphere, particularly formaldehyde and the unsaturated
aldehydes.
(3) Expansion of research on the hydrocarbon control
methods for simultaneous reduction of aldehyde emissions.
(4) Determination of the contribution of atmospheric
photochemical reactions in aldehyde air pollution, particularly
in metropolitan areas.
-------
69
1. Air Pollution/Chemung County (Supplement to Comprehensive
Area Survey Report Number One (Greater Elmira), New York
State Air Pollution Control Board, Albany (1965).
2. Air Pollution in Erie County (Comprehensive Area Survey
Report Number Two), New York State Air Pollution Control
Board, Albany (1963).
3. Air Pollution/The Mid-Hudson: Greene, Ulster, Rockland,
Columbia, Dutchess (Comprehensive Area Survey Report
Number Six), New York State Air Pollution Control Board,
Albany (Feb. 1966).
4. Air Pollution in Westchester, New York State Air Pollution
Control Board, Albany (Dec. 1965).
5. Alkire, G. J. and C. R. Wyss, Air Quality Survey at
Selected Sites on the Hanford Project, Pacific Northwest
Lab., Richland, Wash., Dept. of Environmental and Radio-
logical Sciences (Nov. 1967).
6. Alperstein, M., and R. L. Bradow, Exhaust Emissions
Related to Engine Combustion Reactions, Society of
Automotive Engineers, Fuels and Lubricants Meeting,
Houston, Tex. (Nov. 1-3, 1966).
7. Alpiser, F. M., Air Pollution from Disposal of Junk Autos,
Presented at the 61st Annual Meeting of the Air Pollution
Control Association, St. Paul, Minn. (June 23-27, 1968).
8. Altshuller, A. P., Reactivity of Organic Substances in
Atmospheric Photooxidation Reactions, Intern. J. Air
Water Pollution (Great Britain) .10:713 (1966).
9. Altshuller, A. P., "Analysis of Aliphatic Oxygenated
Compounds," in Air Pollution, vol. 2, A. C. Stern, Ed.
(New York: Academic Press, p. 130, 1968).
10. Altshuller, A. P., Director; Division of Chemistry and
Physics, National Air Pollution Control Administration,
Cincinnati, Ohio, personal communication (May, 1969).
11. Altshuller, A. P., and J. J. Bufalini, Photochemical
Aspects of Air Pollution: A Review, Photochem. Photobiol
4:97 (1965).
-------
70
12. Altshuller, A. P., and I. R. Cohen, Atmospheric Photo-
oxidation of the Ethylene-Nitric Oxide System, Accepted
for publication by J. Air and Water Pollution, Presented
at Symposium on Air Pollution, 145th Mectinq American
Chemical Society, New York (Sept. 8-13, 1963).
13. Altshuller, A. P., and I. R. Cohen, Structural Effects
on the Rate of Nitrogen Dioxide Formation in the Photo-
Oxidation of Organic Compound-Nitric Oxide Miartures in
Air, Intern. J. Air Water Pollution 7;787-97 (1963).
14. Altshuller, A. P., and I. R. Cohen, Photo-oxidation of
Acrolein-Nitrogen Oxide Mixtures in Air, Intern. J. Air
Water Pollution 7;1043 (1963).
15. Altshuller, A. P., and I. R. Cohen, Atmospheric Reactions
of Propionaldehyde in Air Mixtures, Atmospheric Environ.
1(3):319 (1967).
16. Altshuller, A. P., and L. J. Leng, Application of the
3-Methyl-2-Benzothiazolone Hydrazone Method for Atmo-
spheric Analysis of Aliphatic Aldehydes, Anal. Chem.
15(10):1541 (1963).
17. Altshuller, A. P., and S. P. McPherson, Spectrophoto-
metric Analysis of Aldehydes in the Los Angeles Atmo-
sphere, J. Air Pollution Control Assoc. 11(3) :109 (1963).
18. Altshuller, A. P., I. R. Cohen, and T. C. Purcell,
Photooxidation of Propionaldehyde at Low Partial Pressure
of Aldehyde, Can. J. Chem. 44:2973 (1966).
19. Altshuller, A. P., I. R. Cohen, and T. C. Purcell,
Photooxidation of Hydrocarbons in the Presence of
Aliphatic Aldehydes, Science 15j6( 3777) :937 (1967).
20. Altshuller, A. P., L. J. Leng, and A. F. Wartburg, Jr.,
Source and Atmospheric Analyses for Formaldehyde by
Chromotropic Acid Procedures, Intern. J. Air Water
Pollution 6;381 (1962).
21. Altshuller, A. P., D. L. Miller, and S. F. Sleva,
Determination of Formaldehyde in Gas Mixtures by the
Chromotropic Acid Method, Anal. Chem. 33(4):622 (1961).
22. Altshuller, A. P., et a^., Analysis of Aliphatic
Aldehydes in Source Effluents and in the Atmosphere,
Anal. Chim. Acta 25:101 (1961).
-------
71
23. Altshuller, A. P.f .gt al.., Products and Biological
Effects from Irradiation of Nitrogen Oxides with Hydro-
carbons or Aldehydes Under Dynamic Conditions, Intern.
J. Air Water Pollution 10;81 (1966).
24. Amdur, M. O., The Physiological Response of Guinea Pigs
to Atmospheric Pollutants, Intern.J. Air Water Pollution
JL:170 (1959).
25. Amdur, M. O., The Effect of Aerosols on the Response to
Irritant Gases, Inhaled Particles Vapours, Proc. Intern.
Symp., Oxford, Eng. ,pp. 281-92 (1960).
26. Amdur, M. O., The Response of Guinea Pigs to Inhalation
of Formaldehyde and Formic Acid Alone and With a Sodium
Chloride Aerosol, Intern. J. Air Water Pollution 3J4) :201
(1960).
27. Anderson, D. M., J. Lieben, and V. H. Sussman, Pure Air
For Pa., Pennsylvania Dept. of Health and Public Health
Service, U. S. Dept of Health, Education,and Welfare
(1961).
28. Anger, V., and G. Fischer, A New Spot Reaction of
Aldehydes, Mikrochim. Acta. p. 592 (1960).
29. Atmospheric Emissions from Petroleum Refineries (A
Guide for Measurement and Control), Public Health
Service, Cincinnati, Ohio, Division of Air Pollution
(1960).
30. Atmospheric Pollution in the Great Kanawha River Valley
Industrial Area, Bureau of Industrial Hygiene, West
Virginia State Dept. of Health, Charleston, Bureau of
Industrial Hygiene, and Cincinnati Univ., Ohio, Kettering
Lab. (1952).
31. Barber, E. D., and J. P. Lodge, Jr., Paper Chromato-
graphic Identification of Carbonyl Compounds as Their
2,4-Dinitrophenylhydrazones in Automobile Exhaust,
Anal. Chem. 35;348 (1963).
32. Barber, E. D., and E. Sawicki, The Separation and
Identification of Aromatic Carbonyl Compounds as Their
4- itrophenylhydrazones in Automobile Exhaust by Paper
and Thin-Layer Chromatography, Dept. of Health, Educa-
tion, and Welfare, Public Health Service, Cincinnati,
Ohio (1967).
-------
72
33. Barnes, E. C., and H. W. Speicher, The Determination of
Formaldehyde in Air, J. Ind. Hvg. Toxicol 24 ;9 (1942).
34. Basbagill, W. J., Air Contaminant Measurements at
Roosevelt Field, Nassau County, New York (January
February 1964), Public Health Service, Cincinnati,
Ohio, Division of Air Pollution (July 1965).
35. Basbagill, W. J., and J. L. Dallas, Air Quality in
Boston,. Massachusetts (November-December 1963),
Public Health Service, Cincinnati, Ohio, Division of
Air Pollution (Nov. 1964).
36. Battigelli, M. C., Air Pollution from Diesel Exhaust,
J. Occupational Med. 5;54 (1963).
37. Berger, L. B., and R. T. Artz, Kept. Invest. 4287
U. S. Bur, of Mines (May 1948).
38. Bourne, H. G., Jr., and S. Seffrin, Formaldehyde in
Wrinkleproof Apparel Produces Tears for Milady, Ind.
Med. Sura. 28;232 (1959).
39. Brennan, E. G., I. A. Leone, and R. H. Daines, Atmospheric
Aldehydes Related to Petunia Leaf Damage, Science
143(3608):818 (1964).
40. Bricker, C. E., and A. H. Vail, Microdetermination of
Formaldehyde With Chromotropic Acid, Anal. Chem. 22:720
(1950).
41. Brunelle, M. F., J. E. Dickinson, and W. J. Hamming,
Effectiveness of Organic Solvents in Photochemical
Smog Formation (Solvent Project, Final Rept.), Air
Pollution Control District, Los Angeles County, Calif.,
Evaluation and Planning Division (July 1966).
42. Calvert, J. G., and P. L. Hanst, The Mechanism of the
Photooxidation of Acetaldehyde At Room Temperature,
Can. J. Chem. 37;1671 (1959).
43. Catilina, P., L. Thieblot, and J. Champeix, Experimental
Lesions of the Respiratory System of Rats from Inhalation
of Acrolein, Arch, des Maladies Professionelles 27:857
(1966).
44. Chass, R. L., and R. E. George, Contaminant Emission
from Combustion of Fuels, J. Air Pollution Control
Assoc. 10;34 (1960).
45. Chass, R. L., ,£t al.., Total Air Pollution Emissions in
LOB Angeles County, J. Air Pollution Control Assoc.
10:351 (1960).
-------
73
46. Chemical Reactions in Los Angeles Snog, Proc. Natl.
Air Pollution Svmp., 2nd, Pasadena, Calif., pp. 28-34
(1952).
47. Chemical Safety Data Sheet SD-1, Properties and Essential
Information for Safe Handling and Use of Formaldehyde,
Rev. April I960, Mfg. Chemists' Assn., Washington, D.C.
48. Chemical Safety Data Sheet SD-85, Properties and
Essential Information for Safe Handling and Use of
Acrolein, Adopted 1961, Mfg. Chemists' Assn., Washing-
ton, D.C.
49. Cholak, J., Proc. Natl. Air Pollution Svmp., 2nd.,
Pasadena, Calif., pp. 6-15 (May 5-6, 1952).
50. Clean Air for California, State of California, Dept.
of Public Health (March 1955).
51. Cohen, 1. R., and A. P. Altshuller, A New Spectrophoto-
metric Method for the Determination of Acrolein in
Combustion Gases and in the Atmosphere, Anal. Ghent.
.33(6):726 (1961).
52. Community Air Quality Guides—Aldehydes, Am. Ind.
Hyg. Asaoc. J. 29(5):505 (1968).
53. Conlee, C. J., ,et al., Motor Vehicle Exhaust Studies at
Three Selected Sites, Preprint (1964).
54. Coulson, D. M., Polarographic Determination of Semi-
carbazones. Anal. Chim. Acta 19;284 (1958).
55. Cralley, L. V., The Effect of Irritant Gases Upon Rate
of Ciliary Activity, J. Ind. Hyq. & Toxicol. 24:193
(1942).
56. Cuffe, S. T., and R. W. Gerstle, Emissions from Coal-
Fired Power Plants: A Comprehensive Summary, National
Center for Air Pollution Control, U.S. Public Health Serv.
Publ. 999-AP-35 (1967).
57. Cvetanovic, R. J., Electrophilic Character of Oxygen
Atoms, Can. J. Chem. 38; 1678 (1960).
58. Dahle, E. W., Jr., Annual Report of the Bureau of
Industrial Hygiene, 1966, Baltimore City Health Dept.,
Md., Bureau of Industrial Hygiene (1966).
-------
74
59. Dalhamn, T., and J. Rhodin, Mucous Plow and Ciliary
Activity in Trachea of Healthy Rats and Rats Exposed
to Irritant Gases, Acta Phvsiol. Scandinav. 36 (Suppl.
123):1-16 (1956).
60. Danielson, J. A., Air Pollution Engineering Manual,
U.S. Oept. of Health, Education, and Welfare, Public
Health Service, Cincinnati, Ohio (1967).
61. Darley, E. R., J. T. Middleton, and M. J. Garber, Plant
Damage and Eye Irritation from Ozone-Hydrocarbon Reac-
tions, Agr. Food Chem. 8(6):483 (1960).
62. Davis, T. R. A., S. P. Battista, and C. J. Kensler,
Mechanism of Respiratory Effects During Exposure of
Guinea Pigs to Irritants, Arch. Environ. Health 15(4);
412 (1967).
63. Devorkin, H., .et .al.., Air Pollution Source Testing
Manual, Air Pollution Control District, Los Angeles
County, Calif. (1965).
64. Eliassen, K., Domestic and Municipal Sources of Air
Pollution, Proc. National Conference on Air Pollution
(Nov. 18-20, 1958); U. S. Public Health Serv. Publ.
654, Washington, D. C. (1959).
65. Elliott, M. A., and R. F. Davis, Composition of Diesel
Exhaust Gas, Presented at S.A.E. National Diesel
Engine Meeting, St. Louis (Nov. 1949).
66. Elliott, M. A., G. J. Nebel, and F. G. Rounds, The
Composition of Exhaust Gases from Diesel, Gasoline and
Propane Powered Motor Coaches, J. Air Pollution Control
Assoc. 5(2);103 (1955).
67. Ellis, C. P., Chemical Analyses of Automobile Exhaust
Gases for Oxygenates, Bur. Mines Rent. Invest. 5822
(1961).
68. Ellis, C. P., R. F. Kendall, and B. H. Eccleston,
Identification of Some Oxygenates in Automobile Exhausts
by Combined Gas Liquid Chromatography and Infrared
Techniques, Anal. Chem. 37(4);511 (1965).
69. Parr, J. P. G., Analyses for the Industry, Ind. Chemist
389 (1956).
70. Fassett, D. W., "Aldehydes and Acetals," in Industrial
Hygiene and Toxicology, vol. JI, F. A. Patty, Ed. (New York:
Interscience, 196 3).
-------
75
71. Feigl, P., Spot Tests in Organic Analysis (New York:
Elaevier, 1956).
72. Fiero, G. W., Solvents, Snog and Rule 66, J. Am. Soc.
Lubrication Engrs. 23(11);448 (1967).
73. Fleckenstein, L. J., Aldehydes, in Kirk-Othmer Encyclo-
pedia of Chemical Technology, vol. 1 (New York: Inter-
science, p. 639, 1963).
74. Formaldehyde—Controlling Chemical Hazards, Ser. No. 3,
U. S. Dept. of Labor, Govt. Printing Office, Washington,
D. C. (1945).
75. Formaldehyde Finds New Pastures, Chemical Week 95(23):113
(1964).
76. Formaldehyde, Its Toxicity and Potential Bangers,
Supplement, Public Health Rept. U.S. 181 (1945).
77. Fracchia, M. F., F. J. Schuette, and P. K. Mueller, A
Method for Sampling and Determination of Organic
Carbonyl Compounds in Automobile Exhaust, Environ.
Sci. Technol. 1(11):915 (1967).
78. George, R. E., and R. M. Burlin, Air Pollution from
Commercial Jet Aircraft in Los Angeles County, Los
Angeles County Air Pollution Control District, Calif.
(Apr. 1960).
79. Gofmekler, V. A., Effect of Embryonic Development of
Benzene and Formaldehyde in Inhalation Experiments,
Hyq. Sanitation 33;327 (1968).
80. Guest, H. R., B. W. Kiff, and H. A. Stansbury, Acrolein
and Derivatives, in Kirk-Othmer Encyclopedia of
Chemical Technology, vol. 1 iNew York: Interscience,
pp. 255-274, 1963).
81. Gusev, M. I., et al.., Determination of the Daily Average
Maximum Permissible Concentration of Acrolein in the
Atmosphere, Hvg. and Sanitation 31(1):8 (1966).
82. Haagen-Smit, A. J., .et al_.. Investigation on Injury to
Plants from Air Pollution in the Los Angeles Area,
Plant Phvsiol. 27:18 (1952).
83. Haggard, H. W., Action of Irritant Gases Upon Respiratory
Tract, J. Ind. Hyq. 5;390 (1923).
-------
76
84. Hamming, W. J., and R. D. MacPhee, Relationship of
Nitrogen Oxides in Auto Exhaust to Eye Irritation—
Further Results of Chamber Studies, Atmospheric Environ.
1(5):577 (1967).
85. Hangebrauck, R. P., D. S. von Lehmden, and J. E. Meeker*
Emissions of Polynuclear Hydrocarbons and Other Pollu-
tants from Heat-Generation and Incineration Processes,
PUblic Health Service, U. S. Dept. of Health, Education,
and Welfare, for Presentation at the Air Pollution
Control Assoc. Annual Meeting, Paper No. 63-49 (June 1963)
86. Hauser, T. R., and R. L. Cummins, Increasing Sensitivity
of 3-Methyl-2-Benzothiaz olone Hydrazone Test for Analysis
of Aliphatic Aldehydes in Air, Anal. Chem. 36(3);679
(1964).
87. Henson V. E., Toxicology of Some of the Aliphatic
Aldehydes/ J. Occupational Med. 1;457 (1959).
88. Hindawi, I. J., and A. P. Altshuller, Plant Damage
Caused by Irradiation of Aldehydes, Science 146(3643):540
(1964).
89. Hitchcock, L. B., _et al.., Air Pollution Situation in
Los Angeles—An Aerometric Survey, Proc. Natl. Air
Pollution Svmp., 3rd. Pasadena, Calif., pp. 12-23
(1955).
90. Hochheiser, S., M. Burchett, and H. J. Dunsmore, Air
Pollution Measurements in Pittsburgh (January-February
1963), Public Health Service, Cincinnati, Ohio, Division
of Air Pollution and Alleghany County Health Dept.,
Pittsburgh, Pa.,Bureau of Air Pollution Control (Nov.
1963).
91. Hochheiser, S., M. Nolan, and H. J. Dunsmore, Air
Pollution Measurements in Duquesne, Pennsylvania
(September-October 1963), Public Health Service,
Cincinnati, Ohio, Division of Air Pollution and Alle-
gheny County Health Dept., Duquesne, Pa., Bureau of
Air Pollution Control (Oct. 1964).
92. Hornedo, M. D., and J. H. Tillman, Air Pollution in
the El Paso, Texas Area, El Paso City, County Health
Unit, Tex. (1959).
93. Hovey, H. H., A. Risman, and J. F. Cunnan, The Develop-
ment of Air Contaminant Emission Tables for Nonprocess
Emissions, Presented at the 58th Annual Meeting, Air
Pollution Control Assoc., Toronto, Canada, Paper No.
65-17 (June 20-24, 1965).
-------
77
94. Hughes, K. J., and R. W. Hum, A Preliminary Study of
Hydrocarbon-Derived Oxygenated Material in Automobile
Exhaust Gases, J. Air Pollution Control Assoc. 10:367
(1960).
95. Hum, R. W., Comprehensive Analyses of Automotive
Exhausts, Arch. Environ. Health 5;592 (1962).
96. Hurn, R. W., et. al.., The Potpourri That is Exhaust Gas,
Am. Petrol. Inst.. Proc. 42(3);657 (1962).
97. Interstate Air Pollution Study, Phase II Report,
Section II, Air Pollutant Emission Inventory, U. S.
Dept. of Health, Education, and Welfare, Public Health
Service (1966).
98. Jacobs, M. B., Health Aspects of Air Pollution from
Incinerators, Proc. Natl. Incinerator Conf., New York,
pp. 128-31 (19*6471
99. Kaiser, E. R., et, al_., Performance of a Flue-Fed
Incinerator, J. Air Pollution Control Assoc. 9(2):85
(1959).
100. Katz, M., Some Aspects of the Physical and Chemical
Nature of Air Pollution, World Health Organ. Monograph
Ser. 46, pp. 97-158 (1961).
101. Kensler, C. J., and S. P. Battista, Chemical and Physical
Factors Affecting Mammalian Ciliary Activity, Am. Rev.
Respirat. Diseases 93(3);93 (1966).
102. Kinosian, J. R., J. A. Maga, and J. R. Goldsmith, The
Diesel Vehicle and Its Role in Air Pollution, State of
California, Dept. of Public Health, Bureau of Air
Sanitation, Berkeley, Calif. (1962).
103. Kopczynski, S. L., Photo-Oxidation of Alkylbenzene-
Nitrogen Dioxide Mixtures in Air, Intern.J. Air Water
Pollution 8:107 (1964).
104. Kreichelt, T. E., and E. W. Dahle, Jr., Air Pollution
Measurements in Baltimore, Md. (March and April 1964),
Public Health Service, Cincinnati, Ohio, Division of Air
Pollution and Bureau of Industrial Hygiene, Md.,
Baltimore City Health Dept. (Nov. 1964).
105. LaBelle, C. W., J. E. Long, and E. E. Christofano,
Synergistic Effects of Aerosols, A-M^A. Arch. Ind.
Health 11:297 (1955).
-------
78
106. Lahmann, E., and K. Jander, Determination of Formaldehyde
from Street Air, Text in German. Gesundh. Ingr. (Munich)
89(1):18 (1968).
107. Larson, G. P., J. C. Chipman, and E. K. Kauper, Study of
the Distribution and Effects of Auto Exhaust Gas,
J. Air Pollution Control Assoc. 5;84 (1955).
108. Larson, G. P., G. I. Fischer, and W. J. Hamming,
Evaluating Sources of Air Pollution, Ind. Enq. Chem.
.45:1070 (1953).
109. Leach, P. W., et ,al., Effects of HC/fcOx Ratios of
Irradiated Auto Exhaust, Part II, J. Air Pollution
Control Assoc. 14:176 (1964).
110. Leighton, P. A.,"Photochemical Aspects of Air Pollution,"
in Physical Chemistry, vol. IX (New York: Academic
Press, 1961).
111. Leonardos, G., D. A. Kendall, and N. J. Barnard, Odor
Threshold Determinations of 53 Odorant Chemicals, J. Air
Pollution Control Assoc. 19 ;91 (1969).
112. Levaggi, D. A., and M. Feldstein, Gas Chromatographic
Determination of Aldehydes, Bay Area Air Pollution
Control District, San Francisco, Calif. Presented at
State Health Dept. Methods Conference, Pasadena, Calif.
(Feb. 7-9, 1968).
113. Levaggi, D. A., and M. Feldstein, The Collection and
Analysis of Low Molecular Weight Carbonyl Compounds
from Source Effluents, J. Air Pollution Control Assoc.
19:43 (1969).
114. Linnell, R. H., and W. E. Scott, Diesel Exhaust Analysis
(Preliminary Results), Arch. Environ. Health ^:616
(1962).
115. Linnell, R. H., and W. E. Scott, Diesel Exhaust Composi-
tion and Odor Studies, J. Air Pollution Control Assoc.
12:510 (1962).
116. Louw, C. W., Atmospheric Pollutants and Their Analysis,
C.S.I.R. Special Report Smog 2, South African Council
for Scientific and Industrial Research, Pretoria (1966).
117. Lozano, E. R., W. W. Melvin, and S. Hochheiser, Air
Pollution Emissions from Jet Engines, Presented at 60th
Annual Meeting Air Pollution Control Assoc., Cleveland,
Ohio (June 11-16, 1967).
-------
79
118. Lyles, 6. R., F. B. Dowling, and V. J. Blanchard,
Quantitative Determination of Formaldehyde in the Parts
Per Hundred Million Concentration Level, J. Air Pollution
Control Assoc. 15(3)t!06 (1965).
119. Magill, P. L., and R. W. Benoliel, Air Pollution in
Los Angeles County: Contribution of Industrial Products*
Ind. Eng. Chem. 44;1347 (1952).
120. Magill, P. L., F. R. Holden, and C. Ackley, Air Pollution
Handbook (New York: McGraw-Hill, 1956).
121. Mathews, D. S., and J. J. Schueneman, Management of Dade
County's Air Resources, U. S. Dept. of Health, Education
and Welfare, Public Health Service, Cincinnati, Ohio
(1962).
122. Mayer, M., A Compilation of Air Pollutant Emission
Factors for Combustion Processes, Gasoline Evaporation,
and Selected Industrial Processes, Public Health Service,
Cincinnati, Ohio (1965).
123. McDowell, C. A., and L. K. Sharpies, The Photochemical
Oxidation of Aldehydes in the Gaseous Phase, Part 1,
Can. J. Chem. 36:251 (1958).
124. McDowell, C. A., and L. K. Sharpies, The Photochemical
Oxidation of Aldehydes in the Gaseous Phase, Part 2,
Can. J. Chem. 36;258 (1958).
125. McDowell* C. A., and S. Sifniades, Oxygen-18 Tracer
Evidence for the Termination Mechanism in the Photo-
chemical Oxidation of Acetaldehyde, Can. J. Chem.
41;300 (1963).
126. McMullen, T. B.f Technical Reports Unit, Division of Air
Quality and Emission Data, National Air Pollution
Control Administration, personal communication (May, 1969)
127. Melekhina, V. P., Maximum Permissible Concentration of
Formaldehyde in Atmospheric Air, USSR Literature on Air
Pollution and Related Occupational Diseases 3;135 (1960).
128. Melekhina, V. P., Hygienic Evaluation of Formaldehyde as
an Atmospheric Air Pollutant, U.S.S.R. Literature on
Air Pollution and Related Occupational Diseases 9_:9
(1962).
-------
80
129. Mendenhallf M. K., J. A. Jenicek,and J. M. Bryant,
Thermal Decomposition of Ether in the Infant Incubator,
J. Am. Med. Assoc. 173;651 (1960).
130. The Merck Index, 8th ed. (Rahway, N. J. : Merck, 1968).
131. Morgan, G. B., C. Golden, and E. C. Tabor, New and
Improved Procedures for Gas Sampling and Analysis in the
National Air Sampling Network, J. Air Pollution Control
Assoc. 17;300 (1967).
132. Morrill, E. E., Jr., Formaldehyde Exposure from Paper
Process Solved by Air Sampling and Current Studies,
Air Cond. Heat. Ventilating 58 ;94 (1961).
133. Motor Vehicles, Air Pollution and Health. A Report of
the Surgeon General to the U. S. Congress, 87th Congress,
2nd Session, House Document No. 489, Dept. of Health,
Education, and Welfare, Public Health Service, Washing-
ton, D. C. (June 1962).
134. Mueller, P. K., M. F. Fracchia, and F. J. Schuette,
152nd National Meeting, Am. Chem. Soc., New York (1966).
135. Murphy, S. D., and C. E. Ulrich, Multi-Animal Test
System for Measuring Effects of Irritant Gases and
Vapors on Respiratory Function of Guinea Pigs, Am.
Ind. Hva. Assoc. J. 25:28 (1964).
136. Murphy, S. D., H. V. Davis, and V. L. Zaratzian,
Biochemical Effects in Rats from Irritating Air
Contaminants, Toxicol. Appl. Pharmacol. 6(5);520 (1964).
137. Murphy, S. D., D. A. Klingshira, and C. E. Ulrich,
Respiratory Response of Guinea Pigs During Acrolein
Inhalation and Its Modification by Drugs, J. Pharm.
Exotl. Therap. 141 (1963).
138. Orning, A. A., C. H. Schwartz, and J. F. Smith, A Study
of the Minor Products of Coal Combustion, Am. Soc.
Mech. Engrs., Paper 64-PWR-4, Presented at the IEEE-ASME
National Power Conference, Tulsa, Okla. (Sept. 27-
Oct. 1, 1964).
139. Paul, F. M., Report to the Committee on Air Pollution,
Memo 31, Fuel Research Station, London (1954).
140. Perry, H., and J. H. Field, Air Pollution and the Coal
Industry, Trans. AIME 238(4);337 (1967).
-------
81
141. Plotnikova, M. M., Acrolein As an Atmospheric Air
Pollutant, Gjqiena i Sanit. 22:10 (1957); Translated
by B. S. Levine, U.S.S.R. Literature on Air Pollution
and Related Occupational Diseases 3:188 (May 1960).
142. Powick, W. C., A New Test for Acrolein and Its Bearing
on Rancidity in Fats, Ind. Encr. Ghent. 15_:66 (1923).
143. Prentiss, A. M., Chemicals in War (New York: McGraw-
Hill, 1937).
144. Purcell, T. C., and I. R. Cohen, Microdetermination of
Peroxides by Kinetic Colorimetry, Environ. Sci. Technol.
1:431 (1967).
145. Purcell, T. C., amd I. R. Cohen, Photooxidation of
Formaldehyde at Low Partial Pressures of Aldehyde,
Environ. Sci. Technol. 1:845 (1967).
146. Recfener, L. R., W. E. Scott, and W. F. Biller, The
Composition and Odor of Diesel Exhaust, Proc. Am.
Petrol... Inst> 45:133 (1965).
147. Renzetti, N. A., and R. J. Bryan, Atmospheric Sampling
for Aldehydes and Eye Irritation in Los Angeles Smog—
1960, J. Air Pollution Control Assoc. 11(9);421 (1961).
148. Renzetti, N. A., and E. A. Schuck, Preliminary Observa-
tions on the Relationship Between Eye Irritation in
Synthetic Systems and in the Atmosphere, Stanford
Research Inst., South Pasadena, Southern California
Labs (1960).
149. Renzetti, N. A., L. H. Rogers, and R. Tice, in An
Aerometric Survey in the Los Angeles Basin* August-
November 1954. N. A. Renzetti, ed.. Report No. 9, Air
Pollution Foundation, Los Angeles, Calif. (1955).
150. A Review of Air Pollution in New York State, New York
State Air Pollution Control Board, Albany (July 1958).
151. Reynolds, J. G., and M. Irwin, The Determination of
Formaldehyde and Other Aldehydes, Chem. Ind. 419
(1948).
152. Robison, C. B., J. C. Chambers, and J. W. Bates,
Defining the Problem of Air Pollution in Metropolitan
Birmingham, Alabama, Preprint, Ala. Jefferson County
Dept. of Health (1967).
-------
82
153. Rosenthaler, L., and G. Vegezzi, Detection and Determina-
tion of Acrolein in Alcoholic Liquors, Lebensm-Untersuch
U. Forsch.g9;352 (1954).
154. Roth, H. P., and E. A. Swenson, Physiological Studies of
Irritant Aspects of Atmospheric Pollution, Report to
the Los Angeles County Air Pollution Control District,
Los Angeles, Calif. (1957).
155. Rounds, F. G., and H. W. Pearsail, Diesel Exhaust Odor
(Its Evaluation and Relation to Exhaust Gas Composition),
Vehicle Emissions (Selected S.A.E. Papers) .6:45 (1964)
156. Salem, H., and H. Cullumbine, Inhalation Toxicities of
Some Aldehydes, Toxicol. Appl. Pharmacol. 2:183 (1960).
157. Sato, S., and R. J. Cvetanovic, Photooxidation of
Butenes by Nitrogen Dioxide at Different Wave Lengths,
Can. J. Chem. 36:1668 (1958).
158. Sato, S., and R. J. Cvetanovic, The Effect of Molecular
Oxygen on the Reaction of Oxygen Atoms with cis-2-
Pentene, Can. J. Chem. 37:953 (1959J.
159. Sawicki, E., Spot Test Detection and Spectrophoto-
metric Determination of Microgram Amounts of Aldehydes
and Aldehyde-Yielding Compounds—A Review, Preprint,
Presented at International Symposium on Microchemical
Techniques, University Park, Pa. (Aug. 13-18, 1961).
160. Sawicki, E., Airborne Carcinogens and Allied Compounds,
Arch. Environ. Health 14:46 (1967).
161. Sawicki, E., and T. R. Hauser, Infrared Spectral Detec-
tion of Carboxylic Acids and Aldehydes in Air-Borne
Particulates, Anal. Chem. 31;523 (1959).
162. Sawicki, E., and T. R. Hauser, Spot Test Detection and
Colorimetric Determination of Aliphatic Aldehydes with
2-Hydrozinobenzothiazole: Application to Air Pollution,
Presented at Air Pollution Symposium, 138th Meeting,
American Chemical Society, New York (Sept% I960),
163. Sawicki, E., and T. W. Stanley, Sensitive New Test for
Aliphatic, Aromatic and Heterocyclic Aldehydes, Mikrochim.
Acta p. 510 (1960).
-------
83
164. Sawicki, E., T. R. Hauser, and S. McPherson, Spectro-
photometric Determination of Formaldehyde and Formal-
dehyde-Releasing Compounds with Chromotropic Acid,
6-Aniino-l-naphthol-3-sulfonic Acid (J Acid), and
6-Anilino-l-naphthol-3-sulfonic Acid (Phenyl J Acid),
Anal. Chem.34;1460 (1962).
165. Sawicki, E. , T. W. Stanley, and H. Johnson, Comparison
of Spectro photometric and Spectrophotofluorometric
Methods for the Determination of Malonaldehyde, Anal.
Chem. 35:199 (1963).
166. Sawicki, E. , T. W. Stanley, and J. Pfaff, Spectro-
photofluorimetric Determination of Formaldehyde and
Acrolein with J-Acid, Comparison with Other Methods,
Anal. Chim. Acta 28 (1963).
167. Sawicki, E. , sL *L* » The 3-Methyl-2-benzothiazolone
Hydrazone Test. Sensitive New Methods for the Detection,
Rapid Estimation, and Determination of Aliphatic
Aldehydes, Anal. Chem. 33:92 (1961).
168. Sax, N. I., Dangerous Properties of Industrial Materials,
3rd ed. (New York: Reinhold, 1968).
169. Schuck, E. A., and 6. J. Doyle, Photooxidation of
Hydrocarbons in Mixtures Containing Oxides of Nitrogen
and Sulfur Dioxide /Report No. 29, Air Pollution Founda-
tion, San Marino, Calif. (1959).
170. Schuck, E. A., 6. J. Doyle, and N. Endow, A Progress
Report on the Photochemistry of Polluted Atmospheres,
Stanford Research Institute (1960).
171. Schuck, E. A., H. W. Ford, and E. R. Stephens* AJ
Pollution Effects of Irradiated Automobile Exhaust
As Related to Fuel Composition, Report No. 26, Air
Pollution Foundation, San Marino, Calif. (Oct. 1958).
172. Schuck, E. A., E. R. Stephens, and J. T. Middleton,
Eye Irritation Response at Low Concentrations of
Irritants* Arch. Environ. Health 13;570 (1966).
173. Schumann, C. E., and C. W. Gruber, Motorist Exposures
to Aldehydes from Diesel-Powered Buses, J. Air Pollution
Control Assoc. 14;53 (1964).
174. Scott, W. E., and L. R. Reckner, Progress Report on
Atmospheric Reaction Studies in the Los Angeles Basin
November 15, 1968 to January 15, 1969, APRAC Project
CAPA 7-68, Scott Research Laboratory (1969).
-------
84
175. Scott, W. E., .e£ ,al., Further Development in the
Chemistry of the Atmosphere, Am. Petrol. Inst. 37 ;171
(1957).
176. 2nd Technical and Administrative Report on Air Pollution
Control in Los Angeles County, 1950-51, Air Pollution
Control District, County of Los Angeles.
177. Selected Methods for the Measurement of Air Pollutants,
Public Health Service, Cincinnati, Ohio, Division of
Air Pollution (May 1965).
178. Senderikhina, D. P., Determination of Acrolein in the
Air, in Limits of Allowable Concentrations of Atmospheric
Pollutants, Boole 3 (1957).
179. Sheehy, J. P., W. C. Achinger, and R. A. Simon, Handbook
of Air Pollution, U. S. Public Health Serv. Publ.
999-AP-44 (1965).
180. Sigsby, J. E., Jr., T. A. Bellar, and L. J. Leng,
Dynamic Irradiation Chamber Tests of Automotive Exhaust
Part II. Chemical Effects, J. Air Pollution Control
Assoc. 12;522 (1962).
181. Sigsby, J. E., Jr., et .ajL., Behavior of Simple Systems
in a Large Irradiation Chamber, Presented at 145th
National Meeting American Chemical Society, New York,
(1963).
182. Sim, M., and R. E. Pattle, Effect of Possible Smog
Irritants of Human Subjects, J. Am. Med. Assoc. 165(15);
1908 (1957).
183. Skog, E., A Toxicological Investigation of Lower
Aliphatic Aldehydes, Acta Pharmacol. Toxicol. .6;299
(1950).
184. Skog, E., Anaesthetic and Haemolytic Action of Lower
Aldehydes and Their Effect on Respiration and Blood
Pressure, Acta Pharmacol. Toxicol. 8;275 (1952).
185. Smith, C. W. (fid.), Acrolein (New York: Wiley, 1962).
186. Smith, W. S., Atmospheric Emissions from Fuel Oil
Combustion, An Inventory Guide, Public Health Service
(1962).
187. Smith, W. S., and C. W. Gruber, Atmospheric Emissions
from Coal Combustion—An Inventory Guide, Public Health
Service (1966).
-------
85
188. The Smog Problem in Los Angeles County, Stanford
Research Institute, Western Oil and Gas Association
(1954).
189. Stenburg, R. L., .et aJL . , Effects of High Volatile
Fuel on Incinerator Effluents, J. Air Pollution Control
Assoc. 11:376 (1961).
190. Stenburg, R. L., &t ai_. f Field Evaluation of Combustion
Air Effects on Atmospheric Emissions from Municipal
Incinerators, J. Air Pollution Control Assoc. 12:83
(1962).
191. Stephens, E. R. , in Chemical Reactions in the Lower
and Upper Atmosphere, R. D. Cadle, Ed. (New Yorkx Inter-
science, p. 51, 1961),
192. Stephens, E. R. , and W. E. Scott, Relative Reactivity of
Various Hydrocarbons in Polluted Atmospheres, Proc.
A.P.I. 42:665 (1962).
193. Stephens, E. R., .et al.. , Photochemical Reaction Products
in Air Pollution, Intern. J. Air Water Pollution
£(1/2) :79 (1961).
194. Stern, A. C. , Present Status of Atmospheric Pollution
in the United States, Am. J. Public Health 50(3);346
(1960).
195. Stern, A. C. (Ed. ), Air Pollution, I . 2nd ed. (New York;
Academic Press , 1968 ) .
196. Stern, A. C. (Ed.), Air Pollution. II, 2nd ed. (New
York: Academic Press, 1968).
197. Stern, A. C. (Ed.), Air Pollution, III, 2nd ed. (New
York : Academic Press, 1968).
198. A Study of Air Pollution in the Interstate Region of
Lewiston, Idaho and Clarkston, Washington, U. S. Public
Health Serv. Publ. 999-AP-8 (Dec. 1964).
199. Taylor, O. C.,"Oxidant" Air Pollutants as Phototoxi-
cants, California Univ., Riverside, Air Pollution
Research Center Paper No. 64-91 (1964).
200. Taylor, 0. C. , et al . , Effect of Air-borne Oxidants on
Leaves of the Pinto Bean and Petunia, Am. Soc. Hort.
Sci. 75;435 (1960).
-------
86
201. Technical Progress Report, Air Quality of Los Angeles
County, vol. II, Air Pollution Control District County
of Los Angeles (1961).
202. The Tenth Annual Report—1962. New York Citv Dept. of
Air Pollution Control News 9(4) (Apr. 1963).
203. Thomas Register of American Manufacturers (New York:
Thomas Publishing Co., 1968).
204. Threshold Limit Values for 1967, Adopted at the 29th
Annual Meeting of the American Conference of Govern-
mental Industrial Hygienists, Chicago, 111. (May 1-2,
1967).
205. Tuesday, C. S., The Atmospheric Photooxidation of
Transbutene-2 and Nitric Oxide, in Chemical Reactions
in the Lower and Upper Atmosphere (New York: Inter-
science, pp. 1-49,1961).
206. U. S. Tariff Commission, Washington, u. C., personal
communication (Apr. 1969).
207. Uzdina, I. L., Determination of Acrolein and of Formal-
dehyde in the Air, Hig. Truda 15:63 (1937).
208. Vandaveer, R. E., and C. G. Segeler, Partial Combustion
of Gas with a Deficiency of Air, Ind. Encr. Chem. 37:816
(1945).
209. Walker, J. A., Influence of Gasoline Composition on the
Constitution of Engine Exhaust (Part II of Atmospheric
Pollution: A Survey of Some Aspects of the Emissions
from Petrol-Engined Vehicles and Their Treatment),
Brit. Techn. Council of the Motor and Petroleum Indus-
tries, England (Sept. 1965).
210. Walker, J. P., Formaldehyde. 3rd ed. (New York: Reinhold,
1964).
211. Walker, J. F., Formaldehyde, in Kirk-Othmer Encyclopedia
of Chemical Technology, vol. 10 (New York:Interscience,
pp. 77-99, 1966).
212. Wallach, A., Some Data and Observations on Combustion
of Gaseous Effluents from Baked Lithograph Coatings,
J. Air Pollution Control Assoc. 12(3);109 (1962).
-------
87
213. Wayne, L. G., The Chemistry of Urban Atmospheres (Tech-
nical Progress Report —Volume III), Los Angeles County
Air Pollution District, Calif. (Dec. 1962).
214. Weisburd, M. I., (Ed.), Air Pollution Control Field
Operations Manual (A Guide for Inspection and Enforce-
ment), Public Health Service, Washington, D.C.,
Division of Air Pollution (1962).
215. West, P. W., and B. Sen, Spectrophotometric Determination
of Traces of Formaldehyde, Z. Anal. Chem. 153:177 (1956).
216. Wetmiller, R. S., and L. E. Endsley, Effect of Diesel
Fuel on Exhaust Smoke and Odor, S.A.E. J. 50;509 (1942).
217. Williams, R. T., Detoxication Mechanisms, 2nd. ed.
(New York: Wiley, 1959).
218. Wohlers, H. C., and G. B. Bell, Literature Review of
Metropolitan Air Pollutant Concentration—Preparation,
Sampling and Assay of Synthetic Atmosphere, Stanford
Research Institute (1956).
219. Yant, W. P., et al.., Acrolein as a Warning Agent for
Detecting Leakage of Methyl Chloride from Refrigerators.
U. S. Bur, of Mines Kept. Invest. 3027 (1930).
220. Yocum, J. E., G. M. He in, and H. W. Nelson, Effluents
from Backyard Incinerators, J. Air Pollution Control
Assoc. 6;84 (1956).
221. Yunghans, R. S., and W. A. Monroe, Continuous Monitoring
of Ambient Atmospheres with the Technicon Auto Analyzer,
Presented at the Technicon Symposium, Automation in
Analytical Chemistry, New York (Sept. 8, 1965).
-------
APPENDIX
-------
TABLE 10
PROPERTIES, TOXICITY, AND USES OP SOME ALDEHYDES130
Aldehyde
Properties
Toxicitv
Uses
ALIPHATIC
ALDEHYDES
Formaldehyde
HCHO
mp-92°C
bp-19.5°C
Irritating to mucous membranes
Lcetaldehyde
CH3CHO
mp-123.5°C
Tap 21°C
Irritating to mucous membranes
General narcotic action. Large
doses may cause death by re-
spiratory paralysis. Symptoms
of chronic intoxication resem-
ble those of chronic alcohol-
ism. LDso orally in rats:
1.9
In manufacture of paral-
dehyde, acetic acid, bu-
tanol, perfumes, flavors,
cnilinc,dyes, plastics,
synthetic rubber; for
silvering mirrors, hard-
ening gelatin fibers
•
ropionaldehyde
mp-81°C
bp 49°C
May cause respiratory irrita-
tion. See acetaldehyde.
orally in rats: 1.4 g/kg;
lethal concentration for rats
in air: 8,000 ppm
(continued)
oo
v£>
-------
TABLE 10 (Continued)
PROPERTIES, TOXICny, AND USES OF SOME ALDEHYDES
Aldehyde
Properties
Toxicitv
Uses
Butyraldehyde
mp-99°C
bp 74.8°C
May act as irritant, narcotic
Single dose LDgQ orally in
rats: 5.89 g/kg body wt
Chiefly in the manufacture
of rubber accelerators,
synthetic resins, solvents,
plasticizers
C sobutyraldehyde
(CH3)2<
mp-65.9°C
bp 64°C
LDcp orally in rats: 3.7 g/kg
Lethal concentration for rats
in air: 16,000 ppm
In the synthesis of panto-
thenic acid, valine, leu-
cine, cellulose esters,
perfumes, flavors, plasti-
cizers, resins, gasoline
additives
•
-Valeraldehyde
bp 102-3°C
Has narcotic properties
common to most aldehydes;
is also a mild irritant
In flavoring compounds,
resin chemistry, rubber
accelerators
£ sovaleraldehyde
(CH3)2CHCH2CHD
mp-5lOC
bp 92-93°C
In artificial flavors and
perfumes
'ivalaldehyde
(CH3)3CCHO
mp 6°C
bp 75°C
(continued)
-------
TABLE 10 (Continued)
PROPERTIES, TOXICITY, AND USES OF SOME ALDEHYDES
Aldehyde
Properties
Toxicitv
Uses
Caproaldehyde
CH3(CH2)4CHO
mp-56°C
bp-128°C
Enanthaldehyde
CH3(CH2)5CHO
mp-43°C
bp 155°C
Caprylaldehyde
CH3(CH2)6CHD
bp 163.4°C
Pelargonaldehyde
CH3(CH2)7CHO
bp 185°C
Capraldehyde
CH3(CH2)8CHD
bp 208°C
UndecylaIdehyde
CH3(CH2)9CHO
mp -4
(continued)
\o
-------
TABLE 10 (Continued)
PROPERTIES, TOXICITY, AND USES OF SOME ALDEHYDES
Aldehyde
ALDEHYDES
Properties
Toxicity
Uses
&crolein
,=CHCHD
mp—88 C
bp 52.5°C
Irritates skin, mucous mem-
branes. Vapors cause lacrima-
tion. Sensitization, asthma
have been reported. L
30,000 M9/fcg sc in mice
In manufacture of colloidal
forms of metals; in making
plastics, perfumes; as
warning agent in methyl
chloride refrigerant. Has
been used in military poi-
son gas mixtures. Used in
organic syntheses
Crotonaldehyde
CH3CH=CHCHO
mp-76.5°C
bp 104.0°C
Highly irritating to eyes,
skin, and mucous membranes.
Lethal concentrations for
guinea pigs in air, 2,000 ppm
In manufacture of butyl al-
cohol, cutyraldehyde, quin-
aldine. As warning agent in
fuel gases in locating
breaks and leaks in pipes.
Minor amounts are used in
the manufacture of maleic
acid, crotyl alcohol, butyl
chloral hydrate, and in
rubber accelerators. In
organic syntheses; as sol-
vent in purification of
mineral oils; in manufac-
ture of resins, rubber anti
oxidants, insecticides. In
chemical warfare
(continued)
-------
TABLE 10 (Continued)
PROPERTIES, TOXICITY, AND USES OF SOME ALDEHYDES
Aldehyde
Properties
Toxicitv
Uses
rig laidehyde
CH3CH=C ( CH3 ) CHO
bp 102°C
AROMATIC
ALDEHYDES
Benzaldehyde
bp 179°C
Narcotic in high concentra-
tions. May cause contact
dermatitis. LD sc in rats,
In manufacture of dyes,
perfumery, cinnamic and
mandelic acids; as solvent;
in flavors
>-Tolualdehyde
CgHgO
bp 200-202°C
n-Tolualdehyde
bp 199UC
-Tolualdehyde
bp 204-205°C
Cinnamaldehyde
bp 246.0°C
In the flavor and perfume
industry
(continued)
-------
TABLE 10 (Continued)
PROPERTIES, TOXICITY, AMD USES OF SOME ALDEHYDES
Aldehyde
Properties
Toxicitv
Uses
STEROCYCLIC
ALDEHYDES
'urfural
bp 161.8°C
Irritates mucous membranes
and acts on central nervous
system. About one-third as
toxic as formaldehyde. Causes
lacrimation, inflammation of
eyes* irritation of throat,
headache. Chronic toxicity
causes nervous disturbances/
inflammation of eyes, photo-
sensitivity, disturbance of
vision. LD50 orally in dogs,
2.3 gAg
In manufacture of furfural-
phenol plastics such as
Durite; in solvent refining
of petroleum oils; in the
preparation of pyromucic
acid. As a solvent for ni-
trated cotton, cellulose
acetate, and gums; in the
manufacture of varnish;
for accelerating vulcani-
zation; as insecticide,
fungicide, germacide; as
reagent in analytical
chemistry. In the syntheses
of furan derivatives
>OLYFUNCTIONAL
ALDEHYDES
Slyoxal
imp 15°C
bp 51°C
Moderately irritating to skin,
mucous membranes. LD50 orally
in rats, 2.0 g/kg
(continued)
-------
TABLE 10 (Continued)
PROPERTIES, TOXICITY, AND USES OF SOME ALDEHYDES
Aldehyde
Properties
Toxicity
Uses
Pyruvaldehyd e
C 3*1402
top 72°C
Isophthaial-
dehyde
rap 89°-90°C
bp 2450-248°C
rerephthalal-
dehyde
mp 116°C
bp 247°C
vO
ui
-------
96
APPENDIX
TABLE 11
TOXICITY OP ALDEHYDES TO ANIMALS VIA INHALATION70
Compound
Species
ppm
Time.hr
Mortality
SATURATED ALIPHATIC ALDEHYDES
Formal dehyde
Ac et aldehyde
Prop i ona 1 dehyde
Ethoxypropionaldehyde
Oip-Dichloropropion-
aldehyde
n-Butyraldehyde
I sobutyral dehyde
P -Hydroxybutyra Idehyde
(aldol, acetaldol)
n- Val eraldehyde
2-Methylbutyraldehyde
n-Hexa Idehyde
(hexanal )
Rat
Rat
Cat
Cat
Rat
Rat
Rat
Cat
Cat
Cat
Rat
Rat
Rat
Rat
Rat
Rat
Rat
Rat
Rat
Rat
Rat
Rat
Rat
Rat
Rat
Rat
Rat
250
815
650
200
Sat vapb
16,000
20,000
13,600
4,100
256
8,000
60,000
26,000
500
Coned vapc
16
8,000
60,000
8,000
4,000
Sat vap
48,000
1,400
67,000
3,800
1,043
Coned vap
2,000
4
0.5
8
3.5
2 min
4
30 min
0.25
3-5
5
4
0.3
0.5
4
2 min
4
4
0.5
4
4
0.5
1.2
6
0.3
6.0
6.0
4
4
LCso3
LCso
LC5Q approx
All survived
LCiQO
0/6
LC50
1/1
0/1
0/1
5/6
3/3
LC50
6/6
6/6
4/6
1/6
LCso
1/6
2/6
No deaths
3/3
0/3
3/3
0/3
0/3
0/6
1/6
(continued)
-------
97
APPENDIX
TABLE 11 (Continued)
TOXICITY OP ALDEHYDES TO ANIMALS VIA INHALATION
70
Compound
Species
ppm
Time, hr
Mortality
SATURATED ALIPHATIC ALDEHYDES (Continued)
2-Ethylbutyraldehyde
Rat
Rat
2-Ethylhexylaldehyde Rat
(a-ethylcaproa1dehyde) Rat
Rat
Rat
Coned vap
8,000
25,000
4,000
2,000
145
5 min
1
13 min
4
23 min
6
Acrolein
Methacrylaldehyde
(Methacrolein)
2-Ethyl-3-propyl
acrolein
CrotonaIdehyde
(P-methyl acrolein)
Methyl-P-ethyl acrolein
(2-methyl-2-penten-
1-al)
UNSATURATED ALIPHATIC ALDEHYDES
Rat 8 4
Cat 690-1,150 2
Cat 18-92 3-4
Cat 11 3-10
Rat 130 30 min
Rat 250 4
Rat Coned vap 8
Rat Coned vap 1 min
Rat 1,400 30 min
Rat 2,000
Succ ina Idehyde
(25% in H20)
Hexa-2,4-dienal
3-Methyl glutaraIde-
hyde
ALIPHATIC PIALDEHYDES
Rat Coned vap 6
(ca. 15,000
ug/liter)
Rat 2,000 4
Rat Coned vap 8
Rat Coned vap 6
0/6
5/6
3/3
1/6
3/3
0/3
1/6
3/3
0/2
0/2
LC50
5/6
0/6
0/6
LC50
3/6
0/3
1/6
0/6
0/3
(continued)
-------
98
APPENDIX
TABLE 11 (Continued)
TOXICITY OF ALDEHYDES TO ANIMALS VIA INHALATION70
Compound Species ppm Time, hr Mortality
ALIPHATIC DIALDEHYDES (Continued)
a-Hydroxyadipaldehyde Rat Coned vap 8 0/6
5LC = Lethal concentration.
"Sat vap = Saturated vapor.
GConcd vap = Concentrated vapor.
-------
99
APPENDIX
TABLE 12
REPORTED ALDEHYDE EMISSION DATA3
Emissions
Community (tons/year)
Florida
Dade County 1,737
Idaho
Lewi ston, Clark ston, an d
Washington area 169
Illinois
Madison County 534
Monroe County 63
St. Clair County 811
Missouri
Jefferson County 206
St. Charles County 89
St. Louis (city) 1,139
St. Louis County (excluding city
of St. Louis 853
New York
ghemqpy County
Town
Baldwin 1
Catlin 2
Chemung 2
Erin 1
Van Etten 2
Veteran 4
Rest of County 361
Total for Chemung County 373
Columbia County
City
Hudson 35
Town
Ancram 3
Austerlitz 3
Canaan 3
Chatham 11
Claverack 15
(continued)
-------
100
APPENDIX
TABLE 12 (Continued)
REPORTED ALDEHYDE EMISSION DATA
Emissions
Contmunitv (tons/year)
New York (continued)
Columbia County (continued)
Town (continued)
Clermont 2
Copake 4
Gallatin 2
German-town 7
Ghent 13
Greenport 209
Hillsdale 4
Kinderhook 13
Livingston 4
New Lebanon 4
Stockport 6
Stuyvesant 4
Taghkanic 1
Village13
Chatham 6
Philmont 7
Kinderhook 2
Valatie 4
Total for Columbia County 343
Dutchess County
City
Beacon 64
Poughkeepsie 120
Town
Amenia 37
Beekman 4
Clinton 5
Dover 30
East Fishkill 20
Fishkill 26
Hyde Park 45
La Grange 24
Milan 3
Northeast 14
Pawling 16
Pine Plains 6
Pleasant Valley 15
(continued)
-------
101
APPENDIX
TABLE 12 (Continued)
REPORTED ALDEHYDE EMISSION DATA
Emissions
Community _ ____ _ (tons/year)
New York (continued)
Put chess County (continued)
Town .(continued)
Poughkeepsie 168
Red Hook 24
Rhinebeck 18
Stanford 5
Union Vale 3
Wappinger 33
Washington 15
Village^
Wappinger s Falls 18
Fishkill 2
Millerton 2
Pawling 5
Red Hook 5
Tivoli 3
Rhinebeck 6
Millbrook _ 4
Total for Dut chess County 695
City
Buffalo 7,225
Lacka wanna 272
Tonawanda 138
Town
Amherst 227
Cheektowaga 351
Hamburg 205
Tonawanda 3 , 776
West Seneca 160
Alden 40
Aurora 36
Boston 14
Brant 11
Clarence 66
Golden 12
Collins 50
Concord 20
Eden 26
(continued)
-------
102
APPENDIX
TABLE 12 (Continued)
REPORTED ALDEHYDE EMISSION DATA
Emissions
Community (tons/year)
New York (continued)
Eric County (continued)
Town (continued)
Elm 28
Evans 43
Holland 13
Lancaster 34
Marilla 8
Newstead 25
North Collins 11
Orchard Park 26
Sardinia 9
Wales 8
Village0
Blaedell 23
Depew 70
Hamburg 33
Kenmore 97
Lancaster 62
Sloan 34
Williamsville 45
Akron 35
Alden 12
Angola 13
East Aurora 34
Farnham 3
Qowanda 5
Grand Island 32
North Collins 10
Orchard Park 16
Springville 24
Greene County
Town
Ashland 1
Athens 10
Cairo 11
Catskill 472
Coxsackie 20
Durham 8
Greenville 10
Hunter 9
(continued)
-------
103
APPENDIX
TABLE 12 (Continued)
REPORTED ALDEHYDE EMISSION DATA
Emissions
Community (tons/year)
New York (continued)
Greene County (continued)
Town (continued)
Jewett 1
Lexington 2
New Baltimore 7
Prattsville 3
Windham 7
Village*3
Athens 6
Catskill 20
Coxsackie 8
Hunter 2
Tannersville 2
Total for Greene County 561
Rockland County
Town
Clarkstown 100
Haverstraw 78
Orangetown 156
Ramapo 120
Stoney Point 203
Village0^
Stoney Point 203
Spring Valley 21
Upper Nyack 5
Haver straw 37
West Haverstraw 15
Grandview-on-Hudson 1
Nyack 18
Piennont 14
South Nyack 8
Hillbum 29
Suffern 16
Sloatsburg 3
New Square 1
Total for Rockland County 657
~~""~ (continued)
-------
104
APPENDIX
TABLE 12 (Continued)
REPORTED ALDEHYDE EMISSION DATA
Emissions
Community (tons/year)
New York (continued)
Ulster County
City
Kingston 280
Town
Esopus 31
Gardiner 5
Hardenburgh 1
Hurley 14
Kingston 2
Lloyd 21
Marbletown 11
Maryborough 15
New Paltz 18
Olive 5
Plattekill 12
Rochester 9
Rosendale 24
Saugerties 37
Shandaken 9
Shawangunk 14
Ulster 36
Wawarsing 36
Woodstock 25
Village0
New Paltz
Rosendale
Saugerties
Ellenville
Total for Ulster County
Westchester County
City
White Plains 131
Peekskill 98
Mount Vernon 136
New Rochelle 164
Yonkers 396
Rye 37
(cont inued)
-------
105
APPENDIX
TABLE 12 (Continued)
REPORTED ALDEHYDE EMISSION DATA
Emissions
Community (tons/year)
New York (continued)
WestChester County (continued)
Town
Bedford 84
Cortlandt 135
East chaster 128
Greenburg 207
Harrison 77
Lewisboro 37
Mamaroneck 66
Mount Pleasant 129
New Castle 70
North Salem 42
Ossining 72
Pelham 30
Pound Ridge 24
Rye 110
Scarsdale 43
Somers 52
Yorktown 84
Village*
Ossining 42
Port Chester 75
Mamaroneck 40
Scarsdale 43
Mount Kisco 22
Croton 40
Bronxville 13
Tuckahoe 20
Ardsley 10
Dobbs Ferry 15
Hastings 26
Irvington 12
Tarrytown 25
Larchmont 12
Briarcliff Manor 17
North Tarrytown 29
Pleasantville 20
North Pelham 8
Pelham 4
(continued)
-------
106
APPENDIX
TABLE 12 (Continued)
ALDEHYDE EMISSION DATA
Emissions
Community (tons/year)
New York (continued)
Westchester County (continued)
Village (continued)
Pelham Manor 16
Elmsford 14
Buchanan 27
Total for Westchester County 2,400
aThese data compiled from References 1-4,97,98,121
^Village data included in appropriate towns.
-------
APPENDIX
TABLE 13
U.S. PRODUCTION OP FORMALDEHYDE, 1958-68206
Production
Date (Thousands of Pounds)
1958
1959
1960
1961
1962
1963
1964
1965
1966
1967
1968
1,358,444
1,750,218
1,872,448
1,752,395
2,398,067
2,537,236
2,839,884
3,106,572
3,712,568
3,707,093
4,099,586
Quantity of Sales
(Thousands of Pounds)
542,142
685,986
678,262
723,254
835,572
919,763
1,067,340
1,189,434
1,359,981
1,289,720
Value of Sales
(Thousands of Dollars)
19,286
22,965
22,649
23,633
26,474
27,799
27,973
30,199
36,751
33,633
-------
108
APPENDIX
TABLE 14
PRINCIPAL U.S. MANUFACTURERS OF ACROLEIN AND FORMALDEHYDE203
Manufacturer
Location
ACROLEIN (and its derivatives)
Shell Chemical Co.
Union Carbide Corp. Chemicals Div.
New York, N.Y.
New York, N.Y.
FORMALDEHYDE (and its derivatives)
Allied Chemical Corp. Nitrogen Div.
Baker, J. T., Chemical Co.
Big Ben Chemicals & Solvents, Inc.
Borden Chemical Co.
Celanese Chemical Co.
Commerce Chemical Corp.
Commercial Solvents Corp.
Degussa Inc. Chemical Div.
du Pont, E. I., de Nemours & Co., Inc.
General Aniline & Film Corp.
Georgia-Pacific Corp.
Globe Chemical Co., Inc.
Hachik Bleach Co.
Harshaw Chemical Co.
Haviland Products Co.
Hercules Inc.
Hubbard Hall Chemical Co.
King, E. & F., & Co., Inc.
Kraft Chemical Co.
Lewis, John D., Inc.
Mallinckrodt Chemical Works
McKesson & Robbins, Inc.
Merck & Co., Inc.
Monsanto Co. Plastics Div.
Nicholson & Co.
Nitine, Inc.
Octagon Process, Inc.
Philipp Brothers Chemicals, Inc.
Reichhold Chemicals Inc.
Riverside Chemical Co., Inc.
Robinson Brothers Chemicals, Inc.
Scholle Chemical Corp.
Seaway Chemical Corp.
Siegel Chemical Corp.
Tenneco Chemicals, Inc.
Treys, Geo. I., Co.
Union Carbide Corp. Chemicals Div.
Washing Chemical Corp.
N.J
N
N
N
N
.Y.
.Y.
.Y.
.Y.
Del
New York, N.Y.
Phillipsburg,
Chicago, 111.
New York,
New York,
New York,
New York,
Kearny, N.J,
Wilmington,
New York, N.Y.
Portland, Ore.
Cincinnati, Ohio
Philadelphia, Pa.
Cleveland, Ohio
Grand Rapids, Mich.
Wi Imington, Del.
Waterbury, Conn.
Norwood, Mass.
Chicago, 111.
Providence, R. j..
St. Louis, Mo.
New York, N.Y.
Rahway, N.J.
Springfield, Mass.
Cambridge, Mass.
Whippany, N.J.
Edgewater, N.J.
New York, N.Y.
White Plains, N.Y.
North Tonawanda, N.Y.
Brooklyn, N.Y.
Northlake, 111.
Buffalo, N.Y.
Brooklyn, N.Y.
New York, N.Y.
Cooks Falls, N.Y.
New York, N.Y.
Lodi, N.J.
-------
109
APPENDIX
TABLE 15
USES OP FORMALDEHYDE IN THE UNITED STATES, 1964211
Percentage of
Formaldehyde
Use Consumption
Resins
Phenolic
Urea
Melamine
Acetal
Urea-formaldehyde concentrates
Industrial
Agricultrual
Special chemicals
Hexamethylenetetramine
P en tacry thr ito 1
Ethylene glycol
Sequestering agents
Other uses 9.1
-------
APPENDIX
TABLE 16
YIELDS OF ALDEHYDES VIA PHOTOCHEMICAL OXIDATION OF HYDROCARBON-NITROGEN OXIDE MIXTURES
11
Hvdro carbon
Ethylene
Prouvlene
1-Butene
Isobutene
Tr an 8 - 2-but en e
Cis-2-butene
1 , 3 -Butadiene
1-Pentene
2-Methvl-2-butene
1 , 3-Pentadiene
2-Methvl-l , 3-pentadiene
Cis-3-hexene
2, 3-Dimethyl-2-butene
Cvclohexene
2 , 3-Dimethvl-l , 3-butadiene
3-Heptene
Toluene
p-Xylene
o-Xvlene
m-Xvlene
1,3, 5-Trimethvlbenzene
1,2,4, 5-Tetramethvlbenzene
Moles/mole of initial hydrocarbon
Formaldehyde
0.35,0.45
0.32,0.45
0.40,0.45
0.45,0.4
0.7,0.6
0.3-0.45,0.6
0.6,0.5-0.7
0.35,0.35
0.6,0.6,0.5
0.55
0.5,0.3
0.65
0.55
0.25
0.4
0.65
0.8
0.15
0.15
0.15
Acetaldehvde
0.01
0.4,0.15-0.2
0.01
1.40,1.5
0.9-1.2
0.9,0.8-1.0
0.01
0.75,0.4-0.5
Aero le in
0.55,0.25
0.2
0.35
0.4
Total or Other
0.9,0.5
1.0,0.9
0.4
1.3
0.9
1.0,0.9-1.0,
0.9-1.0
1.3
1.2
0.11
0.26
0.22
0.25,0.3
0.6,0.3,0.4
0.45
-------
TABLE 17
REPORTED ALDEHYDE EMISSIONS FROM AUTOMOBILE ENGINES
Source
Automobile, general
(1 gal gasoline =6.25 Ib)
Cruise
Acceleration or deceleration
Automobile, general
Idle
Acceleration
1 Deceleration
Fuel
House Brand (Mid-continent
area regular grade)
Idle
40 raph cruise
50 mph cruise
60 mph cruise
40 mph 2/3 max torque
Acceleration (15 to 60 mph
in 25 sec)
Deceleration (50 to 15 mph
in 25 sec)
Nest Coast regular brand
(WOGA No. 3)
Idle
Aldehydes
(as Formaldehyde)
(ucr/m3)
3.4 lb/1,000 gal gasoline
4 lb/1, 000 gal gasoline
10 lb/1,000 gal gasoline
17.5 lb/1,000 gal gasoline
18.7 lb/1,000 gal gasoline
3.3 lb/1,000 gal gasoline
7.1 lb/1,000 gal gasoline
18, 000
56,400
238,800
58,800
184,800
114, 000
112,800
115,200
72,000-142,800
289,000-967,200
60, 000
Formaldehyde
(ug/nn
24,000
99,600
48, 000
46,800
39,600
36,000-46,800
106,800-282,000
34,800
Acrolein
(ug/m3)
Ref.
218
45
93
50
119
176
176
209
209
209
95,96
95,96
95,96
95,96
95,96
95,96
95,96
95,96
(continued,
-------
TABLE 17 (Continued)
REPORTED ALDEHYDE EMISSIONS FROM AUTOMOBILE ENGINES
Source
40 mph cruise
60 nph cruise
40 mph 2/3 max torque
West Coast aromatic
(WOGA No. 2 A)
Idle
40 mph cruise
60 mph cruise
40 mph 2/3 max torque
West Coast paraffinic
(WOGA No. 2P)
Idle
40 mph cruise
60 mph cruise
40 mph 2/3 max torque
Engine mode
Idle
Cruise
Cruise, 30 mph
Cruise, 15 mph
40 mph
60 mph
Deceleration (coasting)
Aldehydes
(as Formaldehyde)
(ua/m3)
140, 400
114, 000
61,200
88,800
180, 000
106,800
129,600
62,400
163,200
128,400
98,400
100, 000
105,600
72,000
200,000
316,800
168, 000
93,600
105,600
114, 000
Form aldehyde
(uo/m3!
80,400
49,200
36,000
19,200
54, 000
39,600
21,600
32,400
97,200
51,600
57,600
36,000
34,800
54, 000
52,800
Acrolein
(ua/m3)
21,250
17,500
Ref.
95,96
95,96
95,96
95,96
95,96
95,96
95,96
95,96
95,96
95,96
95,96
119
139
150
119
139
150
22,51
67
67
67
22,51
(continued)
-------
TABLE 17 (Continued)
REPORTED ALDEHYDE EMISSIONS FROM AUTOMOBILE ENGINES
Source
Gasoline, 707 in3
(44-passenger coach)
Idle
Acceler at ion
Cruise, 30 xnph
Deceleration
Chicago Transit Driving Pattern
Propane, 477 in3
(50-passenger coach)
Idle
Acceleration
Cruise, 30 roph
Deceleration
Chicago Transit Driving Pattern
Aldehydes
(as Formaldehyde)
(ncr/ma)
Formaldehyde
(ug/m3}
36,000; 0.048 SCFH*
19,200; 0.157 SCFH
8,400; 0.048 SCFH
343,200; 0.756 SCFH
0.17 SCFH
36,000; 0.025 SCFH
21,600; 0.157 SCFH
27,600; 0.123 SCFH
206,400; 0.247 SCFH
0.11 SCFH
Acrolein
(ug/m3)
Ref.
66,155
66,155
66,155
66,155
66,155
66,155
66,155
66,155
66,155
66,155
*Standard cubic feet per hour at 60°C and 760 mm,
H
H
to
-------
APPENDIX
TABLE 18
REPORTED ALDEHYDE EMISSIONS FROM DIESEL ENGINES
Source
Aldehydes
(as Formaldehyde)
(ug/m3)
Formaldehyde
(iiq/m3)
Acrolein
(ug/m3)
Ref,
Diesel engine
Diesel engine
Diesel engine
Diesel, 2 cycle,
No. 2 fuel
Idle
No load
*5 load
Full load
Diesel, 2-cycle,
426 in3, full
load, 2,000 rpm
Diesel, 2 cycle,
6 cylinder, 220 hp,
supercharged,
No. 2 fuel
600 rpm, 0 hp
1,000 rpm, 50 hp
1,200 rpm, 100 hp
1,600 rpm, 150 hp
2,200 rpm, 200 hp
2.5 lb/1,000 Ib fuel
10 lb/1,000 gal burned
16 lb/1,000 gal burned
114,000
13,200; 192,000a
8,760; 84,240a
9,720; 40,200a
15,600; 38,400a
51,600
108
218
93
197
197
197
197
102
6,240
4,056
3,567
12,240
21,720
11,175
2,100
3,500
7,425
7,800
114
114
114
114
114
(continued)
-------
APPENDIX
TABLE 18 (Continued)
REPORTED ALDEHYDE EMISSIONS FROM DIESEL ENGINES
Source
Aldehydes
(as Formaldehyde)
(uq/m3)
Formaldehyde
Cuq/m3)
Acrolein
(Uti/m3)
Ref,
Diesel, 2 cycle,
No. 2 fuel
500 rpm, no load
1,200 rpm, h load
1,600 rpm, full
load
Diesel, 2 cycle,
426 in3 (45-
passenger coach):
Idle
Acceleration
Cruise, 30 mph
Deceleration
Chicato Transit
Driving Pattern
Diesel, 4 cycle,
No. 2 fuel
Idle
No load
% load
Full load
12,720; 0.027
Ib/gal fuel
5,520; 0.004
Ib/gal fuel
22,800; 0.005
Ib/gal fuel
10,500; 0.020
Ib/gal fuel
3,500; 0.002
Ib/gal fuel
12,750; 0.003
Ib/gal fuel
146
146
146
10,800; 0.073
20,400; 0.509 SCFH
13,200; 0.203 SCFH
34,800; 0.541 SCFH
0.24 SCFH
8,160? 130,800a
2,160; 26,160a
8,160; 23,400a
5,160; 7,200a
66,155
66,155
66,155
66,155
66,155
197
197
197
197
(continued)
01
-------
APPENDIX
APPENDIX
TABLE 18 (Continued)
REPORTED ALDEHYDE EMISSIONS FROM DIESEL ENGINES
Source
Diesel* 4 cycle
673 in3
Full load
2,000 rpm
1,000 rpm
Half load
2,000 rpm
1,000 rpm
Diesel/ 4 cycle,
6 cylinder, 300 hp
turbo supercharged ,
No. 2 fuel, club
propeller as a load
700 rpm
800 rpm
1,050 rpm
1,300 rpm
1,520 rpm
1,685 rpm
1,780 rpm
Diesel, 4 cycle,
No. 2 fuel
740 rpm, no load
Aldehydes
(as Formaldehyde)
(ua/m3)
57,600
Formaldehyde
(uq/m3)
5,040
9,240
4,800
4,800
12,600
23,880
18,120
16,800
20,160
32,040
25,080
31,200; 0.036
Ib/gal fuel
Acrolein
(ua/m3)
22,200
40,500
42,500
33,500
43,500
13,000
Ref .
102
102
102
102
114
114
114
114
114
114
114
146
(continued)
a\
-------
APPENDIX
TABLE 18 (Continued)
REPORTED ALDEHYDE EMISSIONS FROM DIESEL ENGINES
Source
1,200 rpm, no load
J* load
*5 load
3/4 load
Full load
1/500 rpm, no load
% load
*5 load
3/4 load
Full load
1,800 rpm, no load
% load
J$ load
3/4 load
Full load
Diesel, 1959
Plymouth Savoy,
Perkins P4C, 4 cyl-
inder, 4 stroke
Idle
Acceleration
Aldehydes
(as Formaldehyde)
(uQ/ma)
49,200
21,600
28,800
26 , 400
38,400
50,400
34,800
32,400
31,200
55,200
48,000
34,800
28,800
44,400
67,200
48,000
7,200
Formaldehyde
(uq/m3)
39,600
14,400; 0.006
Ib/gal fuel
21,600
21,600
31,200; 0.005
Ib/gal fuel
33,600
21,600
20 , 400
22,800
37,200
39,600
24,000
18,000
36,000
48,000
Acrolein
(ua/m3)
12,500
4,500
3,500
4,500
2,000
13,750
3,500
4,250
4,750
7,500
12,500
8,000
6,500
5,750
8,250
[
Ref.
146
146
146
146
146
146
146
146
146
146
146
146
146
146
146
102
102
H
H
•sj
(continued)
-------
APPENDIX
TABLE 18 (Continued)
REPORTED ALDEHYDE EMISSIONS FROM DIESEL ENGINES
Source
Aldehydes
(as Formaldehyde)
(ug/m3)
Forma1dehyde
(ug/m3)
Aerolein
(uq/raa)
Ref.
Diesel, 1959
Mercedes-Benz 1900
Idle
Acceleration
Diesel, mine loco-
motive
Idle
Upgrade haul
Downgrade haul
48,000
20,400
54,000
31,200
69,600
102
102
37,102
jData normalized to (CO+COa) = to 15 percent to correct for dilution by excess air,
Standard cubic feet per hour at 60°C and 760 mm.
H
CO
-------
APPENDIX
TABLE 19
REPORTED ALDEHYDE EMISSIONS FROM COMMERCIAL AIRCRAFT
Source
Aldehydes
(as Formaldehyde)
Formaldehyde
Ref.
Jet Aircraft (Los Angeles
County) 1960
1965 (projected)
Operations3 (I960), total
(below 3,500 ft.)
Taxiing
Take off
Cliirib-out
Approach
Landing
Aircraft., jet turbine
(estimated 15,000 Ib thrust)
Idle
Cruise
Take off
Aircraft, total operations
(below 3,500 ft.)
Jet, 4 engines
Turboprop, 2 engines
Turboprop, 4 engines
Piston engine, 2 engines
Piston engine, 4 engines
0.1 ton/day
0.6 ton/day
230 Ib/day
91 Ib/day
16 Ib/day
15 Ib/day
83 Ib/day
25 Ib/day
6,000 jjig/ma , 2 Ib/hr
1,200 ug/m3, 1.5 Ib/hr
Trace
4 Ib/flight, 6 lb/1,000
gal fuel
0.3 Ib/f light, 5 lb/1,000
gal fuel
1.1 Ib/f light
0.2 Ib/flight, 5 lb/1,000
gal fuel
0.5 Ib/f light
78
78
78
78
78
78
78
78
197
197
197
97,122
97,122
97,122
97,122
97,122
(continued)
-------
TABLE 19 (Continued)
REPORTED ALDEHYDE EMISSIONS FROM COMMERCIAL AIRCRAFT
Source
Aircraft, turboprop, T-56
Departure0
Arrival0
100% power (take off)
75% power (cruise and
approach)
65% power (idle)
Aircraft, conventional jet, J-57
Departure0
Arrival0
100% power (take off)
75% power (cruise)
65% power (idle)
Aircraft, fan- jet, TF-33
Departure0
Arrival0
100% power (take off)
75% power (approach
65% power (idle)
Aldehydes
(as Formaldehyde)
0.14 Ib
0.13 Ib
4,920 ug/m3» 0.5 Ib/hr
2,400 ug/m3, 0.2 Ib/hr
5,760 ug/m3, 0.3 Ib/hr
0.19 Ib
0.25 Ib
960 ug/m3 , 0.5 Ib/hr
960 ug/m3 , 0.4 Ib/hr
3,000 Ug/m3, 0.4 Ib/hr
2.04 Ib
2.62 Ib
720 ug/m3/ 0.4 Ib/hr
360 ug/m3 , 0.3 Ib/hr
25,200 ug/m3, 0.4 Ib/hr
Formaldehyde
1,320 ug/m3, 0.2 Ib/hr
2,280 ug/m3, 0.2 Ib/hr
4,200 ug/m3, 0.2 Ib/hr
600 ug/m3, 0.4 Ib/hr
600 ug/m3 , 0.3 Ib/hr
2,800 ug/m , 0.4 Ib/hr
Ref.
^
117
117
117
1
117
117
117
117
117
117
117
117
117
117
117
117
aBased on 40 arrivals and departures per day.
^Flight defined as a combination of take off and landing.
°Based on 4 engines, taxiing time, plus take off and climb-out or approach
and landing.
N>
o
-------
121
APPENDIX
TABLE 20
REPORTED ALDEHYDE EMISSIONS FROM COMBUSTION OF COAL
Source
Aldehydes (as
Formaldehvde)
Pormaldehvde
Ref.
Bituminous (27,200,000 BTU/ton)
Anthracite (25,200,000 BTU/ton)
Bituminous from pulverized fuel
of cyclone furnaces
Flue gas
Coal-burning power plants,*
full load
Before ash-collecting
Vertical boiler
Corner boiler
Front-wall boiler
Spreader-stoker boiler
Cyclone boiler
Horizontally opposed boiler
After ash-collecting
Vertical boiler
Front-wall boiler
Spreader-stoker boiler
Cyclone boiler
Horizontally opposed boiler
Power plants
Industrial
Domestic and commercial
2 Ib/ton
1 Ib/ton
<0.01 Ib/ton
60-300 ug/m3
0.005 Ib/ton
0.005 Ib/ton
0.005 Ib/ton
300 ug/m3
204 ug/m3
168 ug/m3
72 ug/m
204 ug/m3
120 ug/m3
144 ug/m3
144 ug/m3
96 ug/m3
120 ug/m3
84
93
93
140
140
55,138,
187
122
122
122
*1,200 ug/m3 £ 1 ppm x 10 Ib/lO"8 BTU.
-------
APPENDIX
TABLE 21
REPORTED ALDEHYDE EMISSIONS FROM COMBUSTION OF FUEL OIL
Source
Fuel Oil
Distillate (~7 lb/gal)*
Residual (~8 lb/gal)
No. 2
Small sources
(If 000 hp or less)
(-8 lb/gal)
Extreme range
Usual range
Large sources
(1,000 hp or more)
(~8 lb/gal)
Extreme range
Kerosene burners
Fan-assisted pot
(20,000 kcal/hr output)
Good condition
Bad condition
Wall flame
(10,000 kcalAr output)
Good condition
Bad condition
ug/m3
0-216,000
0-39,600
0-80 , 400
4,800
16,800
3,600
30,000
ppm
0-180
0-33
0-67
4
14
3
25
Ib/hr
lb/
1,000 lb
.28
(0-2.07)
.14
1.3
0-3.3
0-0.6
0-1.2
Ref .
93,218
93,218
93,218
186
186
186
197
197
197
197
(continued)
to
to
-------
APPENDIX
TABLE 21 (Continued)
REPORTED ALDEHYDE EMISSIONS FROM COMBUSTION OF FUEL OIL
Source
Pressure atomizing
(10,500 kcal/hr output)
Good condition
Bad condition
Fuel oil, No, 1
Scotch marine boiler, 150 hp
Ceramic kiln
Ceramic kiln
Fuel oil, heavy
Fire tube boiler, 120 hp
Scotch marine boiler, 125 hp
Water tube boiler, 245 hp
Water tube boiler, 425 hp
Water tube boiler, 460 hp
Water tube boiler, 500 hp
Water tube boiler, 580 hp
Water tube boiler, 870 hp
Fuel oil, No. 2
Fire tube boiler, 60 hp
Fire tube boiler, 300 hp
Scotch marine boiler, 200 hp
Scotch marine boiler, 350 hp
Water tube boiler, 100 hp
Water tube boiler, 200 hp
Water tube boiler, 245 hp
Oil heater
ucr/m3
3,600
12,000
6,000
4,200
4,080
8,400
10,800
9,600
4,800
8,400
20,400
10,200
57,600
10,800
7,200
62,400
3,600
6,000
9,600
8,400
13,200
ppm
3
10
5
3.5
3.4
7
9
8
4
7
17
8.5
48
9
6
52
3
5
8
7
11
Ib/hr
0.04
0.0037
0.020
0.05
0.08
0.2
0.2
0.2
1.0
0.12
1.8
0.017
0.08
0.50
0.06
0.013
0.04
0.04
0.015
lb/
1,000 lb
Ref .
197
197
44
44
44
44
44
44
44
44
44
44
44
44
44
44
44
44
44
44
44
1
to
b)
*1,000 lb £ 140 gal or 84 gal ~ 12 X 106 BTU.
-------
TABLE 22. REPORTED ALDEHYDE EMISSIONS FROM NATURAL GAS COMBUSTION
Source
Aldehyde
Ref.
Natural gas-fired appliances and industrial
and commercial equipment
Bunsen burner
Oven range
Water heater, 100 gal
Floor furnace
Steam boiler (107 BTU/hr) (low fire)
Industrial burners
Boilers and process heaters
Scotch marine boilers
Fire tube boilers
Water tube boilers
75 gal water heater
Space heater
Bake oven
Industrial oven, indirect
Ceramic kilns/ indirect
Natural gas combustion (12 X 10e BTU 3 12,000 ft3 gas)
Natural gas combustion (1,000 Ib gas ~ 21,785 ft3 or
23 X 10s BTU)
Natural gas (~0.045 lb/fta; 1,000 BTU/ft3)
Propane (-0.117 Ib/ft3j 2,522 BTU/fta)
Butane (-0.154 Ib/ft3j 3,261 BTU/ft3)
Power plants
Industrial
Domestic and commercial
2,400
13,200 ug/ma; 0.02 lb/10fl BTU
9,600 ug/ma; 0.01 lb/10e BTU
3,600 ug/ma; 0.005 lb/10e BTU
6,000 ng/ma; 0.01 lb/106 BTU
58,800 ug/ma
0.0028 lb/10e BTU
2,400-8,400 ng/m3
4,800 Mg/ma
3,600-13,200 iag/in3
2,400 ug/in3
2,400 ug/m3
7,200 iag/m
3,600-7,200 ug/m3
2,400-8,400
0.7 lb/12 X 106 BTU
1 lb/1,000 Ib gas
10 lb/10e ft3 gas
26 lb/106 ft3 gas
34 lb/10e ft3 gas
0.02 lb/1,000 Ib gas;
1 lb/10e ft3 gas
0.1 lb/1,000 Ib gas;
2 lb/108 ft3 gas
0.25 lb/1,000 Ib gas
197
197
197
197
197
197
197
197
197
197
197
197
197
197
197
218
50,119,
188
93
93
93
214
214
214
214
214
to
-------
APPENDIX
TABLE 23
REPORTED ALDEHYDE EMISSIONS FROM INCINERATORS
Aldehydes (as Formaldehyde)
Ref.
Domestic incinerators
AOA prototype, shredded paper
AGA prototypef USASI* domestic wastes
AGA prototype, other refuse mixtures
New manufacturers' units* shredded paper
New manufacturers' units, USASI domestic
wastes
Older units, shredded paper
Older units, USASI domestic wastes
Domestic incinerator
Domestic incinerator
Domestic, single chamber
Without auxiliary gas burning
With auxiliary gas burning
[Municipal incinerators
Glendale, Calif., with scrubber
01endale, Calif., without scrubber
Alhambra, Calif., with spray chamber
Three units in Calif.with scrubber
Three units in Calif* without scrubber
Incinerator, municipal
Incinerator, large and/or multistage
Incinerator, multichamber
Other incinerators
Single chamber
Wood waste
Backyard (Battelle), paper and trimmings
Backyard, 6 ft3, paper
Backyard, 6 ft3, trimmings
9,600-25,200 ug/ma; 0.9-2.3 Ib/ton
9,600 ug/m ; 0.8 Ib/ton
20,400-26,400 ug/m3; 1.2-3.1 lb/ ton
4,800-80,400 ug/m3; 0.17-15.9 Ib/ton
30,000-48,000 ug/m3
28,800-57,600 ng/m3
6,000-36,000 ug/m3
4.0 Ib/ton refuse
1.4 Ib/ton refuse
6 Ib/ton refuse
2 Ib/ton refuse
1,200-12,000 ug/m3
1,200-26,400 ug/m3
58,800 ug/m3; 1.1 Ib/ton
10,800-32,400 ug/n»a
1,200-56,400 ug/m3
1.4 Ib/ton refuse
1.1 Ib/ton refuse
1.1 Ib/ton refuse
0.03-2.7 Ib/ton
40,800 ug/m3; 1.8 Ib/ton
912,000 ug/m3; 29 Ib/ton
58,800 ug/m3; 2.1 Ib/ton
122,400 ug/m3; 5.7 Ib/ton
5-6 Ib/ton
197
197
197
197
197
197
197
120
120
97,122
97,122
197
197
197
197
197
, 120
I 120
I 122
197
'• 197
197
\ 197
, 197
to
tn
(continued)
-------
APPENDIX
TABLE 23 (Continued)
REPORTED ALDEHYDE EMISSIONS FROM INCINERATORS
Source
Aldehydes (as Formaldehyde)
Ref.
Other incinerators (continued)
Backyardi 3 ft , mixed rubbish
Incinerator* apartment, flue-fed
Incinerators
Commercial and domestic, small and/or
single-stage
Industrial and commercial, single chamber
Multiple chamber
Apartment, flue-fed
Multiple chamber, experimental (asphalt,
felt roofing, and newspaper)
Incinerator, automobile, afterburner on
Afterburner off
Incinerator, pathological waste
Placental tissue in newspaper
Dogs freshly killed
5.1 Ib/ton
2.5-7.8 Ib/ton refuse
129,600-984,000 ug/m3
3 Ib/ton refuse (0.1-4.5 Ib/ton)
5-64 Ib/ton refuse
0.3 Ib/ton refuse (0.14-0.85 Ib/ton)
5 Ib/ton refuse
0.008-0.32 Ib/ton material;
~120-1,200 ug/m3b
3,600 Mg/m3
19,200 ug/m8
0.985 Ib/ton, 0.013 lb/ hr
0.617 Ib/ton, 0,033 Ib/hr
197
99
98
93
97
60,97,
122
122
189
189
189
189
60
60
&United States of America Standards Institute.
^Figures given are range of formaldehyde.
-------
TABLE 24
ALDEHYDE EMISSIONS FROM OIL REFINERIES29
Equipment
Unit Source
Catalytic cracking unit
Fluid
Thernofor
Boiler* and process heaters
Fuel gas
Fuel oil
Compressor internal
combustion engines
Emission Factors*
ua/m"
pan
3,600-48,000
10,800-212,400
3-130
9-177
19
12
3.1*
25
o.ir
Emission Rates
in Los Angeles
Area, tons/dav
1.9
1.5
0.4
0.5
Calculated as formaldehyde.
blb/l,000 fta fuel gas.
M
-------
128
APPENDIX
TABLE 25
REPORTED ALDEHYDE EMISSIONS PROM VARIOUS SOURCES
Source
Aldehyde Emissions
(as Formaldehyde)
Ref,
Amberglass manufacture
Regenerative furnace, gas fired
Brakeshoe debonding
(single-chamber oven)
Core ovens
Direct gas-fired (phenolic resin
core binder from oven)
Direct gas-fired (linseed oil core
binder from afterburner)
Indirect electric (linseed oil
core binder from oven)
(from afterburner)
Insulated wire reclaiming
Rubber covered 5/8" o.d.
Secondary burner off
Secondary burner on
Cotton-rubber-plastic covered,
3/8" to 5/8" o.d.
Secondary burner off
Secondary burner on
Meat smokehouses
Pressure mixing burner
Afterburner inlet
Afterburner outlet
Multijet burner
Afterburner inlet
Afterburner outlet
Meat smokehouse effluent, gas-fired
boiler-firebox as "afterburner"
Water-tube, 426 hp
Afterburner inlet
Afterburner outlet
Water-tube, 268 hp
Afterburner, inlet
Afterburner, outlet
Water-tube, 200 hp
Afterburner, inlet
Afterburner, outlet
8,400 Mg/m3
0.10 lb/hr
62,400 ug/ra3
<12,000 ug/m3
189,600 ug/m3
<22,800 ug/m3
126,000
6,000 ug/m3
10,800-43,200 ug/m3
4,800 ug/m3
0.04 IbAr
0.22 IbAr
0.49 lb/hr
0.22 IbAr
0.22 IbAr
0.09 lb.hr
0.39 IbAr
0.40 IbAr
0.39 lb/hr
0.30 IbAr
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
(continued)
-------
129
APPENDIX
TABLE 25 (Continued)
ALDEHYDE EMISSIONS FROM VARIOUS SOURCES
Source
Locomotive, 113 hp
Afterburner inlet
Afterburner outlet
HRT, 150 hp
Afterburner inlet
Afterburner outlet
Meat smokehouse exhaust
Gas-fired afterburner, inlet
Outlet
Electrical precipitation system
Inlet
Outlet
Mineral wool production
Blow chambers
Curing ovens
Catalytic afterburner, inlet
Outlet
Direct-flame afterburner, inlet
Outlet
Wool coolers
Litho oven, inlet
Outlet
Outlet
Paint bake oven
Nozzle mixing burner
Afterburner inlet
Afterburner outlet
Atmospheric burner
Catalytic afterburner inlet
Catalytic afterburner outlet
Premix burner
Catalytic afterburner inlet
Catalytic afterburner outlet
Phthalic acid plant
Phthalicanhydride production unit
( mult i jet burner)
Afterburner inlet
Afterburner outlet
Aldehyde Emissions
(as Formaldehyde)
0.03 Ib/hr
0.0 Ib/hr
0.03 Ib/hr
0.18 Ib/hr
104,400 ug/m3
40,200 ug/m3
88,800 ug/m3
56,400 ug/m3
109 ug/m3
1.90 Ib/hr
0.90 Ib/hr
2.20 Ib/hr
0.94 Ib/hr
32 ug/m3
120 ug/m3
32,880 ug/m3
4,680 ug/m3
0.19 Ib/hr
0.03 Ib/hr
0.07 Ib/hr
0.31 Ib/hr
0.3-0.4 Ib/hr
0.2-0.5 Ib/hr
135,600 ug/m3
1.75 Ib/hr
0.43 Ib/hr
Ref.
60
60
60
60
60
60
60
60
60
60
60
60
60
60
113
113
113
60
60
60
60
60
60
113
60
60
(continued)
-------
130
APPENDIX
TABLE 25 (Continued)
REPORTED ALDEHYDE EMISSIONS FROM VARIOUS SOURCES
source
Reclaiming of electrical windings
( single- chamber incinerator)
100 hp generator starter
14 pole pieces
Auto armatures
Auto field coils
(Multiple chamber)
Auto field coils
Afterburner
14 generator pole pieces
Varnish cooking kettles
Four-nozzle mixing burner
Afterburner inlet
Afterburner outlet
Inspirator burner
Afterburner inlet
Afterburner outlet
Webb press
Aldehyde Emissions
(as Formaldehyde)
0.08 Ib/hr
0.08 Ib/hr
0.13-0.29 Ib/hr
0.49 Ib/hr
0.08 Ib/hr
0.08 Ib/hr
0.30 Ib/hr
0.11
0.29 Ib/hr
0.02 Ib/hr
480 ug/m3
360 ug/ro3
480 ug/m
1,920 ug/m3
Ref.
60
60
60
60
60
60
60
60
60
60
113
113
113
113
-------
APPENDIX
TABLE 26 INDUSTRIAL OVEN EFFLUENTS41
[Process
Adhesive
1 coating
Duplicate
1 tests
Tube coating
Duplicate
tests
&uto body
painting
duplicate
tests
Container
coatinq
Container
coating
Container
coatinq
Container
coating
Container
coating
Container
coatinq
Container
coatinq
Predominant
Solvent Type
Low boiling
allcanes
Alcohols
Mixed ketones
High-boiling
allcanes
High-boiling
allcanes
Aromatics
High-boiling
alkanes and
aromatics
Aromatics
Aromatics
Aromatics
Aldehydes (as Formal -
dehvde) (ua/ra3 )
Averaqe**
88,800(5)
3,000(6)
5,100(4)
19,800(6)
15,000(4)
27,960(4) .
52,800(6)
27,000(4)
79,200(4)
22,800(4)
33,960(4)
60,600(4)
79,200(4)
490,800(4)c
82,800(4)
60,000(4)
Ranqe
73,200-
106,800
1,200-
6,000
0-12,000
1,200-
51,600
4,800-
32,400
16,800-
56,400
33,600-
102,000
12,000-
34,800
48,000-
134,400
8,400-
36,000
20,400-
45,600
39 , 600-
87,600
58,800-
120,000
277,200-
820,800°
45,600-
136,800
26,400-
91,200
Formaldehyde
(aq/m3)
Averaqe
600(2)
2,700(4)
9,600(4)
8,520(4)
19,200(3)
9,600(4)
37,200(4)
3,840(4)
15,000(4)
26,400(4)
7,800(4)
27,600(4)
33,600(4)
25,200(4)
Ranqe
0-1 , 200
1,200-
6,000
4,800-
15,600
5,280-
10,320
14,400-
27,600
7,080-
11,880
18,000-
62,400
3,000-
4,200
8,400-
18,000
10,800-
42,000
6,000-
10,800
24,000-
32,400
16,800-
55,200
8,400-
43,200
Acrolein
diq/m3)
Averaqe
12.5
12.5
12.5
12.5
3,325(2)
1,975(2)
9,300(2)
14,000(2)
19,500
1,875(2)
7,000(2)
11,000(2)
1,575(2)
8,225(2)
21,750(2)
11,500(2)
Ranqe
3,225-
3,425
1,825-
2,100
8,450-
10,125
12,500-
15,500
1,775-
1,975
5 , 250-
9,000
9,750-
12.000
1,425-
1,725
5,225-
11,200
18,500-
24,750
11,000-
12,000
Samp-
ling
Point1
A
A
A
A
B
B
C
C
D
C
E
C
C
D
D
^Number in parentheses represents number of determinations made.
"A: From vent near oven entrance; B: From oven; C: Near front of oven at inlet to
exhaust system; D: From stack after passing through direct-flame, gas-fired afterburner; E:
From stack after passing through catalytic afterburner.
cMay be in error due to interfering compound.
-------
132
TABLE 27
CONCENTRATION OF ALDEHYDES IN THE AIR, 1967126
Location
Alaska
Fairbanks County
Arkansas
El Dorado
Colorado
Denver
Delaware
Wilmington
District of Columbia
Washington
Illinois
Chicago
Indiana
East Chicago
Indianapolis
Iowa
Des Moines
Massachusetts
Boston
Michigan
Detroit
Minnesota
Minneapolis
Missouri
Kansas City
St. Louis*
New Jersey
Camden
Newark
New York
New York City
Ohio
Cincinnati
Cleveland
Oklahoma
Oklahoma City
Tulsa
Oregon
Portland
Min
2
4
2
7
1
1
1
1
1
2
1
2
4
1
1
7
1
1
1
17
1
1
uq/m3
Max
12
20
21
67
24
25
40
35
16
78
129
19
18
92
39
91
22
35
15
161
151
5
Avg
5
13
9
30
8
9
17
13
5
31
29
8
10
21
12
22
12
11
6
79
42
3
No. of
Samples
4
7
8
11
16
18
18
17
13
12
17
12
16
36
14
16
12
22
16
14
14
5
(continued)
-------
133
TABLE 27 (Continued)
CONCENTRATION OP ALDEHYDES IN THE AIR, 1967126
Location
Pennsylvania
Philadelphia
Pittsburgh
Tennessee
Chattanooga
Texas
El Paso
Pasadena
Utah
Salt Lake City
Washington
Seattle
West Virginia
Charleston
Min
1
2
2
2
1
2
1
1
uq/m3
Max
27
36
11
30
81
19
16
85
Avq
9
9
6
9
25
9
5
28
No. of
Samples
11
9
12
9
12
9
11
16
*Figures given are from two sites.
-------
>PENDIX
TABLE 28
CONCENTRATION OP ALDEHYDES IN THE AIR, 1958-67a
(ng/m3)
r
Location
[
Alabama
1 Jefferson County
California
1 Los Angeles
1 County
1 ' Los Angeles
1 South Pasadena
•Indiana
1 Indianapolis
Maryland
1 Baltimore
Ma s sa chu sett s
Boston
Mew York
Manhattan
Roosevelt Field
Pennsylvania
Duquesne
Pittsburgh
1958
Max
.30
i
Avq
.10
1959
Max
.23
Avq
.10
1960
Max
.43
.32
.24
Avq
.17
.13
1961
Max
.06 '.27
Avq
.08
1962
Max
.37
Avq
.11
i
1963
Max
1.6
.13
.22
.23
.10
Avq
1964 * 1966
Max
;
i
I
.08
.07
.23
.11
.02
i
Avq Max
.05
.02
Avq
I
.10
.05
t
'<
•
1967
Max
Avq
.01
(continued)
W
-------
TABLE 28(Continued)
CONCENTRATION OF ALDEHYDES IN THE AIR, 1958-67
Location
Texas
El Paso
East El Paso
Northwest
El Paso
Washington
Hanford Project,
near Richland
1958
Max
Avq
1959
Max
• .20
• .59
. CO
• . D
-------
TABLE 29
CONCENTRATION OF ALDEHYDES IN THE AIR, 1951-57a
(ug/ma)
Location
California
Los Angeles
West Los Angeles
Los Angeles County
Highland Park
Pasadena
Rivera
El Monte
Azusa
Bur bank
[Kentucky
1 Louisville
Michigan
Jew York
Manhattan
Ohio
Cincinnati
West Virginia
Kanawha River Valley
1951
Max
.40
.24
.54
Avq
.14
1952
Max
.32
i J>
.04
.06
Avq
.20
1953
Max
.90
Avq
.18
1954
Max
1.0
Avq
.14
1955
Max
.82
.78
Avq
.13
.16
1956
Max
1.6
«
Avq
.10
1957
Max
.54
Avq
.06
c ooD «>il> _
1.8
.73
.92
.78
.56
.17
.18
.14
.14
.17
.18
.06
.54
•
.25
• V/Tr
.16
10
2.2
.47
.44
.56
1.3
.18
.06
.05
.05
.07
.10
aData compiled from References 30,116,150,201,202.
bArrow indicates time period for sample.
Ok
-------
137
TABLE 30
CONCENTRATION OF ALDEHYDES3 IN METROPOLITAN
AREAS BY POPULATION, 1958194
Metropolitan Area
Population
Average Values
Average Range
Maximum Values
Average
Range
Greater than 2,000,000
500,000 to 2,000,000
Less than 500,000
290 240-340b x,100b i,000-1,200
80 840b 140-2,200
50b 440 160-720
*As formaldehyde.
bLess than three cities reported in "average."
-------
TABLE 31
COMPARISON OF METHODS FOR THE DETERMINATION OF FORMALDEHYDE166
peacrent
p-Aminobenzaldehyde
Ischiff
phromotropic acid
J-acid (dication)
fflT + NBD
J-acid (monocation)
Phenylhydrazine
max
440
550
578
468
610
612
520
peer ' s Law
€ X io"3 Ranae(ur)a
2.5
3.5
15.7
21.0
24
34
34.2
12-120
2 . 0-40
1.5-32
0.88-15
0.88-15
dilution
Factorb
2.5
5
10
5
10
12.5
25
Sensitivity0
1.0
0.7
1.57
4.2
2.4
2.7
1.4
Color
Stability
Time
~30 rain
>24 hr
>24 hr
10 roin
15 min
Interferences
Aliphatic aldehydes
Formaldehyde-yielding
compounds
Formaldehyde -y ie Id ing
compounds
All aldehydes
Formaldehyde-yielding
compounds
(continued)
<*J
oo
-------
COMPARISON OF METHODS FOR THE DETERMINATION OF FORMALDEHYDES
Reaaeni^
HBT
Fhenyl J-acid
IMBTH
l-Ethylquinal-
dinium iodide
T-acid fluor.
max
582
660
670
608
Excit.
A max
470
exio'3
48.0
51.4
65.0
73d
Emiss.
A max
520
Beer's law
Ranqe(uq)
0.62-12.5
0.56-13
0.5-9.2
0.40-8.2
0.01-2
Dilution
Factor6
10
20
12.5
10
20
10
Sensitivity0
4.8
2.4
4.1
6.5
3.25
7.3
Color
Stability
20 min
>24 hr
>40 min
30 min
>120 min
Water-soluble aliphatic
aldehydes give molar
absorptivities of about
1,800
Formaldehyde-yielding
compounds
Water-soluble aliphatic
aldehydes, aromatic
amines, imino hetero-
cyclic compounds
Other aliphatic alde-
hydes give molar ab-
sorptivities of about
1,500 to 15,000
Formaldehyde-yielding
compounds, acrolein
Seer's law is not obeyed in Schiff and 1-ethylquinaldinium procedures. The Beer's law
range is based on 10 ml final volume; lower limits for this range are taken at an absorbance of
0.1.
^Dilution factor is the proportion of final volume to test solution volume.
GSensitivity =
H
w
VO
dilution factor
dFor 9.9 IJL of formaldehyde.
------- |